NOVEL RU-NI-S ELECTRODE CATALYST FOR PEMFC

Science.gov (United States)

The expected results from this project include: a new formula and preparation procedures for Ru-Ni-S catalyst; demonstration of CO and S tolerance of the new catalyst; a small size PEMFC with Ru-Ni-S catalyst and good performance; an...

Coherence Kondo gap in CeNiSn and CeRhSb

International Nuclear Information System (INIS)

Takabatake, T.; Nakamoto, G.; Tanaka, H.; Bando, Y.; Fujii, H.; Nishigori, S.; Goshima, H.; Suzuki, T.; Fujita, T.; Oguro, I.; Hiraoka, T.; Malik, S.K.

1994-01-01

CeNiSn and CeRhSb are Kondo-lattice compounds showing the behavior of a small-gap semiconductor at temperatures below 7 K. We review and discuss the magnetic, transport and specific-heat measurements performed on single crystals of CeNiSn and polycrystals of CeRhSb. Prerequisites for gap formation are deduced from the effects of substitution and application of a magnetic field and pressure on the gapped state. ((orig.))

The role of Ni in sulfided carbon-supported Ni-Mo hydrodesulfurization catalysts

NARCIS (Netherlands)

Bouwens, S.M.A.M.; Barthe-Zahir, N.; Beer, de V.H.J.; Prins, R.

1991-01-01

The thiophene hydrodesulfurization activities of Ni and Ni---Mo sulfide catalysts supported on activated carbon were measured at atmospheric pressure and the catalyst structures were studied by means of X-ray photoelectron spectroscopy, dynamic oxygen chemisorption, and chemical sulfur analysis. The

Energetic Mapping of Ni Catalysts by Detailed Kinetic Modeling

DEFF Research Database (Denmark)

Bjørgum, Erlend; Chen, De; Bakken, Mari G.

2005-01-01

Temperature-programmed desorption (TPD) of CO has been performed on supported and unsupported nickel catalysts. The unsupported Ni catalyst consists of a Ni(14 13 13) single crystal which has been studied under ultrahigh vacuum conditions. The desorption energy for CO at low CO surface coverage...... was found to be 119 kJ/mol, and the binding energy of C to the Ni(111) surface of the crystal was 703 kJ/mol. The supported catalysts consist of nickel supported on hydrotalcite-like compounds with three different Mg2+/Al3+ ratios. The experimental results show that for the supported Ni catalysts TPD of CO...... precursor seems to result in more steplike sites, kinks, and defects for carbon monoxide dissociation. A detailed kinetic modeling of the TPO results based on elementary reaction steps has been conducted to give an energetic map of supported Ni catalysts. Experimental results from the ideal Ni surface fit...

Density functional theory study for the enhanced sulfur tolerance of Ni catalysts by surface alloying

Science.gov (United States)

Hwang, Bohyun; Kwon, Hyunguk; Ko, Jeonghyun; Kim, Byung-Kook; Han, Jeong Woo

2018-01-01

Sulfur compounds in fuels deactivate the surface of anode materials in solid oxide fuel cells (SOFCs), which adversely affect the long-term durability. To solve this issue, it is important to design new SOFC anode materials with high sulfur tolerance. Unfortunately, it is difficult to completely replace the traditional Ni anode owing to its outstanding reactivity with low cost. As an alternative, alloying Ni with transition metals is a practical strategy to enhance the sulfur resistance while taking advantage of Ni metal. Therefore, in this study, we examined the effects of transition metal (Cu, Rh, Pd, Ag, Pt, and Au) doping into a Ni catalyst on not only the adsorption of H2S, HS, S, and H but also H2S decomposition using density functional theory (DFT) calculations. The dopant metals were selected rationally by considering the stability of the Ni-based binary alloys. The interactions between sulfur atoms produced by H2S dissociation and the surface are weakened by the dopant metals at the topmost layer. In addition, the findings show that H2S dissociation can be suppressed by doping transition metals. It turns out that these effects are maximized in the Au-doped Ni catalyst. Our DFT results will provide useful insights into the design of sulfur-tolerant SOFC anode materials.

Effect of preparation method on catalytic activity of Ni/ γ-Al2O3 catalysts

International Nuclear Information System (INIS)

Miranda Morales, Barbara

2017-01-01

The performance of catalysts was shown to be strongly dependent on their methods of preparation. A study to examine the relationship between catalyst preparation procedures and the structure, dispersion, activity, and selectivity of the finished catalyst is reported. 10 wt.%Ni/γ-Al 2 O 3 catalysts were prepared by incipient wetness impregnation and by wet impregnation. The catalysts were used in the conversion of glycerol in gas phase and atmospheric pressure. The selectivity and activity of the catalysts were affected by the preparation method employed. The catalysts were characterized by thermogravimetric analysis (TGA), temperature-programmed reduction (TPR), N 2 -physorption, H 2 -chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR) and temperature-programmed oxidation (TPO). The Ni particle size and dispersion of the catalysts affected the selectivity to hydrogenolysis and dehydration routes, and the formation of carbon deposits was also affected. (author) [es

More active and sulfur resistant bimetallic Pd-Ni catalysts

Energy Technology Data Exchange (ETDEWEB)

Betti, Carolina; Carrara, Nicolás; Badano, Juan; Lederhos, Cecilia; Vera, Carlos; Quiroga, Mónica, E-mail: mquiroga@fiq.unl.edu.ar [Instituto de Investigaciones en Catálisis y Petroquímica, INCAPE (FIQ-UNL, CONICET), Santa Fe (Argentina)

2018-02-15

The influence of the kind of metal precursor and the sequence of impregnation on the properties of Pd-Ni catalysts was evaluated during the test reaction of selective hydrogenation of styrene to ethylbenzene by means of physicochemical characterization. The focus was put on the final hydrogenating activity and the resistance to deactivation by sulfide compounds (thiophene). The used techniques of characterization were ICP, XPS, XDR, TPR, CO chemisorption and TEM. XPS results indicated the presence of different Pd species: Pd{sup δ-}, Pd{sup 0} and Pd{sup δ+}. In the case of the Ni containing catalysts, Ni{sup 0} and NiO species were also detected. These palladium and nickel species would be responsible of the variation of activity and sulfur resistance of the catalysts. NiClPd catalysts had a higher resistance to deactivation by sulfur poisoning. This was associated to a higher concentration of Pd{sup η+}Cl{sub x}O{sub y} species that would prevent the adsorption of thiophene by both steric and electronic effects. It could also be due to the lower concentration of Pd{sup 0} and Ni{sup 0} on these catalysts, as compared to those shown by the PdNiCl catalysts. Both the Pd{sup 0} and Ni{sup 0} species are more prone to poisoning because of their higher electronic availability. (author)

Reduction of a Ni/Spinel Catalyst for Methane Reforming

DEFF Research Database (Denmark)

Kehres, Jan; Andreasen, Jens Wenzel; Fløystad, Jostein Bø

2015-01-01

microscopy (HRTEM) was performed on the fresh catalyst sample. The Ni particles in the fresh catalyst sample were observed to exhibit a Ni/NiO core/shell structure. A decrease of the Ni lattice parameter is observed during the reduction in a temperature interval from 413 – 453 K, which can be related...

Syngas production from ethanol dry reforming over Rh/CeO2 catalyst

Directory of Open Access Journals (Sweden)

Shulin Zhao

2018-01-01

Full Text Available Carbon dioxide reforming of ethanol over Rh/CeO2 catalyst was deeply investigated at different reaction temperatures of 450–700 °C and reactant ratios (CO2/ethanol from 1 to 3 under atmospheric pressure. The obtained results indicated that Rh/CeO2 catalyst presented a promising activity and stability for syngas production from renewable bio-ethanol instead of conventional methane. Typically, CO2-rich conditions (CO2/ethanol = 3 were favorable for reaction process and dynamic coke cleaning, which led to remarkably stable performance over 65 h on stream. The strong redox capacity of CeO2 support might also accelerate CO2 activation and prevent the carbon accumulation over the catalyst surface. Additionally, tunable H2/CO ratios were available by changing the CO2/ethanol ratios. The results from characterization of samples before and after catalytic tests allowed to establish the relationship between textural properties and catalytic performance.

Catalyst Deactivation and Regeneration in Low Temperature Ethanol Steam Reforming with Rh/CeO2-ZrO2 Catalysts

Energy Technology Data Exchange (ETDEWEB)

Roh, Hyun-Seog; Platon, Alex; Wang, Yong; King, David L.

2006-08-01

Rh/CeO2-ZrO2 catalysts with various CeO2/ZrO2 ratios have been applied to H2 production from ethanol steam reforming at low temperatures. The catalysts all deactivated with time on stream (TOS) at 350 C. The addition of 0.5% K has a beneficial effect on catalyst stability, while 5% K has a negative effect on catalytic activity. The catalyst could be regenerated considerably even at ambient temperature and could recover its initial activity after regeneration above 200 C with 1% O2. The results are most consistent with catalyst deactivation due to carbonaceous deposition on the catalyst.

Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation.

Science.gov (United States)

Feng, Yue; Bin, Duan; Yan, Bo; Du, Yukou; Majima, Tetsuro; Zhou, Weiqiang

2017-05-01

Porous bimetallic PdNi catalysts were fabricated by a novel method, namely, reduction of Pd and Ni oxides prepared via calcining the complex chelate of PdNi-dimethylglyoxime (PdNi-dmg). The morphology and composition of the as-prepared PdNi were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Furthermore, the electrochemical properties of PdNi catalysts towards ethanol electrooxidation were also studied by electrochemical impedance spectrometry (EIS), cyclic voltammetry (CV) and chronoamperometry (CA) measurement. In comparison with porous Pd and commercial Pd/C catalysts, porous structural PdNi catalysts showed higher electrocatalytic activity and durability for ethanol electrooxidation, which may be ascribed to Pd and Ni property, large electroactive surface area and high electron transfer property. The Ni exist in the catalyst in the form of the nickel hydroxides (Ni(OH) 2 and NiOOH) which have a high electron and proton conductivity enhances the catalytic activity of the catalysts. All results highlight the great potential application of the calcination-reduction method for synthesizing high active porous PdNi catalysts in direct ethanol fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Enhanced activity of Pt/CNTs anode catalyst for direct methanol fuel cells using Ni2P as co-catalyst

Science.gov (United States)

Li, Xiang; Luo, Lanping; Peng, Feng; Wang, Hongjuan; Yu, Hao

2018-03-01

The direct methanol fuel cell is a promising energy conversion device because of the utilization of the state-of-the-art platinum (Pt) anode catalyst. In this work, novel Pt/Ni2P/CNTs catalysts were prepared by the H2 reduction method. It was found that the activity and stability of Pt for methanol oxidation reaction (MOR) could be significantly enhanced while using nickel phosphide (Ni2P) nanoparticles as co-catalyst. X-ray photoelectron spectroscopy revealed that the existence of Ni2P affected the particle size and electronic distribution of Pt obviously. Pt/CNTs catalyst, Pt/Ni2P/CNTs catalysts with different Ni2P amount were synthesized, among which Pt/6%Ni2P/CNTs catalyst exhibited the best MOR activity of 1400 mAmg-1Pt, which was almost 2.5 times of the commercial Pt/C-JM catalyst. Moreover, compared to other Pt-based catalysts, this novel Pt/Ni2P/CNTs catalyst also exhibited higher onset current density and better steady current density. The result of this work may provide positive guidance to the research on high efficiency and stability of Pt-based catalyst for direct methanol fuel cells.

Preparation of Rh/Ag bimetallic nanoparticles as effective catalyst for hydrogen generation from hydrolysis of KBH4

Science.gov (United States)

Huang, Liang; Jiao, Chengpeng; Wang, Liqiong; Huang, Zili; Liang, Feng; Liu, Simin; Wang, Yuhua; Zhang, Haijun; Zhang, Shaowei

2018-01-01

ISOBAM-104 protected Rh/Ag bimetallic nanoparticles (NPs) with average diameter less than 3.0 nm were synthesized by a co-reduction method. Ultraviolet-visible spectroscopy, transmission electron microscopy (TEM), high-resolution TEM and x-ray photoelectron spectroscopy (XPS) were employed to characterize the structure, particle size, and electronic structure of the prepared bimetallic NPs. The catalytic activities of prepared bimetallic NPs for hydrogen generation from hydrolysis of a basic KBH4 solution were evaluated in detail. The results indicated that as-prepared Rh/Ag bimetallic NPs showed a higher catalytic activity than corresponding monometallic NPs. Among all the monometallic NPs and bimetallic NPs, Rh80Ag20 bimetallic NPs exhibited the highest catalytic activity with a value of 6010 mol-H2·h-1·mol-catalyst-1 at pH = 12 and 303 K. The high catalytic activities of Rh/Ag bimetallic NPs could be attributed to presence of negatively charged Rh atoms and positively charged Ag atoms, which is supported by the results of XPS and density functional theory calculation. Based on the kinetic study, the apparent activation energy for the hydrolysis reaction of the basic KBH4 solution catalyzed by Rh80Ag20 bimetallic NPs was about 47.0 ± 3.9 kJ mol-1.

Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts.

Science.gov (United States)

Yamazaki, Shin-ichi; Yamada, Yusuke; Takeda, Sahori; Goto, Midori; Ioroi, Tsutomu; Siroma, Zyun; Yasuda, Kazuaki

2010-08-21

Electrochemical CO oxidation by several carbon-supported rhodium tetraphenylporphyrins with systematically varied meso-substituents was investigated. A quantitative analysis revealed that the p-substituents on the meso-phenyl groups significantly affected CO oxidation activity. The electrocatalytic reaction was characterized in detail based on the spectroscopic and X-ray structural results as well as electrochemical analyses. The difference in the activity among Rh porphyrins is discussed in terms of the properties of p-substituents along with a proposed reaction mechanism. Rhodium tetrakis(4-carboxyphenyl)porphyrin (Rh(TCPP)), which exhibited the highest activity among the porphyrins tested, oxidized CO at a high rate at much lower potentials (means that CO is electrochemically oxidized by this catalyst when a slight overpotential is applied during the operation of a proton exchange membrane fuel cell. This catalyst exhibited little H(2) oxidation activity, in contrast to Pt-based catalysts.

A comparison of Rh/CeO2/SiO2 catalysts with steam reforming catalysts, dolomite and inert materials as bed materials in low throughput fluidized bed gasification systems

International Nuclear Information System (INIS)

Asadullah, Mohammad; Miyazawa, Tomohisa; Ito, Shin-ichi; Kunimori, Kimio; Koyama, Shuntarou; Tomishige, Keiichi

2004-01-01

The gasification of cedar wood in the presence of Rh/CeO 2 /SiO 2 has been conducted in the laboratory scale fluidized bed reactor using air as a gasifying agent at low temperatures (823-973 K) in order to produce high-quality fuel gas for gas turbine for power generation. The performance of the Rh/CeO 2 /SiO 2 catalyst has been compared with conventional catalysts such as commercial steam reforming catalyst G-91, dolomite and noncatalyst systems by measurements of the cold gas efficiency, tar concentration, carbon conversion to gas and gas composition. The tar concentration was completely negligible in the Rh/CeO 2 /SiO 2 -catalyzed product gas whereas it was about 30, 113, and 139 g/m 3 in G-91, dolomite and noncatalyzed product gas, respectively. Since the carbon conversion to useful gas such as CO, H 2 , and CH 4 are much higher on Rh/CeO 2 /SiO 2 catalyst than others at 873 K, the cold gas efficiency is much higher (71%) in this case than others. The hydrogen content in the product gas is much higher (>24 vol%) than the specified level (>10 vol%) for efficient combustion in the gas turbine engine. The char and coke formation is also very low on Rh/CeO 2 /SiO 2 catalyst than on the conventional catalysts. Although the catalyst surface area was slightly decreased after using the same catalyst in at least 20 experiments, the deactivation problem was not severe

ANODE CATALYST MATERIALS FOR USE IN FUEL CELLS

DEFF Research Database (Denmark)

2002-01-01

Catalyst materials having a surface comprising a composition M¿x?/Pt¿3?/Sub; wherein M is selected from the group of elements Fe, Co, Rh and Ir; or wherein M represent two different elements selected from the group comprising Fe, CO, Rh, Ir, Ni, Pd, CU, Ag, Au and Sn; and wherein Sub represents...

Size and morphology controlled NiSe nanoparticles as efficient catalyst for the reduction reactions

Energy Technology Data Exchange (ETDEWEB)

Subbarao, Udumula; Marakatti, Vijaykumar S. [New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore 560064 (India); Amshumali, Mungalimane K. [New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore 560064 (India); Department of Chemistry and Industrial Chemistry, Vijayanagara Sri Krishnadevaraya University, Jnanasagara Campus, Cantonment, Bellary 583105 (India); Loukya, B. [International Center for Materials Science, Jakkur P.O., Bangalore 560064 (India); Singh, Dheeraj Kumar [Chemistry & Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore 560064 (India); Datta, Ranjan [International Center for Materials Science, Jakkur P.O., Bangalore 560064 (India); Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in [New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore 560064 (India)

2016-12-15

Facile and efficient ball milling and polyol methods were employed for the synthesis of nickel selenide (NiSe) nanoparticle. The particle size of the NiSe nanoparticle has been controlled mechanically by varying the ball size in the milling process. The role of the surfactants in the formation of various morphologies was studied. The compounds were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray energy dispersive spectroscopy (EDS). The efficiency of the NiSe nanoparticle as a catalyst was tested for the reduction of para-nitroaniline (PNA) to para-phenyldiamine (PPD) and para-nitrophenol (PNP) to para-aminophenol (PAP) using NaBH{sub 4} as the reducing agent. Particle size, morphology and the presence of surfactant played a crucial role in the reduction process. - Graphical abstract: NiSe nanoparticles in different size and morphology were synthesized using facile ball milling and polyol methods. Particle size, morphology and the presence of surfactant in these materials played a crucial role in the hydrogenation of PNA and PNP. - Highlights: • NiSe nanoparticles synthesized using ball milling and solution phase methods. • NiSe nanoparticle is an efficient catalyst for the reduction of PNA and PNP. • NiSe is found to be better than the best reported noble metal catalysts.

Size and morphology controlled NiSe nanoparticles as efficient catalyst for the reduction reactions

International Nuclear Information System (INIS)

Subbarao, Udumula; Marakatti, Vijaykumar S.; Amshumali, Mungalimane K.; Loukya, B.; Singh, Dheeraj Kumar; Datta, Ranjan; Peter, Sebastian C.

2016-01-01

Facile and efficient ball milling and polyol methods were employed for the synthesis of nickel selenide (NiSe) nanoparticle. The particle size of the NiSe nanoparticle has been controlled mechanically by varying the ball size in the milling process. The role of the surfactants in the formation of various morphologies was studied. The compounds were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray energy dispersive spectroscopy (EDS). The efficiency of the NiSe nanoparticle as a catalyst was tested for the reduction of para-nitroaniline (PNA) to para-phenyldiamine (PPD) and para-nitrophenol (PNP) to para-aminophenol (PAP) using NaBH 4 as the reducing agent. Particle size, morphology and the presence of surfactant played a crucial role in the reduction process. - Graphical abstract: NiSe nanoparticles in different size and morphology were synthesized using facile ball milling and polyol methods. Particle size, morphology and the presence of surfactant in these materials played a crucial role in the hydrogenation of PNA and PNP. - Highlights: • NiSe nanoparticles synthesized using ball milling and solution phase methods. • NiSe nanoparticle is an efficient catalyst for the reduction of PNA and PNP. • NiSe is found to be better than the best reported noble metal catalysts.

Catalyst Deactivation and Regeneration Processes in Biogas Tri-Reforming Process. The Effect of Hydrogen Sulfide Addition

Directory of Open Access Journals (Sweden)

Urko Izquierdo

2018-01-01

Full Text Available This work studies Ni-based catalyst deactivation and regeneration processes in the presence of H2S under a biogas tri-reforming process for hydrogen production, which is an energy vector of great interest. 25 ppm of hydrogen sulfide were continuously added to the system in order to provoke an observable catalyst deactivation, and once fully deactivated two different regeneration processes were studied: a self-regeneration and a regeneration by low temperature oxidation. For that purpose, several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on alumina modified with CeO2 and ZrO2 were used as well as a commercial Katalco 57-5 for comparison purposes. Ni/Ce-Al2O3 and Ni/Ce-Zr-Al2O3 catalysts almost recovered their initial activity. For these catalysts, after the regeneration under oxidative conditions at low temperature, the CO2 conversions achieved—79.5% and 86.9%, respectively—were significantly higher than the ones obtained before sulfur poisoning—66.7% and 45.2%, respectively. This effect could be attributed to the support modification with CeO2 and the higher selectivity achieved for the Reverse Water-Gas-Shift (rWGS reaction after catalysts deactivation. As expected, the bimetallic Rh-Ni/Ce-Al2O3 catalyst showed higher resistance to deactivation and its sulfur poisoning seems to be reversible. In the case of the commercial and Ni/Zr-Al2O3 catalysts, they did not recover their activity.

Insight into the effects of different ageing protocols on Rh/Al{sub 2}O{sub 3} catalyst

Energy Technology Data Exchange (ETDEWEB)

Zhao, Baohuai [Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, 100084 Beijing (China); Ran, Rui, E-mail: ranr@tsinghua.edu.cn [Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, 100084 Beijing (China); Cao, Yidan; Wu, Xiaodong; Weng, Duan [Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, 100084 Beijing (China); Fan, Jun [The Administrative Center for China' s Agenda 21, 100038 Beijing (China); Wu, Xueyuan [Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, 100084 Beijing (China)

2014-07-01

In this work, a catalyst of Rh loaded on Al{sub 2}O{sub 3} was prepared by impregnating method with rhodium nitrate aqueous solution as the Rh precursor. The catalyst was aged under different protocols (lean, rich, inert and cyclic) to obtain several aged samples. All the Rh/Al{sub 2}O{sub 3} samples were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, CO-chemisorption, H{sub 2}-temperature programmed reduction (H{sub 2}-TPR), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). It was found that a specific ageing treatment could strongly affect the catalytic activity. The N{sub 2} aged and the H{sub 2} aged samples had a better catalytic activity for CO + NO reaction than the fresh sample while the air aged and the cyclic aged samples exhibited much worse activity. More surface Rh content and better reducibility were obtained in the N{sub 2} and the H{sub 2} aged samples and the Rh particles existed with an appropriate size, which were all favorable to the catalytic reaction. However, the air and the cyclic ageing protocols induced a strong interaction between Rh species and the Al{sub 2}O{sub 3} support, which resulted in a severe sintering of particles of Rh species and the loss of active sites. The structure evolution scheme of the catalysts aged in different protocols was also established in this paper.

Support effects on hydrotreating activity of NiMo catalysts

International Nuclear Information System (INIS)

Dominguez-Crespo, M.A.; Arce-Estrada, E.M.; Torres-Huerta, A.M.; Diaz-Garcia, L.; Cortez de la Paz, M.T.

2007-01-01

The effect of the gamma alumina particle size on the catalytic activity of NiMoS x catalysts prepared by precipitation method of aluminum acetate at pH = 10 was studied. The structural characterization of the supports was measured by using XRD, pyridine FTIR-TPD and nitrogen physisorption. NiMo catalysts were characterized during the preparation steps (annealing and sulfidation) using transmission electron microscopy (TEM). Hydrogen TPR studies of the NiMo catalysts were also carried out in order to correlate their hydrogenating properties and their catalytic functionality. Catalytic tests were carried out in a pilot plant at 613, 633 and 653 K temperatures. The results showed that the rate constants of hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatizing (HDA) at 613-653 K decreased in the following order: A > B > C corresponding to the increase of NiMoS particle size associated to these catalysts

Electrochemical behavior of Ni-Mo electro catalyst for water electrolysis

Energy Technology Data Exchange (ETDEWEB)

Fernandez V, S. M.; Ordonez R, E. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Cabanas M, G. [IPN, Centro de Nanociencias y Micro y Nanotecnologias, A. P. 75-874, 07300 Mexico D. F. (Mexico); Solorza F, O., E-mail: suilma.fernandez@inin.gob.m [IPN, Centro de Investigacion y de Estudios Avanzados, Departamento de Quimica, A. P. 14-740, 07000 Mexico D. F. (Mexico)

2010-07-01

Nickel-molybdenum based electrocatalysts were synthesized in organic media for the hydrogen evolution reaction and oxygen evolution reaction in alkaline media. The structure, morphology and chemical composition of the catalysts were evaluated by X-ray diffraction, scanning electron microscopy and Aas. Results revealed nanocrystalline powder materials with Ni{sub 0.006}Mo, Ni{sub 0.1}Mo and Ni Mo compositions. The best performance for hydrogen evolution reaction, was obtained on Ni{sub 0.1}Mo electrode, whereas Ni Mo was for the oxygen evolution reaction. Results suggest that the material with 1:1 stoichiometric ratio could be considered as a promising electro catalyst for oxygen evolution reaction. This nanocrystalline powder is formed by Ni{sub 2}Mo{sub 3}O{sub 8} and a crystalline structure attributed to the possible formation of a Ni Mo cluster, becomes NiMoO{sub 4} after thermal treatment at 1073 K in air. The Ni Mo 1:1 cluster catalyst presented electrochemical stability during the oxygen evolution reaction. (Author)

Electrochemical behavior of Ni-Mo electro catalyst for water electrolysis

International Nuclear Information System (INIS)

Fernandez V, S. M.; Ordonez R, E.; Cabanas M, G.; Solorza F, O.

2010-01-01

Nickel-molybdenum based electrocatalysts were synthesized in organic media for the hydrogen evolution reaction and oxygen evolution reaction in alkaline media. The structure, morphology and chemical composition of the catalysts were evaluated by X-ray diffraction, scanning electron microscopy and Aas. Results revealed nanocrystalline powder materials with Ni 0.006 Mo, Ni 0.1 Mo and Ni Mo compositions. The best performance for hydrogen evolution reaction, was obtained on Ni 0.1 Mo electrode, whereas Ni Mo was for the oxygen evolution reaction. Results suggest that the material with 1:1 stoichiometric ratio could be considered as a promising electro catalyst for oxygen evolution reaction. This nanocrystalline powder is formed by Ni 2 Mo 3 O 8 and a crystalline structure attributed to the possible formation of a Ni Mo cluster, becomes NiMoO 4 after thermal treatment at 1073 K in air. The Ni Mo 1:1 cluster catalyst presented electrochemical stability during the oxygen evolution reaction. (Author)

TiO2 nanotubes supported NiW hydrodesulphurization catalysts: Characterization and activity

International Nuclear Information System (INIS)

Palcheva, R.; Dimitrov, L.; Tyuliev, G.; Spojakina, A.; Jiratova, K.

2013-01-01

Highlights: ► NiW catalysts supported on TiO 2 nanotubes, titania and alumina. ► The best results are obtained with NiW/TiO 2 nanotubes in hydrodesulfurization (HDS) of thiophene. ► Active phase is Ni-WO x S y . ► Electronic promotion of W by Ti. - Abstract: High surface area TiO 2 nanotubes (Ti-NT) synthesized by alkali hydrothermal method were used as a support for NiW hydrodesulphurization catalyst. Nickel salt of 12-tungstophosphoric acid – Ni 3/2 PW 12 O 40 was applied as oxide precursor of the active components. The catalyst was characterized by S BET , XRD, UV–vis DRS, Raman spectroscopy, XPS, TPR and HRTEM. The results obtained were compared with those for the NiW catalysts prepared over high surface area titania and alumina supports. A polytungstate phase evidenced by Raman spectroscopy was observed indicating the destruction of the initial heteropolyanion. The catalytic experiments revealed two times higher thiophene conversion on NiW catalyst supported on Ti-NT than those of catalysts supported on alumina and titania. Increased HDS activity of the NiW catalyst supported on Ti-NT could be related to a higher amount of W oxysulfide entities interacting with Ni sulfide particles as consequence of the electronic effects of the Ti-NT observed with XPS analysis.

MOF derived Ni/Co/NC catalysts with enhanced properties for oxygen evolution reaction

Science.gov (United States)

Hu, Jiapeng; Chen, Juan; Lin, Hao; Liu, Ruilai; Yang, Xiaobing

2018-03-01

Designing efficient electrocatalysts for oxygen evolution reaction (OER) is very important for renewable energy storage and conversion devices. In this paper, we introduced a new strategy to synthesize Ni doped Co/NC catalysts (NC is the abbreviation of nitrogen-doped graphitic carbon), which were derived from ZIF-67. All catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and oxygen evolution reaction (OER). The results show that Ni was well doped in the Ni/Co/NC catalysts and the doping of Ni has great influence on the OER activity of Ni/Co/NC catalysts. Among these catalysts, 0.50Ni/Co/NC exhibits the highest OER activity. The onset potential of 0.50Ni/Co/NC is 1.47 V, which is superior than the onset potential of Co/NC (1.54 V), 0.25Ni/Co/NC (1.48 V), 1.00Ni/Co/NC (1.53 V). The excellent OER activity of 0.50Ni/Co/NC catalyst makes its potential to be used on renewable energy storage.

Renewable hydrogen: carbon formation on Ni and Ru catalysts during ethanol steam-reforming

DEFF Research Database (Denmark)

Rass-Hansen, Jeppe; Christensen, Christina Hviid; Sehested, J.

2007-01-01

for the production of hydrogen is investigated, along with quantitative and qualitative determinations of carbon formation on the catalysts by TPO and TEM experiments. A Ru/ MgAl2O4 catalyst, a Ni/MgAl2O4 catalyst as well as Ag-and K-promoted Ni/ MgAl2O4 catalysts were studied. The operating temperature was between...... addition was a rapid deactivation of the catalyst due to an enhanced gum carbon formation on the Ni crystals. Contrary to this, the effect of K addition was a prolonged resistance against carbon formation and therefore against deactivation. The Ru catalyst operates better than all the Ni catalysts...

Ternary Pt9RhFex Nanoscale Alloys as Highly Efficient Catalysts with Enhanced Activity and Excellent CO-Poisoning Tolerance for Ethanol Oxidation.

Science.gov (United States)

Wang, Peng; Yin, Shibin; Wen, Ying; Tian, Zhiqun; Wang, Ningzhang; Key, Julian; Wang, Shuangbao; Shen, Pei Kang

2017-03-22

To address the problems of high cost and poor stability of anode catalysts in direct ethanol fuel cells (DEFCs), ternary nanoparticles Pt 9 RhFe x (x = 1, 3, 5, 7, and 9) supported on carbon powders (XC-72R) have been synthesized via a facile method involving reduction by sodium borohydride followed by thermal annealing in N 2 at ambient pressure. The catalysts are physically characterized by X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy, and their catalytic performance for the ethanol oxidation reaction (EOR) is evaluated by cyclic and linear scan voltammetry, CO-stripping voltammograms, and chronopotentiometry. All the Pt 9 RhFe x /C catalysts of different atomic ratios produce high EOR catalytic activity. The catalyst of atomic ratio composition 9:1:3 (Pt/Rh/Fe) has the highest activity and excellent CO-poisoning tolerance. Moreover, the enhanced EOR catalytic activity on Pt 9 RhFe 3 /C when compared to Pt 9 Rh/C, Pt 3 Fe/C, and Pt/C clearly demonstrates the presence of Fe improves catalytic performance. Notably, the onset potential for CO oxidation on Pt 9 RhFe 3 /C (0.271 V) is ∼55, 75, and 191 mV more negative than on Pt 9 Rh/C (0.326 V), Pt 3 Fe/C (0.346 V), and Pt/C (0.462 V), respectively, which implies the presence of Fe atoms dramatically improves CO-poisoning tolerance. Meanwhile, compared to the commercial PtRu/C catalyst, the peak potential on Pt 9 RhFe 3 /C for CO oxidation was just slightly changed after several thousand cycles, which shows high stability against the potential cycling. The possible mechanism by which Fe and Rh atoms facilitate the observed enhanced performance is also considered herein, and we conclude Pt 9 RhFe 3 /C offers a promising anode catalyst for direct ethanol fuel cells.

Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

KAUST Repository

Al-ShaikhAli, Anaam H.

2016-11-30

Liquid organic chemical hydride is a promising candidate for hydrogen storage and transport. Methylcyclohexane (MCH) to toluene (TOL) cycle has been considered as one of the feasible hydrogen carrier systems, but selective dehydrogenation of MCH to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based catalysts. Mono-metallic Ni based catalyst is a well-known dehydrogenation catalyst, but the major drawback with Ni is its hydrogenolysis activity to cleave C-C bonds, which leads to inferior selectivity towards dehydrogenation of MCH to TOL. This study elucidate addition of the second metal to Ni based catalyst to improve the TOL selectivity. Herein, ubiquitous bi-metallic nanoparticles catalysts were investigated including (Ni–M, M: Ag, Zn, Sn or In) based catalysts. Among the catalysts investigated, the high TOL selectivity (> 99%) at low conversions was achieved effectively using the supported NiZn catalyst under flow of excess H2. In this work, a combined study of experimental and computational approaches was conducted to determine the main role of Zn over Ni based catalyst in promoting the TOL selectivity. A kinetic study using mono- and bimetallic Ni based catalysts was conducted to elucidate reaction mechanism and site requirement for MCH dehydrogenation reaction. The impact of different reaction conditions (feed compositions, temperature, space velocity and stability) and catalyst properties were evaluated. This study elucidates a distinctive mechanism of MCH dehydrogenation to TOL reaction over the Ni-based catalysts. Distinctive from Pt catalyst, a nearly positive half order with respect to H2 pressure was obtained for mono- and bi-metallic Ni based catalysts. This kinetic data was consistent with rate determining step as (somewhat paradoxically) hydrogenation

Effects of preparation method and active metal content on of Ni/kieselguhr catalyst activity

International Nuclear Information System (INIS)

Galuh Widiyarti; Wuryaningsih Sri Rahayu

2010-01-01

The preparation and the active metal content influence the activity of catalyst. Study has been conducted to see the activity of Ni/kieselguhr based on preparation method and Nickel (Ni) contents in the catalyst in the laboratory scale. The Ni/kieselguhr catalyst were prepared by impregnation and precipitation methods, with Ni active contents of 10, 20, and 30 % by weight. The catalysts characterization was analyzed using X-Ray Diffraction (XRD). Catalysts activities were analyzed based on decreasing of iodine number from hydrogenation of crude palm oil for 2 hours. The activity tests results show that precipitation catalysts are more active than impregnation catalysts. The decreasing in iodine number of fatty acid after 2 hours of hydrogenation process using precipitation catalysts and impregnation catalysts are 51.53 and 21.85 %, respectively. In addition, the catalysts are more active with increasing Ni contents. (author)

Microwave sinthesys and characterization of Pt and Pt-Rh-Sn electrocatalysts for ethanol oxidation

Directory of Open Access Journals (Sweden)

Jovanović Vladislava M.

2011-01-01

Full Text Available Carbon supported Pt and Pt-Rh-Sn catalysts were synthesized by microwave-polyol method in ethylene glycol solution and investigated for the ethanol electro-oxidation reaction. The catalysts were characterized in terms of structure, morphology and composition by employing XRD, STM and EDX techniques. STM analysis indicated rather uniform particles and particle size of below 2 nm for both catalysts. XRD analysis of the Pt/C catalyst revealed two phases, one with the main characteristic peaks of face centered cubic crystal structure (fcc of platinum and another related to graphite like structure of carbon support Vulcan XC-72R. However, in XRD pattern of the Pt-Rh-Sn/C catalyst diffraction peaks for Pt, Rh or Sn cannot be resolved, indicating an extremely low crystallinity. The small particle sizes and homogeneous size distributions of both catalysts should be attributed to the advantages of microwave assisted modified polyol process in ethylene glycol solution. Pt-Rh- Sn/C catalyst is highly active for the ethanol oxidation with the onset potential shifted for more than 150 mV to negative values and with currents nearly 5 times higher in comparison to Pt/C catalyst. The stability tests of the catalysts, as studied by the chronoamperometric experiments, reveal that the Pt-Rh-Sn/C catalyst is evidently less poisoned then Pt/C catalyst. The increased activity of Pt-Rh-Sn/C in comparison to Pt/C catalyst is most probably promoted by bifunctional mechanism and the electronic effect of alloyed metals.

Propene and l-octene hydroformylation with silica-supported, ionic liquid-phase (SILP) Rh-phosphine catalysts in continuous fixed-bed mode

DEFF Research Database (Denmark)

Riisager, Anders; Eriksen, Kim Michael; Wasserscheid, Peter

2003-01-01

- and liquid-phase hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h(-1) for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase hydroformylation using SILP catalysts.......Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium) phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM] [PF6], on a silica support. The catalysts were active in continuous gas...

Hydrogenation of naphthalene on NiMo- Ni- and Ru/Al{sub 2}O{sub 3} catalysts. Langmuir-Hinshelwood kinetic modelling

Energy Technology Data Exchange (ETDEWEB)

Monteiro-Gezork, Ana Cristina Alves; Winterbottom, John Mike [Department of Chemical Engineering, School of Engineering, The University of Birmingham, Birmingham B15 2TT (United Kingdom); Natividad, Reyna [Department of Chemical Engineering, Faculty of Chemistry, Universidad Autonoma del Estado de Mexico, Paseo Colon Esq. Tollocan, Toluca, Edo. de Mexico, Mexico CP 50120 (Mexico)

2008-01-30

The importance of the hydrodearomatisation (HDA) is increasing together with tightening legislation of fuel quality and exhaust emissions. The present study focuses on hydrogenation (HYD) kinetics of the model aromatic compound naphthalene, found in typical diesel fraction, in n-hexadecane over a NiMo (nickel molybdenum), Ni (nickel) and Ru (ruthenium) supported on trilobe alumina (Al{sub 2}O{sub 3}) catalysts. Kinetic reaction expressions based on the mechanistic Langmuir-Hinshelwood (L-H) model were derived and tested by regressing the experimental data that translated the effect of both naphthalene and hydrogen concentration at a constant temperature (523.15 and 573.15 K over the NiMo catalyst and at 373.15 K over the Ni and Ru/Al{sub 2}O{sub 3} catalysts) on the initial reaction rate. The L-H equation, giving an adequate fit to the experimental data with physically meaningful parameters, suggested a competitive adsorption between hydrogen and naphthalene over the presulphided NiMo catalyst and a non-competitive adsorption between these two reactants over the prereduced Ni and Ru/Al{sub 2}O{sub 3} catalysts. In addition, the adsorption constant values indicated that the prereduced Ru catalyst was a much more active catalyst towards naphthalene HYD than the prereduced Ni/Al{sub 2}O{sub 3} or the presulphided NiMo/Al{sub 2}O{sub 3} catalyst. (author)

Co-catalytic effect of Rh and Ru for the ethanol electro-oxidation in amorphous microparticulated alloys

Energy Technology Data Exchange (ETDEWEB)

Blanco, Tamara C.; Pierna, Angel R.; Barroso, Javier [Dpto. de Ingenieria Quimica y del Medio Ambiente, Universidad del Pais Vasco, San Sebastian (Spain)

2011-11-15

The ethanol electro-oxidation on platinum catalyst in acid media leads to the formation of acetaldehyde and acetic acid as main products. Another problem is the poisoning of the electro-catalyst surface with CO formed during the fuel oxidation reaction. To increase the performance of Direct Ethanol Fuel Cells (DEFCs) it is necessary to develop new electrode materials or modification of the existing Pt catalysts. This work presents the electrochemical response to ethanol and CO oxidation of different compositional amorphous alloys obtained by ball milling technique, used as electrodes. Alloys with Ni{sub 59}Nb{sub 40}Pt{sub 0.6}Rh{sub 0.4} and Ni{sub 59}Nb{sub 40}Pt{sub 0.6}Rh{sub 0.2}Ru{sub 0.2} composi-tions were studied. The current density towards ethanol oxidation decreases with the presence of ruthenium; however, this electrode shows the best tolerance to CO, with lower surface coverage (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Co-catalytic effect of Rh and Ru for the ethanol electro-oxidation in amorphous microparticulated alloys

International Nuclear Information System (INIS)

Blanco, Tamara C.; Pierna, Angel R.; Barroso, Javier

2011-01-01

The ethanol electro-oxidation on platinum catalyst in acid media leads to the formation of acetaldehyde and acetic acid as main products. Another problem is the poisoning of the electro-catalyst surface with CO formed during the fuel oxidation reaction. To increase the performance of Direct Ethanol Fuel Cells (DEFCs) it is necessary to develop new electrode materials or modification of the existing Pt catalysts. This work presents the electrochemical response to ethanol and CO oxidation of different compositional amorphous alloys obtained by ball milling technique, used as electrodes. Alloys with Ni 59 Nb 40 Pt 0.6 Rh 0.4 and Ni 59 Nb 40 Pt 0.6 Rh 0.2 Ru 0.2 composi-tions were studied. The current density towards ethanol oxidation decreases with the presence of ruthenium; however, this electrode shows the best tolerance to CO, with lower surface coverage (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Ni catalysts with different promoters supported on zeolite for dry reforming of methane

KAUST Repository

Alotaibi, Raja; Alenazey, Feraih; Alotaibi, Faisal; Wei, Nini; Al-Fatesh, Ahmed; Fakeeha, Anis

2015-01-01

Dry reforming of methane (DRM) is considered a high endothermic reaction with operating temperatures between 700 and 1000 °C to achieve high equilibrium conversion of CH4 and CO2 to the syngas (H2 and CO). The conventional catalysts used for DRM are Ni-based catalysts. However, many of these catalysts suffer from the short longevity due to carbon deposition. This study aims to evaluate the effect of La and Ca as promoters for Ni-based catalysts supported on two different zeolite supports, ZL (A) (BET surface area = 925 m2/g, SiO2/Al2O3 mol ratio = 5.1), and ZL (B) (BET surface area = 730 m2/g, SiO2/Al2O3 mol ratio = 12), for DRM. The physicochemical properties of the prepared catalysts were characterized with XRD, BET, TEM and TGA. These catalysts were tested for DRM in a microtubular reactor at reaction conditions of 700 °C. The catalyst activity results show that the catalysts Ni/ZL (B) and Ca-Ni/ZL (B) give the highest methane conversion (60 %) with less time on stream stability compared with promoted Ni on ZL (A). In contrast, La-containing catalysts, La-Ni/ZL (B), show more time on stream stability with minimum carbon content for the spent catalyst indicating the enhancement of the promoters to the Ni/ZL (A) and (B), but with less catalytic activity performance in terms of methane and carbon dioxide conversions due to rapid catalyst deactivation.

Ni catalysts with different promoters supported on zeolite for dry reforming of methane

KAUST Repository

Alotaibi, Raja

2015-07-08

Dry reforming of methane (DRM) is considered a high endothermic reaction with operating temperatures between 700 and 1000 °C to achieve high equilibrium conversion of CH4 and CO2 to the syngas (H2 and CO). The conventional catalysts used for DRM are Ni-based catalysts. However, many of these catalysts suffer from the short longevity due to carbon deposition. This study aims to evaluate the effect of La and Ca as promoters for Ni-based catalysts supported on two different zeolite supports, ZL (A) (BET surface area = 925 m2/g, SiO2/Al2O3 mol ratio = 5.1), and ZL (B) (BET surface area = 730 m2/g, SiO2/Al2O3 mol ratio = 12), for DRM. The physicochemical properties of the prepared catalysts were characterized with XRD, BET, TEM and TGA. These catalysts were tested for DRM in a microtubular reactor at reaction conditions of 700 °C. The catalyst activity results show that the catalysts Ni/ZL (B) and Ca-Ni/ZL (B) give the highest methane conversion (60 %) with less time on stream stability compared with promoted Ni on ZL (A). In contrast, La-containing catalysts, La-Ni/ZL (B), show more time on stream stability with minimum carbon content for the spent catalyst indicating the enhancement of the promoters to the Ni/ZL (A) and (B), but with less catalytic activity performance in terms of methane and carbon dioxide conversions due to rapid catalyst deactivation.

Catalytic hydrodechlorination of trichloroethylene in a novel NaOH/2-propanol/methanol/water system on ceria-supported Pd and Rh catalysts.

Science.gov (United States)

Cobo, Martha; Becerra, Jorge; Castelblanco, Miguel; Cifuentes, Bernay; Conesa, Juan A

2015-08-01

The catalytic hydrodechlorination (HDC) of high concentrations of trichloroethylene (TCE) (4.9 mol%, 11.6 vol%) was studied over 1%Pd, 1%Rh and 0.5%Pd-0.5%Rh catalysts supported on CeO2 under conditions of room temperature and pressure. For this, a one-phase system of NaOH/2-propanol/methanol/water was designed with molar percentages of 13.2/17.5/36.9/27.6, respectively. In this system, the alcohols delivered the hydrogen required for the reaction through in-situ dehydrogenation reactions. PdRh/CeO2 was the most active catalyst for the degradation of TCE among the evaluated materials, degrading 85% of the trichloroethylene, with alcohol dehydrogenation rates of 89% for 2-propanol and 83% for methanol after 1 h of reaction. Fresh and used catalysts were characterized by Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and Thermogravimetric analysis (TGA). These results showed important differences of the active phase in each catalyst sample. Rh/CeO2 had particle sizes smaller than 1 nm and the active metal was partially oxidized (Rh(0)/Rh(+δ) ratio of 0.43). This configuration showed to be suitable for alcohols dehydrogenation. On the contrary, Pd/CeO2 showed a Pd completed oxidized and with a mean particle size of 1.7 nm, which seemed to be unfavorable for both, alcohols dehydrogenation and TCE HDC. On PdRh/CeO2, active metals presented a mean particle size of 2.7 nm and more reduced metallic species, with ratios of Rh(0)/Rh(+δ) = 0.67 and Pd(0)/Pd(+δ) = 0.28, which showed to be suitable features for the TCE HDC. On the other hand, TGA results suggested some deposition of NaCl residues over the catalyst surfaces. Thus, the new reaction system using PdRh/CeO2 allowed for the degradation of high concentrations of the chlorinated compound by using in situ hydrogen liquid donors in a reaction at room temperature and pressure. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evaluation of Pt-Ru-Ni and Pt-Sn-Ni catalysts as anodes in direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Ribadeneira, Esteban; Hoyos, Bibian A. [Escuela de Procesos y Energia, Facultad de Minas, Universidad Nacional de Colombia, Medellin (Colombia)

2008-05-15

In this study, the electrooxidation of ethanol on carbon supported Pt-Ru-Ni and Pt-Sn-Ni catalysts is electrochemically studied through cyclic voltammetry at 50 C in direct ethanol fuel cells. All electrocatalysts are prepared using the ethylene glycol-reduction process and are chemically characterized by energy-dispersive X-ray analysis (EDX). For fuel cell evaluation, electrodes are prepared by the transfer-decal method. Nickel addition to the anode improves DEFC performance. When Pt{sub 75}Ru{sub 15}Ni{sub 10}/C is used as an anode catalyst, the current density obtained in the fuel cell is greater than that of all other investigated catalysts. Tri-metallic catalytic mixtures have a higher performance relative to bi-metallic catalysts. These results are in agreement with CV results that display greater activity for PtRuNi at higher potentials. (author)

Effect of Phosphine Doping and the Surface Metal State of Ni on the Catalytic Performance of Ni/Al2O3 Catalyst

Directory of Open Access Journals (Sweden)

Xiaoru Li

2015-04-01

Full Text Available Ni-based catalysts as replacement for noble metal catalysts are of particular interest in the catalytic conversion of biomass due to their cheap and satisfactory catalytic activity. The Ni/SiO2 catalyst has been studied for the hydrogenolysis of glycerol, and doping with phosphorus (P found to improve the catalytic performance significantly because of the formation of Ni2P alloys. However, in the present work we disclose a different catalytic phenomenon for the P-doped Ni/Al2O3 catalyst. We found that doping with P has a significant effect on the state of the active Ni species, and thus improves the selectivity to 1,2-propanediol (1,2-PDO significantly in the hydrogenolysis of glycerol, although Ni-P alloys were not observed in our catalytic system. The structure and selectivity correlations were determined from the experimental data, combining the results of X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, hydrogen temperature-programmed reduction (H2-TPR and ammonia temperature-programmed desorption (NH3-TPD. The presence of NiO species, formed from P-doped Ni/Al2O3 catalyst, was shown to benefit the formation of 1,2-PDO. This was supported by the results of the Ni/Al2O3 catalyst containing NiO species with incomplete reduction. Furthermore, the role the NiO species played in the reaction and the potential reaction mechanism over the P-doped Ni/Al2O3 catalyst is discussed. The new findings in the present work open a new vision for Ni catalysis and will benefit researchers in designing Ni-based catalysts.

Enhancing Pt-Ni/CeO2 performances for ethanol reforming by catalyst supporting on high surface silica

NARCIS (Netherlands)

Palma, V.; Ruocco, C; Meloni, E.; Gallucci, F.; Ricca, A.

2018-01-01

In this paper, bimetallic Pt-Ni/CeO2 catalysts supported over mesoporous silica were employed for ethanol reforming in the low-temperature range. In particular, catalyst behaviour was investigated under a H2O/C2H5OH/N2 as well as H2O/C2H5OH/AIR mixture between 300 and 600 °C at different space

The Deoxygenation Pathways of Palmitic Acid into Hydrocarbons on Silica-Supported Ni12P5 and Ni2P Catalysts

Directory of Open Access Journals (Sweden)

Wenjun Zhou

2018-04-01

Full Text Available Pure Ni12P5/SiO2 and pure Ni2P/SiO2 catalysts were obtained by adjusting the Ni and P molar ratios, while Ni/SiO2 catalyst was prepared as a reference against which the deoxygenation pathways of palmitic acid were investigated. The catalysts were characterized by N2 adsorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission election microscopy (TEM, infrared spectroscopy of pyridine adsorption (Py-IR, H2-adsorption and temperature-programmed desorption of hydrogen (H2-TPD. The crystallographic planes of Ni(111, Ni12P5(400, Ni2P(111 were found mainly exposed on the above three catalysts, respectively. It was found that the deoxygenation pathway of palmitic acid mainly proceeded via direct decarboxylation (DCO2 to form C15 on Ni/SiO2. In contrast, on the Ni12P5/SiO2 catalyst, there were two main competitive pathways producing C15 and C16, one of which mainly proceeded via the decarbonylation (DCO to form C15 accompanying water formation, and the other pathway produced C16 via the dehydration of hexadecanol intermediate, and the yield of C15 was approximately twofold that of C16. Over the Ni2P/SiO2 catalyst, two main deoxygenation pathways formed C15, one of which was mainly the DCO pathway and the other was dehydration accompanying the hexadecanal intermediate and then direct decarbonylation without water formation. The turn over frequency (TOF followed the order: Ni12P5/SiO2 > Ni/SiO2 > Ni2P/SiO2.

The Enhanced Catalytic Performance and Stability of Rh/γ-Al₂O₃ Catalyst Synthesized by Atomic Layer Deposition (ALD) for Methane Dry Reforming.

Science.gov (United States)

Li, Yunlin; Jiang, Jing; Zhu, Chaosheng; Li, Lili; Li, Quanliang; Ding, Yongjie; Yang, Weijie

2018-01-22

Rh/γ-Al₂O₃ catalysts were synthesized by both incipient wetness impregnation (IWI) and atomic layer deposition (ALD). The TEM images of the two catalysts showed that the catalyst from ALD had smaller particle size, and narrower size distribution. The surface chemical states of both catalysts were investigated by both XPS and X-ray Absorption Near Edge Structure (XANES), and the catalyst from IWI had higher concentration of Rh 3+ than that from ALD. The catalytic performance of both catalysts was tested in the dry reforming of methane reaction. The catalyst from ALD showed a higher conversion and selectivity than that from IWI. The stability testing results indicated that the catalyst from ALD showed similar stability to that from IWI at 500 °C, but higher stability at 800 °C.

An Alumina-Supported Ni-La-Based Catalyst for Producing Synthetic Natural Gas

Directory of Open Access Journals (Sweden)

Daniel E. Rivero-Mendoza

2016-10-01

Full Text Available LaNi5, known for its hydrogen storage capability, was adapted to the form of a metal oxide-supported (γ-Al2O3 catalyst and its performance for the Sabatier reaction assessed. The 20 wt % La-Ni/γ-Al2O3 particles were prepared via solution combustion synthesis (SCS and exhibited good catalytic activity, achieving a CO2 conversion of 75% with a high CH4 selectivity (98% at 1 atm and 300 °C. Characteristics of the La-Ni/γ-Al2O3 catalyst were identified at various stages of the catalytic process (as-prepared, activated, and post-reaction and in-situ DRIFTS was used to probe the reaction mechanism. The as-prepared catalyst contained amorphous surface La–Ni spinels with particle sizes <6 nm. The reduction process altered the catalyst make-up where, despite the reducing conditions, Ni2+-based particles with diameters between 4 and 20 nm decorated with LaOx moieties were produced. However, the post-reaction catalyst had particle sizes of 4–9 nm and comprised metallic Ni, with the LaOx decoration reverting to a form akin to the as-prepared catalyst. DRIFTS analysis indicated that formates and adsorbed CO species were present on the catalyst surface during the reaction, implying the reaction proceeded via a H2-assisted and sequential CO2 dissociation to C and O. These were then rapidly hydrogenated into CH4 and H2O.

Ni-CeO2/C Catalysts with Enhanced OSC for the WGS Reaction

Directory of Open Access Journals (Sweden)

Laura Pastor-Pérez

2015-03-01

Full Text Available In this work, the WGS performance of a conventional Ni/CeO2 bulk catalyst is compared to that of a carbon-supported Ni-CeO2 catalyst. The carbon-supported sample resulted to be much more active than the bulk one. The higher activity of the Ni-CeO2/C catalyst is associated to its oxygen storage capacity, a parameter that strongly influences the WGS behavior. The stability of the carbon-supported catalyst under realistic operation conditions is also a subject of this paper. In summary, our study represents an approach towards a new generation of Ni-ceria based catalyst for the pure hydrogen production via WGS. The dispersion of ceria nanoparticles on an activated carbon support drives to improved catalytic skills with a considerable reduction of the amount of ceria in the catalyst formulation.

Pyrolysis of polyethylene terephthalate containing real waste plastics using Ni loaded zeolite catalysts

Science.gov (United States)

Al-asadi, M.; Miskolczi, N.

2018-05-01

In this work the pyrolysis of polyethylene terephthalate (PET) containing real waste plastic was investigated using different Ni loaded catalysts: Ni/ZSM-5, Ni/y-zeolite, Ni/β-zeolite and Ni/natural zeolite (clinoptilolite). Raw materials were pyrolyzed in a horizontal tubular reactor between 600 and 900°C using 10% of catalysts. It was found, that both temperature increasing and catalysts presence can increase the gas yields, however owing to gasification reactions, the pyrolysis oil yield decreased with increasing temperature. Ni/y-zeolite catalyst had the most benefit in gas yield increasing at low temperature; however Ni/ZSM-5 showed advanced property in gas yield increasing at high temperature. Gases contained hydrogen, carbon oxides and hydrocarbons, which composition was significantly affected by catalysts. Ni loaded zeolites favoured to the formation of hydrogen and branched hydrocarbons; furthermore the concentrations of both CO and CO2 were also increased as function of elevated temperature. That phenomenon was attributed to the further decomposition of PET, especially to the side chain scission reactions. Owing to the Boudouard reaction, the ratio of CO2/CO can increased with temperature. Pyrolysis oils were the mixtures of n-saturated, n-unsaturated, branched, oxygen free aromatics and oxygenated hydrocarbons. Temperature increasing has a significant effect to the aromatization and isomerization reactions, while the catalysts can efficiently decreased the concentration of oxygen containing compounds.

Alloyed Ni-Fe nanoparticles as catalysts for NH₃ decomposition

DEFF Research Database (Denmark)

Simonsen, Søren Bredmose; Chakraborty, Debasish; Chorkendorff, Ib

2012-01-01

A rational design approach was used to develop an alloyed Ni-Fe/Al2O3 catalyst for decomposition of ammonia. The dependence of the catalytic activity is tested as a function of the Ni-to-Fe ratio, the type of Ni-Fe alloy phase, the metal loading and the type of oxide support. In the tests with high...... temperatures and a low NH3-to-H2 ratio, the catalytic activity of the best Ni-Fe/Al2O3 catalyst was found to be comparable or even better to that of a more expensive Ru-based catalyst. Small Ni-Fe nanoparticle sizes are crucial for an optimal overall NH3 conversion because of a structural effect favoring...

Synthesis and characterization of Pt-Sn-Ni alloys to application as catalysts for direct ethanol fuel cells

International Nuclear Information System (INIS)

Silva, E.L. da; Correa, P.S.; Oliveira, E.L. de; Takimi, A.S.; Malfatti, C.F.; Radtke, C.

2010-01-01

Direct ethanol fuel cells (DEFCs) have been the focus of recent research due its application in mobile energy sources. In order to obtain the maximum efficiency from these systems, it is necessary the total ethanol oxidation, which implies in C-C bond break. Different catalysts described in literature are employed with this intent. This work consists in studying PtSnNi catalysts supported on carbon Vulcan XC72R, to application in DEFCs. Thus, it was used the impregnation/reduction method, varying the atomic proportion among Pt, Sn and Ni. The alloys were characterized by X-Ray Diffraction, Cyclic Voltammetry and Transmission Microscopy. Preliminary results show that predominant structure on the catalysts is the face centered cubic platinum and the densities currents are dependent on the platinum amount. (author)

Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

KAUST Repository

Zhu, Haibo

2014-06-01

The sol-gel method was applied to the synthesis of Zr, Ti, Mo, W, and V modified NiO based catalysts for the ethane oxidative dehydrogenation reaction. The synthesized catalysts were characterized by XRD, N2 adsorption, SEM and TPR techniques. The results showed that the doping metals could be highly dispersed into NiO domains without the formation of large amount of other bulk metal oxide. The modified NiO materials have small particle size, larger surface area, and higher reduction temperature in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result, these two catalysts show improved efficiency of ethylene production in the ethane ODH reaction. © 2014 Elsevier B.V. All rights reserved.

Partial oxidation of dimethyl ether using the structured catalyst Rh/Al2O3/Al prepared through the anodic oxidation of aluminum.

Science.gov (United States)

Yu, B Y; Lee, K H; Kim, K; Byun, D J; Ha, H P; Byun, J Y

2011-07-01

The partial oxidation of dimethyl ether (DME) was investigated using the structured catalyst Rh/Al2O3/Al. The porous Al2O3 layer was synthesized on the aluminum plate through anodic oxidation in an oxalic-acid solution. It was observed that about 20 nm nanopores were well developed in the Al2O3 layer. The thickness of Al2O3 layer can be adjusted by controlling the anodizing time and current density. After pore-widening and hot-water treatment, the Al2O3/Al plate was calcined at 500 degrees C for 3 h. The obtained delta-Al2O3 had a specific surface area of 160 m2/g, making it fit to be used as a catalyst support. A microchannel reactor was designed and fabricated to evaluate the catalytic activity of Rh/Al2O3/Al in the partial oxidation of DME. The structured catalyst showed an 86% maximum hydrogen yield at 450 degrees C. On the other hand, the maximum syngas yield by a pack-bed-type catalyst could be attained by using a more than fivefold Rh amount compared to that used in the structured Rh/Al2O3/Al catalyst.

Hydrotreatment of heavy oil from coal liquefaction on Sulfide Ni - W Catalysts

International Nuclear Information System (INIS)

Zhi-ping Lei; Li-juan Gao; Heng-fu Shui; Shi-biao, Ren; Zhi-cai Wang; Kang-shi Gang

2011-01-01

Heavy oil (distillation temperature: 320-340 deg C) derived from the direct coal liquefaction process using Shengli coal were hydrotreated using sulfided Ni-Mo/Al 2 O 3 , Ni-W/Al 2 O 3 , and Ni-W/SiO 2 catalysts respectively. The sulfided catalysts were characterized by BET, XRD, H 2 -TPR and NH 3 -TPD respectively. The evaluations of the hydrodenitrogenation (HDN) and hydrodearomatization (HDA) properties of heavy oil on the three catalysts were carried out at 400 deg C and 5.0 MPa initial H2 pressure. The W-based catalysts displayed better performances than Mo-based catalysts for the HDN and HDA reactions. Al 2 O 3 supported catalysts were found to have higher catalytic activities than on SiO 2 supported ones. The activities of sulfided catalysts were associated mainly with the nature of active sites, acidity, metal sulfide crystallite size and the amount of the reducible sulfur species of metal sulfide. (author)

Continuous fixed-bed gas-phase hydroformylation using supported ionic liquid-phase (SILP) Rh catalysts

DEFF Research Database (Denmark)

Riisager, Anders; Wasserscheid, Peter; Van Hal, R.

2003-01-01

Continuous flow gas-phase hydroformylation of propene was performed using novel supported ionic liquid-phase (SILP) catalysts containing immobilized Rh complexes of the biphosphine ligand sulfoxantphos in the ionic liquids 1-n-butyl-3-methylimidazolium hexafluorophosphate and halogen-free 1-n-butyl...

Ordered Mesoporous NiCeAl Containing Catalysts for Hydrogenolysis of Sorbitol to Glycols

Science.gov (United States)

Zhou, Zhiwei; Zhang, Jiaqi; Qin, Juan; Li, Dong; Wu, Wenliang

2018-03-01

Cellulose-derived sorbitol is emerging as a feasible and renewable feedstock for the production of value-added chemicals. Highly active and stable catalyst is essential for sorbitol hydrogenolysis. Ordered mesoporous M- xNi yCeAl catalysts with different loadings of nickel and cerium species were successfully synthesized via one-pot evaporation-induced self-assembly strategy (EISA) and their catalytic performance were tested in the hydrogenolysis of sorbitol. The physical chemical properties for the catalysts were characterized by XRD, N2 physisorption, H2-TPR, H2 impulse chemisorption, ICP and TEM techniques. The results showed that the ordered mesopores with uniform pore sizes can be obtained and the Ni nanoparticles around 6 nm in size were homogeneously dispersed in the mesopore channels. A little amount of cerium species introduced would be beneficial to their textural properties resulting in higher Ni dispersion, metal area and smaller size of Ni nanoparticles. The M-10Ni2CeAl catalyst with Ni and Ce loading of 10.9 and 6.3 wt % shows better catalytic performance than other catalysts, and the yield of 1,2-PG and EG can reach 56.9% at 493 K and 6 MPa pressure for 8 h after repeating reactions for 12 times without obvious deterioration of physical and chemical properties. Ordered mesoporous M-NiCeAl catalysts are active and stable in sorbitol hydrogenolysis.

Bimetallic Ag–Ni/C particles as cathode catalyst in AFCs (alkaline fuel cells)

International Nuclear Information System (INIS)

Song, Xingjuan; Zhang, Dongming

2014-01-01

AFCs (alkaline fuel cells) is one of the promising fuel cells, due to their low working temperature and less corrosive environment. However, decreasing the catalyst cost and improving its performance are still the challenges in its application. Transition metal as the catalyst for AFCs not only can reduce its cost, but also has great electro-catalytic efficiency. In this paper, Carbon supported Ag–Ni bimetallic catalysts with differential Ag/Ni atomic ratios were prepared by chemically reducing silver and nickel salts. Ag 3 Ni/C shows the relatively higher ORR (oxygen reduction reaction) activity among the differential Ag/Ni bimetallic particles. In order to improve the activity and stability, the catalysts were heat-treated at the temperature of 500 °C. The results indicate that the limiting current density has been improved greatly for Ag 3 Ni/C-500 °C, which is as high as 2.5× that of Ag/C. The microstructure investigation show that the non-equilibrium state of Ag–Ni alloy by heat treatment is confirmed by HRTEM (high-resolution transmission electron microscopy) images, and Ag(111) surfaces are decreased in XRD pattern, which results in the ORR activity improved and overpotential decreased. Heat treatment also has contributed to Ag–Ni/C electrochemistry stability in some degree. - Highlights: • Ag–Ni/C is applied as cathode catalyst for AFCs (alkaline fuel cells). • Ag 3 Ni/C-500 °C shows the best performance. • Non-equilibrium state of Ag–Ni alloy by heat treatment is observed. • The decreased Ag(111) surfaces are favor to improve the catalyst activity

Catalytic Steam Reforming of Toluene as a Model Compound of Biomass Gasification Tar Using Ni-CeO2/SBA-15 Catalysts

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Erik Dahlquist

2013-07-01

Full Text Available Nickel supported on SBA-15 doped with CeO2 catalysts (Ni-CeO2/SBA-15 was prepared, and used for steam reforming of toluene which was selected as a model compound of biomass gasification tar. A fixed-bed lab-scale set was designed and employed to evaluate the catalytic performances of the Ni-CeO2/SBA-15 catalysts. Experiments were performed to reveal the effects of several factors on the toluene conversion and product gas composition, including the reaction temperature, steam/carbon (S/C ratio, and CeO2 loading content. Moreover, the catalysts were subjected to analysis of their carbon contents after the steam reforming experiments, as well as to test the catalytic stability over a long experimental period. The results indicated that the Ni-CeO2/SBA-15 catalysts exhibited promising capabilities on the toluene conversion, anti-coke deposition and catalytic stability. The toluene conversion reached as high as 98.9% at steam reforming temperature of 850 °C and S/C ratio of 3 using the Ni-CeO2(3wt%/SBA-15 catalyst. Negligible coke formation was detected on the used catalyst. The gaseous products mainly consisted of H2 and CO, together with a little CO2 and CH4.

Catalytic upgrading of oleic acid into biofuel using Mo modified zeolite supported Ni oxalate catalyst functionalized with fluoride ion

International Nuclear Information System (INIS)

Ayodele, O.B.; Abbas, Hazzim F.; Daud, Wan Mohd Ashri Wan

2014-01-01

Highlights: • Modification of zeolite with freshly prepared molybdenum oxalate. • Functionalization of Ni oxalate with HF and incorporation into Mo modified zeolite. • Characterization of synthesized Mo modified zeolite supported Ni oxalate catalyst. • Deoxygenation of oleic acid with the synthesized zeolite supported catalyst. • Reusability study on the synthesized zeolite supported catalyst. - Abstract: In this study, fluoride ion functionalized nickel oxalate supported on molybdenum modified zeolite (NiMoFOx/Zeol) catalyst was synthesized, characterized and tested on the hydrodeoxygenation (HDO) of oleic acid (OA) into paraffinic fuel. The NiMoFOx/Zeol characterization results confirmed the presence of both Ni and Mo as well as the formation of NiMoO 4 which is a highly HDO reactive specie at 2θ value of 43.6° according to the XRD result. NiMoFOx/Zeol also showed loss in crystallinity and reduction in the average particle size leading to increase in the pore volume and specific surface area due to the combined effects of fluoride ion presence, oxalic acid functionalization and calcination. The effect of temperature, pressure and NiMoFOx/Zeol loading studied showed that initial increase in their values increased the yield of the target fractions until some points where reduction was observed. The best observed experimental conditions to hydrodeoxygenate 40 g (∼45 mL) of OA into 75% n-C 18 and 23% i-C 18 were 360 °C, 30 mg NiMoFOx/Zeol loading and 20 bar using 100 mL H 2 /min. The presence of i-C 18 was due to the functionalization of the catalyst with fluoride ion. The catalyst reusability result displayed excellent qualities with marginal loss of only 2% in activity after third reuse due to the improved synthesis protocol that employed organometallic precursor. The results are strongly encouraging for further studies toward industrialization of HDO process

Hydrogen generation from decomposition of hydrous hydrazine over Ni-Ir/CeO2 catalyst

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Hongbin Dai

2017-02-01

Full Text Available The synthesis of highly active and selective catalysts is the central issue in the development of hydrous hydrazine (N2H4·H2O as a viable hydrogen carrier. Herein, we report the synthesis of bimetallic Ni-Ir nanocatalyts supported on CeO2 using a one-pot coprecipitation method. A combination of XRD, HRTEM and XPS analyses indicate that the Ni-Ir/CeO2 catalyst is composed of tiny Ni-Ir alloy nanoparticles with an average size of around 4 nm and crystalline CeO2 matrix. The Ni-Ir/CeO2 catalyst exhibits high catalytic activity and excellent selectivity towards hydrogen generation from N2H4·H2O at mild temperatures. Furthermore, in contrast to previously reported Ni-Pt catalysts, the Ni-Ir/CeO2 catalyst shows an alleviated requirement on alkali promoter to achieve its optimal catalytic performance.

Study of PtNi/C catalyst for direct ethanol fuel cell

International Nuclear Information System (INIS)

Moraes, L.P.R. de; Silva, E.L. da; Amico, S.C.; Malfatti, C.F.

2014-01-01

In this work, PtNi binary catalyst and pure platin catalyst were synthesized by the impregnation-reduction method, using Vulcan XC72R as support, for direct ethanol fuel cells. The composition and structure of the catalysts were analyzed by X-ray diffraction, the electrochemical behavior was evaluated by cyclic voltammetry and morphology of the catalysts was studied by high-resolution transmission electron microscopy. The results showed that the addition of Ni to Pt led to the contraction of the crystal lattice, increased the catalytic activity compared to pure Pt and initiated the electrooxidation of ethanol at lower potential. (author)

Steam Reforming of CH4 Using Ni- Substituted Pyrochlore Catalysts

Science.gov (United States)

Haynes, Daniel J.

The steam reforming of methane (SMR) continues to remain an important industrial reaction for large-scale production of H2 as well as synthesis gas mixtures which can be used for the production of useful chemicals (e.g. methanol). Although SMR is a rather mature technology, traditional nickel based catalysts used industrially are subjected to severe temperatures and reaction conditions, which lead to irreversible activity loss through sintering, support collapse, and carbon formation. Pyrochlore-based mixed oxide have been identified as refractory materials that can be modified through the substitution of catalytic metals and other promoting species into the structure to mitigate these issues causing deactivation. For this study, a lanthanum zirconate pyrochlore catalyst was substituted with Ni to determine whether the oxide structure could effectively stabilize the activity of the catalytic metal during the SMR. The effect of different variables including calcination temperature, a comparison of a substituted versus supported Ni pyrochlore catalyst, Ni weight loading, and Sr promotion have been evaluated to determine the location of the Ni in the structure, and their effect on catalytic behavior. It was revealed that the effect of calcination temperature on a 6wt% Ni substituted pyrochlore produced by the Pechini method demonstrated very little Ni was soluble in the pyrochlore lattice. It was further revealed that by XRD, TEM, and atom probe tomography that, despite the metal loading, Ni exsolves from the structure upon crystallization of the pyrochlore at 700°C, and forms NiO at the surface and grain boundaries. An additional separate La2ZrNiO6 perovskite phase also began to form at higher temperatures (>800°C). Increasing calcination temperature was found to lead to slight sintering of the NiO at the surface, which made the NiO more reducible. Meanwhile decreasing the Ni weight loading was found to produce a lower reduction temperature due to the presence of

Hydrotreatment of heavy oil from coal liquefaction on Sulfide Ni - W Catalysts

Energy Technology Data Exchange (ETDEWEB)

Zhi-ping Lei; Li-juan Gao; Heng-fu Shui; Shi-biao, Ren; Zhi-cai Wang; Kang-shi Gang, E-mail: shhf@ahut.edu.c [Anhui University of Technology, Maanshan (China). School of Chemistry and Chemical Engineering. Anhui Key Lab. of Coal Clean Conversion and Utilization

2011-07-01

Heavy oil (distillation temperature: 320-340 deg C) derived from the direct coal liquefaction process using Shengli coal were hydrotreated using sulfided Ni-Mo/Al{sub 2}O{sub 3}, Ni-W/Al{sub 2}O{sub 3}, and Ni-W/SiO{sub 2} catalysts respectively. The sulfided catalysts were characterized by BET, XRD, H{sub 2}-TPR and NH{sub 3}-TPD respectively. The evaluations of the hydrodenitrogenation (HDN) and hydrodearomatization (HDA) properties of heavy oil on the three catalysts were carried out at 400 deg C and 5.0 MPa initial H2 pressure. The W-based catalysts displayed better performances than Mo-based catalysts for the HDN and HDA reactions. Al{sub 2}O{sub 3} supported catalysts were found to have higher catalytic activities than on SiO{sub 2} supported ones. The activities of sulfided catalysts were associated mainly with the nature of active sites, acidity, metal sulfide crystallite size and the amount of the reducible sulfur species of metal sulfide. (author)

Preparation and Characterization of NiMo/Al2O3Catalyst for Hydrocracking Processing

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Widiyadi Aditya

2018-01-01

Full Text Available Hydrocracking is a chemical process used in petroleum refineries for converting high boiling hydrocarbons in petroleum crude oils to more valuable lower boiling products such as gasoline, kerosene, and diesel oil that operate at high temperature and pressure. Catalyst was used in hydrocracking to reduce temperature and pressure. Hydrocracking catalyst are composed of active components and support. Alumina is widely used in hydrocracking process as catalyst support due to its high surface area, high thermal stability, and low prices. The objective of this research was preparated NiMo/Al2O3 catalyst that used as hydrocracking catalyst. Catalyst was synthesized by wetness impregnation method and simple heating method with various kind of Al2O3. The physicochemical properties of catalyst were investigated by X-ray diffraction (XRD to determine type of crystal and scanning electron microscopy (SEM to determine morphology of the catalyst. The NiMo/Al2O3 catalyst prepared by aluminium potassium sulfate dodecahydrate exhibited the highest crystallinity of 90.23% and it is clear that MoO3 and NiO crystallites are highly dispersed on the NiMo/Al2O3 catalyst which indicates as the best catalyst. The catalytic activity in hydrocracking process was successfully examined to convert fatty acid into hydrocarbon.

Preparation and Characterization of NiMo/Al2O3Catalyst for Hydrocracking Processing

Science.gov (United States)

Widiyadi, Aditya; Guspiani, Gema Adil; Riady, Jeffry; Andreanto, Rikky; Chaiunnisa, Safina Dea; Widayat

2018-02-01

Hydrocracking is a chemical process used in petroleum refineries for converting high boiling hydrocarbons in petroleum crude oils to more valuable lower boiling products such as gasoline, kerosene, and diesel oil that operate at high temperature and pressure. Catalyst was used in hydrocracking to reduce temperature and pressure. Hydrocracking catalyst are composed of active components and support. Alumina is widely used in hydrocracking process as catalyst support due to its high surface area, high thermal stability, and low prices. The objective of this research was preparated NiMo/Al2O3 catalyst that used as hydrocracking catalyst. Catalyst was synthesized by wetness impregnation method and simple heating method with various kind of Al2O3. The physicochemical properties of catalyst were investigated by X-ray diffraction (XRD) to determine type of crystal and scanning electron microscopy (SEM) to determine morphology of the catalyst. The NiMo/Al2O3 catalyst prepared by aluminium potassium sulfate dodecahydrate exhibited the highest crystallinity of 90.23% and it is clear that MoO3 and NiO crystallites are highly dispersed on the NiMo/Al2O3 catalyst which indicates as the best catalyst. The catalytic activity in hydrocracking process was successfully examined to convert fatty acid into hydrocarbon.

Hydrodeoxygenation of bio-oil using different mesoporous supports of NiMo catalysts

Science.gov (United States)

Rinaldi, Nino; Simanungkalit, Sabar P.; Kristiani, Anis

2017-11-01

Biomass as a renewable and sustainable resources need to utilize in many applications, especially for energy application. One of its energy application is about converting biomass into bio-oil. High oxygen content in bio-oil needs to be upgraded through hydrodeoxygenation process before being used as transportation fuel. The development of heterogenenous catalysts become an important aspect in hydrodeoxygenation process, in particular the upgrading process of bio-oil. Several supporting mesoporous materials, such as TiO2, Al2O3 and MCM-41 have unique properties, both physical and chemical properties that can be utilized in various application, including catalyst. These heterogeneous catalysts were modified their catalytic properties by impregnation with some transition metal. The effect of various supporting material and transition metal impregnated were also studied. Their chemical and physical properties were characterized by X-Ray Diffraction, X-Ray Fluororesence, Fourier Transform Infra-Red, and Surface Area Analyzer. The result of characterizations showed that Ni-Mo/TiO2 is more crystalline than Ni-Mo/MCM-41 and Ni-Mo/Al2O3. In other hand, the specific surface area of Ni-Mo/TiO2 is lower than others. These heterogeneous catalysts were tested their catalytic activity in upgrading bio-oil. The liquid products produced were analyzed by using Elemental Analyzer. The result of catalytic activity tests showed catalysts resulted Ni-Mo/TiO2 exhibits best catalytic activity in hydrodeoxygenation process. The oxygen content decreased significantly from 41.61% to 26.22% by using Ni-Mo/TiO2. Compared with Ni-Mo/TiO2, Ni-Mo/MCM-41 and Ni-Mo/Al2O3 decrease lower to 33.22% % and 28.34%, respectively. Ni-Mo/TiO2 also resulted the highest Deoxygenation Degree (DOD) as of 55% compared with Ni-Mo/MCM-41 and Ni-Mo/Al2O3 as of 31.99 % and 47.99%, respectively.

Ni/La2O3 catalyst containing low content platinum-rhodium for the dehydrogenation of N2H4·H2O at room temperature

Science.gov (United States)

O, Song-Il; Yan, Jun-Min; Wang, Hong-Li; Wang, Zhi-Li; Jiang, Qing

2014-09-01

Ni/La2O3 nanocatalyst with Pt and Rh content as low as 5 mol%, respectively, is successfully synthesized by a facile co-reduction method in the presence of hexadecyl trimethyl ammonium chloride aqueous solution under ambient atmosphere. Interestingly, the resulted Ni/La2O3 catalyst with low cost exhibits excellent catalytic activity to dehydrogenation of hydrous hydrazine (N2H4·H2O), producing hydrogen with 100% selectivity at room temperature (298 K), which represents a promising step toward the practical application for N2H4·H2O system on fuel cells.

Effect of Rh-based additives on NO and CO formed during regeneration of spent FCC catalyst

Energy Technology Data Exchange (ETDEWEB)

Iliopoulou, E.F.; Efthimiadis, E.A.; Vasalos, I.A. [Aristotle University of Thessaloniki and Center for Research and Technology Hellas, Chemical Process Engineering Research Institute, Department of Chemical Engineering, P.O. Box 1517, 54006 University City, Thessaloniki (Greece); Barth, J.-O.; Lercher, J.A. [Institut fur Technische Chemie, Technische Universitat Munchen, Lichtenbergstrasse 4, D-85748 Garching (Germany)

2004-02-10

Regeneration studies of spent FCC catalyst were performed in a bench-scale unit under reaction conditions that sufficiently simulate those in the regenerator of the fluid catalytic cracking (FCC) unit. The effect of a conventional Pt-based CO promoter (CP-3) on the composition of flue gases was examined. As expected addition of CP-3 in the catalytic inventory decreased CO emissions by one order of magnitude, but tripled the NO emissions independently of the concentration of CO promoter used. Addition of a series of Rh-based catalysts modified the composition of flue gases emitted during regeneration. The parameters under study were the catalytic support, the Rh loading on the additive, and the amount of additive used during regeneration. Both a stoichiometric spinel MgO{center_dot}Al{sub 2}O{sub 3} of high crystallinity and a commercial alumina were competent supports. Promotion of the alumina support with Ce or performing regeneration introducing CO did not affect the additive performance significantly. A combined performance of CO oxidation and NO reduction was achieved minimizing both the Rh loading in the additive (0.1wt.%) and the concentration of additive used during regeneration (1wt.%). IR studies suggest that NO reduction by CO over Rh/alumina additives proceeds via the dissociative adsorption of NO, the formation of NCO species on Rh and their migration to the alumina support to finally yield N{sub 2} and CO{sub 2}.

Hydrogen production from bio-fuels using precious metal catalysts

Science.gov (United States)

Pasel, Joachim; Wohlrab, Sebastian; Rotov, Mikhail; Löhken, Katrin; Peters, Ralf; Stolten, Detlef

2017-11-01

Fuel cell systems with integrated autothermal reforming unit require active and robust catalysts for H2 production. Thus, an experimental screening of catalysts for autothermal reforming of commercial biodiesel fuel was performed. Catalysts consisted of a monolithic cordierite substrate, an oxide support (γ-Al2O3) and Pt, Ru, Ni, PtRh and PtRu as active phase. Experiments were run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. Fresh and aged catalysts were characterized by temperature programmed methods and thermogravimetry to find correlations with catalytic activity and stability.

Ni Catalysts Supported on Modified Alumina for Diesel Steam Reforming

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Antonios Tribalis

2016-01-01

Full Text Available Nickel catalysts are the most popular for steam reforming, however, they have a number of drawbacks, such as high propensity toward coke formation and intolerance to sulfur. In an effort to improve their behavior, a series of Ni-catalysts supported on pure and La-, Ba-, (La+Ba- and Ce-doped γ-alumina has been prepared. The doped supports and the catalysts have been extensively characterized. The catalysts performance was evaluated for steam reforming of n-hexadecane pure or doped with dibenzothiophene as surrogate for sulphur-free or commercial diesel, respectively. The undoped catalyst lost its activity after 1.5 h on stream. Doping of the support with La improved the initial catalyst activity. However, this catalyst was completely deactivated after 2 h on stream. Doping with Ba or La+Ba improved the stability of the catalysts. This improvement is attributed to the increase of the dispersion of the nickel phase, the decrease of the support acidity and the increase of Ni-phase reducibility. The best catalyst of the series doped with La+Ba proved to be sulphur tolerant and stable for more than 160 h on stream. Doping of the support with Ce also improved the catalytic performance of the corresponding catalyst, but more work is needed to explain this behavior.

Enhanced MEA Performance for PEMFCs under Low Relative Humidity and Low Oxygen Content Conditions via Catalyst Functionalization

Energy Technology Data Exchange (ETDEWEB)

Xin, Le; Yang, Fan; Xie, Jian; Yang, Zhiwei; Kariuki, Nancy N.; Myers, Deborah J.; Peng, Jui-Kun; Wang, Xiaohua; Ahluwalia, Rajesh K.; Yu, Kang; Ferreira, Paulo J.; Bonastre, Alex Martinez; Fongalland, Dash; Sharman, Jonathan

2017-01-01

This work demonstrates that functionalizing annealed-Pt/Ketjen black EC300j (a-Pt/KB) and dealloyed-PtNi/Ketjen black EC300j (d-PtNi/KB) catalysts using p-phenyl sulfonic acid can effectively enhance performance in the membrane electrode assemblies (MEAs) of proton exchange membrane fuel cells (PEMFCs). The functionalization increased the size of both Pt and PtNi catalyst particles and resulted in the further leaching of Ni from the PtNi catalyst while promoting the formation of nanoporous PtNi nanoparticles. The size of the SO3H-Pt/KB and SO3H-PtNi/KB carbon-based aggregates decreased dramatically, leading to the formation of catalyst layers with narrower pore size distributions.MEA tests highlighted the benefits of the surface functionalization, in which the cells with SO3H-Pt/KB and SO3H-PtNi/KB cathode catalysts showed superior high current density performance under reduced RH conditions, in comparison with cells containing annealed Pt/KB (a-Pt/KB) and de-alloyed PtNi/KB (d-PtNi/KB) catalysts. The performance improvement was particularly evident when using reactant gases with low relative humidity, indicating that the hydrophilic functional groups on the carbon improved the water retention in the cathode catalyst layer. These results show a new avenue for enhancing catalyst performance for the next generation of catalytic materials for PEMFCs.

Characterization and parametrical study of Rh-TPPTS supported ionic liquid phase (SILP) catalysts for ethylene hydroformylation

DEFF Research Database (Denmark)

Hanh, Nguyen Thi Ha; Duc, Duc Truong; Thang, Vu Dao

2012-01-01

The supported ionic liquid phase (SILP) catalysis technology was applied to continuous, gas-phase hydroformylation of ethylene. Rh-TPPTS SILP catalysts with relatively low ionic liquid loading were shown to be stable and highly activity for ethylene hydroformylation. However, the catalytic activity......, BET surface area and pore morphology of the catalysts depended on the content of ionic liquid. Hence, catalysts with high ionic liquid loading content showed deactivation at high reaction temperatures, possibly caused by redistribution of ionic liquid out of the pores under these conditions. (C) 2012...

Efficient Cycloaddition Reaction of Carbon Dioxide with Epoxide by Rhodamine Based Catalyst Under 1 atm Pressure

Energy Technology Data Exchange (ETDEWEB)

Gong, Qing; Luo, Huadong; Cao, Di; Zhang, Haibo; Wang, Wenjing; Zhou, Xiaohai [Wuhan University, Wuhan (China)

2012-06-15

Rhodamine B (RhB) and rhodamine 6G (Rh6G) were employed as catalysts for the synthesis of cyclic carbonate from carbon dioxide and epoxide. It turned out that the catalytic activity of Rh6G was nearly 29 times higher than that of RhB at 1 atm pressure, 90 .deg. C. Furthermore, the catalytic efficiency of RhB and Rh6G was greatly enhanced with triethylamine as co-catalyst. Under the optimized conditions, the best isolated yield (93%) of cyclic carbonate was achieved without organic solvent and metal component

Ni-Based Catalysts for Low Temperature Methane Steam Reforming: Recent Results on Ni-Au and Comparison with Other Bi-Metallic Systems

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Anna M. Venezia

2013-06-01

Full Text Available Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside of the carbon-forming regime. Reactivity and deactivation by carbon formation can be tuned by modifying Ni surfaces with a second metal, such as Au through alloy formation. In the present review, we summarize the very recent progress in the design, synthesis, and characterization of supported bimetallic Ni-based catalysts for steam reforming. The progress in the modification of Ni with noble metals (such as Au and Ag is discussed in terms of preparation, characterization and pretreatment methods. Moreover, the comparison with the effects of other metals (such as Sn, Cu, Co, Mo, Fe, Gd and B is addressed. The differences of catalytic activity, thermal stability and carbon species between bimetallic and monometallic Ni-based catalysts are also briefly shown.

Recent Scientific Progress on Developing Supported Ni Catalysts for Dry (CO2 Reforming of Methane

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Hyun Ook Seo

2018-03-01

Full Text Available Two major green house gases (CO2 and CH4 can be converted into useful synthetic gas (H2 and CO during dry reforming of methane (DRM reaction, and a lot of scientific efforts has been made to develop efficient catalysts for dry reforming of methane (DRM. Noble metal-based catalysts can effectively assist DRM reaction, however they are not economically viable. Alternatively, non-noble based catalysts have been studied so far, and supported Ni catalysts have been considered as a promising candidate for DRM catalyst. Main drawback of Ni catalysts is its catalytic instability under operating conditions of DRM (>700 °C. Recently, it has been demonstrated that the appropriate choice of metal-oxide supports can address this issue since the chemical and physical of metal-oxide supports can prevent coke formation and stabilize the small Ni nanoparticles under harsh conditions of DRM operation. This mini-review covers the recent scientific findings on the development of supported Ni catalysts for DRM reaction, including the synthetic methods of supported Ni nanoparticles with high sintering resistance.

Fe/Ni-N-CNFs electrochemical catalyst for oxygen reduction reaction/oxygen evolution reaction in alkaline media

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhuang [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Li, Mian [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Fan, Liquan; Han, Jianan [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Xiong, Yueping, E-mail: ypxiong@hit.edu.cn [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China)

2017-04-15

Highlights: • Novel Fe/Ni-N-CNFs electrocatalysts are prepared by electrospinning technique. • The Fe1Ni1-N-CNFs catalyst exhibits the excellent ORR and OER catalytic activity. • Synergy of Fe/Ni alloy is responsible for the excellent catalytic performance. - Abstract: The novel of iron, nickel and nitrogen doped carbon nanofibers (Fe/Ni-N-CNFs) as bifunctional electrocatalysts are prepared by electrospinning technique. In alkaline media, the Fe/Ni-N-CNFs catalysts (especially for Fe1Ni1-N-CNFs) exhibit remarkable electrocatalytic performances of oxygen reduction reaction (ORR)/oxygen evolution reaction (OER). For ORR catalytic activity, Fe1Ni1-N-CNFs catalyst offers a higher onset potential of 0.903 V, a similar four-electron reaction pathway, and excellent stability. For OER catalytic activity, Fe1Ni1-N-CNFs catalyst possesses a lower onset potential of 1.528 V and a smaller charge transfer resistance of 48.14 Ω. The unparalleled catalytic activity of ORR and OER for the Fe1Ni1-N-CNFs is attributed to the 3D porous cross-linked microstructures of carbon nanofibers with Fe/Ni alloy, N dopant, and abundant M-N{sub x} and NiOOH as catalytic active sites. Thus, Fe1Ni1-N-CNFs catalyst can be acted as one of the efficient and inexpensive catalysts of metal-air batteries.

pH-dependent release of trace elements including platinum group elements (PGEs) from gasoline and diesel catalysts

Science.gov (United States)

Sucha, Veronika; Mihaljevic, Martin; Ettler, Vojtech; Strnad, Ladislav

2014-05-01

The release of trace metals and platinum group elements (PGEs) from automobile exhaust catalysts represents a remarkable source of higly dispersed environmental contamination. Especially, PGEs have shown increasing research interest due to their possible bioaccessibility. In our research, we focused on leaching behaviour of trace metals from gasoline and diesel automobile catalysts. While catalysts for gasoline engines contain a mixture of Pt-Pd-Rh or Pd-Rh, catalysts for diesel engines are composed only of Pt. We used dust from two crushed gasoline and two crushed diesel catalysts (new and aged). The dust of gasoline catalysts contains significant concentrations of Pt (700 mg.kg-1), Pd (11 000 mg.kg-1) and Rh (700 mg.kg-1). And the dust of diesel catalysts are composed of Pt (3 900 mg.kg-1) and they contains negligible amounts of Pd dan Rh (leaching of trace metals from dust we used pH-stat leaching test according to the European standard CEN/TS 14997. The concentrations of cations: PGEs (Pt, Pd a Rh), K, Na, Ca, Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, La and Ce were determined by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS), and anions: F-, Cl-, SO42- and NO3- by high-performance liquid chromatography. Although the dusts from catalysts were relatively stable to acid/base influence, the leaching of trace metals from catalysts showed a dependence on pH. Generally, the highest concentrations were released under acidic conditions. The leaching of PGEs was higher for Pt in diesel catalysts and for Pd and Rh in gasoline catalysts. The highest concentrations of Zn and Pb were observed in old catalysts. The rare earth metals were released more from gasoline catalysts. Catalysts particles represent health risk especially with respect to their PGEs contents.

Catalytic performance of Ni/MgO catalyst in methane dry reforming

Science.gov (United States)

Al-Swai, Basem M.; Osman, N. B.; Abdullah, Bawadi

2017-10-01

Methane dry reforming to synthesis gas over nickel catalysts supported on magnesium oxide has been studied. The support was prepared via co-precipitation method using ammonia solution (20 wt% in water) as the precipitating agent. 10 wt% of Ni metal was impregnated to form Ni/MgO catalyst. The prepared catalyst was characterized by different techniques, such as XRD, BET, SEM, and TGA analysis. The effect of reaction conditions on the conversions of CH4 and CO2, selectivity of H2 and CO, and carbon deposition were investigated in a tabular furnace reactor. The catalyst afforded as high as 93% CH4 conversion at 900 °C. The catalyst has also shown excellent stability during reaction at relatively higher space velocity (1.8×104 ml g-1 h-1) and 800 °C reaction temperature. TGA characterization of spent catalyst has shown lesser magnitude of carbon deposition on the surface of the catalyst at 900 °C.

Understanding the Performance and Stability of Supported Ni-Co-Based Catalysts in Phenol HDO

Directory of Open Access Journals (Sweden)

Thuan M. Huynh

2016-11-01

Full Text Available Performances of bimetallic catalysts (Ni-Co supported on different acidic carriers (HZSM-5, HBeta, HY, ZrO2 and corresponding monometallic Ni catalysts in aqueous phase hydrodeoxygenation of phenol were compared in batch and continuous flow modes. The results revealed that the support acidity plays an important role in deoxygenation as it mainly controls the oxygen-removing steps in the reaction network. At the same time, sufficient hydrothermal stability of a solid catalyst is essential. Batch experiments revealed 10Ni10Co/HZSM-5 to be the best-performing catalyst in terms of conversion and cyclohexane yield. Complementary continuous runs provided more insights into the relationship between catalyst structure, efficiency and stability. After 24 h on-stream, the catalyst still reveals 100% conversion and a slight loss (from 100% to 90% in liquid hydrocarbon selectivity. The observed alloy of Co with Ni increased dispersion and stability of Ni-active sites, and combination with HZSM-5 resulted in a well-balanced ratio of metal and acid sites which promoted all necessary steps in preferred pathways. This was proved by studies of fresh and spent catalysts using various characterization techniques (N2 physisorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscopy (TEM and infrared spectroscopy of adsorbed pyridine (pyr-IR.

The Enhanced Catalytic Performance and Stability of Rh/γ-Al2O3 Catalyst Synthesized by Atomic Layer Deposition (ALD for Methane Dry Reforming

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Yunlin Li

2018-01-01

Full Text Available Rh/γ-Al2O3 catalysts were synthesized by both incipient wetness impregnation (IWI and atomic layer deposition (ALD. The TEM images of the two catalysts showed that the catalyst from ALD had smaller particle size, and narrower size distribution. The surface chemical states of both catalysts were investigated by both XPS and X-ray Absorption Near Edge Structure (XANES, and the catalyst from IWI had higher concentration of Rh3+ than that from ALD. The catalytic performance of both catalysts was tested in the dry reforming of methane reaction. The catalyst from ALD showed a higher conversion and selectivity than that from IWI. The stability testing results indicated that the catalyst from ALD showed similar stability to that from IWI at 500 °C, but higher stability at 800 °C.

A general approach for the synthesis of bimetallic M–Sn (M = Ru, Rh and Ir) catalysts for efficient hydrogenolysis of ester

KAUST Repository

Samal, Akshaya Kumar

2016-11-24

A versatile synthetic method was applied for the preparation of Sn containing bimetallic catalysts. The synthesis was performed by simply mixing the super hydride [LiB(C2H5)(3)H], with a metal (Ru, Rh or Ir) salt and an organotin complex in tetrahydrofuran solvent without using any surfactant. This leads to the formation of monodispersed M-Sn (M = Ru, Rh or Ir) bimetallic nanoparticles (NPs). These bimetallic catalysts show high performances in the hydrogenolysis of ester to the corresponding alcohol.

Unsupported NiPt alloy metal catalysts prepared by water-in-oil (W/O) microemulsion method for methane cracking

KAUST Repository

Zhou, Lu

2016-05-18

Unsupported NiPt metal catalyst with Ni/Pt molar ratio of 88/12 is prepared by water-in-oil (W/O) microemulsion method in this study. Compared to monometallic Ni and Pt catalysts, the NiPt catalyst exhibits superior activity and stability for methane cracking. By XRD (X-ray powder diffraction), XPS (X-ray photoelectron spectroscopy) and TEM (Transmission electron microscopy) analyses, the formation of Ni(0)Pt(0) alloy is believed to be the main reason for the reactivity improvement of this catalyst. Carbon nano tube (CNT) with Ni(0)Pt(0) particles anchored on the top of tube are found for the NiPt catalyst. © 2016 Elsevier Ltd.

Ni-Based Catalysts for the Hydrotreatment of Fast Pyrolysis Oil

NARCIS (Netherlands)

Ardiyanti, A. R.; Bykova, M. V.; Khromova, S. A.; Yin, W.; Venderbosch, R. H.; Yakovlev, V. A.; Heeres, Hero

Catalytic hydrotreatment is an attractive technology to convert fast pyrolysis oil to stabilized oil products for co processing in conventional crude oil refinery units. We report here the use of novel bimetallic NiCu- and NiPd-based (Picula) catalysts characterized by a high Ni content (29-58 wt %)

Catalytic hydrothermal liquefaction (HTL of biomass for bio-crude production using Ni/HZSM-5 catalysts

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Shouyun Cheng

2017-04-01

Full Text Available Hydrothermal liquefaction (HTL is an effective method that can convert biomass into bio-crude, but direct use of bio-crude derived from biomass HTL remains a challenge due to the lower quality. In this study, bifunctional Ni/HZSM-5 catalysts and zinc hydrolysis were combined to produce upgraded bio-crude in an in-situ HTL process. The K2CO3 and HZSM-5 catalysts with different Ni loading ratios were tested. The effects of different catalysts on the yield and quality of bio-crude and gas were investigated. The results indicated that the catalysts improved bio-crude and gas yields, compared to pine sawdust liquefaction without catalyst. The catalysts reduced the contents of undesirable oxygenated compounds such as acids, ketones, phenols, alcohols and esters in bio-crude products while increased desirable hydrocarbons content. K2CO3 produced highest bio-crude yield and lowest solid residue yield among all catalysts. Compared to parent HZSM-5 catalyst, bifunctional Ni/HZSM-5 catalysts exhibited higher catalyst activity to improve quality of upgraded bio-crude due to its integration of cracking and hydrodeoxygenation reactions. 6%Ni/HZSM-5 catalyst produced the bio-crude with the highest hydrocarbons content at 11.02%. This catalyst can be a candidate for bio-crude production from biomass HTL.

Energies of Electronic States of Ni (II) Ion in NiO-Al2O3 Catalyst Prepared by Impregnation

International Nuclear Information System (INIS)

Obadovic, D. Z.; Kiurski, J.; Marinkovic-Neducin, R. P.

2007-01-01

The behavior of NiO-Al2O3 catalysts is strongly dependent on the preparation method, as well as on pretreatment conditions. In the present work we investigated the influences of Ni(II) ion on NiO-Al2O3 catalysts properties due to the preparation by impregnation method. Based on experimental diffuse reflectance spectroscopy (DRS) data of electronic d-d transitions of Ni (II) promoter ion the energies of electronic states in spinel-like structure were calculated, and the most probable scheme of molecular orbital have been proposed

Unraveling the role of support surface hydroxyls and its effect on the selectivity of C{sub 2} species over Rh/γ-Al{sub 2}O{sub 3} catalyst in syngas conversion: A theoretical study

Energy Technology Data Exchange (ETDEWEB)

Zhang, Riguang; Duan, Tian; Wang, Baojun, E-mail: wangbaojun@tyut.edu.cn; Ling, Lixia

2016-08-30

Highlights: • The selectivity toward CH{sub x} (x = 1–3) depends on γ-Al{sub 2}O{sub 3} support and its surface properties. • Rh/γ-Al{sub 2}O{sub 3} catalyst exhibits the higher selectivity toward CH{sub x} (x = 1,2) formation from syngas. • C{sub 2} species (C{sub 2}H{sub 2},CHCO,CH{sub 2}CHO) are the main products on Rh/γ-Al{sub 2}O{sub 3} catalyst. • γ-Al{sub 2}O{sub 3} surface hydroxyls affect the selectivity of C{sub 2} species over Rh/γ-Al{sub 2}O{sub 3} catalyst. - Abstract: The supported Rh-based catalysts exhibit the excellent catalytic performances for syngas conversion to C{sub 2} species. In this study, all possible elementary steps leading to C{sub 2} species from syngas have been explored to identify the role of support and its surface hydroxyls over Rh/γ-Al{sub 2}O{sub 3} catalyst; Here, the results are obtained using density functional theory (DFT) method. Two models: Rh4 cluster supported on the dry γ-Al{sub 2}O{sub 3}(110) surface, D(Rh4), and on the hydroxylated γ-Al{sub 2}O{sub 3}(110) surface, H(Rh4), have been used to model Rh/γ-Al{sub 2}O{sub 3} catalyst. Our results show that CO prefers to be hydrogenated to CHO, subsequently, starting from CHO species, CH and CH{sub 2} species are the dominate monomers among CH{sub x}(x = 1–3) species rather than CH{sub 3} and CH{sub 3}OH on D(Rh4) and H(Rh4) surfaces, suggesting that γ-Al{sub 2}O{sub 3}-supported Rh catalyst exhibits the high selectivity towards CH{sub x} formation compared to the pure Rh catalyst. On the other hand, D(Rh4) is more favorable for C{sub 2} hydrocarbon (C{sub 2}H{sub 2}) formation, whereas H(Rh4) surface easily produces C{sub 2} hydrocarbon (C{sub 2}H{sub 2}) and C{sub 2} oxygenates (CHCO,CH{sub 2}CHO), indicating that the surface hydroxyls of support can affect the selectivity of C{sub 2} species over Rh/γ-Al{sub 2}O{sub 3} catalyst in syngas conversion. Moreover, compared to the pure Rh(111) surface, Rh/γ-Al{sub 2}O{sub 3} catalyst can achieve the

Deactivation Studies of Rh/Ce0.8Zr0.2O2 Catalysts in Low Temperature Ethanol Steam Reforming

Energy Technology Data Exchange (ETDEWEB)

Platon, Alex; Roh, Hyun-Seog; King, David L.; Wang, Yong

2007-10-30

Rapid deactivation of Rh/Ce0.8Zr0.2O2 catalysts in low temperature ethanol steam reforming was studied. A significant build-up of carbonaceous intermediate, instead of carbon deposit, was observed at a lower reaction temperature which was attributed to the rapid catalyst deactivation. Co-feed experiments indicated that acetone and ethylene caused more severe catalyst deactivation than other oxygenates such as acidic acid and acetaldehyde.

Hydrogen production from bio-fuels using precious metal catalysts

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Pasel Joachim

2017-01-01

Full Text Available Fuel cell systems with integrated autothermal reforming unit require active and robust catalysts for H2 production. Thus, an experimental screening of catalysts for autothermal reforming of commercial biodiesel fuel was performed. Catalysts consisted of a monolithic cordierite substrate, an oxide support (γ-Al2O3 and Pt, Ru, Ni, PtRh and PtRu as active phase. Experiments were run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. Fresh and aged catalysts were characterized by temperature programmed methods and thermogravimetry to find correlations with catalytic activity and stability.

Pt-Rh/g Al2O3 Influence of Catalyst Preparation Methods on Metallic Particle Dispersion and Size Distribution

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N.M. da Fonseca

1998-06-01

Full Text Available - Pt-Rh/Al2O3 catalysts were prepared by successive incipient impregnations or coimpregnation. Characterization was achieved by H2 chemisorption and transmission electron microscopy. It was verified that method of preparation, ratio of metal weights and sequence of deposition are factors that result in very distinct catalysts.

Structured Ni catalysts on porous anodic alumina membranes for methane dry reforming: NiAl 2 O 4 formation and characterization

KAUST Repository

Zhou, Lu

2015-06-29

This communication presents the successful design of a structured catalyst based on porous anodic alumina membranes for methane dry reforming. The catalyst with a strong Ni-NiAl2O4 interaction shows both excellent activity and stability. This journal is © The Royal Society of Chemistry.

Structured Ni catalysts on porous anodic alumina membranes for methane dry reforming: NiAl 2 O 4 formation and characterization

KAUST Repository

Zhou, Lu; Guo, Y.; Basset, Jean-Marie; Kameyama, H.

2015-01-01

This communication presents the successful design of a structured catalyst based on porous anodic alumina membranes for methane dry reforming. The catalyst with a strong Ni-NiAl2O4 interaction shows both excellent activity and stability. This journal is © The Royal Society of Chemistry.

Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol

DEFF Research Database (Denmark)

Studt, Felix; Sharafutdinov, Irek; Abild-Pedersen, Frank

2014-01-01

The use of methanol as a fuel and chemical feedstock could become very important in the development of a more sustainable society if methanol could be efficiently obtained from the direct reduction of CO 2 using solar-generated hydrogen. If hydrogen production is to be decentralized, small-scale CO...... 2 reduction devices are required that operate at low pressures. Here, we report the discovery of a Ni-Ga catalyst that reduces CO 2 to methanol at ambient pressure. The catalyst was identified through a descriptor-based analysis of the process and the use of computational methods to identify Ni......-Ga intermetallic compounds as stable candidates with good activity. We synthesized and tested a series of catalysts and found that Ni 5 Ga 3 is particularly active and selective. Comparison with conventional Cu/ZnO/Al 2 O 3 catalysts revealed the same or better methanol synthesis activity, as well as considerably...

ACTIVITY TEST AND REGENERATION OF NiMo/Z CATALYST FOR HYDROCRACKING OF WASTE PLASTIC FRACTION TO GASOLINE FRACTION

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Rodiansono Rodiansono

2010-06-01

Full Text Available Activity test and regeneration of NiMo/active natural zeolite catalyst for hydrocracking of waste plastic fraction of polyprophylene (PP type have been carried out. The catalysts was prepared by loading Mo followed by Ni Metals onto the natural zeolite (Z sample, then calcined at 500oC, oxidized and reduced at 400oC under nitrogen, oxygen and hydrogen stream, respectively. The characterization of catalysts including spesific surface area, average pore radius, and total pore volume were performed by gas sorption analyzer, amount of total acid sites was determined by gas sorption method, and acid site strength was confirmed by IR spectroscopy. The hydrocracking process was carried out in a semi-flow reactor system at 360 oC and catalyst:feed ratio 0.5 under hydrogen stream (150 mL/hour. The feed was vaporized from the pyrolisis reactor into the hydrocracking reactor. A liquid product was collected and analyzed by gas chromatography (GC and gas chromatography-mass spectroscopy (GC-MS. The characterization results showed that spesific surface area, average pore radius, and total pore volume of the Z sample decreased after loading of the Ni and Mo metals. Amount of total acid sites of the NiMo/Z catalyst was higher than that of the Z sample. The activity of NiMo/Z catalyst decreased after several continously runs. Its regeneration produced the NiMo/Z reg catalyst with similar activity and selectivity to the fresh catalyst (NiMo/Z. The activity of catalysts at the optimum condition followed the order of NiMo/Z reg>NiMo/Z>Z (conversion of hydrocarbon C>12 and NiMo/Z reg>NiMo/Z>Z (total yield of gasoline fraction. The selectivity of catalysts for C7-C8 product followed the order of Z>NiMo/Z>NiMo/Z reg. Keywords: activity, polyprophylene, catalyst, gasoline fraction.

Hydrogen Production by Steam Reforming of Ethanol on Rh-Pt Catalysts: Influence of CeO2, ZrO2, and La2O3 as Supports

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Bernay Cifuentes

2015-11-01

Full Text Available CeO2-, ZrO2-, and La2O3-supported Rh-Pt catalysts were tested to assess their ability to catalyze the steam reforming of ethanol (SRE for H2 production. SRE activity tests were performed using EtOH:H2O:N2 (molar ratio 1:3:51 at a gaseous space velocity of 70,600 h−1 between 400 and 700 °C at atmospheric pressure. The SRE stability of the catalysts was tested at 700 °C for 27 h time on stream under the same conditions. RhPt/CeO2, which showed the best performance in the stability test, also produced the highest H2 yield above 600 °C, followed by RhPt/La2O3 and RhPt/ZrO2. The fresh and aged catalysts were characterized by TEM, XPS, and TGA. The higher H2 selectivity of RhPt/CeO2 was ascribed to the formation of small (~5 nm and stable particles probably consistent of Rh-Pt alloys with a Pt surface enrichment. Both metals were oxidized and acted as an almost constant active phase during the stability test owing to strong metal-support interactions, as well as the superior oxygen mobility of the support. The TGA results confirmed the absence of carbonaceous residues in all the aged catalysts.

Selective Conversion of Furfural to Cyclopentanone or Cyclopentanol Using Co-Ni Catalyst in Water

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Yaru Li

2018-05-01

Full Text Available Co-Ni catalysts, prepared by a typical wetness impregnation method, can selectively convert furfural (FFA to cyclopentanone (CPO or cyclopentanol (CPL in water, respectively. The catalytic performance depends strongly on the support. It is also strongly influenced by the Co-Ni loadings of the catalyst. The 10%Co-10%Ni/TiO2 catalyst showed the highest selectivity toward CPO (53.3% with almost complete FFA conversion, and the main product was CPL (45.4% over 20%Co/TiO2 at the optimized conditions (150 °C, 4 MPa H2, 4 h. The surface morphology, surface area, composition and reducibility properties of these catalysts were fully characterized by XRD, H2-TPR, ICP-AES and SEM. The factors that influenced the activity of catalysts were also investigated in detail. Additionally, the stability of catalyst for the hydrogenative rearrangement of FFA was studied.

High-performance bimetallic alloy catalyst using Ni and N co-doped composite carbon for the oxygen electro-reduction.

Science.gov (United States)

Jung, Won Suk

2018-03-15

In this study, a novel synthesis method for the bimetallic alloy catalyst is reported, which is subsequently used as an oxygen reduction catalyst in polymer electrolyte membrane fuel cells (PEMFCs). The support prepared from the Ni-chelate complex shows a mesoporous structure with a specific surface area of ca. 400 m 2  g -1 indicating the suitable support for PEMFC applications. Ethylenediamine is converted to the nitrogen and carbon layers to protect the Ni particles which will diffuse into the Pt lattice at 800 °C. The PtNi/NCC catalyst with PtNi cores and Pt-rich shells is successfully formed when acid-treated as evidenced by line scan profiles. The catalyst particles thus synthesized are well-dispersed on the N-doped carbon support, while the average particle size is ca. 3 nm. In the PEMFC test, the maximum power density of the PtNi/NCC catalyst shows approximately 25% higher than that of the commercial Pt/C catalyst. The mass activity of the PtNi/NCC catalyst showed approximately 3-fold higher than that of the commercial Pt/C catalyst. The mass activity strongly depends on the ratio of Pt to Ni since the strain effect can be strong for catalysts due to the mismatch of lattice parameters of the Ni and Pt. Copyright © 2017 Elsevier Inc. All rights reserved.

Preparation and characterization of NiW-nHA composite catalyst for hydrocracking

Science.gov (United States)

Zhou, Gang; Hou, Yongzhao; Liu, Lei; Liu, Hongru; Liu, Can; Liu, Jing; Qiao, Huiting; Liu, Wenyong; Fan, Yubo; Shen, Shituan; Rong, Long

2012-11-01

The synthesis, characterization and catalytic capability of the NiW-nano-hydroxyapatite (NiW-nHA) composite were investigated in this paper. The NiW-nHA catalyst was prepared by a co-precipitation method. Then Fourier transform infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDX) were used to analyze this material. In addition, the catalytic capacity of the NiW-nHA composite was also examined by FT-IR and gas chromatography (GC). The results of FT-IR analysis indicated that Ni, W and nHA combined closely. TEM observation revealed that this catalyst was needle shaped and the crystal retained a nanometer size. XRD data also suggested that a new phase of CaWO4 appeared and the lattice parameters of nHA changed in this system. nHA was the carrier of metals. The rates of Ni/W-loading were 73.24% and 65.99% according to the EDX data, respectively. Furthermore, the conversion of 91.88% Jatropha oil was achieved at 360 °C and 3 MPa h-1 over NiW-nHA catalyst. The straight chain alkanes ranging from C15 to C18 were the main components in the production. The yield of C15-C18 alkanes was up to 83.56 wt%. The reaction pathway involved hydrocracking of the C&z.dbd;C bonds of these triglycerides from Jatropha oil. This paper developed a novel non-sulfided catalyst to obtain a ``green biofuel'' from vegetable oil.

The Influence of oxide additives on Ni/Al2O3 catalysts in low temperature methane steam reforming

International Nuclear Information System (INIS)

Lazar, Mihaela; Dan, Monica; Mihet, Maria; Almasan, Valer

2009-01-01

Hydrogen is industrially produced by methane steam reforming. The process is catalytic and the usual catalyst is based on Ni as the active element. The main problem of this process is its inefficiency. It requires high temperatures at which Ni also favors the formation of graphite, which deactivates the catalysts. Ni has the advantage of being much cheaper than noble metal catalysts, so many researches are done in order to improve the properties of supported Ni catalysts and to decrease the temperature at which the process is energetically efficient. In order to obtain catalysts with high activity and stability, it is essential to maintain the dispersion of the active phase (Ni particles) and the stability of the support. Both properties can be improved by addition of a second oxide to the support. In this paper we present the results obtained in preparation and characterization of Ni/Al 2 O 3 catalysts modified by addition of CeO 2 and La 2 O 3 to alumina support. The following catalysts were prepared by impregnation method: Ni/Al 2 O 3 , Ni/CeO 2 -Al 2 O 3 and Ni/La 2 O 3 -Al 2 O 3 (10 wt.% Ni and 6 wt.% additional oxide). The catalytic surface was characterized by N 2 adsorption - desorption isotherms. The hydrogen - surface bond was characterized by Thermo-Programmed-Desorption (TPD) method. All catalysts were tested in steam reforming reaction of methane in the range of 600 - 700 deg. C, at atmospheric pressure working with CH 4 :H 2 O ratio of 1:3. The modified catalysts showed a better catalytic activity and selectivity for H 2 and CO 2 formation, at lower temperatures than the simple Ni/Al 2 O 3 catalyst. (authors)

Electro-oxidation of Ethanol on Carbon Supported PtSn and PtSnNi Catalysts

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Nur Hidayati

2016-03-01

Full Text Available Even though platinum is known as an active electro-catalyst for ethanol oxidation at low temperatures (< 100 oC, choosing the electrode material for ethanol electro-oxidation is a crucial issue. It is due to its property which easily poisoned by a strong adsorbed species such as CO. PtSn-based electro-catalysts have been identified as better catalysts for ethanol electro-oxidation. The third material is supposed to improved binary catalysts performance. This work presents a study of the ethanol electro-oxidation on carbon supported Pt-Sn and Pt-Sn-Ni catalysts. These catalysts were prepared by alcohol reduction. Nano-particles with diameters between 2.5-5.0 nm were obtained. The peak of (220 crystalline face centred cubic (fcc Pt phase for PtSn and PtSnNi alloys was repositioned due to the presence of Sn and/or Ni in the alloy. Furthermore, the modification of Pt with Sn and SnNi improved ethanol and CO electro-oxidation. Copyright © 2016 BCREC GROUP. All rights reserved Received: 10th November 2015; Revised: 1st February 2016; Accepted: 1st February 2016 How to Cite: Hidayati, N., Scott, K. (2016. Electro-oxidation of Ethanol on Carbon Supported PtSn and PtSnNi Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 10-20. (doi:10.9767/bcrec.11.1.394.10-20 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.394.10-20

Preparation of Au/Y2O3 and Au/NiO catalysts by co-precipitation and their oxidation activities

International Nuclear Information System (INIS)

Sreethawong, Thammanoon; Sitthiwechvijit, Norsit; Rattanachatchai, Apiwat; Ouraipryvan, Piya; Schwank, Johannes W.; Chavadej, Sumaeth

2011-01-01

Research highlights: → The catalytic activity of Au catalysts supported on Y 2 O 3 and NiO prepared by co-precipitation was investigated for CO and methanol oxidation. → The phase transformation of yttrium support greatly affected the CO oxidation activity. → The Au/Y 2 O 3 exhibited the same activity as Au/NiO for the methanol oxidation while the Au/NiO gave higher activity for CO oxidation. - Abstract: The objective of this work was to investigate the catalytic activity of gold catalysts supported on two metal oxides, yttrium oxide and nickel oxide, prepared by co-precipitation for CO and methanol oxidation reactions. The TGA and XRD results confirmed that yttrium hydroxide (Y(OH) 3 ) was formed at calcination temperature below 300 deg. C. When it was calcined at 400 deg. C, the Y(OH) 3 was transformed to yttrium oxide hydroxide (YOOH). Finally, when calcination temperature was raised to 600 deg. C, the YOOH was completely transformed to yttrium oxide (Y 2 O 3 ). Interestingly, the gold loaded on YOOH calcined at 400 deg. C and gold loaded on Y 2 O 3 calcined at 500 deg. C comparatively showed the highest catalytic activity for complete CO oxidation at a reaction temperature of 300 deg. C. The 0.12% Au/Y 2 O 3 catalyst calcined at 500 deg. C was employed for both CO and methanol oxidation studies. For complete CO oxidation, the reaction temperatures of Au/Y 2 O 3 and Au/NiO catalysts were 325 deg. C and 250 deg. C, respectively. The light-off temperatures of Au/Y 2 O 3 and Au/NiO catalysts for methanol oxidation were 210 deg. C and 205 deg. C, respectively. Conclusively, the Au/Y 2 O 3 clearly exhibited the same activity as that of Au/NiO for methanol oxidation while the Au/NiO gave higher activity for CO oxidation.

Activity of platinum/carbon and palladium/carbon catalysts promoted by Ni2 P in direct ethanol fuel cells.

Science.gov (United States)

Li, Guoqiang; Feng, Ligang; Chang, Jinfa; Wickman, Björn; Grönbeck, Henrik; Liu, Changpeng; Xing, Wei

2014-12-01

Ethanol is an alternative fuel for direct alcohol fuel cells, in which the electrode materials are commonly based on Pt or Pd. Owing to the excellent promotion effect of Ni2 P that was found in methanol oxidation, we extended the catalyst system of Pt or Pd modified by Ni2 P in direct ethanol fuel cells. The Ni2 P-promoted catalysts were compared to commercial catalysts as well as to reference catalysts promoted with only Ni or only P. Among the studied catalysts, Pt/C and Pd/C modified by Ni2 P (30 wt %) showed both the highest activity and stability. Upon integration into the anode of a homemade direct ethanol fuel cell, the Pt-Ni2 P/C-30 % catalyst showed a maximum power density of 21 mW cm(-2) , which is approximately two times higher than that of a commercial Pt/C catalyst. The Pd-Ni2 P/C-30 % catalyst exhibited a maximum power density of 90 mW cm(-2) . This is approximately 1.5 times higher than that of a commercial Pd/C catalyst. The discharge stability on both two catalysts was also greatly improved over a 12 h discharge operation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen Production via Glycerol Dry Reforming over La-Ni/Al2O3 Catalyst

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Kah Weng Siew

2013-12-01

Full Text Available Glycerol (a bio-waste generated from biodiesel production has been touted as a promising bio-syngas precursor via reforming route. Previous studies have indicated that carbon deposition is the major performance-limiting factor for nickel (Ni catalyst during glycerol steam reforming. In the current paper, dry (CO2-reforming of glycerol, a new reforming route was carried out over alumina (Al2O3-supported non-promoted and lanthanum-promoted Ni catalysts. Both sets of catalysts were synthesized via wet co-impregnation procedure. The physicochemical characterization of the catalyst showed that the promoted catalyst possessed smaller metal crystallite size, hence higher metal dispersion compared to the virgin Ni/Al2O3 catalyst. This was also corroborated by the surface images captured by the FESEM analysis. In addition, BET surface area measurement gave 92.05m²/g for non-promoted Ni catalyst whilst promoted catalysts showed an average of 1 to 6% improvement depending on the La loading. Reaction studies at 873 K showed that glycerol dry reforming successfully produced H2 with glycerol conversion and H2 yield that peaked at 9.7% and 25% respectively over 2wt% La content. The optimum catalytic performance by 2%La-Ni/Al2O3 can be attributed to the larger BET surface area and smaller crystallite size that ensured accessibility of active catalytic sites.  © 2013 BCREC UNDIP. All rights reservedReceived: 12nd May 2013; Revised: 7th October 2013; Accepted: 16th October 2013[How to Cite: Siew, K.W., Lee, H.C., Gimbun, J., Cheng, C.K. (2013. Hydrogen Production via Glycerol Dry Reforming over La-Ni/Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 160-166. (doi:10.9767/bcrec.8.2.4874.160-166][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4874.160-166

Influence of ni addition to a low-loaded palladium catalyst on the selective hydrogenation of 1-heptyne

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Cecilia R. Lederhos

2010-01-01

Full Text Available Semi-hydrogenation of alkynes has industrial and academic relevance on a large scale. To increase the activity, selectivity and lifetime of monometallic catalysts, the development of bimetallic catalysts has been investigated. 1-Heptyne hydrogenation over low-loaded Pd and Ni monometallic and PdNi bimetallic catalysts was studied in liquid phase at mild conditions. XPS results suggest that nickel addition to Pd modifies the electronic state of palladium as nickel loading is increased. Low-loaded Pd catalysts showed the highest selectivities (> 95%. The most active prepared catalyst, PdNi(1%, was more selective than the Lindlar catalyst.

Hydrotreatment of bio-oil over Ni-based catalyst.

Science.gov (United States)

Zhang, Xinghua; Wang, Tiejun; Ma, Longlong; Zhang, Qi; Jiang, Ting

2013-01-01

Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrotreatments using phenol as model compound. HZSM-5, a zeolite with different ratio of Si/Al and γ-Al(2)O(3) were impregnated with Ni(NO(3))(2) · 6H(2)O and calcined at 450 °C. Conversion rates and product distribution for treatment of phenol at 160-240 °C in the presence of catalysts with nickel loads of 6, 10, 14 and 17 wt.% were determined. Phenol conversion was highest (91.8%) at 240 °C in the presence of HZSM-5(Si/Al = 38) loaded with 10% Ni. When hydrotreatment was carried out with bio-oil obtained from pyrolysis of pine sawdust under the optimal conditions determined for phenol, the pH of bio-oil increased from 2.27 to 4.07, and the hydrogen content increased from 6.28 to 7.01 wt.%. The decrease in acidity is desirable for the use of upgraded bio-oil. Copyright © 2012. Published by Elsevier Ltd.

Hydrogen production from raw bioethanol steam reforming: optimization of catalyst composition with improved stability against various impurities

International Nuclear Information System (INIS)

Le Valant, A.; Can, F.; Bion, N.; Epron, F.; Duprez, D.

2009-01-01

Usually, ethanol steam reforming is performed using pure ethanol, whereas the use of raw bioethanol is of major importance for a cost effective industrial application. Raw bioethanol contains higher alcohols as the main impurities and also aldehydes, amines, acids and esters. The effect of these impurities on the catalytic performances for ethanol steam reforming (ESR) has been studied, using a reference catalyst, Rh/MgAl 2 O 4 . It was shown that the aldehyde, the amine and methanol has no negative effect on the catalytic performances, contrary to the ester, acid and higher alcohols. The deactivation is mainly explained by coke formation favored by the presence of these impurities in the feed. In order to improve the stability of the catalyst and its performances in the presence of these deactivating impurities, the catalyst formulation, i.e. the composition of the support and of the metallic phase, was modified. The addition of rare earth elements instead of magnesium to the alumina support leads to a decrease of the strong and medium acid sites and to an increase of the basicity. On these modified supports, the dehydration reaction, leading to olefins, which are coke precursors, is disfavored, the ethanol conversion and the hydrogen yield are increased. The best catalytic performances were obtained with Rh/Y-Al 2 O 3 . Then, the metallic phase was also modified by adding a second metal (Ni, Pt or Pd). The Rh-Ni/Y-Al 2 O 3 catalyst leads to the highest hydrogen yield. This catalyst, tested in the presence of raw bioethanol during 24h was very stable compared to the reference catalyst Rh/MgAl 2 O 4 , which was strongly deactivated after 2h of time-on-stream. (author)

A Study of CO2 Methanation over Ni-Based Catalysts Supported by CNTs with Various Textural Characteristics

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Yanyan Feng

2015-01-01

Full Text Available This work studied the influence of textural characteristics of CNTs on catalytic performance of Ni/CNTs for CO2 methanation. The CNTs supports were prepared by chemical vapor deposition method using Ni/MgO catalysts, and acetonitrile and ethanol were used as carbon sources, respectively. The Ni/CNTs catalysts were prepared via impregnation method and characterized by X-ray diffraction (XRD, N2 adsorption/desorption, and temperature-programmed reduction (H2-TPR techniques. The results indicated that the textural characteristics of CNTs supports significantly impacted on the catalytic performance of Ni/CNTs. The catalyst Ni/CNTs-E (CNTs using ethanol as carbon source had good reducibility, high specific surface area, and moderate defects, resulting in higher CO2 conversion and CH4 yield, followed by Ni/CNTs-C (commercial CNTs and Ni/CNTs-A (CNTs using acetonitrile as carbon source. Based on Arrhenius formula, activation energies of the catalysts were calculated and were found decreased for Ni/CNTs-A and Ni/CNTs-E.

Process for the regeneration of metallic catalysts

Science.gov (United States)

Katzer, James R.; Windawi, Hassan

1981-01-01

A method for the regeneration of metallic hydrogenation catalysts from the class consisting of Ni, Rh, Pd, Ir, Pt and Ru poisoned with sulfur, with or without accompanying carbon deposition, comprising subjecting the catalyst to exposure to oxygen gas in a concentration of about 1-10 ppm. intermixed with an inert gas of the group consisting of He, A, Xe, Kr, N.sub.2 and air substantially free of oxygen to an extent such that the total oxygen molecule throughout is in the range of about 10 to 20 times that of the hydrogen sulfide molecular exposure producing the catalyst poisoning while maintaining the temperature in the range of about 300.degree. to 500.degree. C.

Lanthanum and cerium co-modified Ni/SiO2 catalyst for CO methanation from syngas

Science.gov (United States)

Gong, Dandan; Li, Shuangshuang; Guo, Shaoxia; Tang, Honggui; Wang, Hong; Liu, Yuan

2018-03-01

Sintering of active metal nanoparticles (NPs) and carbon deposition is critical problems for many metal catalysts, such as nickel based catalysts for generating methane from syngas. To improve the resistance to the sintering and carbon deposition, a new scheme was proposed in this work. Lanthanum and cerium co-modified Ni/SiO2 catalysts were synthesized by using perovskite type oxide of La1-xCexNiO3 loaded on SiO2 as the precursor. In a nanocrystallite of La1-xCexNiO3, ions of nickel, lanthanum and cerium are evenly mixed at atomic level and confined in the nanocrystallite, therefore, Ni NPs and the two promoters of La2O3 and CeO2 should be in close contact and highly dispersed on SiO2 after reduction. The catalysts were characterized by using XRD, TEM, BET, H2-TPD, XPS, TG and Raman techniques. Compared with the mono-promoted catalysts, the bi-promoted La0.75Ce0.25NiO3/SiO2 showed much better resistance to carbon deposition, higher resistance to sintering and higher activity for CO methanation, which are attributed to co-eliminating effect of the two promoters for the deposited carbon, confinement of the interacted two promoters for Ni NPs and the higher dispersion of Ni NPs derived from the smaller size of La0.75Ce0.25NiO3.

Formation and Yield of Multi-Walled Carbon Nanotubes Synthesized via Chemical Vapour Deposition Routes Using Different Metal-Based Catalysts of FeCoNiAl, CoNiAl and FeNiAl-LDH

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Mohd Zobir Hussein

2014-11-01

Full Text Available Multi-walled carbon nanotubes (MWCNTs were prepared via chemical vapor deposition (CVD using a series of different catalysts, derived from FeCoNiAl, CoNiAl and FeNiAl layered double hydroxides (LDHs. Catalyst-active particles were obtained by calcination of LDHs at 800 °C for 5 h. Nitrogen and hexane were used as the carrier gas and carbon source respectively, for preparation of MWCNTs using CVD methods at 800 °C. MWCNTs were allowed to grow for 30 min on the catalyst spread on an alumina boat in a quartz tube. The materials were subsequently characterized through X-ray diffraction, Fourier transform infrared spectroscopy, surface area analysis, field emission scanning electron microscopy and transmission electron microscopy. It was determined that size and yield of MWCNTs varied depending on the type of LDH catalyst precursor that is used during synthesis. MWCNTs obtained using CoNiAl-LDH as the catalyst precursor showed smaller diameter and higher yield compared to FeCoNiAl and FeNiAl LDHs.

Effects of adding lanthanum to Ni/ZrO2 catalysts on ethanol steam reforming

International Nuclear Information System (INIS)

Profeti, Luciene Paula Roberto; Habitzheuter, Filipe; Assaf, Elisabete Moreira

2012-01-01

The catalytic performance of Ni/ZrO 2 catalysts loaded with different lanthanum content for steam reforming of ethanol was investigated. Catalysts were characterized by BET surface area, X-ray diffraction, UV-vis spectroscopy, temperature programmed reduction, and X-ray absorption fine structure techniques. Results showed that lanthanum addition led to an increase in the degree of reduction of both NiO and nickel surface species interacting with the support, due to the higher dispersion effect. The best catalytic performance at 450 deg C was found for the Ni/12LZ catalyst, which exhibited an effluent gaseous mixture with the highest H 2 yield. (author)

Ultrasound assisted dispersion of different amount of Ni over ZSM-5 used as nanostructured catalyst for hydrogen production via CO2 reforming of methane

International Nuclear Information System (INIS)

Vafaeian, Yaser; Haghighi, Mohammad; Aghamohammadi, Sogand

2013-01-01

Graphical abstract: A series of Ni/ZSM-5 nanocatalysts with different amount of Ni were prepared via ultrasound assisted method and characterized with XRD, FESEM, TEM, BET and FTIR techniques. The research deals with catalyst development for dry reforming of methane with the aim of reaching the most stable catalyst specifically over nano-sized catalysts. About more than 99% of Ni particles size is less than 100 nm for the sample prepared with 8% Ni, which is essential to the relative suppression of the carbon formation on catalysts. Catalyst prepared with 8% Ni content showed superior activity in process expected due to its better catalytic properties. - Highlights: • Using ZSM-5 zeolite in dry reforming of methane. • Employing ultrasound energy in synthesis of Ni/ZSM-5 nanocatalyst. • Enhancement of Ni particles size to meet desired catalyst at lower amount of Ni loading. • Dry reforming of methane over Ni/ZSM-5 nanocatalyst with different Ni-loading. • Superior activity of Ni/ZSM-5 nanocatalyst synthesized with 8% Ni content. - Abstract: Carbon dioxide reforming of methane is an interesting route for synthesis gas production especially over nanostructured catalysts. The present research deals with nanocatalyst development by sonochemical method for dry reforming of methane with the aim of reaching the most efficient nanocatalyst. Effect of Ni metal content, one of the most significant variables, on the properties of the ZSM-5 supported nanocatalysts was taken into account. The Ni/ZSM-5 nanocatalysts were prepared via assisted traditional impregnation method via ultrasound irradiation and characterized with XRD, FESEM, TEM, BET and FTIR techniques. Comparison of XRD patterns implies that the peaks related to NiO become sharper by increasing metal content over the support. In the case of nanocatalysts with lower metal content (3% and 8%), the beneficial influence of ultrasound assisted procedure become more pronounced and the observed reduction in

Quaternary Pt{sub 2}Ru{sub 1}Fe{sub 1}M{sub 1}/C (M=Ni, Mo, or W) catalysts for methanol electro-oxidation reaction

Energy Technology Data Exchange (ETDEWEB)

Jeon, Min Ku; Lee, Ki Rak; Kang, Kweon Ho; Park, Geun Il [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Jeon, Hyung Joon [Kyoto University, Kyoto (Japan); McGinn, Paul J. [University of Notre Dame, Indiana (United States)

2015-02-15

Quaternary Pt{sub 2}Ru{sub 1}Fe{sub 1}M{sub 1}/C (M=Ni, Mo, or W) catalysts were investigated for the methanol electro-oxidation reaction (MOR). Electrocatalytic activities of the quaternary catalysts for CO electro-oxidation were studied via CO stripping experiments, and the Pt{sub 2}Ru{sub 1}Fe{sub 1}Ni{sub 1}/C and Pt{sub 2}Ru{sub 1}Fe{sub 1}W{sub 1}/C catalysts exhibited lowered on-set potential compared to that of a commercial PtRu/C catalyst. MOR activities of the quaternary catalysts were determined by linear sweep voltammetry (LSV) experiments, and the Pt{sub 2}Ru{sub 1}Fe{sub 1}W{sub 1}/C catalyst outperformed the commercial PtRu/C catalyst by 170 and 150% for the mass and specific activities, respectively. X-ray photoelectron spectroscopy (XPS) was employed to analyze surface oxidation states of constituent atoms, and it was identified that the structure of the synthesized catalysts are close to a nano-composite of Pt and constituent metal hydroxides and oxides. In addition, the XPS results suggested that the bi-functional mechanism accounts for the improved performance of the Pt{sub 2}Ru{sub 1}Fe{sub 1}Ni{sub 1}/C and Pt{sub 2}Ru{sub 1} Fe{sub 1}W{sub 1}/C catalysts.

PREPARATION, CHARACTERIZATIONS AND MODIFICATION OF Ni-Pd/NATURAL ZEOLITE CATALYSTS

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Wega Trisunaryanti

2010-06-01

Full Text Available Preparation, and modification of Ni-Pd/natural zeolite as well as their characterizations had been carried out. The aim of this research for the fututure is to prepare the best characters catalyst for the conversion of waste plastics fraction to gasoline fraction (C5-C12 hydrocarbons. The preparation of catalysts was performed by reacting a natural zeolite with the precursor of Ni(NO32. 9H2O and PdCl2 in an ammonia solution (25%. The modifications were performed by varying the rasio of Ni/Pd loaded to the zeolite, whereas the Pd was previously loaded and total metal content was 1 wt.% based on the zeolite. The characterization of catalysts included determination of acidity gravimetrically by adsorption of ammonia or pyridine vapour  base method, metal content by Atomic Adsorption Spectrophotometer (AAS and X-ray Fluoresence (XRF and crystallinity by X-ray Diffraction (XRD. The treatment of catalysts using Etilene Diamine Tetra Acetic acid  (EDTA was performed to study the metal distribution on the outer or inner surface of the zeolite. The characterization results showed that the loading of metals to the zeolite increased its acidity and decreased its spesific surface area, however, did not defect its crystallnity.  The metals loaded on the zeolite were distributed inside the pore and at outer surface of the zeolite. For all catalyst samples, the acidities determined using ammonia were higher than those of pyridine, and the acidities determined before the EDTA treatment was lower than those after the treatment.  Metal contents of the zeolite before the EDTA treatment were higher than those after the treatment. The EDTA treatment enhanced the crystallinity of the sampel. The relationship between the metal rasio towards the acidity of the catalyst samples were in variation. Catalyst samples produced in this research have good characters, thus promisingly can be used for conversion process of waste plastics to gasoline fraction.    Keywords

Hydroprocessing of Jatropha Oil for Production of Green Diesel over Non-sulfided Ni-PTA/Al2O3 Catalyst

Science.gov (United States)

Liu, Jing; Lei, Jiandu; He, Jing; Deng, Lihong; Wang, Luying; Fan, Kai; Rong, Long

2015-01-01

The non-sulfided Ni-PTA/Al2O3 catalyst was developed to produce green diesel from the hydroprocessing of Jatropha oil. The Ni-PTA/Al2O3 catalyst was prepared by one-pot synthesis of Ni/Al2O3 with the co-precipitation method and then impregnanting Ni/Al2O3 with PTA solution. The catalysts were characterized with BET, SEM-EDX, TEM, XRD, XPS, TGA and NH3-TPD. The Ni and W species of the Ni-PTA/Al2O3 catalyst were much more homogeneously distributed on the surface than that of commercial Al2O3. Catalytic performance in the hydroprocessing of Jatropha oil was evaluated by GC. The maximum conversion of Jatropha oil (98.5 wt%) and selectivity of the C15-C18 alkanes fraction (84.5 wt %) occurred at 360 °C, 3.0 MPa, 0.8 h−1. The non-sulfided Ni-PTA/Al2O3 catalyst is more environmentally friendly than the conventional sulfided hydroprocessing catalyst, and it exhibited the highest catalytic activity than the Ni-PTA catalyst supported with commercial Al2O3 grain and Al2O3 powder. PMID:26162092

Effect of Ce and Zr Addition to Ni/SiO2 Catalysts for Hydrogen Production through Ethanol Steam Reforming

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Jose Antonio Calles

2015-01-01

Full Text Available A series of Ni/Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\/SiO\\(_{2}\\ catalysts with different Zr/Ce mass ratios were prepared by incipient wetness impregnation. Ni/SiO\\(_{2}\\, Ni/CeO\\(_{2}\\ and Ni/ZrO\\(_{2}\\ were also prepared as reference materials to compare. Catalysts' performances were tested in ethanol steam reforming for hydrogen production and characterized by XRD, H\\(_{2}\\-temperature programmed reduction (TPR, NH\\(_{3}\\-temperature programmed desorption (TPD, TEM, ICP-AES and N\\(_{2}\\-sorption measurements. The Ni/SiO\\(_{2}\\ catalyst led to a higher hydrogen selectivity than Ni/CeO\\(_{2}\\ and Ni/ZrO\\(_{2}\\, but it could not maintain complete ethanol conversion due to deactivation. The incorporation of Ce or Zr prior to Ni on the silica support resulted in catalysts with better performance for steam reforming, keeping complete ethanol conversion over time. When both Zr and Ce were incorporated into the catalyst, Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\ solid solution was formed, as confirmed by XRD analyses. TPR results revealed stronger Ni-support interaction in the Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\-modified catalysts than in Ni/SiO\\(_{2}\\ one, which can be attributed to an increase of the dispersion of Ni species. All of the Ni/Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\/SiO\\(_{2}\\ catalysts exhibited good catalytic activity and stability after 8 h of time on stream at 600°. The best catalytic performance in terms of hydrogen selectivity was achieved when the Zr/Ce mass ratio was three.

Catalytic Chemical Vapor Deposition of Methane to Carbon Nanotubes: Copper Promoted Effect of Ni/MgO Catalysts

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Wen Yang

2014-01-01

Full Text Available The Ni/MgO and Ni-Cu/MgO catalysts were prepared by sol-gel method and used as the catalysts for synthesis of carbon nanotubes by thermal chemical vapor deposition. The effect of Cu on the carbon yield and structure was investigated, and the effects of calcination temperature and reaction temperature were also investigated. The catalysts and synthesized carbon materials were characterized by temperature programmed reduction (TPR, thermogravimetric analysis (TGA, and scanning electron microscopy (SEM. Results showed that the addition of Cu promoted the reduction of nickel species, subsequently improving the growth and yield of CNTs. Meanwhile, CNTs were synthesized by the Ni/MgO and Ni-Cu/MgO catalysts with various calcination temperatures and reaction temperatures, and results suggested that the obtained CNTs on Ni-Cu/MgO catalyst with the calcination temperature of 500°C and the reaction temperature of 650°C were of the greatest yield and quantity of 927%.

Pt-Ni and Pt-M-Ni (M = Ru, Sn Anode Catalysts for Low-Temperature Acidic Direct Alcohol Fuel Cells: A Review

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Ermete Antolini

2017-01-01

Full Text Available In view of a possible use as anode materials in acidic direct alcohol fuel cells, the electro-catalytic activity of Pt-Ni and Pt-M-Ni (M = Ru, Sn catalysts for methanol and ethanol oxidation has been widely investigated. An overview of literature data regarding the effect of the addition of Ni to Pt and Pt-M on the methanol and ethanol oxidation activity in acid environment of the resulting binary and ternary Ni-containing Pt-based catalysts is presented, highlighting the effect of alloyed and non-alloyed nickel on the catalytic activity of these materials.

Selective hydrogenation of furfural to cyclopentanone over Cu-Ni-Al hydrotalcite-based catalysts

Energy Technology Data Exchange (ETDEWEB)

Zhu, Hongyan; Zhou, Minghao; Zeng, Zuo; Xiao, Guomin; Xiao, Rui [Southeast University, Nanjing (China)

2014-04-15

A series of Cu-Ni-Al hydrotalcites derived oxides with a (Cu+Ni)/Al mole ratio of 3 with varied Cu/Ni mole ratio (from 0.017 to 0.5, with a Cu ratio of 0.0125 to 0.25) were prepared by co-precipitation method, then applied to the hydrogenation of furfural in aqueous. Their catalytic performance for liquid phase hydrogenation of furfural to prepare cyclopentanone was described in detail, considering reaction temperature, catalyst composition, reaction time and so on. The yield of cyclopentanone was influenced by the mole ratio of Cu-Ni-Al based heterogeneous catalyst and depended on the reaction conditions. The yield of cyclopentanone was up to 95.8% when the reaction was carried out under 413 K with H{sub 2} pressure of 40 bar for 8 h. The catalysts were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM) and H{sub 2} temperature-programmed reduction (H{sub 2}-TPR)

CuNi NPs supported on MIL-101 as highly active catalysts for the hydrolysis of ammonia borane

Science.gov (United States)

Gao, Doudou; Zhang, Yuhong; Zhou, Liqun; Yang, Kunzhou

2018-01-01

The catalysts containing Cu, Ni bi-metallic nanoparticles were successfully synthesized by in-situ reduction of Cu2+ and Ni2+ salts into the highly porous and hydrothermally stable metal-organic framework MIL-101 via a simple liquid impregnation method. When the total amount of loading metal is 3 × 10-4 mol, Cu2Ni1@MIL-101 catalyst shows higher catalytic activity comparing to CuxNiy@MIL-101 with different molar ratio of Cu and Ni (x, y = 0, 0.5, 1.5, 2, 2.5, 3). Cu2Ni1@MIL-101 catalyst has the highest catalytic activity comparing to mono-metallic Cu and Ni counterparts and pure bi-metallic CuNi nanoparticles in hydrolytic dehydrogeneration of ammonia borane (AB) at room temperature. Additionally, in the hydrolysis reaction, the Cu2Ni1@MIL- 101 catalyst possesses excellent catalytic performances, which exhibit highly catalytic activity with turn over frequency (TOF) value of 20.9 mol H2 min-1 Cu mol-1 and a very low activation energy value of 32.2 kJ mol-1. The excellent catalytic activity has been successfully achieved thanks to the strong bi-metallic synergistic effects, uniform distribution of nanoparticles and the bi-functional effects between CuNi nanoparticles and the host of MIL-101. Moreover, the catalyst also displays satisfied durable stability after five cycles for the hydrolytically releasing H2 from AB. The non-noble metal catalysts have broad prospects for commercial applications in the field of hydrogen-stored materials due to the low prices and excellent catalytic activity.

Highly active Ni/Y-doped ZrO{sub 2} catalysts for CO{sub 2} methanation

Energy Technology Data Exchange (ETDEWEB)

Takano, H., E-mail: takano_hi@hitachizosen.co.jp [Hitachi Zosen Corporation, Kashiwa, 277-8515 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Kirihata, Y.; Izumiya, K.; Kumagai, N. [Hitachi Zosen Corporation, Kashiwa, 277-8515 (Japan); Habazaki, H., E-mail: habazaki@eng.hokudai.ac.jp [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Division of Applied Chemistry & Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Hashimoto, K. [Tohoku Institute of Technology, Sendai, 277-8515 (Japan)

2016-12-01

Highlights: • The Ni/Y-doped ZrO{sub 2} catalysts show highly catalytic activity for CO{sub 2} methanation. • Bidentate carbonate is a major adsorption spice on the Ni/Y-doped ZrO{sub 2} catalysts. • The oxide support of t-ZrO{sub 2} and/or c-ZrO{sub 2} with oxygen vacancies plays a key role. - Abstract: The catalytic methanation of CO{sub 2} was carried out on Ni catalysts supported on Y-doped ZrO{sub 2} with various Y{sup 3+} concentrations and Ni/(Zr + Y) molar ratio = 1. The catalysts were characterized by X-ray diffraction, scanning transmission electron microscopy, specific surface area, temperature-programmed desorption of CO{sub 2}, and temperature-programmed reaction. In addition, operando diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFT) was used to identify the adsorbed reaction intermediate. Catalysts supported on Y-doped ZrO{sub 2} show higher catalytic activity than the catalyst on Y-free ZrO{sub 2} with a monoclinic ZrO{sub 2} phase. The catalytic activity is also dependent upon the Y{sup 3+} concentration, and the highest activity was obtained for the catalyst with a Y/(Zr + Y) molar ratio of 0.333, which consists mainly of fcc Ni and cubic ZrO{sub 2} phase. Y{sup 3+} doping into ZrO{sub 2} introduces oxygen vacancies, which play an important role in enhancing the catalytic activity. The operando DRIFT study reveals that a CO adsorption intermediate is absent, and bidentate carbonate is an important intermediate for CH{sub 4} formation.

Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

KAUST Repository

Zhu, Haibo; Dong, Hailin; Laveille, Paco; Saih, Youssef; Caps, Valerie; Basset, Jean-Marie

2014-01-01

in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result

Alkali resistant Ni-loaded yolk-shell catalysts for direct internal reforming in molten carbonate fuel cells

Science.gov (United States)

Jang, Won-Jun; Hong, Young Jun; Kim, Hak-Min; Shim, Jae-Oh; Roh, Hyun-Seog; Kang, Yun Chan

2017-06-01

A facile and scalable spray pyrolysis process is applied to synthesize multi-shelled Ni-loaded yolk-shell catalysts on various supports (Al2O3, CeO2, ZrO2, and La(OH)3). The prepared catalysts are applied to direct internal reforming (DIR) in a molten carbonate fuel cell (MCFC). Even on exposure to alkali hydroxide vapors, the Ni-loaded yolk-shell catalysts remain highly active for DIR-MCFCs. The Ni@Al2O3 microspheres show the highest conversion (92%) of CH4 and the best stability among the prepared Ni-loaded yolk-shell catalysts. Although the initial CH4 conversion of the Ni@ZrO2 microspheres is higher than that of the Ni@CeO2 microspheres, the Ni@CeO2 microspheres are more stable. The catalytic performance is strongly dependent on the surface area and acidity and also partly dependent on the reducibility. The acidic nature of Al2O3 combined with its high surface area and yolk-shell structure enhances the adsorption of CH4 and resistance against alkali poisoning, resulting in efficient DIR-MCFC reactions.

Role of CeO2 promoter in NiO/α-Al2O3 catalyst for dry reforming of methane

Science.gov (United States)

Loc, Luu Cam; Phuong, Phan Hong; Tri, Nguyen

2017-09-01

A series of Ni/α-Al2O3 (NiAl) catalysts promoted by CeO2 was prepared by co-impregnation methods with content of (NiO+CeO2) being in the range of 10-30 wt%. The NiO:CeO2 weight ratio was fluctuated at 1:1, 1:2 and 1:3. Several techniques, including X-ray powder diffraction (XRD), Hydrogen temperature-programmed reduction (H2-TPR), and transmission electron microscopy (TEM) were used to investigate catalysts' physico-chemical properties. The activity of these catalysts in dry reforming of CH4 was investigated at temperature range of 550-800 °C. The results revealed that the most suitable CeO2 promoted Ni catalyst contained 20 wt% of (NiO+CeO2) and NiO:CeO2 weight ratio of 1:2. The best catalytic performance of catalyst [20(1Ni2Ce)Al] due to a better reducibility resulted in a higher amount of free small particle NiO. At 700 °C and CH4:CO2 molar ratio of 1:1, the conversion of CH4 and CO2 on the most suitable CeO2 promoted Ni catalyst reached 86% and 67%, respectively; H2 and CO selectivity of 90% and H2:CO molar ratio of 1.15 were obtained. Being similar to MgO [1], promoter CeO2 could improve catalytic activity of Ni/α-Al2O3 catalyst at a lower range of temperature. Besides, both MgO and CeO2 had a great impact on improving coke resistance of Ni catalysts. At higher temperature, the role of CeO2 as well as MgO in preventing coke formation on catalyst was clarified by temperature-programmed oxidation (TPO) technique. Coke amount formed after 30-h TOS on 20(1Ni2Ce) catalyst was found to be 22.18 mgC/gcat, being less than on non-promoted catalyst (36.75 mgC/gcat), but more than on 20(1Ni2Mg)Al one (5.25 mgC/gcat).

UV Light-Assisted Synthesis of Highly Efficient Pd-Based Catalyst over NiO for Hydrogenation of o-Chloronitrobenzene.

Science.gov (United States)

Jiang, Weidong; Xu, Bin; Fan, Guangyin; Zhang, Kaiming; Xiang, Zhen; Liu, Xiaoqiang

2018-04-14

Supported Pd-based catalyst over active nickel oxide (NiO) was repared using the impregnation method companying with UV-light irradiation. Moreover, the catalytic performance of the obtained Pd-based catalysts was evaluated towards the hydrogenation of o -chloronitrobenzene ( o -CNB). Observations indicate that the as-prepared UV-irradiated Pd/NiO catalyst with a mole fraction 0.2% (0.2%Pd/NiO) has higher activity and selectivity in the o -CNB hydrogenation. Especially, UV-light irradiation played a positive role in the improvement of catalytic activity of 0.2%Pd/NiO catalyst, exhibiting an excess 11-fold activity superiority in contrast with non-UV-irradiated 0.2%Pd/NiO catalyst. In addition, it was investigated that effects of varied factors (i.e., reaction time, temperature, o -CNB/Pd ratio, Pd loading, hydrogen pressure) on the selective hydrogenation of ο -CNB catalyzed by UV-irradiated 0.2%Pd/NiO catalyst. Under the reaction conditions of 60 °C, 0.5 h, 1 MPa H₂ pressure, 100% conversion of o -CNB, and 81.1% o -CAN selectivity were obtained, even at high molar ratio (8000:1) of o -CNB to Pd.

Sodium borohydride hydrogen generator using Co–P/Ni foam catalysts for 200 W proton exchange membrane fuel cell system

International Nuclear Information System (INIS)

Oh, Taek Hyun; Gang, Byeong Gyu; Kim, Hyuntak; Kwon, Sejin

2015-01-01

The response characteristics of electroless-deposited Co–P/Ni foam catalysts for sodium borohydride hydrolysis were investigated. The effect of nickel foam geometry on the properties of the catalysts was evaluated. As the PPI (pores per inch) of the nickel foam increased, the hydrogen generation rate per gram of the deposited catalyst increased due to an increase in surface area. The response characteristics of various catalysts were compared under real operating conditions. When a thin nickel foam with high PPI was used, the response characteristics of the catalyst improved due to an increase in the amount of the deposited catalyst and surface area. Finally, a 200 W PEMFC (proton exchange membrane fuel cell) system using electroless-deposited Co–P/Ni foam (110 PPI) catalyst was investigated. The response time to reach a hydrogen generation rate sufficient for a 200 W PEMFC was 71 s, and the energy density of a 200 W fuel cell system for producing 600 Wh was 252.1 Wh/kg. A fuel cell system using Co–P/Ni foam catalysts can be widely used as a power source for mobile applications due to fast response characteristics and high energy density. - Highlights: • Response characteristics of Co–P/Ni foam catalysts are investigated. • Catalytic activity is improved with increase in PPI (pores per inch) of Ni foam. • Co–P/Ni foam (110 PPI) catalyst has improved response characteristics. • The energy density of a 200 W PEMFC system for producing 600 Wh is 252.1 Wh/kg. • Co–P/Ni foam (110 PPI) catalyst is suitable for fuel cell system.

Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process

Science.gov (United States)

Cui, Xin; Qi, Cong; Li, Liang; Li, Yimin; Li, Song

2017-08-01

In order to facilitate efficient and clean utilization of coal, a series of Ni-Co ternary molten salt crystals are explored and the catalytic pyrolysis mechanism of Datong coal is investigated. The reaction mechanisms of coal are achieved by thermal gravimetric analyzer (TGA), and a reactive kinetic model is constructed. The microcosmic structure and macerals are observed by scanning electron microscope (SEM). The catalytic effects of ternary molten salt crystals at different stages of pyrolysis are analyzed. The experimental results show that Ni-Co ternary molten salt catalysts have the capability to bring down activation energy required by pyrolytic reactions at its initial phase. Also, the catalysts exert a preferable catalytic action on macromolecular structure decomposition and free radical polycondensation reactions. Furthermore, the high-temperature condensation polymerization is driven to decompose further with a faster reaction rate by the additions of Ni-Co ternary molten salt crystal catalysts. According to pyrolysis kinetic research, the addition of catalysts can effectively decrease the activation energy needed in each phase of pyrolysis reaction.

CH{sub 4} dehydrogenation on Cu(1 1 1), Cu@Cu(1 1 1), Rh@Cu(1 1 1) and RhCu(1 1 1) surfaces: A comparison studies of catalytic activity

Energy Technology Data Exchange (ETDEWEB)

Zhang, Riguang; Duan, Tian [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Ling, Lixia [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Wang, Baojun, E-mail: wangbaojun@tyut.edu.cn [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China)

2015-06-30

Highlights: • Adsorbed Rh atom on Cu catalyst exhibits better catalytic activity for CH{sub 4} dehydrogenation. • The adsorbed Rh atom is the reaction active center for CH{sub 4} dehydrogenation. • The morphology of Cu substrate has negligible effect on CH{sub 4} dehydrogenation. - Abstract: In the CVD growth of graphene, the reaction barriers of the dehydrogenation for hydrocarbon molecules directly decide the graphene CVD growth temperature. In this study, density functional theory method has been employed to comparatively probe into CH{sub 4} dehydrogenation on four types of Cu(1 1 1) surface, including the flat Cu(1 1 1) surface (labeled as Cu(1 1 1)) and the Cu(1 1 1) surface with one surface Cu atom substituted by one Rh atom (labeled as RhCu(1 1 1)), as well as the Cu(1 1 1) surface with one Cu or Rh adatom (labeled as Cu@Cu(1 1 1) and Rh@Cu(1 1 1), respectively). Our results show that the highest barrier of the whole CH{sub 4} dehydrogenation process is remarkably reduced from 448.7 and 418.4 kJ mol{sup −1} on the flat Cu(1 1 1) and Cu@Cu(1 1 1) surfaces to 258.9 kJ mol{sup −1} on RhCu(1 1 1) surface, and to 180.0 kJ mol{sup −1} on Rh@Cu(1 1 1) surface, indicating that the adsorbed or substituted Rh atom on Cu catalyst can exhibit better catalytic activity for CH{sub 4} complete dehydrogenation; meanwhile, since the differences for the highest barrier between Cu@Cu(1 1 1) and Cu(1 1 1) surfaces are smaller, the catalytic behaviors of Cu@Cu(1 1 1) surface are very close to the flat Cu(1 1 1) surface, suggesting that the morphology of Cu substrate does not obviously affect the dehydrogenation of CH{sub 4}, which accords with the reported experimental observations. As a result, the adsorbed or substituted Rh atom on Cu catalyst exhibit a better catalytic activity for CH{sub 4} dehydrogenation compared to the pure Cu catalyst, especially on Rh-adsorbed Cu catalyst, we can conclude that the potential of synthesizing high-quality graphene with the

Reductive amination of ethanol to ethylamines over Ni/Al_2O_3 catalysts

International Nuclear Information System (INIS)

Park, Jun Hyun; Hong, Eunpyo; An, Sang Hee; Shin, Chae-Ho; Lim, Dong-Hee

2017-01-01

Ni(x)/Al_2O_3 (x=wt%) catalysts with Ni loadings of 5-25 wt% were prepared via a wet impregnation method on an γ-Al_2O_3 support and subsequently applied in the reductive amination of ethanol to ethylamines. Among the various catalysts prepared, Ni(10)/Al2O3 exhibited the highest metal dispersion and the smallest Ni particle size, resulting in the highest catalytic performance. To reveal the effects of reaction parameters, a reductive amination process was performed by varying the reaction temperature (T), weight hourly space velocity (WHSV), and NH_3 and H_2 partial pressures in the reactions. In addition, on/off experiments for NH_3 and H_2 were also carried out. In the absence of NH_3 in the reactant stream, the ethanol conversion and selectivities towards the different ethylamine products were significantly reduced, while the selectivity to ethylene was dominant due to the dehydration of ethanol. In contrast, in the absence of H_2, the selectivity to acetonitrile significantly increased due to dehydrogenation of the imine intermediate. Although a small amount of catalyst deactivation was observed in the conversion of ethanol up to 10 h on stream due to the formation of nickel nitride, the Ni(10)/Al_2O_3 catalyst exhibited stable catalytic performance over 90 h under the optimized reaction conditions (i.e., T=190 .deg. C, WHSV=0.9 h"-"1, and EtOH/NH_3/H_2 molar ratio=1/1/6).

Highly stable and active Ni-doped ordered mesoporous carbon catalyst on the steam reforming of ethanol application

Directory of Open Access Journals (Sweden)

Josh Y.Z. Chiou

2017-02-01

Full Text Available A novel one-step direct synthesis of nickel embedded in an ordered mesoporous carbon catalyst (NiOMC is done in a basic medium of nonaqueous solution by a solvent evaporation-induced self-assembly process. The NiOMC sample is characterized by a variety of analytical and spectroscopy techniques, e.g., N2 adsorption/desorption isotherm measurement, X-ray diffraction (XRD, transmission electron microscopy (TEM and temperature-programed reduction (TPR. In this study, the NiOMC catalyst is found to exhibit superior catalytic activity for the steam reforming of ethanol (SRE, showing high hydrogen selectivity and durability. Ethanol can be completely converted at 350 °C over the NiOMC catalyst. Also, the durability of the NiOMC catalyst on the SRE reaction exceeds 100 h at 450 °C, with SH2 approaching 65% and SCO of less than 1%.

Preparation, characterization of Mo catalysts supported on Ni- containing calcium deficient hydroxyapatite and reactivity for the thiophene HDS reaction

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Cherif A.

2013-09-01

Full Text Available Ni-containing Calcium Hydroxyapatite (NiCaHAp; 3.31 wt.% Ni was synthesized by coprecipitation and used as catalyst support. Molybdenum was supported on NiCaHAp by impregnation using ammonium heptamolybdate. The prepared catalysts Mo(x/NiCaHAp (x: 2 to 8 wt % in Mo were characterized by elemental analysis, XRD, FT-IR, N2 adsorption-desorption and TEM-EDX. The catalysts were sulfided in-situ at 673 K under flowing H2S/H2 (15 Vol.% H2S and tested in hydrodesulfurization (HDS of thiophene at 673 K. The main XRD peaks of hydroxyapatite CaHAp phase were observed in all samples and a peak due probably to crystalline MoO3 phase was also identified from the results. However, no crystalline phase of NiO was found for the catalysts, which showed its Ni species were highly dispersed. The sulfided catalysts Mo(x/NiCaHAp presented are active in HDS of thiophene, despite the presence of some large MoO3 crystallites and incomplete sulfidation. This activity may be due to interaction of NiO and MoO3 on CaHAp resulting in the formation of Ni-Mo-S phase under flowing H2S/H2. When the molybdenum content increased the HDS activity increasead slightly, which was caused by the agglomeration of MoO3. The Mo(8/NiCaHAp catalyst is about two times less active for thiophene HDS than the commercial NiMoP/Al2O3.

Structural, electronic and adsorption properties of Rh(111)/Mo(110) bimetallic catalyst: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Palotás, K., E-mail: palotas@phy.bme.hu [Budapest University of Technology and Economics, Department of Theoretical Physics, H-1111 Budapest (Hungary); Slovak Academy of Sciences, Institute of Physics, Department of Complex Physical Systems, Center for Computational Materials Science, SK-84511 Bratislava (Slovakia); Bakó, I. [Hungarian Academy of Sciences, Research Center for Natural Sciences, Institute of Organic Chemistry, H-1117 Budapest (Hungary); Bugyi, L. [MTA-SZTE, Reaction Kinetics and Surface Chemistry Research Group, Rerrich B. Sqr. 1, H-6720 Szeged (Hungary)

2016-12-15

Highlights: • 1 ML of Rh on Mo(110) forms a wavy structure propagating along the [001] direction. • Strain & ligand effects in the Rh film cause a downward shift of the d-band center. • CO adsorption energies are decreased by about 35% compared to pure Rh(111). • Depending on adsorption site, 0.28–0.46 e is transferred to adsorbed CO from Rh film. • CO adsorption generates 0.15–0.22 e transfer from Rh film to Mo in the unit cell. - Abstract: Geometric and electronic characterizations of one monolayer rhodium with Nishiyama-Wassermann (NW) structure on Mo(110) substrate have been performed by density functional theory (DFT) calculations. In the NW structure the Rh atoms form a wavy structure propagating along the [001] direction, characterized by an amplitude of 0.26 Å in the [110] direction and by 0.10 Å in the [110] direction of the Mo(110) substrate. Strain and ligand effects operating in the rhodium film are distinguished and found to be manifested in the downward shift of the d-band center of the electron density of states (DOS) by 0.11 eV and 0.18 eV, respectively. The shift in the d-band center of Rh DOS predicts a decrease in the surface reactivity toward CO adsorption, which has been verified by detailed calculations of bond energies of CO located at on-top, bridge and hollow adsorption sites. The CO adsorption energies are decreased by about 35% compared to those reported for pure Rh(111), offering novel catalytic pathways for the molecule. An in-depth analysis of the charge transfer and the partial DOS characters upon CO adsorption on the NW-structured Rh(111)/Mo(110) bimetallic catalyst and on the pure Rh(111) surface sheds light on the bonding mechanism of CO and on the governing factors determining its lowered bond energy on the bimetallic surface.

Towards Highly Performing and Stable PtNi Catalysts in Polymer Electrolyte Fuel Cells for Automotive Application

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Sabrina C. Zignani

2017-03-01

Full Text Available In order to help the introduction on the automotive market of polymer electrolyte fuel cells (PEFCs, it is mandatory to develop highly performing and stable catalysts. The main objective of this work is to investigate PtNi/C catalysts in a PEFC under low relative humidity and pressure conditions, more representative of automotive applications. Carbon supported PtNi nanoparticles were prepared by reduction of metal precursors with formic acid and successive thermal and leaching treatments. The effect of the chemical composition, structure and surface characteristics of the synthesized samples on their electrochemical behavior was investigated. The catalyst characterized by a larger Pt content (Pt3Ni2/C presented the highest catalytic activity (lower potential losses in the activation region among the synthesized bimetallic PtNi catalysts and the commercial Pt/C, used as the reference material, after testing at high temperature (95 °C and low humidification (50% conditions for automotive applications, showing a cell potential (ohmic drop-free of 0.82 V at 500 mA·cm−2. In order to assess the electro-catalysts stability, accelerated degradation tests were carried out by cycling the cell potential between 0.6 V and 1.2 V. By comparing the electrochemical and physico-chemical parameters at the beginning of life (BoL and end of life (EoL, it was demonstrated that the Pt1Ni1/C catalyst was the most stable among the catalyst series, with only a 2% loss of voltage at 200 mA·cm−2 and 12.5% at 950 mA·cm−2. However, further improvements are needed to produce durable catalysts.

Study of Pt–Rh/CeO2–ZrO2–MxOy (M = Y, La)/Al2O3 three-way catalysts

International Nuclear Information System (INIS)

Jiaxiu, Guo; Zhonghua, Shi; Dongdong, Wu; Huaqiang, Yin; Maochu, Gong; Yaoqiang, Chen

2013-01-01

CeO 2 –ZrO 2 –M x O y (M = Y; La) mixed oxides, prepared by co-precipitation method and characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), Raman spectra (RM) and oxygen pulse reaction, were comparatively investigated to elucidate the combinational effects of Y and/or La oxide promoters on the catalytic activity and anti-aging performance of monolithic cordierite honeycomb catalysts with low Pt and Rh content. The catalytic activities, water-gas shift (WGS) and steam reforming reaction (SR) were studied under a simulated gas mixture. The catalysts were also characterized by H 2 -temperature-programmed reduction (H 2 -TPR) and O 2 -temperature-programmed desorption (O 2 -TPD). The results showed that the prepared CeO 2 –ZrO 2 –M x O y oxides have a face-centered cubic fluorite structure and are nanosize. La 3+ ions can significantly improve thermal stability and efficiently retard CeO 2 –ZrO 2 crystal sintering and growth. Doped CeO 2 –ZrO 2 with Y 3+ and La 3+ has 105 and 60 m 2 /g surface area and 460 and 390 μmol/g OSC before and after aging. The T 50 of fresh Pt–Rh/CZYL/LA is 170 °C for CO, 222 °C for C 3 H 8 and 189 °C for NO, and shift to 205, 262 and 228 °C after hydrothermal aging, which are better than those of Pt–Rh/CZY/LA or Pt–Rh/CZL/LA. WGS and SR are relate to the OSC of oxygen storage materials and absorbed oxygen species on the catalyst surface and affect the three-way catalytic activities of catalysts. The reductive property of noble metals and the dissociatively adsorbed O 2 on the surface of catalysts are closely related to the catalytic activities.

Multiphase catalysts for selective reduction of NOx with hydrocarbons

International Nuclear Information System (INIS)

Maisuls, S.E.

2000-01-01

Among the existing proposed solutions to reduce emission of NOx there is a promising alternative, the so-called (HC-SCR) selective catalytic reduction of NOx using hydrocarbons as reductant. This thesis is part of a worldwide effort devoted to gain knowledge on the selective catalytic reduction of NOx with hydrocarbons with the final goal to contribute to the development of suitable catalysts for the above mentioned process. Chapter 2 describes the details of the experimental set-up and of the analytical methods employed. Among the catalyst for HC-SCR, Co-based catalyst are known to be active and selective, thus, a study on a series of Co-based catalysts, supported on zeolites, was undertaken and the results are presented in Chapter 3. Correlation between catalytic characteristics and kinetic results are employed to understand the working catalyst and this is used as a basis for catalyst optimization. With the intention to prepare a multi-functional catalyst that will preserve the desired characteristics of the individual components, minimizing their negative aspects, catalysts based on Co-Pt, supported on ZSM-5, were investigated. In Chapter 4 the results of this study are discussed. A bimetallic Co-Pt/ZSM-5 catalysts with low Pt contents (0.1 wt %) showed a synergistic effect by combining high stability and activity of Pt catalysts with the high N2 selectivity of Co catalysts. Furthermore, it was found to be sulfur- and water-tolerant. Its positive qualities brought us to study the mechanism that takes place over this catalyst during HC-SCR. The results of an in-situ i.r mechanistic study over this catalyst is reported in Chapter 5. From the results presented in Chapter 5 a mechanism operating over the Co-Pt/ZSM-5 catalyst is proposed. The modification of Co catalyst with Pt improved the catalysts. However, further improvement was found to be hindered by high selectivity to N2O. Since Rh catalysts are generally less selective to N2O, the modification of Co

A Comparative Study of Carbon Nanotubes Synthesized from Co/Zn/Al and Fe/Ni/Al Catalyst

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Ezekiel Dixon Dikio

2011-01-01

Full Text Available The catalyst systems Fe/Ni/Al and Co/Zn/Al were synthesized and used in the synthesis of carbon nanotubes. The carbon nanotubes produced were characterized by Field Emission Scanning Electron Microscope (FE-SEM, Energy Dispersive x-ray Spectroscopy (EDS, Raman spectroscopy, Thermogravimetric Analysis (TGA and Transmission Electron Microscope (TEM. A comparison of the morphological profile of the carbon nanotubes produced from these catalysts indicates the catalyst system Fe/Ni/Al to have produced higher quality carbon nanotubes than the catalyst system Co/Zn/Al.

Mechanochemical synthesis of TiO2/NiFe2O4 magnetic catalysts for operation under RF field

International Nuclear Information System (INIS)

Houlding, Thomas K.; Gao, Pengzhao; Degirmenci, Volkan; Tchabanenko, Kirill; Rebrov, Evgeny V.

2015-01-01

Highlights: • Novel NiFe 2 O 4 –TiO 2 composite magnetic catalysts have been prepared by mechanochemical synthesis. • The synthesis time of 30 min provides the highest specific absorption rate (SAR) in RF heating. • Formation of NiTiO 3 phase during calcination decreases the SAR of the catalysts. • High stability of the NiFe 2 O 4 –TiO 2 catalyst was observed in a continuous amide bond synthesis under RF heating. - Abstract: Composite NiFe 2 O 4 –TiO 2 magnetic catalysts were prepared by mechanochemical synthesis from a mixture of titania supported nickel ferrite nanoparticles and P25 titania (Evonic). The former provides fast and efficient heating under radiofrequency field, while the latter serves as an active catalyst or catalyst support. The highest heating rate was observed over a catalyst prepared for a milling time of 30 min. The catalytic activity was measured over the sulfated composite catalysts in the condensation of aniline and 3-phenylbutyric acid in a stirred tank reactor and in a continuous RF heated flow reactor in the 140–170 °C range. The product yield of 47% was obtained over the sulfated P25 titania catalyst in the flow reactor

Synthesis and characterization of Pt-Sn-Ni alloys to application as catalysts for direct ethanol fuel cells; Sintese e caracterizacao de ligas de Pt-Sn-Ni para aplicacao como caztalisadores em celulas a combustivel do tipo DEFC

Energy Technology Data Exchange (ETDEWEB)

Silva, E.L. da; Correa, P.S.; Oliveira, E.L. de; Takimi, A.S.; Malfatti, C.F., E-mail: celia.malfatti@ufrgs.b [Universidade Federal do Rio Grande do Sul (LAPEC/UFRGS), Porto Alegre, RS (Brazil). Programa de Pos-Graduacao em Engenharia Mecanica. Lab. de Pesquisa em Corrosao; Radtke, C. [Universidade Federal do Rio Grande do Sul (IQ/UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica

2010-07-01

Direct ethanol fuel cells (DEFCs) have been the focus of recent research due its application in mobile energy sources. In order to obtain the maximum efficiency from these systems, it is necessary the total ethanol oxidation, which implies in C-C bond break. Different catalysts described in literature are employed with this intent. This work consists in studying PtSnNi catalysts supported on carbon Vulcan XC72R, to application in DEFCs. Thus, it was used the impregnation/reduction method, varying the atomic proportion among Pt, Sn and Ni. The alloys were characterized by X-Ray Diffraction, Cyclic Voltammetry and Transmission Microscopy. Preliminary results show that predominant structure on the catalysts is the face centered cubic platinum and the densities currents are dependent on the platinum amount. (author)

Intermetallic compounds of Ni and Ga as catalysts for the synthesis of methanol

DEFF Research Database (Denmark)

Sharafutdinov, Irek; Elkjær, Christian Fink; de Carvalho, Hudson Wallace Pereira

2014-01-01

In this work, we present a detailed study of the formation of supported intermetallic Ni–Ga catalysts for CO2 hydrogenation to methanol. The bimetallic phase is formed during a temperature-programmed reduction of the metal nitrates. By utilizing a combination of characterization techniques......, in particular in situ and ex situ X-ray diffraction, in situ X-ray absorption spectroscopy, transmission electron microscopy combined with electron energy loss spectroscopy and X-ray fluorescence, we have studied the formation of intermetallic Ni–Ga catalysts of two compositions: NiGa and Ni5Ga3. These methods...... demonstrate that the catalysts with the desired intermetallic phase and composition are formed upon reduction in hydrogen and enable us to propose a mechanism of the Ni–Ga nanoparticles formation. By studying the effect of calcination prior to catalyst reduction, we show that the reactivity depends...

Efficient Hydrogenolysis of Guaiacol over Highly Dispersed Ni/MCM-41 Catalyst Combined with HZSM-5

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Songbai Qiu

2016-09-01

Full Text Available A series of MCM-41 supported Ni catalysts with high metal dispersion was successfully synthesized by simple co-impregnation using proper ethylene glycol (EG. The acquired Ni-based catalysts performed the outstanding hydrogenolysis activity of guaiacol. The effects of the synthesis parameters including drying temperature, calcination temperature, and metal loading on the physical properties of NiO nanoparticles were investigated through the use of X-ray diffraction (XRD. The drying temperature was found to significantly influence the particle sizes of NiO supported on MCM-41, but the calcination temperature and metal loading had less influence. Interestingly, the small particle size (≤3.3 nm and the high dispersion of NiO particles were also obtained for co-impregnation on the mixed support (MCM-41:HZSM-5 = 1:1, similar to that on the single MCM-41 support, leading to excellent hydrogenation activity at low temperature. The guaiacol conversion could reach 97.9% at 150 °C, and the catalytic activity was comparative with that of noble metal catalysts. The hydrodeoxygenation (HDO performance was also promoted by the introduction of acidic HZSM-5 zeolite and an 84.1% yield of cyclohexane at 240 °C was achieved. These findings demonstrate potential applications for the future in promoting and improving industrial catalyst performance.

Catalytic reforming of glycerol in supercritical water over bimetallic Pt-Ni catalyst

NARCIS (Netherlands)

Chakinala, A.G.; van Swaaij, Willibrordus Petrus Maria; Kersten, Sascha R.A.; de Vlieger, Dennis; Seshan, Kulathuiyer; Brilman, Derk Willem Frederik

2013-01-01

Catalytic reforming of pure glycerol for the production of hydrogen at low temperature and short residence times in supercritical water was investigated using a bimetallic Pt–Ni catalyst supported on alumina. Initial tests were carried out to study the reforming activity of bimetallic Pt–Ni

Production of Renewable Hydrogen from Glycerol Steam Reforming over Bimetallic Ni-(Cu,Co,Cr Catalysts Supported on SBA-15 Silica

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Alicia Carrero

2017-02-01

Full Text Available Glycerol steam reforming (GSR is a promising alternative to obtain renewable hydrogen and help the economics of the biodiesel industry. Nickel-based catalysts are typically used in reforming reactions. However, the choice of the catalyst greatly influences the process, so the development of bimetallic catalysts is a research topic of relevant interest. In this work, the effect of adding Cu, Co, and Cr to the formulation of Ni/SBA-15 catalysts for hydrogen production by GSR has been studied, looking for an enhancement of its catalytic performance. Bimetallic Ni-M/SBA-15 (M: Co, Cu, Cr samples were prepared by incipient wetness co-impregnation to reach 15 wt % of Ni and 4 wt % of the second metal. Catalysts were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES, N2-physisorption, X-ray powder diffraction (XRD, hydrogen temperature programmed reduction (H2-TPR, transmission electron microscopy (TEM, scanning electron microscopy (SEM, and thermogravimetric analyses (TGA, and tested in GSR at 600 °C and atmospheric pressure. The addition of Cu, Co, and Cr to the Ni/SBA-15 catalyst helped to form smaller crystallites of the Ni phase, this effect being more pronounced in the case of the Ni-Cr/SBA-15 sample. This catalyst also showed a reduction profile shifted towards higher temperatures, indicating stronger metal-support interaction. As a consequence, the Ni-Cr/SBA-15 catalyst exhibited the best performance in GSR in terms of glycerol conversion and hydrogen production. Additionally, Ni-Cr/SBA-15 achieved a drastic reduction in coke formation compared to the Ni/SBA-15 material.

Adsorption and oxidation of acetaldehyde on carbon supported Pt, PtSn and PtSn-based trimetallic catalysts by in situ Fourier transform infrared spectroscopy

Science.gov (United States)

Beyhan, Seden; Léger, Jean-Michel; Kadırgan, Figen

2013-11-01

The adsorption and oxidation of acetaldehyde on carbon supported Pt, Pt90Sn10 and Pt80Sn10M10 (M = Ni, Co, Rh, Pd) catalysts have been investigated by using in situ Fourier transform infrared (FTIR) spectroscopy. The result revealed that Pt90Sn10/C catalyst is not very efficient for the conversion of acetaldehyde to CO2 due to the weak adsorption of acetaldehyde in the presence of Sn. However, the addition of a third metal to Pt--Sn facilitates the C-C bond cleavage of acetaldehyde. It seems that acetaldehyde is adsorbed dissociatively on the surface of Pt80Sn10Ni10/C, Pt80Sn10Co10/C, Pt80Sn10Rh10/C catalysts, producing CH3 and CHO adsorbate species, which can be further oxidized to CO2. However, the pathway forming CO2 for Pt80Sn10Pd10/C catalyst mainly originates from the oxidation of CH3CO species. Thus, the presence of third metal in the PtSn catalyst has a strong impact upon the acetaldehyde adsorption behaviour and its reaction products.

A Non-sulfided flower-like Ni-PTA Catalyst that Enhances the Hydrotreatment Efficiency of Plant Oil to Produce Green Diesel

Science.gov (United States)

Liu, Jing; Chen, Pan; Deng, Lihong; He, Jing; Wang, Luying; Rong, Long; Lei, Jiandu

2015-01-01

The development of a novel non-sulfided catalyst with high activity for the hydrotreatment processing of plant oils, is of high interest as a way to improve the efficient production of renewable diesel. To attempt to develop such a catalyst, we first synthesized a high activity flower-like Ni-PTA catalyst used in the hydrotreatment processes of plant oils. The obtained catalyst was characterized with SEM, EDX, HRTEM, BET, XRD, H2-TPR, XPS and TGA. A probable formation mechanism of flower-like Ni(OH)2 is proposed on the basis of a range of contrasting experiments. The results of GC showed that the conversion yield of Jatropha oil was 98.95%, and the selectivity of C11-C18 alkanes was 70.93% at 360 °C, 3 MPa, and 15 h−1. The activity of this flower-like Ni-PTA catalyst was more than 15 times higher than those of the conventional Ni-PTA/Al2O3 catalysts. Additionally, the flower-like Ni-PTA catalyst exhibited good stability during the process of plant oil hydrotreatment. PMID:26503896

Structure of a Rh/TiO2 catalyst in the strong metal-support interaction state as determined by EXAFS

International Nuclear Information System (INIS)

Koningsberger, D.C.; Martens, J.H.A.; Prins, R.; Short, D.R.; Sayers, D.E.

1986-01-01

Reduction of a highly dispersed 2.85 wt% Rh/TiO 2 catalyst at 473 K after previous calcination at 623 K resulted in EXAFS whose primary contributions are due to nearest rhodium (average coordination number of 3.1 and distance of 2.67 A) and oxygen neighbors (coordination 2.5 and distance 2.71 A). These oxygen neighbors originated at the metal-support interface. The average rhodium-rhodium coordination number did not change in the SMSI state produced by reducing the catalyst at 673 K. However, the average coordination distance contracted by 0.04 A with an accompanying decrease of the Debye-Waller factor of the Rh-Rh bond of 0.0012 A 2 . This is due to the fact that in the SMSI state the surface of the metal particles is not covered with chemisorbed hydrogen. The SMSI state leads to a structural reorganization of the support in the vicinity of the rhodium metal particles. This can be concluded from the appearance of a Rh-Ti bond at 3.42 A in the SMSI state coupled with the fact that the average coordination number of the rhodium-support oxygen bonds does not increase. Other types of rhodium-oxygen bonds could not be detected with EXAFS in this state. Thus, these results provide no evidence for coverage of the metal particle by a suboxide of TiO 2 in the SMSI state

Development of Highly Nano-Dispersed NiO/GDC Catalysts from Ion Exchange Resin Templates

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Angel Caravaca

2017-11-01

Full Text Available Novel NiO/GDC (Gadolinium-doped Ceria cermet catalysts were developed by the Weak Acid Resin (WAR method using an ion exchange resin template. In addition, the specific surface area of these tunable materials was enhanced by NiO partial dissolution in aqueous acid solution. The whole procedure highly improved the micro-structural properties of these materials compared to previous studies. Catalysts with high metal loadings (≥10%, small Ni nanoparticles (<10 nm, and high specific surface areas (>70 m2/g were achieved. These properties are promising for catalytic applications such as methane steam reforming for H2 production.

Hydrodeoxygenation of prairie cordgrass bio-oil over Ni based activated carbon synergistic catalysts combined with different metals.

Science.gov (United States)

Cheng, Shouyun; Wei, Lin; Zhao, Xianhui; Kadis, Ethan; Cao, Yuhe; Julson, James; Gu, Zhengrong

2016-06-25

Bio-oil can be upgraded through hydrodeoxygenation (HDO). Low-cost and effective catalysts are crucial for the HDO process. In this study, four inexpensive combinations of Ni based activated carbon synergistic catalysts including Ni/AC, Ni-Fe/AC, Ni-Mo/AC and Ni-Cu/AC were evaluated for HDO of prairie cordgrass (PCG) bio-oil. The tests were carried out in the autoclave under mild operating conditions with 500psig of H2 pressure and 350°C temperature. The catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscope (TEM). The results show that all synergistic catalysts had significant improvements on the physicochemical properties (water content, pH, oxygen content, higher heating value and chemical compositions) of the upgraded PCG bio-oil. The higher heating value of the upgraded bio-oil (ranging from 29.65MJ/kg to 31.61MJ/kg) improved significantly in comparison with the raw bio-oil (11.33MJ/kg), while the oxygen content reduced to only 21.70-25.88% from 68.81% of the raw bio-oil. Compared to raw bio-oil (8.78% hydrocarbons and no alkyl-phenols), the Ni/AC catalysts produced the highest content of gasoline range hydrocarbons (C6-C12) at 32.63% in the upgraded bio-oil, while Ni-Mo/AC generated the upgraded bio-oil with the highest content of gasoline blending alkyl-phenols at 38.41%. Copyright © 2016 Elsevier B.V. All rights reserved.

Study of PtNi/C catalyst for direct ethanol fuel cell; Estudo do catalisador PtNi/C para celula a combustivel de etanol direto

Energy Technology Data Exchange (ETDEWEB)

Moraes, L.P.R. de; Silva, E.L. da; Amico, S.C.; Malfatti, C.F., E-mail: eticiaprm@gmail.com [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil)

2014-07-01

In this work, PtNi binary catalyst and pure platin catalyst were synthesized by the impregnation-reduction method, using Vulcan XC72R as support, for direct ethanol fuel cells. The composition and structure of the catalysts were analyzed by X-ray diffraction, the electrochemical behavior was evaluated by cyclic voltammetry and morphology of the catalysts was studied by high-resolution transmission electron microscopy. The results showed that the addition of Ni to Pt led to the contraction of the crystal lattice, increased the catalytic activity compared to pure Pt and initiated the electrooxidation of ethanol at lower potential. (author)

Microwave effects on NiMoS and CoMoS single-sheet catalysts.

Science.gov (United States)

Borges, I; Silva, Alexander M; Modesto-Costa, Lucas

2018-05-04

Single-sheet nanoclusters of MoS 2 , NiMoS or CoMoS are widely used in hydrodesulfurization (HDS) catalysis in the petroleum industry. In HDS reactions under microwave irradiation, experiments indirectly pointed out that for pristine MoS 2 reaction rates are accelerated because hot spots are generated on the catalyst bed. In this work, we investigated NiMoS and CoMoS isolated single-sheet substituted catalysts before and after thiophene adsorption focusing on quantifying the effect of microwave irradiation. For that purpose, density functional theory (DFT) molecular charge densities of each system were decomposed according to the distributed multipole analysis (DMA) of Stone. Site dipole values of each system were directly associated with a larger or smaller interaction with the microwave field according to a proposed general approach. We showed that microwave enhancement of HDS reaction rates can occur more efficiently in the CoMoS and NiMoS promoted clusters compared to pristine MoS 2 in the following order: CoMoS > NiMoS > MoS 2 . The atomic origin of the catalyst hot spots induced by microwaves was clearly established in the promoted clusters.

Pt-Ni/WC Alloy Nanorods Arrays as ORR Catalyst for PEM Fuel Cells

Energy Technology Data Exchange (ETDEWEB)

Begum, Mahbuba; Yurukcu, Mesut; Yurtsever, Fatma; Ergul, Busra; Kariuki, Nancy; Myers, Deborah J.; Karabacak, Tansel

2017-08-24

Polymer electrolyte membrane fuel cells (PEMFCs) among the other types of fuel cell technology are attractive power sources, especially for electric vehicle applications. While significant progress and plausible prospects of PEMFCs have been achieved, there are still some challenges related to the performance, durability, and cost that need to be overcome to make them economically viable for widespread commercialization. Our strategy is to develop thin films of high-active and stable catalyst coated on vertically aligned nanorod arrays of conductive and stable support. In this work, we fabricated tungsten carbide (WC) nanorods as support and coated them with a platinum-nickel (Pt-Ni) alloy shell denoted as Pt-Ni/WC catalysts. The Pt- Ni/WC nanorods were deposited on glassy carbon disks as well as on silicon substrates for evaluation of their electrocatalytic oxygen reduction reaction (ORR) activity and physical properties. Cyclic voltammetry experiments using rotating disk electrode were performed in perchloric acid (0.1 M HClO4) electrolyte at room temperature to characterize the ORR activity and stability of Pt-Ni/WC nanorods catalysts. Scanning electron microscopy and X-ray diffraction techniques were utilized to study the morphology and crystallographic properties, respectively.

Investigation of ethanol electrooxidation on a Pt-Ru-Ni/C catalyst for a direct ethanol fuel cell

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhen-Bo; Yin, Ge-Ping; Zhang, Jian; Sun, Ying-Chao; Shi, Peng-Fei [Department of Applied Chemistry, Harbin Institute of Technology, Harbin (China 150001)

2006-09-29

This research is aimed to improve the utilization and activity of anodic alloy catalysts and thus to lower the contents of noble metals and the catalyst loading on anodes for ethanol electrooxidation. The DEFC anodic catalysts, Pt-Ru-Ni/C and Pt-Ru/C, were prepared by a chemical reduction method. Their performances were tested by using a glassy carbon working electrode and cyclic voltammetric curves, chronoamperometric curves and half cell measurement in a solution of 0.5molL{sup -1} CH{sub 3}CH{sub 2}OH and 0.5molL{sup -1} H{sub 2}SO{sub 4}. The composition of the Pt-Ru-Ni and Pt-Ru surface particles were determined by EDAX analysis. The particle size and lattice parameter of the catalysts were determined by means of X-ray diffraction (XRD). XRD analysis showed that both of the catalysts exhibited face centered cubic structures and had smaller lattice parameters than a Pt-alone catalyst. Their particle sizes were small, about 4.5nm. No significant differences in the ethanol electrooxidation on both electrodes were found using cyclic voltammetry, especially regarding the onset potential for ethanol electrooxidation. The electrochemically active specific areas of the Pt-Ru-Ni/C and Pt-Ru/C catalysts were almost the same. But, the catalytic activity of the Pt-Ru-Ni/C catalyst was higher for ethanol electrooxidation than that of the Pt-Ru/C catalyst. Their tolerance to CO formed as one of the intermediates of ethanol electrooxidation, was better than that of the Pt-Ru/C catalyst. (author)

Activity Tests of Macro-Meso Porous Catalysts over Metal Foam Plate for Steam Reforming of Bio-Ethanol.

Science.gov (United States)

Park, No-Kuk; Jeong, Yong Han; Kang, Misook; Lee, Tae Jin

2018-09-01

The catalytic activity of a macro-mesoporous catalyst coated on a metal foam plate in the reforming of bio-ethanol to synthesis gas was investigated. The catalysts were prepared by coating a support with a noble metal and transition metal. The catalytic activity for the production of synthetic gas by the reforming of bio-ethanol was compared according to the support material, reaction temperature, and steam/carbon ratio. The catalysts coated on the metal foams were prepared using a template method, in which macro-pores and meso-pores were formed by mixing polymer beads. In particular, the thermodynamic equilibrium composition of bio-ethanol reforming with the reaction temperature and steam/carbon ratio to produce synthetic gas was examined using the HSC (Enthalpy-Entropy-Heat capacity) chemistry program in this study. The composition of hydrogen and carbon monoxide in the reformate gas produced by steam reforming over the Rh/Ni-Ce-Zr/Al2O3-based pellet type catalysts and metal foam catalysts that had been coated with the Rh/Al-Ce-Zr-based catalysts was investigated by experimental activity tests. The activity of the metal foam catalyst was higher than that of the pellet type catalyst.

CO2 methanation on the catalyst of Ni/MCM-41 promoted with CeO2.

Science.gov (United States)

Wang, Xiaoliu; Zhu, Lingjun; Liu, Yincong; Wang, Shurong

2018-06-01

CO 2 as a raw feed combined with renewable hydrogen for the production of useful chemicals and alternative energy products is one of the solutions to environmental and energy problems. In this study, a series of Ni-xCeO 2 /MCM-41 catalysts with a nickel content of 20wt% were prepared through deposition precipitation method for CO 2 methanation. Different characterization methods, including BET, XRD, TEM, SEM, H 2 -TPR and H 2 -TPD were applied to help explore the influence mechanism of CeO 2 on Ni/MCM-41 in CO 2 methanation. It was found that all CeO 2 -promoted catalysts exhibited enhanced catalytic activity when compared to Ni/MCM-41. The catalyst modified with 20wt% CeO 2 showed the best catalytic performance, with CO 2 conversion and CH 4 selectivity of 85.6% and 99.8%, respectively, at the temperature of 380°C under atmospheric pressure. The synergetic effects among Ni 0 active sites, the promoter and the support, including nickel dispersion improvement and increased CO 2 adsorption sites due to the addition of CeO 2 , were considered as important factors for high reactivity of the promoted catalysts. The stability test showed that the promoted catalyst maintained its high reactivity after 30h. Copyright © 2017 Elsevier B.V. All rights reserved.

Selective hydrogenation of acetylene on SiO{sub 2} supported Ni-In bimetallic catalysts: Promotional effect of In

Energy Technology Data Exchange (ETDEWEB)

Chen, Yanjun; Chen, Jixiang, E-mail: jxchen@tju.edu.cn

2016-11-30

Graphical abstract: A suitable Ni/In ratio remarkably enhanced the acetylene conversion, the selectivity to ethylene and the catalyst stability. Display Omitted - Highlights: • There was a promotional effect of In on the performance of Ni/SiO{sub 2}. • A suitable Ni/In ratio was required for good performance of Ni{sub x}In/SiO{sub 2}. • Both geometrical and electronic effects of In contributed to good performance. • Ni/SiO{sub 2} deactivation is mainly owing to phase change from Ni to nickel carbide. • The carbonaceous deposit was the main reason for Ni{sub x}In/SiO{sub 2} deactivation. - Abstract: Ni/SiO{sub 2} and the bimetallic Ni{sub x}In/SiO{sub 2} catalysts with different Ni/In ratios were tested for the selective hydrogenation of acetylene, and their physicochemical properties before and after the reaction were characterized by means of N{sub 2}-sorption, H{sub 2}-TPR, XRD, TEM, XPS, H{sub 2} chemisorption, C{sub 2}H{sub 4}-TPD, NH{sub 3}-TPD, FT-IR of adsorbed pyridine, and TG/DTA and Raman. A promotional effect of In on the performance of Ni/SiO{sub 2} was found, and Ni{sub x}In/SiO{sub 2} with a suitable Ni/In ratio gave much higher acetylene conversion, ethylene selectivity and catalyst stability than Ni/SiO{sub 2}. This is ascribed to the geometrical isolation of the reactive Ni atoms with the inert In ones and the charge transfer from the In atoms to Ni ones, both of which are favorable for reducing the adsorption strength of ethylene and restraining the C−C hydrogenolysis and the polymerizations of acetylene and the intermediate compounds. On the whole, Ni{sub 6}In/SiO{sub 2} and Ni{sub 10}In/SiO{sub 2} had better performance. Nevertheless, with increasing the In content, the selectivity to the C4+ hydrocarbons tended to increase due to the enhanced catalyst acidity because of the charge transfer from the In atoms to Ni ones. As the Lewis acid ones, the In sites could promote the polymerization. The catalyst deactivation was also analyzed

Co-Production of Ethanol and 1,2-Propanediol via Glycerol Hydrogenolysis Using Ni/Ce–Mg Catalysts: Effects of Catalyst Preparation and Reaction Conditions

Directory of Open Access Journals (Sweden)

Russel N. Menchavez

2017-09-01

Full Text Available Crude glycerol from biodiesel production is a biobased material capable of co-producing biofuels and chemicals. This study aimed to develop a line of Ni catalysts supported on cerium–magnesium (Ce–Mg to improve the process efficiency of glycerol hydrogenolysis for ethanol and 1,2-propanediol (1,2-PDO. Results showed that catalytic activity was greatly improved by changing the preparation method from impregnation to deposition precipitation (DP, and by adjusting calcination temperatures. Prepared via DP, the catalysts of 25 wt % Ni supported on Ce–Mg (9:1 mol/mol greatly improved the effectiveness in glycerol conversion while maintaining the selectivities to ethanol and 1,2-PDO. Calcination at 350 °C provided the catalysts better selectivities of 15.61% to ethanol and 67.93% to 1,2-PDO. Increases in reaction temperature and time improved the conversion of glycerol and the selectivity to ethanol, but reduced the selectivity to 1,2-PDO. A lower initial water content led to a higher conversion of glycerol, but lower selectivities to ethanol and 1,2-PDO. Higher hydrogen application affected the glycerol conversion rate positively, but the selectivities to ethanol and 1,2-PDO negatively. A comparison to the commercial Raney® Ni catalyst showed that the Ni/Ce–Mg catalyst developed in this study showed a better potential for the selective co-production of ethanol and 1,2-PDO from glycerol hydrogenolysis.

O-Carboxymethyl Chitosan Supported Heterogeneous Palladium and Ni Catalysts for Heck Reaction

Directory of Open Access Journals (Sweden)

Dongjun Lv

2017-01-01

Full Text Available Two polymer catalysts (Pd-OCMCS and Ni-OCMCS with good reusability were synthesized by coordinating Pd and Ni onto O-carboxymethyl chitosan (OCMCS. The chemical structure and thermal stability of prepared catalysts were determined by Fourier transform infrared (FT-IR spectra, Energy Dispersive Spectrometer (EDSanalysis, X-ray diffraction (XRD, and thermogravimetric analyzer (TG-DTG, and the analysis results showed that the Pd and Ni ions coordinated onto the OCMCS and formed a ligand with the –COOH group, amino groups, and –OH group on the OCMCS, and the EDS and Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES analysis results showed that the loading amounts of Pd and Ni were approximately 8.3% and 8.9%, respectively. In the Heck reaction between aryl halides and n-butyl acrylate catalyzed by the prepared catalyst, the test results showed that the product yield followed the order of aryl iodide > aryl bromide > aryl chloride. Additionally, the product yield for the aryl iodide and aryl bromide could reach up to 99% and 96%, respectively. Moreover, the electron-withdrawing and electron-donating property of the group on the aryl also affected the product yield, and the product yield for aryl halides with electron-withdrawing group p-NO2, p-CH3CO, and p-CHO was higher than that with electron-donating group p-CH3.

Synthesis and characterization of NiFe2O4–Pd magnetically recyclable catalyst for hydrogenation reaction

International Nuclear Information System (INIS)

Karaoğlu, E.; Özel, U.; Caner, C.; Baykal, A.; Summak, M.M.; Sözeri, H.

2012-01-01

Graphical abstract: Display Omitted Highlights: ► Novel superparamagnetic NiFe 2 O 4 –Pd magnetically recyclable catalyst was fabricated through co-precipitation. ► It could be reused several times without significant loss in catalytic activity for hydrogenation reaction. ► No further modification of the NiFe 2 O 4 –Pd magnetically recyclable catalyst is necessary for utilization as catalyst. -- Abstract: Herein we report the fabrication and characterization magnetically recyclable catalysts of NiFe 2 O 4 –Pd nanocomposite as highly effective catalysts for reduction reactions in liquid phase. The reduction Pd 2+ was accomplished with polyethylene glycol 400 (PEG-400) instead of sodium borohydride (NaBH 4 ) and NiFe 2 O 4 nanoparticles was prepared by sonochemically using FeCI 3 ·6H 2 O and NiCl 2 . The chemical characterization of the product was done with X-ray diffractometry, Infrared spectroscopy, transmission electron microscopy, UV–Vis spectroscopy, thermal gravimetry and inductively coupled plasma. Thus formed NiFe 2 O 4 –Pd MRCs showed a very high activity in reduction reactions of 4-nitro aniline and 1,3-dinitrobenzene in liquid phase. It was found out that the catalytic activity of NiFe 2 O 4 –Pd MRCs on the reduction of 4-nitro aniline and 1,3-dinitrobenzene in liquid phase are between 99–93% and 98–93%, respectively. Magnetic character of this system allowed recovery and multiple use without significant loss of its catalytic activity. It is found that NiFe 2 O 4 –Pd MRCs showed very efficient catalytic activity and multiple usability.

Production of liquid alkanes by controlling reactivity of sorbitol hydrogenation with a Ni/HZSM-5 catalyst in water

International Nuclear Information System (INIS)

Zhang, Qing; Wang, Tiejun; Xu, Ying; Zhang, Qi; Ma, Longlong

2014-01-01

Graphical abstract: MCM-41-modified Ni/HZSM-5 catalyst was developed by impregnation method with high catalytic performance for sorbitol hydrogenation in water. Appropriate amount of MCM-41 addition can distinctly promote the improvement in the surface structure and modulation of acidic sites of the catalyst. The scission of C–O bond in the sorbitol molecule into liquid alkanes was easily carried out on the catalyst containing more Lewis acidic sites. - Highlights: • Ni/HZSM-5 promoted with MCM-41 is active for sorbitol hydrogenation to liquid alkanes. • Lewis acidic sites of Ni/HZSM-5 can be modulated by pure silica MCM-41. • MCM-41 added can distinctly decrease carbon deposition on the catalyst surface. - Abstract: Liquid fuels derived from renewable biomass are of great importance on the potential substitution for diminishing fossil fuels. The conversion of sorbitol (a product of biomass-derived glucose hydrogenation) into liquid alkanes such as pentane and hexane over the Ni/HZSM-5 catalysts with or without MCM-41 addition was investigated in the presence of hydrogen in water medium. The production distribution of sorbitol hydrogenation can be controlled by adjusting the acidity of the catalyst. The scission of C–C bond in the sorbitol molecule into light C 1 –C 4 alkanes was mainly carried out over Ni/HZSM-5 containing strong Brønsted acid sites, while C–O bond scission into heavier alkanes was dominated over the catalysts added by MCM-41 containing weak Lewis acid sites. The sorbitol conversion and total liquid alkanes selectivity were found to be 67.1% and 98.7% over 2%Ni/HZSM-5 modified by 40 wt% of MCM-41, whereas the corresponding value was 40% and 35.6% over 2%Ni/HZSM-5 in the absence of MCM-41. The effect of MCM-41 on the structure, acidity, and reducibility of Ni/HZSM-5 was investigated by using XRD, Py-IR, IR, and H 2 -TPR. Meanwhile, the resistance of carbon deposition over the catalyst modified by MCM-41 was studied by using TG�

Steam reforming of different biomass tar model compounds over Ni/Al_2O_3 catalysts

International Nuclear Information System (INIS)

Artetxe, Maite; Alvarez, Jon; Nahil, Mohamad A.; Olazar, Martin; Williams, Paul T.

2017-01-01

Highlights: • Order of reactivity: anisole > furfural > indene > phenol > toluene > methyl naphthalene. • Higher coke deposition for oxygenates (1.5–2.8%) than for aromatics (0.5–0.8%). • Amorphous coke is deposited for oxygenates and filamentous carbon for aromatics. • Ni content of 20 wt.% shows the higher conversion (90%) and H_2 potential (63%). - Abstract: This work focuses on the removal of the tar derived from biomass gasification by catalytic steam reforming on Ni/Al_2O_3 catalysts. Different tar model compounds (phenol, toluene, methyl naphthalene, indene, anisole and furfural) were individually steam reformed (after dissolving each one in methanol), as well as a mixture of all of them, at 700 °C under a steam/carbon (S/C) ratio of 3 and 60 min on stream. The highest conversions and H_2 potential were attained for anisole and furfural, while methyl naphthalene presented the lowest reactivity. Nevertheless, the higher reactivity of oxygenates compared to aromatic hydrocarbons promoted carbon deposition on the catalyst (in the 1.5–2.8 wt.% range). When the concentration of methanol is decreased in the feedstock and that of toluene or anisole is increased, the selectivity to CO is favoured in the gaseous products, thus increasing coke deposition on the catalyst and decreasing catalyst activity for the steam reforming reaction. Moreover, an increase in Ni loading in the catalyst from 5 to 20% enhances carbon conversion and H_2 formation in the steam reforming of a mixture of all the model compounds studied, but these values decrease for a Ni content of 40%. Coke formation also increased by increasing Ni loading, attaining its maximum value for 40% Ni (6.5 wt.%).

An anodic alumina supported Ni-Pt bimetallic plate-type catalysts for multi-reforming of methane, kerosene and ethanol

KAUST Repository

Zhou, Lu

2014-05-01

An anodic alumina supported Ni-Pt bimetallic plate-type catalyst was prepared by a two-step impregnation method. The trace amount 0.08 wt% of Pt doping efficiently suppressed the nickel particle sintering and improved the nickel oxides reducibility. The prepared Ni-Pt catalyst showed excellent performance during steam reforming of methane, kerosene and ethanol under both 3000 h stationary and 500-time daily start-up and shut-down operation modes. Self-activation ability of this catalyst was evidenced, which was considered to be resulted from the hydrogen spillover effect over Ni-Pt alloy. In addition, an integrated combustion-reforming reactor was proposed in this study. However, the sintering of the alumina support is still a critical issue for the industrialization of Ni-Pt catalyst. Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Catalysts characteristics of Ni/YSZ core-shell according to plating conditions using electroless plating

Science.gov (United States)

Park, Hyun-Wook; Jang, Jae-Won; Lee, Young-Jin; Kim, Jin-Ho; Jeon, Dae-Woo; Lee, Jong-Heun; Hwang, Hae-jin; Lee, Mi-Jai

2017-11-01

This study aims to develop an anode catalyst for a solid oxide fuel cell (SOFC) using electroless nickel plating. We have proposed a new method for electroless plating of Ni metal on yttria-stabilized zirconia (YSZ) particles. We examine the uniformity of the Ni layer on the plated core-shell powder, in addition to the content of Ni and the reproducibility of the plating. We have also evaluated the carbon deposition rate and characteristics of the SOFC anode catalyst. To synthesize Ni-plated YSZ particles, the plated powder is heat-treated at 1200 °C. The resultant particles, which have an average size of 50 μm, were subsequently used in the experiment. The size of the Ni particles and the Ni content both increase with increasing plating temperature and plating time. The X-ray diffraction pattern reveals the growth of Ni particles. After heat-treatment, Ni is oxidized to NiO, leading to the co-existence of Ni and NiO; Ni3P is also observed due to the presence of phosphorous in the plating solution. Following heat treatment for 1 h at 1200 °C, Ni is mostly oxidized to NiO. The carbon deposition rate of the reference YSZ powder is 135%, while that of the Ni-plated YSZ is 1%-6%.

Chemoselective hydrogenation of arenes by PVP supported Rh nanoparticles

DEFF Research Database (Denmark)

Ibrahim, Mahmoud; Poreddy, Raju; Philippot, Karine

2016-01-01

Polyvinylpyrrolidone-stabilized Rh nanoparticles (RhNPs/PVP) of ca. 2.2 nm in size were prepared by the hydrogenation of the organometallic complex [Rh(η3-C3H5)3] in the presence of PVP and evaluated as a catalyst in the hydrogenation of a series of arene substrates as well as levulinic acid...... for the hydrogenation of levulinic acid and methyl levulinate in water leading to quantitative formation of the fuel additive γ-valerolactone under moderate reaction conditions compared to previously reported catalytic systems....... and methyl levulinate. The catalyst showed excellent activity and selectivity towards aromatic ring hydrogenation compared to other reported transition metal-based catalysts under mild reaction conditions (room temperature and 1 bar H2). Furthermore, it was shown to be a highly promising catalyst...

How easy is CO2 fixation by M-C bond containing complexes (M = Cu, Ni, Co, Rh, Ir)?

KAUST Repository

Nolan, Steve; Cavallo, Luigi; Poater, Albert; Vummaleti, Sai V. C.; Talarico, Giovanni

2015-01-01

A comparison between different M–C bonds (M = Cu(I), Ni(II), Co(I), Rh(I) and Ir(I)) has been reported by using density functional theory (DFT) calculations to explore the role of the metal in the fixation or incorporation of CO2 into such complexes. The systems investigated are various metal based congeners of the Ir-complex 8 [(cod)(IiPr)Ir-CCPh], with a ligand scaffold based on cod and IiPr ligands (cod = 1,5-cyclooctadiene; IiPr = 1,3-bis(isopropyl)imidazol-2-ylidene). The results of this study show that the calculated CO2 insertion barriers follow the trend: Cu(I) (20.8 kcal mol−1) < Rh(I) (30.0 kcal mol−1) < Co(I) (31.3 kcal mol−1) < Ir(I) (37.5 kcal mol−1) < Ni(II) (45.4 kcal mol−1), indicating that the Cu(I) based analogue is the best CO2 fixer, while Ni(II) is the worst in the studied series.

How easy is CO2 fixation by M-C bond containing complexes (M = Cu, Ni, Co, Rh, Ir)?

KAUST Repository

Nolan, Steve

2015-11-27

A comparison between different M–C bonds (M = Cu(I), Ni(II), Co(I), Rh(I) and Ir(I)) has been reported by using density functional theory (DFT) calculations to explore the role of the metal in the fixation or incorporation of CO2 into such complexes. The systems investigated are various metal based congeners of the Ir-complex 8 [(cod)(IiPr)Ir-CCPh], with a ligand scaffold based on cod and IiPr ligands (cod = 1,5-cyclooctadiene; IiPr = 1,3-bis(isopropyl)imidazol-2-ylidene). The results of this study show that the calculated CO2 insertion barriers follow the trend: Cu(I) (20.8 kcal mol−1) < Rh(I) (30.0 kcal mol−1) < Co(I) (31.3 kcal mol−1) < Ir(I) (37.5 kcal mol−1) < Ni(II) (45.4 kcal mol−1), indicating that the Cu(I) based analogue is the best CO2 fixer, while Ni(II) is the worst in the studied series.

Simple synthesis of mesoporous FeNi/graphitic carbon nanocomposite catalysts and study on their activities in catalytic cracking of toluene

Energy Technology Data Exchange (ETDEWEB)

Wang, Yangang, E-mail: ygwang8136@gmail.com [Department of Environmental Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China); Chen, Yuting; Yao, Mingcui [Department of Environmental Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China); Qin, Hengfei; Kang, Shifei; Li, Xi [Department of Environmental Science and Engineering, Fudan University, Shanghai 200433 (China); Zuo, Yuanhui; Zhang, Xiaodong [Department of Environmental Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China); Cui, Li-Feng, E-mail: lifeng.cui@gmail.com [Department of Environmental Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China)

2015-11-01

Mesoporous FeNi alloy/graphitic carbon nanocomposite catalysts with different Fe/Ni molar ratios have been synthesized through a simple solid–liquid grinding/templating method using mesoporous silica SBA-15 as the template. Metal nitrates and natural soybean oil were respectively used as the magnetic particle precursors and carbon source, which can be infiltrated into the silica template after simple impregnation, grinding and subsequent heat treatment. X-ray diffraction, nitrogen adsorption–desorption, transmission electron microscopy and thermogravimetric analysis techniques were used to characterize the samples. It is observed that high contents of FeNi alloy nanoparticles with the sizes of 3–6 nm are well dispersed into the walls of graphitic mesoporous carbon matrix, and the resulting nanocomposites have a uniform mesostructure with a high specific surface area and large pore volume. Because of these properties, the obtained FeNi/graphitic carbon nanocomposites can be used as novel catalysts for the catalytic cracking of toluene and exhibit a higher activity and stability than FeNi/commercial activated carbon (AC) catalyst. After a period of 810 min reaction at 700 °C, the toluene conversion on the FeNi/graphitic carbon nanocomposites can be maintained at a level of more than 75% and this value is 2.5 times as high as that of the FeNi/AC catalyst. - Highlights: • Mesoporous FeNi alloy/graphitic carbon nanocomposites (FeNi/GCN) were synthesized. • High contents of FeNi alloy nanoparticles are well embedded into the graphitic carbon walls. • The obtained FeNi/GCN catalysts have a high surface area and uniform mesostructure. • The FeNi/GCN catalysts exhibited excellent catalytic performance in the cracking of toluene.

Nickel-based xerogel catalysts: Synthesis via fast sol-gel method and application in catalytic hydrogenation of p-nitrophenol to p-aminophenol

Energy Technology Data Exchange (ETDEWEB)

Feng, Jin; Wang, Qiang; Fan, Dongliang; Ma, Lirong; Jiang, Deli; Xie, Jimin, E-mail: xiejm391@sohu.com; Zhu, Jianjun, E-mail: zhjj029@sina.com

2016-09-30

Graphical abstract: In order to investigate the roles of three-dimensional network structure and calcium on Ni catalysts, the Ni, Ni-Al{sub 2}O{sub 3}, Ni-Ca-Al{sub 2}O{sub 3} xerogel catalysts were successfully synthesized via the fast sol-gel process and chemical reduction method. - Highlights: • Epoxide-driven sol-gel and chemical reduction method subsequently were used to prepare Ni, Ni-Al{sub 2}O{sub 3} and Ni-Ca-Al{sub 2}O{sub 3} catalysts. • Three-dimensional network structure of the gel was employed to adjust the size and distribution of Ni nanoparticles. • Calcium was employed to shorten the gelation time, improve the nickel dispersion, decrease thenickel particle size and strengthen the Ni-Al{sub 2}O{sub 3} interaction. • The rate constants of Ni-Ca-Al2O3 catalysts (2.85 × 10{sup −3} s{sup −1}) is 2.8 times higher than the Ni catalysts (1.02 × 10{sup −3} s{sup −1}) and 2 times higher than the Ni-Al{sub 2}O{sub 3} catalysts(1.42 × 10{sup −3} s{sup −1}). • After 5 cycles, the conversion of PNP to PAP catalyzed by Ni, Ni-Al{sub 2}O{sub 3}, Ni-Ca-Al{sub 2}O{sub 3} remained 85%, 82%, 80%, respectively. - Abstract: In order to investigate the roles of three-dimensional network structure and calcium on Ni catalysts, the Ni, Ni-Al{sub 2}O{sub 3}, Ni-Ca-Al{sub 2}O{sub 3} xerogel catalysts were successfully synthesized via the fast sol-gel process and chemical reduction method. The crystal structure of three different catalysts was observed with X-ray powder diffraction (XRD). Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and nitrogen adsorption-desorption were employed to investigate the role of network structure of xerogel catalysts and the size distribution of Ni nanoparticles. The catalyst composition was determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) measurement and energy-dispersive X-ray spectroscopy (EDS). Temperature-programmed reduction (TPR) experiments were carried

Ni2P Makes Application of the PtRu Catalyst Much Stronger in Direct Methanol Fuel Cells.

Science.gov (United States)

Chang, Jinfa; Feng, Ligang; Liu, Changpeng; Xing, Wei

2015-10-12

PtRu is regarded as the best catalyst for direct methanol fuel cells, but the performance decay resulting from the loss of Ru seriously hinders commercial applications. Herein, we demonstrated that the presence of Ni2 P largely reduces Ru loss, which thus makes the application of PtRu much stronger in direct methanol fuel cells. Outstanding catalytic activity and stability were observed by cyclic voltammetry. Upon integrating the catalyst material into a practical direct methanol fuel cell, the highest maximum power density was achieved on the PtRu-Ni2P/C catalyst among the reference catalysts at different temperatures. A maximum power density of 69.9 mW cm(-2) at 30 °C was obtained on PtRu-Ni2P/C, which is even higher than the power density of the state-of-the-art commercial PtRu catalyst at 70 °C (63.1 mW cm(-2)). Moreover, decay in the performance resulting from Ru loss was greatly reduced owing to the presence of Ni2 P, which is indicative of very promising applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen generation from deliquescence of ammonia borane using Ni-Co/r-GO catalyst

Science.gov (United States)

Chou, Chang-Chen; Chen, Bing-Hung

2015-10-01

Hydrogen generation from the catalyzed deliquescence/hydrolysis of ammonia borane (AB) using the Ni-Co catalyst supported on the graphene oxide (Ni-Co/r-GO catalyst) under the conditions of limited water supply was studied with the molar feed ratio of water to ammonia borane (denoted as H2O/AB) at 2.02, 3.97 and 5.93, respectively. The conversion efficiency of ammonia borane to hydrogen was estimated both from the cumulative volume of the hydrogen gas generated and the conversion of boron chemistry in the hydrolysates analyzed by the solid-state 11B NMR. The conversion efficiency of ammonia borane could reach nearly 100% under excess water dosage, that is, H2O/AB = 3.97 and 5.93. Notably, the hydrogen storage capacity could reach as high as 6.5 wt.% in the case with H2O/AB = 2.02. The hydrolysates of ammonia borane in the presence of Ni-Co/r-GO catalyst were mainly the mixture of boric acid and metaborate according to XRD, FT-IR and solid-state 11B NMR analyses.

Effect of Ca, Ce or K oxide addition on the activity of Ni/SiO{sub 2} catalysts for the methane decomposition reaction

Energy Technology Data Exchange (ETDEWEB)

Zapata, Beatriz; Torres-Garcia, Enelio [Instituto Mexicano del Petroleo, Programa de Procesos y Reactores, Eje C. 152, Mexico, D.F., C.P. 07730 (Mexico); Valenzuela, Miguel A.; Palacios, Jorge [Instituto Politecnico Nacional-ESIQIE, Lab. Catalisis y Materiales, Zacatenco, Mexico, D.F., C.P. 07738 (Mexico)

2010-11-15

To increase the activity and stability of Ni/SiO{sub 2} catalysts, a series of Ni-Ca, Ni-K and Ni-Ce promoted catalysts were prepared by successive impregnations. The textural properties, reducibility and catalytic performance in the methane decomposition reaction were investigated. The catalyst containing 30 wt.% Ni and 30 wt.% cerium oxide greatly increased the conversion of methane (90% of equilibrium value) and improved the stability, whereas the Ni-K and Ni-Ca were less active and stable than the Ni/SiO{sub 2} catalyst. The results suggest that Ce addition prevents the sintering of nickel particles during reduction process maintaining a random distribution between the silica and cerium oxide improving the distribution and migration of deposited carbon. (author)

Synthesis and characterization of Ni-CeO2 catalysts by the hydrothermal method

International Nuclear Information System (INIS)

Lazcano O, I.

2013-01-01

At the present time the necessity exists to reduce the level of atmospheric pollutants, because these are the main originators of such problems as: the greenhouse effect, acid rain, global heating, among others and that are affecting the human being seriously. In this context, is necessary to look for new solutions that contribute to the improvement of the problems without appealing to limitations in the energy production, because this would imply a non only delay in the economic development, but also in the cultural, technological and of research in our country. An alternative for the energy solution is the use of renewable fuels, because they will decrease the production costs with the time, as well as to diminish the dependence of the fossil fuels, contributing this way to the improvement of the environment quality. The use of the hydrogen as an alternating fuel to the petroleum, is intends as energy solution. The objective of the present work is to develop Ni-CeO 2 catalysts through the hydrothermal method for the hydrogen production starting from the partial oxidation reaction of methanol for the clean fuel generation that does not produce polluting emissions to the environment. As well as, to determine the importance of the metallic load in the catalytic activity for which catalysts to 1 and 2% in weight of Ni were prepared. To achieve these objective different techniques were used to characterize the prepared catalysts, as: Temperature Programmed Reduction to evidence the metal-support interaction, Scanning Electron Microscopy (Sem) to determine the morphology of the catalysts, Surface Area (Bet) with respect to the adsorption-desorption of N 2 and X-Rays Diffraction (XRD) to know the crystalline structure of the catalysts. Also the catalytic properties (activity and selectivity) were studied under the reaction: CH 3 OH + 1/2 O 2 obtaining as products to the CO 2 + 2H 2 , with the help of the multi-tasks equipment Rig-100 that operated to temperatures among

Steam Reforming of Ethylene Glycol over Ni/Al2O3 Catalysts: Effect of the Preparation Method and Reduction Temperature

International Nuclear Information System (INIS)

Choi, Dong Hyuck; Park, Jung Eun; Park, Eun Duck

2015-01-01

The effect of preparation method on the catalytic activities of the Ni/Al 2 O 3 catalysts on steam reforming of ethylene glycol was investigated. The catalysts were prepared with various preparation methods such as an incipient wetness impregnation, wet impregnation, and coprecipitation method. In the case of coprecipitation method, various precipitants such as KOH, K 2 CO 3 , and NH 4 OH were compared. The prepared catalysts were characterized by using N 2 physisorption, inductively coupled plasma-atomic emission spectroscopy, X-ray diffraction, temperature programmed reduction, pulsed H 2 chemisorption, temperature-programmed oxidation, scanning electron microscopy, and thermogravimetric analysis. Among the catalysts reduced at 773 K, the Ni/Al 2 O 3 catalyst prepared by a coprecipitation with KOH or K 2 CO 3 as precipitants showed the best catalytic performance. The preparation method affected the particle size of Ni, reducibility of nickel oxides, catalytic performance (activity and stability), and types of coke formed during the reaction. The Ni/Al 2 O 3 catalyst prepared by a coprecipitation with KOH showed the increasing catalytic activity with an increase in the reduction temperature from 773 to 1173 K because of an increase in the reduction degree of Ni oxide species even though the particle size of Ni increased with increasing reduction temperature

Carbon Dioxide Dry Reforming of Glycerol for Hydrogen Production using Ni/ZrO2 and Ni/CaO as Catalysts

Directory of Open Access Journals (Sweden)

Nur Nabillah Mohd Arif

2016-08-01

Full Text Available Glycerol, byproduct from the biodiesel production can be effectively utilized as the promising source of synthesis gas (syngas through a dry reforming reaction. Combination of these waste materials with greenhouse gases which is carbon dioxide (CO2 will help to reduce environmental problem such as global warming. This dry reforming reaction has been carried out in a fixed bed batch reactor at 700 °C under the atmospheric pressure for 3 hours. In this experiment, reforming reaction was carried out using Nickel (Ni as based catalyst and supported with zirconium (ZrO2 and calcium (CaO oxides. The catalysts were prepared by wet impregnation method and characterized using Bruanaer-Emmett-Teller (BET surface area, Scanning Electron Microscopy (SEM, X-ray Diffraction (XRD, Thermo Gravimetric (TGA, and Temperature Programmed Reduction (TPR analysis. Reaction studies show that 15% Ni/CaO give the highest hydrogen yield and glycerol conversion that peaked at 24.59% and 30.32%, respectively. This result is verified by XRD analysis where this catalyst shows low crystallinity and fine dispersion of Ni species resulted in high specific surface area which gives 44.93 m2/g that is validated by BET.  Copyright © 2016 BCREC GROUP. All rights reserved Received: 21st January 2016; Revised: 24th February 2016; Accepted: 29th February 2016 How to Cite: Arif, N.M.M., Vo, D.V.N., Azizan,M.T., Abidin S.Z. (2016. Carbon Dioxide Dry Reforming of Glycerol for Hydrogen Production using Ni/ZrO2 and Ni/CaO as Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 200-209 (doi:10.9767/bcrec.11.2.551.200-209 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.551.200-209

Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions

Directory of Open Access Journals (Sweden)

Yasuharu Kanda

2018-04-01

Full Text Available In this work, the development of a highly active noble metal phosphide (NMXPY-based hydrodesulfurization (HDS catalyst with a high hydrogenating ability for heavy oils was studied. NMXPY catalysts were obtained by reduction of P-added noble metals (NM-P, NM: Rh, Pd, Ru supported on SiO2. The order of activities for the hydrogenation of biphenyl was Rh-P > NiMoS > Pd-P > Ru-P. This order was almost the same as that of the catalytic activities for the HDS of dibenzothiophene. In the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT, the HDS activity of the Rh-P catalyst increased with increasing reaction temperature, but the maximum HDS activity for the NiMoS catalyst was observed at 270 °C. The Rh-P catalyst yielded fully hydrogenated products with high selectivity compared with the NiMoS catalyst. Furthermore, XRD analysis of the spent Rh-P catalysts revealed that the Rh2P phase possessed high sulfur tolerance and resistance to sintering.

Nickel oxide and carbon nanotube composite (NiO/CNT) as a novel cathode non-precious metal catalyst in microbial fuel cells.

Science.gov (United States)

Huang, Jianjian; Zhu, Nengwu; Yang, Tingting; Zhang, Taiping; Wu, Pingxiao; Dang, Zhi

2015-10-15

Comparing with the precious metal catalysts, non-precious metal catalysts were preferred to use in microbial fuel cells (MFCs) due to the low cost and high oxygen reduction reaction (ORR) efficiency. In this study, the transmission electron microscope and X-ray diffraction as well as Raman investigation revealed that the prepared nanoscale NiO was attached on the surface of CNT. Cyclic voltammogram and rotating ring-disk electrode tests showed that the NiO/CNT composite catalyst had an apparent oxygen reduction peak and 3.5 electron transfer pathway was acquired under oxygen atmosphere. The catalyst performance was highly dependent on the percentage of NiO in the CNT nanocomposites. When 77% NiO/CNT nano-sized composite was applied as cathode catalyst in membrane free single-chamber air cathode MFC, a maximum power density of 670 mW/m(2) and 0.772 V of OCV was obtained. Moreover, the MFC with pure NiO (control) could not achieve more than 0.1 V. All findings suggested that NiO/CNT could be a potential cathode catalyst for ORR in MFCs. Copyright © 2015 Elsevier B.V. All rights reserved.

Catalytic reforming of toluene as tar model compound: effect of Ce and Ce-Mg promoter using Ni/olivine catalyst.

Science.gov (United States)

Zhang, Ruiqin; Wang, Huajian; Hou, Xiaoxue

2014-02-01

Tar produced by biomass gasification as a route of renewable energy must be removed before the gas can be used. This study was undertaken using toluene as a model tar compound for evaluating its steam reforming conversion with three Ni-based catalysts, Ni/olivine, Ni-Ce/olivine and Ni-Ce-Mg/olivine. Effects of Ce and Mg promoters on the reaction activity and coke deposition were studied. Overall the performance of Ce and Mg promoted Ni/olivine catalysts is better than that of only Ce promoter and Ni/olivine alone. The experimental results indicate that Ni-Ce-Mg/olivine catalysts could improve the resistance to carbon deposition, enhance energy gases yield and resist 10ppm H2S poison at 100mLmin(-1) for up to 400min. Furthermore, the activity of catalysts was related to the steam/carbon (S/C) ratios; at S/C ratio=5, T=790°C, space velocity=782h(-1) and t=2h, the Ni-Ce-Mg/olivine system yielded 89% toluene conversion, 5.6Lh(-1) product gas rate, 62.6mol% H2 content and 10% (mol useful gas mol(-1) toluene) energy yield. Moreover, at low S/C ratio, it had higher reaction activity and better ability to prevent coking. There is a small amount of carbon deposition in the form of amorphous carbon after 7h. Various characterization techniques such as XRD, FTIR and thermogravimetric were performed to investigate the coke deposition of Ni/olivine, Ni-Ce/olivine and Ni-Ce-Mg/olivine. It is suggested that 3% Ni-1% Ce-1% Mg/olivine was the most promising catalyst due to its minimum coke amount and the lower activation energy of coke burning. Copyright © 2014. Published by Elsevier Ltd.

A Study of CO2 Methanation over Ni-Based Catalysts Supported by CNTs with Various Textural Characteristics

OpenAIRE

Yanyan Feng; Wen Yang; Wei Chu

2015-01-01

This work studied the influence of textural characteristics of CNTs on catalytic performance of Ni/CNTs for CO2 methanation. The CNTs supports were prepared by chemical vapor deposition method using Ni/MgO catalysts, and acetonitrile and ethanol were used as carbon sources, respectively. The Ni/CNTs catalysts were prepared via impregnation method and characterized by X-ray diffraction (XRD), N2 adsorption/desorption, and temperature-programmed reduction (H2-TPR) techniques. The results indica...

Effect of phosphorus addition on the hydrotreating activity of NiMo/Al{sub 2}O{sub 3} carbide catalyst

Energy Technology Data Exchange (ETDEWEB)

Sundaramurthy, V.; Dalai, A.K. [Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon, SK S7N 5A9 (Canada); Adjaye, J. [Syncrude Edmonton Research Centre, Edmonton, AB T6N 1H4 (Canada)

2007-07-30

A series of phosphorus promoted {gamma}-Al{sub 2}O{sub 3} supported NiMo carbide catalysts with 0-4.5 wt.% P, 13 wt.% Mo and 2.5 wt.% Ni were synthesized and characterized by elemental analysis, pulsed CO chemisorption, BET surface area measurement, X-ray diffraction, near-edge X-ray absorption fine structure, DRIFT spectroscopy of CO adsorption and H{sub 2} temperature programmed reduction. X-ray diffraction patterns and CO uptake showed the P addition to NiMo/{gamma}-Al{sub 2}O{sub 3} carbide, increased the dispersion of {beta}-Mo{sub 2}C particles. DRIFT spectra of adsorbed CO revealed that P addition to NiMo/{gamma}-Al{sub 2}O{sub 3} carbide catalyst not only increases the dispersion of Ni-Mo carbide phase, but also changes the nature of surface active sites. The hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) activities of these P promoted NiMo/{gamma}-Al{sub 2}O{sub 3} carbide catalysts were performed in trickle bed reactor using light gas oil (LGO) derived from Athabasca bitumen and model feed containing quinoline and dibenzothiophene at industrial conditions. The P added NiMo/{gamma}-Al{sub 2}O{sub 3} carbide catalysts showed enhanced HDN activity compared to the NiMo/{gamma}-Al{sub 2}O{sub 3} catalysts with both the feed stocks. The P had almost no influence on the HDS activity of NiMo/{gamma}-Al{sub 2}O{sub 3} carbide with LGO and dibenzothiophene. P addition to NiMo/{gamma}-Al{sub 2}O{sub 3} carbide accelerated C-N bond breaking and thus increased the HDN activity. (author)

Glucose- and Cellulose-Derived Ni/C-SO3H Catalysts for Liquid Phase Phenol Hydrodeoxygenation

Energy Technology Data Exchange (ETDEWEB)

Kasakov, Stanislav; Zhao, Chen; Barath, Eszter; Chase, Zizwe A.; Fulton, John L.; Camaioni, Donald M.; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A.

2015-01-19

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalyzed the reduction of phenol to cyclohexanol in water. The state of 3 – 5 nm grafted Ni particles was analyzed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt.% C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.

A possible highly active supported Ni dimer catalyst for O{sub 2} dissociation: A first-principles study

Energy Technology Data Exchange (ETDEWEB)

Dong, Shan [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Zhang, Yanxing, E-mail: 2016025@htu.edu.cn [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Zhang, Xilin; Mao, Jianjun [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Yang, Zongxian, E-mail: yzx@henannu.edu.cn [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Collaborative Innovation Center of Nano Functional Materials and Applications, Henan Province (China)

2017-04-30

Graphical abstract: The minimum energy paths (MEPs) for the dissociation process of O{sub 2} on the surfaces of bare YSZ (111) and Ni{sub n}/YSZ (111) (n = 1, 2 and 3). - Highlights: • The catalytic activity of supported metal catalysts is closely related to the size of metal particles. • The dissociation of O{sub 2} on the YSZ (111) surface is largely enhanced by the supported Ni cluster. • The supported Ni dimer is predicted to be the smallest Ni cluster needed for efficient O{sub 2} dissociation. • The results would provide an important reference to improve the activity and efficiency of the Ni/YSZ(111) nanocomposite catalysts in cost-effective materials. - Abstract: The adsorption and dissociation of O{sub 2} on the supported small nickel clusters with one-, two-, three-Ni atoms on yttria-stabilized zirconia (YSZ) (111) surfaces, as well as those on the bare YSZ(111) and Ni(111) surfaces are comparatively studied using ab initio density functional theory calculations. It is found that the dissociation of O{sub 2} on the YSZ(111) surface is largely enhanced by the supported Ni dimer, which is predicted to be the smallest Ni cluster needed for efficient O{sub 2} dissociation. The results would provide an important reference to improve the activity and efficiency of the Ni/YSZ(111) nanocomposite catalysts in cost-effective materials.

Ni/Ce-MCM-41 mesostructured catalysts for simultaneous production of hydrogen and nanocarbon via methane decomposition

Energy Technology Data Exchange (ETDEWEB)

Guevara, J.C.; Wang, J.A.; Chen, L.F.; Valenzuela, M.A. [ESIQIE, Instituto Politecnico Nacional, Col. Zacatenco, Av. Politecnico s/n, 07738 Mexico D. F. (Mexico); Salas, P. [Centro de Fisica Aplicada y Tecnologia Avanzada, Universidad Nacional Autonoma de Mexico, Apartado Postal 1-1010, Queretaro 76000 (Mexico); Garcia-Ruiz, A. [UPIICSA, Instituto Politecnico Nacional, Te 950 Col. Granjas-Mexico, 08400 Mexico D.F. (Mexico); Toledo, J.A.; Cortes-Jacome, M.A.; Angeles-Chavez, C. [Programa de Molecular Ingenieria, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, 07730 Mexico D. F. (Mexico); Novaro, O. [Instituto de Fisica, Universidad Nacional Autonoma de Mexico, A. P. 20-364, 01000 Mexico D.F. (Mexico)

2010-04-15

For the first time, simultaneous production of hydrogen and nanocarbon via catalytic decomposition of methane over Ni-loaded mesoporous Ce-MCM-41 catalysts was investigated. The catalytic performance of the Ni/Ce-MCM-41 catalysts is very stable and the reaction activity remained almost unchanged during 1400 min steam on time at temperatures 540, 560 and 580 C, respectively. The methane conversion level over these catalysts reached 60-75% with a 100% selectivity towards hydrogen. TEM observations revealed that most of the Ni particles located on the tip of the carbon nanofibers/nanotubes in the used catalysts, keeping their exposed surface clean during the test and thus remaining active for continuous reaction without obvious deactivation. Two kinds of carbon materials, graphitic carbon (C{sub g}) as major and amorphous carbon (C{sub A}) as minor were produced in the reaction, as confirmed by XRD analysis and TEM observations. Carbon nanofibers/nanotubes had an average diameter of approximately 30-50 nm and tens micrometers in length, depending on the reaction temperature, reaction time and Ni particle diameter. Four types of carbon nanofibers/nanotubes were detected and their formations greatly depend on the reaction temperature, time on steam and degree of the interaction between the metallic Ni and support. The respective mechanisms of the formation of nanocarbons were postulated and discussed. (author)

[In situ diffuse reflectance FTIR spectroscopy study of CO adsorption on Ni2P/mesoporous molecule sieve catalysts].

Science.gov (United States)

Liu, Qian-qian; Ji, Sheng-fu; Wu, Ping-yi; Hu, Lin-hua; Huang, Xiao-fan; Zhu, Ji-qin; Li, Cheng-yue

2009-05-01

Abstract The supported nickel phosphate precursors were prepared by incipient wetness impregnation using nickel nitrate as nickel source, diammonium hydrogen phosphate as phosphorus source, and MCM-41, MCM-48, SBA-15 and SBA-16 as supports, respectively. Then, the supported Ni2 P catalysts were prepared by temperature-programmed reduction in flowing Hz from their nickel phosphate precursors. The in situ diffuse reflectance FTIR spectroscopy (DRIFTS) analysis with the probe molecule CO was carried out to characterize the surface properties. The results indicated that there were significant differences in the spectral features of the samples. The upsilon(CO) absorbances observed for adsorbed CO on mesoporous molecule sieve was attributed to weak physical adsorption. There are four different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2 P/MCM-41 catalyst with the following assignments: (1) the formation of Ni(CO)4 at 2055 cm(-1). (2) CO terminally bonded to cus Ni(delta+) (0Ni+ sites at 2127 cm(-1). (4) CO terminally bonded to P and form P==C==O between 2198 and 2202 cm(-1). There are two different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2P/MCM-48, Ni2P/ SBA-15 and Ni2P/SBA-16 catalysts. The absorbance observed at 2051-2055 cm(-1) for CO adsorption on Ni2P/MCM-48, Ni2P/SBA-15 and Ni2P/SBA-16 catalysts is due to the formation of Ni(CO)4 species. The other upsilon absorbances observed at 2093-2096 cm(-1) was attributed to CO terminally bonded to cus Ni(delta+) (0

Mathematical Modelling of Catalytic Fixed-Bed Reactor for Carbon Dioxide Reforming of Methane over Rh/Al2O3 Catalyst

Directory of Open Access Journals (Sweden)

New Pei Yee

2008-04-01

Full Text Available A one-dimensional mathematical model was developed to simulate the performance of catalytic fixed bedreactor for carbon dioxide reforming of methane over Rh/Al2O3 catalyst at atmospheric pressure. The reactionsinvolved in the system are carbon dioxide reforming of methane (CORM and reverse water gas shiftreaction (RWGS. The profiles of CH4 and CO2 conversions, CO and H2 yields, molar flow rate and molefraction of all species as well as reactor temperature along the axial bed of catalyst were simulated. In addition,the effects of different reactor temperature on the reactor performance were also studied. The modelscan also be applied to analyze the performances of lab-scale micro reactor as well as pilot-plant scale reactorwith certain modifications and model verification with experimental data. © 2008 BCREC UNDIP. All rights reserved.[Received: 20 August 2008; Accepted: 25 September 2008][How to Cite: N.A.S. Amin, I. Istadi, N.P. Yee. (2008. Mathematical Modelling of Catalytic Fixed-Bed Reactor for Carbon Dioxide Reforming of Methane over Rh/Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering and Catalysis, 3 (1-3: 21-29. doi:10.9767/bcrec.3.1-3.19.21-29

Design of heterogeneous catalysts

DEFF Research Database (Denmark)

Frey, Anne Mette

was inspired by a computational screening, suggesting that alloys such as Ni-Fe, Co-Ni, and Co-Fe should show superior activity to the industrially used nickel catalyst. Especially the Ni-Fe system was considered to be interesting, since such alloy catalysts should be both more active and cheaper than the Ni...... catalyst. The results from the screening were experimentally verified for CO hydrogenation, CO2 hydrogenation, and simultaneous CO and CO2 hydrogenation by bimetallic Ni-Fe catalysts. These catalysts were found to be highly active and selective. The Co-Ni and Co-Fe systems were investigated for CO...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...

Reductive amination of ethanol to ethylamines over Ni/Al{sub 2}O{sub 3} catalysts

Energy Technology Data Exchange (ETDEWEB)

Park, Jun Hyun [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Hong, Eunpyo; An, Sang Hee; Shin, Chae-Ho; Lim, Dong-Hee [Chungbuk National University, Chungju (Korea, Republic of)

2017-10-15

Ni(x)/Al{sub 2}O{sub 3} (x=wt%) catalysts with Ni loadings of 5-25 wt% were prepared via a wet impregnation method on an γ-Al{sub 2}O{sub 3} support and subsequently applied in the reductive amination of ethanol to ethylamines. Among the various catalysts prepared, Ni(10)/Al2O3 exhibited the highest metal dispersion and the smallest Ni particle size, resulting in the highest catalytic performance. To reveal the effects of reaction parameters, a reductive amination process was performed by varying the reaction temperature (T), weight hourly space velocity (WHSV), and NH{sub 3} and H{sub 2} partial pressures in the reactions. In addition, on/off experiments for NH{sub 3} and H{sub 2} were also carried out. In the absence of NH{sub 3} in the reactant stream, the ethanol conversion and selectivities towards the different ethylamine products were significantly reduced, while the selectivity to ethylene was dominant due to the dehydration of ethanol. In contrast, in the absence of H{sub 2}, the selectivity to acetonitrile significantly increased due to dehydrogenation of the imine intermediate. Although a small amount of catalyst deactivation was observed in the conversion of ethanol up to 10 h on stream due to the formation of nickel nitride, the Ni(10)/Al{sub 2}O{sub 3} catalyst exhibited stable catalytic performance over 90 h under the optimized reaction conditions (i.e., T=190 .deg. C, WHSV=0.9 h{sup -1}, and EtOH/NH{sub 3}/H{sub 2} molar ratio=1/1/6).

Mössbauer emission study on 57Co doped carbon-supported Ni and Ni-Mo sulfide hydrotreating catalysts : the influence of phosphorus on the structure

NARCIS (Netherlands)

Crajé, M.W.J.; Beer, de V.H.J.; Kraan, van der A.M.

1991-01-01

In the present study it is demonstrated that Mössbauer emission spectroscopy (MES) can generate information on the various Ni phases present in sulfided Ni containing catalysts when a small amount of 57Co is used as a probe for Ni.Application of MES to 57Co:Ni(4.5)Mo(8.0)/C and 57Co:Ni(5.6)/C

A comparative study of alumina-supported Ni catalysts prepared by photodeposition and impregnation methods on the catalytic ozonation of 2,4-dichlorophenoxyacetic acid

International Nuclear Information System (INIS)

Rodríguez, Julia L.; Valenzuela, Miguel A.; Tiznado, Hugo; Poznyak, Tatiana; Chairez, Isaac; Magallanes, Diana

2017-01-01

The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH) 2 , NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

A comparative study of alumina-supported Ni catalysts prepared by photodeposition and impregnation methods on the catalytic ozonation of 2,4-dichlorophenoxyacetic acid

Energy Technology Data Exchange (ETDEWEB)

Rodríguez, Julia L., E-mail: ozliliana@yahoo.com.mx [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico); Valenzuela, Miguel A. [Lab.Catálisis y Materiales. ESIQIE–Instituto Politécnico Nacional. Zacatenco (Mexico); Tiznado, Hugo [Centro de Nanociencias y Nanotecnología. CNyN Universidad Nacional Autónoma de México (Mexico); Poznyak, Tatiana [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico); Chairez, Isaac [Departamento de Bioprocesos, UPIBI- Instituto Politécnico Nacional (Mexico); Magallanes, Diana [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico)

2017-02-15

The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH){sub 2}, NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

Glucose- and cellulose-derived Ni/C-SO3H catalysts for liquid phase phenol hydrodeoxygenation.

Science.gov (United States)

Kasakov, Stanislav; Zhao, Chen; Baráth, Eszter; Chase, Zizwe A; Fulton, John L; Camaioni, Donald M; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A

2015-01-19

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalysed the reduction of phenol to cyclohexanol in water. The state of 3-5 nm grafted Ni particles was analysed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in the presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt % C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NiCo as catalyst for magnetically induced dry reforming of methane

Science.gov (United States)

Varsano, F.; Bellusci, M.; Provini, A.; Petrecca, M.

2018-03-01

In this paper we report the activation of the dry reforming reaction by induction heating of a NiCo alloy. The catalyst plays a double role, serving both as a promoter for the reforming reaction and producing the heat induced by dissipation of the electromagnetic energy. The elevated temperatures imposed by the reforming reaction suggest the choice of an alloy with a Curie temperature >800°C. In this respect Ni:Co ratio 60:40 was chosen. Alloy active sites for CH4and CO2activation are created by a mechanochemical treatment of the alloy that increases solid-state defects. The catalyst has been successfully tested in a continuous-flow reactor working under atmospheric pressure. Methane conversion and hydrogen production yields have been measured as a function of the applied magnetic field, reactant flow rate and time on stream.

Synthesis of a carbon-coated NiO/MgO core/shell nanocomposite as a Pd electro-catalyst support for ethanol oxidation

International Nuclear Information System (INIS)

Mahendiran, C.; Maiyalagan, T.; Scott, K.; Gedanken, A.

2011-01-01

Highlights: → Carbon coated on NiO/MgO in a core/shell nanostructure is synthesized by RAPET. → The carbon-coated NiO/MgO is supported by Pd. → The electrocatalytic properties of the Pd/(NiO/MgO-C) catalyst for ethanol oxidation studied. - Abstract: Carbon coated on NiO/MgO in a core/shell nanostructure was synthesized by the single-step RAPET (reaction under autogenic pressure at elevated temperatures) technique, and the obtained formation mechanism of the core/shell nanocomposite was presented. The carbon-coated NiO/MgO and its supported Pd catalyst, Pd/(NiO/MgO-C), were characterized by SEM, HR-TEM, XRD and cyclic voltammetry. The X-ray diffraction patterns confirmed the face-centered cubic crystal structure of NiO/MgO. Raman spectroscopy measurements provided structural evidence for the formation of a NiO/MgO composite and the nature of the coated carbon shell. The high-resolution transmission electron microscopy images showed the core and shell morphologies individually. The electrocatalytic properties of the Pd/(NiO/MgO-C) catalyst for ethanol oxidation were investigated in an alkaline solution. The results indicated that the prepared Pd-NiO/MgO-C catalyst has excellent electrocatalytic activity and stability.

Structure and magnetic properties of Sm{sub 2}Rh{sub 3}Sn{sub 5}. An intergrowth of TiNiSi- and NdRh{sub 2}Sn{sub 4}-related slabs

Energy Technology Data Exchange (ETDEWEB)

Heying, Birgit; Koesters, Jutta; Hoffmann, Rolf-Dieter; Heletta, Lukas; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

2017-07-01

The stannide Sm{sub 2}Rh{sub 3}Sn{sub 5} was obtained by arc-melting of the elements and subsequent annealing at 1070 K in a silica tube. Sm{sub 2}Rh{sub 3}Sn{sub 5} crystallizes with the orthorhombic Y{sub 2}Rh{sub 3}Sn{sub 5} type structure, space group Cmc2{sub 1}, Z=4: a=444.46(8), b=2636.2(4), c=718.3(1) pm, wR=0.0711, 1761 F{sup 2} values and 61 variables. The three crystallographically independent rhodium atoms show tricapped trigonal prismatic coordination by samarium and tin atoms. Sm{sub 2}Rh{sub 3}Sn{sub 5} can be considered as a simple 1:1 intergrowth structure of TiNiSi- and NdRh{sub 2}Sn{sub 4}-related slabs of compositions SmRhSn and SmRh{sub 2}Sn{sub 4}. Temperature dependent magnetic susceptibility data revealed van Vleck type behavior caused by the proximity of the exited {sup 6}H{sub 7/2} state to the {sup 6}H{sub 5/2} ground state of Sm{sup 3+}, and an antiferromagnetic ordering occurs at T{sub N}=3.5(5) K.

Hydrogenation of toluene on Ni-Co-Mo supported zeolite catalysts ...

African Journals Online (AJOL)

-a, HY-b and Mordenite were prepared and characterized using many techniques for use as hydrotreating catalysts. In a preliminary investigation, toluene was employed as model compound to test the catalysts in hydrogenation, as a major ...

Design of bimetal catalysts Pt-Ni/CeO_2-1D for generation of H_2 by the reforming reaction of methanol

International Nuclear Information System (INIS)

Sarmiento F, I.

2016-01-01

CeO_2 nano rods were synthesized by hydrothermal method and were used as support for preparing catalysts bimetallic Pt Ni / CeO_2-1D. The catalysts were prepared by classical impregnation by the conventional wet method. The prepared catalysts are Pt (0.5 %) - Ni (5 %) / CeO_2 and Pt (0.5 %) - Ni (15 %) / CeO_2, which were characterized by different physico-chemical techniques: Bet, Sem, TPR and XRD, that were evaluated in the Auto thermal Steam reforming of Methanol for H_2 production. The Bet surface area results, show that the surface area of the catalysts decreases as the nominal load of Ni in the catalyst, increases. Sem shows, that the catalyst support (CeO_2-1D) and the bimetallic catalysts are conformed by nano rods. By XRD were identified the crystalline phases present, in the catalytic material: cerianite distinctive phase of cerium oxide and metallic Ni; however it was not possible to observe diffraction peaks of Platinum using this technique. The temperature-programmed reduction (TPR) analysis allowed to obtain the reduction profiles, of the different species present on the catalysts. The catalytic activity tests carried out, showed that the catalysts total 100% methanol conversion is achieved at 300 degrees Celsius, making them excellent, to be used in reactions at low temperature conditions. Selectivity towards H_2, is very similar in both catalysts, and it reaches a 50% yield per mole of methanol fed stoichiometrically. (Author)

One-Step Condensation and Hydrogenation of Furfural-Acetone Using Mixed and Single Catalyst Based on Ni/M-Oxide [M=Al; Mg

Science.gov (United States)

Ulfa, S. M.; Pramesti, I. N.; Mustafidah, H.

2018-01-01

Modification of furfural by condensation and hydrogenation reaction is a promising approach to produce higher alkane derivatives (C8-C13) as diesel fraction. This research investigated the catalytic activity of Ni/MgO as bifunctional catalyst compared with MgO-Ni/Al2O3 mixed catalyst for condensation-hydrogenation reaction. The Ni/MgO and Ni/Al2O3 with 20% Ni loading were prepared by wet impregnation methods using Ni(NO3)2.6H2O salt, calcined and reduced at 500°C. The catalyst performance was tested for one-step condensation-hydrogenation reaction using autoclave oil batch reactor. The reaction was conducted by reacting furfural and acetone in 1:1 ratio using water as solvent. Condensation reaction was performed at 100°C for 8 hours, followed by hydrogenation at 120°C during 7 hours. Analysis by gas chromatography showed that C=C double bond of furfurylidene acetone were successfully hydrogenated. Using Ni/MgO catalyst at 120°C, the products were identified as 1,5-bis-(2-furanyl)-1,4-penta-1-ene-3-one (2.68%) and 1,5-bis-(2-furanyl)-1,4-pentan-3-one (trace amount). On the other hand, reaction using mixed catalyst, MgO-Ni/Al2O3 showed better activity over bifunctional Ni/MgO at the same reaction temperature. The products were identified as 4-(2-furanyl)-3-butan-2-one (27.30%); 1,5-bis-(2-furanyl)-1,4-penta-1-ene-3-one (3.82%) and 1,5-bis-(2-furanyl)-1,4-pentan-3-one (1.11%). The impregnation of Ni on MgO decrease the physical properties of catalyst, confirmed by surface area analysis (SAA).

Ni-M-O (M=Sn, Ti and W) catalysts prepared from dry mixing method for oxidative dehydrogenation of ethane

KAUST Repository

Zhu, Haibo; Rosenfeld, Devon C.; Harb, Moussab; Anjum, Dalaver H.; Hedhili, Mohamed N.; Ould-Chikh, Samy; Basset, Jean-Marie

2016-01-01

A new generation of Ni-Sn-O, Ni-Ti-O, and Ni-W-O catalysts has been prepared by a solid state grinding method. In each case the doping metal varied from 2.5% to 20%. These catalysts exhibited higher activity and selectivity for ethane oxidative dehydrogenation (ODH) than conventionally prepared mixed oxides. Detailed characterisation was achieved using XRD, N2 adsorption, H2-TPR, SEM, TEM, and HAADF-STEM in order to study the detailed atomic structure and textural properties of the synthesized catalysts. Two kinds of typical structures are found in these mixed oxides, which are (major) “NixMyO” (M = Sn, Ti or W) solid solution phases (NiO crystalline structure with doping atom incorporated in the lattice) and (minor) secondary phases (SnO2, TiO2 or WO3). The secondary phase exists as a thin layer around small “NixMyO” particles, lowering the aggregation of nanoparticles during the synthesis. DFT calculations on the formation energies of M-doped NiO structures (M = Sn, Ti, W) clearly confirm the thermodynamic feasibility of incorporating these doping metals into NiO struture. The incorporation of doping metals into the NiO lattice decreases the number of holes (h+) localized on lattice oxygen (O2- + h+ ➔ O●-), which is the main reason for the improved catalytic performance (O●- is known to favor complete ethane oxidation to CO2). The high efficiency of ethylene production achieved in these particularly prepared mixed oxide catalysts indicates that the solid grinding method could serve as a general and practical approach for the preparation of doped NiO based catalysts.

Ni-M-O (M=Sn, Ti and W) catalysts prepared from dry mixing method for oxidative dehydrogenation of ethane

KAUST Repository

Zhu, Haibo

2016-03-25

A new generation of Ni-Sn-O, Ni-Ti-O, and Ni-W-O catalysts has been prepared by a solid state grinding method. In each case the doping metal varied from 2.5% to 20%. These catalysts exhibited higher activity and selectivity for ethane oxidative dehydrogenation (ODH) than conventionally prepared mixed oxides. Detailed characterisation was achieved using XRD, N2 adsorption, H2-TPR, SEM, TEM, and HAADF-STEM in order to study the detailed atomic structure and textural properties of the synthesized catalysts. Two kinds of typical structures are found in these mixed oxides, which are (major) “NixMyO” (M = Sn, Ti or W) solid solution phases (NiO crystalline structure with doping atom incorporated in the lattice) and (minor) secondary phases (SnO2, TiO2 or WO3). The secondary phase exists as a thin layer around small “NixMyO” particles, lowering the aggregation of nanoparticles during the synthesis. DFT calculations on the formation energies of M-doped NiO structures (M = Sn, Ti, W) clearly confirm the thermodynamic feasibility of incorporating these doping metals into NiO struture. The incorporation of doping metals into the NiO lattice decreases the number of holes (h+) localized on lattice oxygen (O2- + h+ ➔ O●-), which is the main reason for the improved catalytic performance (O●- is known to favor complete ethane oxidation to CO2). The high efficiency of ethylene production achieved in these particularly prepared mixed oxide catalysts indicates that the solid grinding method could serve as a general and practical approach for the preparation of doped NiO based catalysts.

Catalytic Hydrogenation of Levulinic Acid in Water into g-Valerolactone over Bulk Structure of Inexpensive Intermetallic Ni-Sn Alloy Catalysts

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Rodiansono Rodiansono

2015-07-01

Full Text Available A bulk structure of inexpensive intermetallic nickel-tin (Ni-Sn alloys catalysts demonstrated highly selective in the hydrogenation of levulinic acid in water into g-valerolactone. The intermetallic Ni-Sn catalysts were synthesized via a very simple thermochemical method from non-organometallic precursor at low temperature followed by hydrogen treatment at 673 K for 90 min. The molar ratio of nickel salt and tin salt was varied to obtain the corresponding Ni/Sn ratio of 4.0, 3.0, 2.0, 1.5, and 0.75. The formation of Ni-Sn alloy species was mainly depended on the composition and temperature of H2 treatment. Intermetallics Ni-Sn that contain Ni3Sn, Ni3Sn2, and Ni3Sn4 alloy phases are known to be effective heterogeneous catalysts for levulinic acid hydrogenation giving very excellence g-valerolactone yield of >99% at 433 K, initial H2 pressure of 4.0 MPa within 6 h. The effective hydrogenation was obtained in H2O without the formation of by-product. Intermetallic Ni-Sn(1.5 that contains Ni3Sn2 alloy species demonstrated very stable and reusable catalyst without any significant loss of its selectivity. © 2015 BCREC UNDIP. All rights reserved. Received: 26th February 2015; Revised: 16th April 2015; Accepted: 22nd April 2015  How to Cite: Rodiansono, R., Astuti, M.D., Ghofur, A., Sembiring, K.C. (2015. Catalytic Hydrogenation of Levulinic Acid in Water into g-Valerolactone over Bulk Structure of Inexpensive Intermetallic Ni-Sn Alloy Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 192-200. (doi:10.9767/bcrec.10.2.8284.192-200Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.8284.192-200  

Design of ultrathin Pt-Mo-Ni nanowire catalysts for ethanol electrooxidation.

Science.gov (United States)

Mao, Junjie; Chen, Wenxing; He, Dongsheng; Wan, Jiawei; Pei, Jiajing; Dong, Juncai; Wang, Yu; An, Pengfei; Jin, Zhao; Xing, Wei; Tang, Haolin; Zhuang, Zhongbin; Liang, Xin; Huang, Yu; Zhou, Gang; Wang, Leyu; Wang, Dingsheng; Li, Yadong

2017-08-01

Developing cost-effective, active, and durable electrocatalysts is one of the most important issues for the commercialization of fuel cells. Ultrathin Pt-Mo-Ni nanowires (NWs) with a diameter of ~2.5 nm and lengths of up to several micrometers were synthesized via a H 2 -assisted solution route (HASR). This catalyst was designed on the basis of the following three points: (i) ultrathin NWs with high numbers of surface atoms can increase the atomic efficiency of Pt and thus decrease the catalyst cost; (ii) the incorporation of Ni can isolate Pt atoms on the surface and produce surface defects, leading to high catalytic activity (the unique structure and superior activity were confirmed by spherical aberration-corrected electron microscopy measurements and ethanol oxidation tests, respectively); and (iii) the incorporation of Mo can stabilize both Ni and Pt atoms, leading to high catalytic stability, which was confirmed by experiments and density functional theory calculations. Furthermore, the developed HASR strategy can be extended to synthesize a series of Pt-Mo-M (M = Fe, Co, Mn, Ru, etc.) NWs. These multimetallic NWs would open up new opportunities for practical fuel cell applications.

Selective Ring Opening of 1-Methylnaphthalene Over NiW-Supported Catalyst Using Dealuminated Beta Zeolite.

Science.gov (United States)

Kim, Eun-Sang; Lee, You-Jin; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

2016-02-01

Nanoporous Beta zeolite was dealuminated by weak acid treatment for reducing the acidity. Bi-functional catalysts were prepared using commercial Beta zeolites and the dealuminated zeolites for acidic function, NiW for metallic function. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction has been investigated using the prepared bi-functional catalysts with different acidity in fixed bed reaction system. The dealuminated Beta zeolites, which crystal structure and nanoporosity were maintained, showed the higher SiO2/Al2O3 ratio and smaller acidity than their original zeolite. NiW-supported catalyst using the dealuminated Beta zeolite with SiO2/Al203 mole ratio of 55 showed the highest performance for the selective ring opening. The acidity of catalyst seemed to play an important role as active sites for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. The acidity of Beta zeolite could be controlled by the acid treatment and the catalyst with the optimum acidity for the selective ring opening could be prepared.

Development of Ni-Based Catalysts Derived from Hydrotalcite-Like Compounds Precursors for Synthesis Gas Production via Methane or Ethanol Reforming

Directory of Open Access Journals (Sweden)

Ya-Li Du

2017-02-01

Full Text Available As a favorably clean fuel, syngas (synthesis gas production has been the focus of concern in past decades. Substantial literatures reported the syngas production by various catalytic reforming reactions particularly in methane or ethanol reforming. Among the developed catalysts in these reforming processes, Ni-based catalysts from hydrotalcite-like compounds (HTLcs precursors have drawn considerable attention for their preferable structural traits. This review covers the recent literature reporting syngas production with Ni-based catalysts from HTLc precursors via methane or ethanol reforming. The discussion was initiated with catalyst preparation (including conventional and novel means, followed by subsequent thermal treatment processes, then composition design and the addition of promoters in these catalysts. As Ni-based catalysts have thermodynamic potential to deactivate because of carbon deposition or metal sintering, measures for dealing with these problems were finally summarized. To obtain optimal catalytic performances and resultantly better syngas production, based on analyzing the achievements of the references, some perspectives were finally proposed.

Development of Sulfur and Carbon Tolerant Reforming Alloy Catalysts Aided Fundamental Atomistic Insights

Energy Technology Data Exchange (ETDEWEB)

Suljo Linic

2008-12-31

Current hydrocarbon reforming catalysts suffer from rapid carbon and sulfur poisoning. Even though there is a tremendous incentive to develop more efficient catalysts, these materials are currently formulated using inefficient trial and error experimental approaches. We have utilized a hybrid experimental/theoretical approach, combining quantum Density Functional Theory (DFT) calculations and various state-of-the-art experimental tools, to formulate carbon tolerant reforming catalysts. We have employed DFT calculations to develop molecular insights into the elementary chemical transformations that lead to carbon poisoning of Ni catalysts. Based on the obtained molecular insights, we have identified, using DFT quantum calculation, various Ni alloy catalysts as potential carbon tolerant reforming catalysts. The alloy catalysts were synthesized and tested in steam reforming and partial oxidation of methane, propane, and isooctane. We demonstrated that the alloy catalysts are much more carbon-tolerant than monometallic Ni catalysts under nearly stoichiometric steam-to-carbon ratios. Under these conditions, monometallic Ni is rapidly poisoned by sp2 carbon deposits. The research approach is distinguished by two characteristics: (a) knowledge-based, bottomup approach, compared to the traditional trial and error approach, allows for a more efficient and systematic discovery of improved catalysts. (b) the focus is on exploring alloy materials which have been largely unexplored as potential reforming catalysts.

Synthesis and characterization of NiFe{sub 2}O{sub 4}–Pd magnetically recyclable catalyst for hydrogenation reaction

Energy Technology Data Exchange (ETDEWEB)

Karaoğlu, E., E-mail: ekaraoglu@fatih.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Fatih University, 34500 B. Cekmece, Istanbul (Turkey); Özel, U.; Caner, C.; Baykal, A.; Summak, M.M. [Department of Chemistry, Faculty of Arts and Sciences, Fatih University, 34500 B. Cekmece, Istanbul (Turkey); Sözeri, H. [TUBITAK-UME, National Metrology Institute, PO Box 54, 41470 Gebze-Kocaeli (Turkey)

2012-12-15

Graphical abstract: Display Omitted Highlights: ► Novel superparamagnetic NiFe{sub 2}O{sub 4}–Pd magnetically recyclable catalyst was fabricated through co-precipitation. ► It could be reused several times without significant loss in catalytic activity for hydrogenation reaction. ► No further modification of the NiFe{sub 2}O{sub 4}–Pd magnetically recyclable catalyst is necessary for utilization as catalyst. -- Abstract: Herein we report the fabrication and characterization magnetically recyclable catalysts of NiFe{sub 2}O{sub 4}–Pd nanocomposite as highly effective catalysts for reduction reactions in liquid phase. The reduction Pd{sup 2+} was accomplished with polyethylene glycol 400 (PEG-400) instead of sodium borohydride (NaBH{sub 4}) and NiFe{sub 2}O{sub 4} nanoparticles was prepared by sonochemically using FeCI{sub 3}·6H{sub 2}O and NiCl{sub 2}. The chemical characterization of the product was done with X-ray diffractometry, Infrared spectroscopy, transmission electron microscopy, UV–Vis spectroscopy, thermal gravimetry and inductively coupled plasma. Thus formed NiFe{sub 2}O{sub 4}–Pd MRCs showed a very high activity in reduction reactions of 4-nitro aniline and 1,3-dinitrobenzene in liquid phase. It was found out that the catalytic activity of NiFe{sub 2}O{sub 4}–Pd MRCs on the reduction of 4-nitro aniline and 1,3-dinitrobenzene in liquid phase are between 99–93% and 98–93%, respectively. Magnetic character of this system allowed recovery and multiple use without significant loss of its catalytic activity. It is found that NiFe{sub 2}O{sub 4}–Pd MRCs showed very efficient catalytic activity and multiple usability.

Catalytic hydrotreatment of fast pyrolysis oil using bimetallic Ni-Cu catalysts on various supports

NARCIS (Netherlands)

Ardiyanti, A. R.; Khromova, S. A.; Venderbosch, R. H.; Yakovlev, V. A.; Melian-Cabrera, I. V.; Heeres, H. J.

2012-01-01

Bimetallic Ni-Cu catalysts on various Supports (CeO2-ZrO2, ZrO2, SiO2, TiO2, rice husk carbon, and Sibunite) with metal contents ranging from 7.5 to 9.0 (Ni) and 3.1-3.6 wt.% (Cu) for the inorganic supports and 17.1-17.8 (Ni) and 7.1-7.8 (Cu) for the carbon supports were synthesised and screened for

High performance Pd–Rh/YBaCo4O7/γ-Al2O3 three-way catalysts for gasoil engine

Directory of Open Access Journals (Sweden)

Brou Albert Kouadio

2017-11-01

Full Text Available The evaluation of catalytic activity for Rh–Pd/YBa(Co1−xMx4O7/γ-Al2O3 (M = Al, Ce, Zr, and La showed that the efficiency of NOx reduction depends strongly on the nature of the OSMs. Among a series of oxygen storage materials, YBa(Co1−xMx4O7 (M = Ce, Zr, La, Ga and In studied for catalyst enhancement, only the catalyst with YBa(Co0.9Ce0.14O7 has better conversion efficiency respectively (85% of NO, 96% of CO and 92% of HC. After treatment at 1000 °C for 3 h, these fresh catalysts showed a substantial decrease of their catalytic activities, only Rh–Pd/YBa(Co0.9Ce0.14O7/γ-Al2O3 retains its high catalytic activity. Keywords: Chemical synthesis, X-ray diffraction, Oxygen storage and catalytic activity

Experimental investigation of air relative humidity (RH) cycling tests on MEA/cell aging in PEMFC. Pt. I. Study of high RH cycling test with air RH at 62%/100%

Energy Technology Data Exchange (ETDEWEB)

Huang, B.T.; Chatillon, Y.; Bonnet, C.; Lapicque, F. [Laboratoire Reactions et Genie des Procedes, CNRS-Nancy University, Nancy (France); Leclerc, S. [Laboratoire d' Energetique et de Mecanique Theorique et Appliquee, CNRS-Nancy University, Vandoeuvre-les-Nancy (France); Hinaje, M.; Rael, S. [Groupe de Recherche en Electrotechnique et Electronique de Nancy, CNRS-Nancy University, Vandoeuvre-les-Nancy (France)

2012-06-15

The effect of high air relative humidity (RH) cycling (RH{sub C} 62%/100%) on the degradation mechanisms of a single (5 x 5 cm{sup 2}) proton exchange membrane fuel cells was investigated. The cell performance was compared to a cell operated at constant humidification (RH{sub C} = 62%). Runs were conducted over approximately 1,500 h at 0.3 A cm{sup -2}. The overall loss in cell performance for the high RH cycling test was 12 {mu}V h{sup -1} whereas it was at 3 {mu}V h{sup -1} under constant humidification. Impedance spectroscopy reveals that the ohmic and charge transfer resistances were little modified in both runs. H{sub 2} crossover measurement indicated that both high RH cycling and constant RH test did not promote serious effect on gas permeability. The electroactive surface loss for anode and cathode during high air RH cycling was more significant than at constant RH operation. The water uptake determined by {sup 1}H nuclear magnetic resonance within the membrane electrode assembly (MEA) after high RH cycling was reduced by 12% in comparison with a fresh MEA. Transmission electron microscopy showed bubbles and pinholes formation in the membrane, catalyst particles agglomeration (also observed by X-ray diffraction), catalyst particles migration in the membrane and thickness reduction of the catalytic layers. Scanning electron microscopy was conducted to observe the changes in morphology of gas diffusion layers after the runs. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Co-catalytic effect of Ni in the methanol electro-oxidation on Pt-Ru/C catalyst for direct methanol fuel cell

International Nuclear Information System (INIS)

Wang, Z.B.; Yin, G.P.; Zhang, J.; Sun, Y.C.; Shi, P.F.

2006-01-01

This research is aimed to improve the utilization and activity of anodic catalysts, thus to lower the contents of noble metals loading in anodes for methanol electro-oxidation. The direct methanol fuel cell anodic catalysts, Pt-Ru-Ni/C and Pt-Ru/C, were prepared by chemical reduction method. Their performances were tested by using a glassy carbon working electrode through cyclic voltammetric curves, chronoamperometric curves and half-cell measurement in a solution of 0.5 mol/L CH 3 OH and 0.5 mol/L H 2 SO 4 . The composition of the Pt-Ru-Ni and Pt-Ru surface particles were determined by EDAX analysis. The particle size and lattice parameter of the catalysts were determined by means of X-ray diffraction (XRD). XRD analysis showed that both of the catalysts exhibited face-centered cubic structures and had smaller lattice parameters than Pt-alone catalyst. Their sizes are small, about 4.5 nm. No significant differences in the methanol electro-oxidation on both electrodes were found by using cyclic voltammetry, especially regarding the onset potential for methanol electro-oxidation. The electrochemically active-specific areas of the Pt-Ru-Ni/C and Pt-Ru/C catalysts are almost the same. But, the catalytic activity of the Pt-Ru-Ni/C catalyst is higher for methanol electro-oxidation than that of the Pt-Ru/C catalyst. Its tolerance performance to CO formed as one of the intermediates of methanol electro-oxidation is better than that of the Pt-Ru/C catalyst

OXIDATIVE-REFORMING OF METHANE AND PARTIAL OXIDATION OF METHANE REACTIONS OVER NiO/PrO2/ZrO2 CATALYSTS: EFFECT OF NICKEL CONTENT

Directory of Open Access Journals (Sweden)

Y. J. O. Asencios

Full Text Available Abstract In this work the behavior of NiO-PrO2-ZrO2 catalysts containing various nickel loadings was evaluated in the partial oxidation of methane and oxidative-reforming reactions of methane. The catalysts were characterized by X-Ray Diffraction Analysis (in situ-XRD, Temperature Programmed Reduction (H2-TPR, Scanning Electron Microscopy (SEM/EDX and Adsorption-Desorption of nitrogen (BET area. The reactions were carried out at 750 °C and 1 atm for 5 hours. The catalysts were studied with different nickel content: 0, 5, 10 and 15% (related to total weight of catalyst, wt%. In both reactions, the catalyst containing the mixture of the three oxides (NiO/PrO2/ZrO2 with 15% nickel (15NiPrZr catalyst showed the best activity for the conversion of the reactants into Syngas and showed high selectivity for H2 and CO. The results suggest that the promoter PrO2 and the Niº centers are in a good proportion in the catalyst with 15% Ni. Our results showed that low nickel concentrations in the catalyst led to high metallic dispersion; however, very low nickel concentrations did not favor the methane transformation into Syngas. The catalyst containing only NiO/ZrO2 in the mixture was not sufficient for the catalysis. The presence of the promoter PrO2 was very important for the catalysis of the POM.

Hydrocracking of Cerbera manghas Oil with Co-Ni/HZSM-5 as Double Promoted Catalyst

Directory of Open Access Journals (Sweden)

Lenny Marlinda

2017-05-01

Full Text Available The effect of various reaction temperature on the hydrocracking of Cerbera manghas oil to produce a paraffin-rich mixture of hydrocarbons with Co-Ni/HZSM-5 as doubled promoted catalyst were studied. The Co-Ni/HZSM-5 catalyst with various metal loading and metal ratio was prepared by incipient wetness impregnation. The catalysts were characterized by XRD, AAS, and N2 adsorption-desorption. Surface area, pore diameter, and pore volume of catalysts decreased with the increasing of metals loading. The hydrocracking process was conducted under hydrogen initial pressure in batch reactor equipped with a mechanical stirrer. The reaction was carried out at a temperature of 300-375 oC for 2 h.  Depending on the experimental condition, the reaction pressure changed between 10 bar and 15 bar.   Several parameters were used to evaluate biofuel produced, including oxygen removal, hydrocarbon composition and gasoline/kerosene/diesel yields. Biofuel was analyzed by Fourier Transform Infrared Spectroscopic (FTIR and gas chromatography-mass spectrometry (GC-MS. The composition of hydrocarbon compounds in liquid products was similar to the compounds in the gasoil sold in unit of Pertamina Gas Stations, namely pentadecane, hexadecane, heptadecane, octadecane, and nonadecane with different amounts for each biofuel produced at different reaction temperatures. However, isoparaffin compounds were not formed at all operating conditions. Pentadecane (n-C15 and heptadecane (n-C17 were the most abundant composition in gasoil when Co-Ni/HZSM-5 catalyst was used. Cerbera Manghas oil can be recommended as the source of non-edible vegetable oil to produce gasoil as an environmentally friendly transportation fuel. Copyright © 2017 BCREC Group. All rights reserved Received: 20th May 2016; Revised: 30th January 2017; Accepted: 10th February 2017 How to Cite: Marlinda, L., Al-Muttaqii, M., Gunardi, I., Roesyadi, A., Prajitno, D.H. (2017. Hydrocracking of Cerbera manghas Oil

Adsorption of Rh(III) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion-exchange resin Diaion WA21J

International Nuclear Information System (INIS)

Shen Shaobo; Pan Tonglin; Liu Xinqiang; Yuan Lei; Wang Jinchao; Zhang Yongjian; Guo Zhanchen

2010-01-01

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Rh(III) ions contained in the chloride solutions obtained, thermodynamic and kinetics studies for adsorption of Rh(III) complexes from the chloride solutions on an anionic exchange resin Diaion WA21J were carried out. Rh, Pd, Pt, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The distribution coefficients (K d ) of Rh(III) decreased with the increase in initial Rh(III) concentration or in adsorption temperature. The isothermal adsorption of Rh(III) was found to fit Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The maximum monolayer adsorption capacities Q max based on Langmuir adsorption isotherms were 6.39, 6.61 and 5.81 mg/g for temperatures 18, 28 and 40 deg. C, respectively. The apparent adsorption energy of Rh was about -7.6 kJ/mol and thus Rh(III) adsorption was a physical type. The experimental data obtained could be better simulated by pseudo-first-order kinetic model and the activation energy obtained was 6.54 J/mol. The adsorption rate of Rh(III) was controlled by intraparticle diffusion in most of time of adsorption process.

Preparation and characterization of Ni based on natural zeolite catalyst for citronellol conversion to 3,7-Dimethyl-1-Octanol

Science.gov (United States)

Sudiyarmanto, Hidayati, Luthfiana N.; Kristiani, Anis; Ghaisani, Almira; Sukandar, Dede; Adilina, Indri B.; Tursiloadi, Silvester

2017-11-01

Citronella oil is a kind of essential oil that contains three main components, namely citronellal, citronellol, and geraniol. The high demand of citronellal and geraniol derivative prompted scientists to develop methods which are stereo-selective synthesis. A hydrogenation reaction using heterogeneous catalyst is one way of synthesis of citronella oil derivatives. In this research, synthesis of citronellol oil derivatives using Ni based on natural zeolite (Ni/ZAB) catalyst which is expected to produce the compound of 3,7-dimethyl-1-octanol. The catalyst was prepared by supporting Ni on natural zeolite by impregnation method. The physical and chemical properties of Ni/ZAB catalyst have been characterized by TGA, BET, XRD and FTIR instrumentations. Variation of pressure and temperature reactions were conducted to determine the optimum conditions for the hydrogenation of citronellol. The products from this reaction were analyzed using GC-MS instrumentation. The yield and selectivity of 3,7-dimethyl-1-octanol compound were achieved with optimum conditions at 200°C and 20 bar during 3 hours which produced around 51.97% and 47.81% respectively.

Hydrogen production from steam reforming of ethanol over Ni/MgO-CeO_2 catalyst at low temperature

Institute of Scientific and Technical Information of China (English)

石秋杰; 刘承伟; 谌伟庆

2009-01-01

MgO,CeO2 and MgO-CeO2 with different mole ratio of Mg:Ce were prepared by solid-phase burning method.Catalysts Ni/MgO,Ni/CeO2 and Ni/MgO-CeO2 were prepared by impregnation method.The catalytic properties were evaluated in ethanol steam reforming(ESR) reaction.Specific surface areas of the supports were measured by nitrogen adsorption-desorption at 77 K,and the catalysts were characterized with X-ray diffraction(XRD),temperature programmed reduction(TPR) and thermogravimetric(TG).The results showed that well...

Catalyst effects of fabrication of carbon nanotubes synthesized by chemical vapor deposition

International Nuclear Information System (INIS)

Tian, F.; Li, H.P.; Zhao, N.Q.; He, C.N.

2009-01-01

Catalytic effects of the fabrication of carbon nanotubes (CNTs) by chemical vapor deposition of methane were investigated by thermogravimetric analysis. More specifically, the total yield and thermal stability characteristics of the product were examined with respect to physicochemical characteristics of the catalyst. Three kinds of Ni/Al catalysts with 5 wt%, 10 wt% and 15 wt% Ni, respectively were employed to synthesize CNTs. It was determined that an optimal Ni content of the catalyst resulted in maximum yield and most stable product. With increasing the Ni content, the CNT yield increased but they became less stable during heat treatment in air. According to transmission electron microscopy observations, the defect sites along the walls and at the ends of the raw CNTs facilitated the thermal oxidative destruction of the CNTs.

TiO2 Nanotubes Supported NiW Hydrodesulphurization Catalysts: Characterization and Activity

Czech Academy of Sciences Publication Activity Database

Palcheva, R.; Dimitrov, L.; Tyuliev, G.; Spojakina, A.; Jirátová, Květa

2013-01-01

Roč. 265, JAN 15 (2013), s. 309-313 ISSN 0169-4332 Institutional support: RVO:67985858 Keywords : nano-structured TiO2 * NiW catalysts * XPS Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.538, year: 2013

The Effect of Surface Site Ensembles on the Activity and Selectivity of Ethanol Electrooxidation by Octahedral PtNiRh Nanoparticles.

Science.gov (United States)

Erini, Nina; Beermann, Vera; Gocyla, Martin; Gliech, Manuel; Heggen, Marc; Dunin-Borkowski, Rafal E; Strasser, Peter

2017-06-01

Direct ethanol fuel cells are attractive power sources based on a biorenewable, high energy-density fuel. Their efficiency is limited by the lack of active anode materials which catalyze the breaking of the C-C bond coupled to the 12-electron oxidation to CO 2 . We report shape-controlled PtNiRh octahedral ethanol oxidation electrocatalysts with excellent activity and previously unachieved low onset potentials as low as 0.1 V vs. RHE, while being highly selective to complete oxidation to CO 2 . Our comprehensive characterization and in situ electrochemical ATR studies suggest that the formation of a ternary surface site ensemble around the octahedral Pt 3 Ni 1 Rh x nanoparticles plays a crucial mechanistic role for this behavior. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supported Rh-phosphine complex catalysts for continuous gas-phase decarbonylation of aldehydes

DEFF Research Database (Denmark)

Malcho, Phillip; Garcia-Suarez, Eduardo J.; Mentzel, Uffe Vie

2014-01-01

Heterogeneous silica supported rhodium-phosphine complex catalysts are employed for the first time in the catalytic decarbonylation of aldehydes in continuous gas-phase. The reaction protocol is exemplified for the decarbonylation of p-tolualdehyde to toluene and further extended to other aromatic...

Bio-dissolution of Ni, V and Mo from spent petroleum catalyst using iron oxidizing bacteria.

Science.gov (United States)

Pradhan, Debabrata; Kim, Dong J; Roychaudhury, Gautam; Lee, Seoung W

2010-01-01

Bioleaching studies of spent petroleum catalyst containing Ni, V and Mo were carried out using iron oxidizing bacteria. Various leaching parameters such as Fe(II) concentration, pulp density, pH, temperature and particle size were studied to evaluate their effects on the leaching efficiency as well as the kinetics of dissolution. The percentage of leaching of Ni and V were higher than Mo. The leaching process followed a diffusion controlled model and the product layer was observed to be impervious due to formation of ammonium jarosite (NH(4))Fe(3)(SO(4))(2)(OH)(6). Apart from this, the lower leaching efficiency of Mo was due to a hydrophobic coating of elemental sulfur over Mo matrix in the spent catalyst. The diffusivities of the attacking species for Ni, V and Mo were also calculated.

Effect of Nano-Ni Catalyst on the Growth and Characterization of Diamond Films by HFCVD

Directory of Open Access Journals (Sweden)

Chien-Chung Teng

2010-01-01

Full Text Available Four different catalysts, nanodiamond seed, nano-Ni, diamond powder, and mixture of nano-Ni/diamond powder, were used to activate Si wafers for diamond film growth by hot-filament CVD (HFCVD. Diamond crystals were shown to grow directly on both large diamond powder and small nanodiamond seed, but a better crystallinity of diamond film was observed on the ultrasonicated nanodiamond seeded Si substrate. On the other hand, nano-Ni nanocatalysts seem to promote the formation of amorphous carbon but suppress transpolyacetylene (t-PA phases at the initial growth of diamond films. The subsequent nucleation and growth of diamond crystals on the amorphous carbon layer leads to generation of the spherical diamond particles and clusters prior to coalescence into continuous diamond films based on the CH3 addition mechanism as characterized by XRD, Raman, ATR/FT-IR, XPS, TEM, SEM, and AFM techniques. Moreover, a 36% reduction in surface roughness of diamond film assisted by nano-Ni catalyst is quite significant.

Hydrodesulfurization of Iraqi Atmospheric Gasoil by Ti-Ni-Mo/γ-Al2O3 Prepared Catalyst

Directory of Open Access Journals (Sweden)

Abdul Halim Abdul Karim Mohammed

2017-11-01

Full Text Available This study investigates the improvement of Iraqi atmospheric gas oil characteristics which contains 1.402 wt. % sulfur content and 16.88 wt. % aromatic content supplied from Al-Dura Refinery by using hydrodesulfurization (HDS process using Ti-Ni-Mo/γ-Al2O3 prepared catalyst in order to achieve low sulfur and aromatic saturation gas oil. Hydrodearomatization (HDA occurs simultaneously with hydrodesulfurization (HDS process. The effect of titanium on the conventional catalyst Ni-Mo/γ-Al2O3 was investigated by physical adsorption and catalytic activity test.Ti-Ni-Mo/γ-Al2O3 catalyst was prepared under vacuum impregnation condition to ensure efficient precipitation of metals within the carrier γ-Al2O3. The loading percentage of metals as oxide; titanium oxide 3 wt. %, nickel oxide 5 wt. % and molybdenum oxide 12 wt. %. The performance of the synthesized catalyst for removing sulfur and aromatic saturation were tested at various temperatures 275 to 350°C, LHSV 1 to 4h-1, constant pressure 40 bar and H2/HC ratio 500 ml/ml.Results showed that the sulfur and aromatic content were reduced at all operating conditions. Maximum sulfur removal was 75.52 wt. % in gas oil on Ti-Ni-Mo/γ-Al2O3 at temperature 350˚C, LHSV 1h-1, while minimum aromatic content achieved was 15.6 wt. % at the same conditions.

Synergetic effects leading to coke-resistant NiCo bimetallic catalysts for dry reforming of methane

KAUST Repository

Li, Lidong

2015-01-08

A new dry reforming of methane catalyst comprised of NiCo bimetallic nanoparticles and a Mgx(Al)O support that exhibits high coke resistance and long-term on-stream stability is reported. The structural characterization by XRD, TEM, temperature-programmed reduction, and BET analysis demonstrates that the excellent performance of this catalyst is ascribed to the synergy of various parameters, including metal-nanoparticle size, metal-support interaction, catalyst structure, ensemble size, and alloy effects.

MORE ACTIVE AND SULFUR RESISTANT BIMETALLIC Pd-Ni CATALYSTS

OpenAIRE

Betti, Carolina; Carrara, Nicolás; Badano, Juan; Lederhos, Cecilia; Vera, Carlos; Quiroga, Mónica

2018-01-01

The influence of the kind of metal precursor and the sequence of impregnation on the properties of Pd-Ni catalysts was evaluated during the test reaction of selective hydrogenation of styrene to ethylbenzene by means of physicochemical characterization. The focus was put on the final hydrogenating activity and the resistance to deactivation by sulfided compounds (thiophene). The used techniques of characterization were ICP, XPS, XDR, TPR, CO chemisorption and TEM. XPS results indicated the pr...

Automotive catalyst strategies for future emission systems

International Nuclear Information System (INIS)

Williamson, W.B.; Summers, J.C.; Scaparo, J.A.

1992-01-01

This paper reports that while significant advances in Pt/Rh three-way catalyst (TWC) formulations have been accomplished, the use of Pd-containing catalysts for three-way emission control are of interest for overall noble metal cost reduction, lower Rh usage, and potential durability improvements. Applications of Pd are demonstrated for replacement of Pt in conventional Pt/Rh TWC systems, for use in Pd-only three-way catalysts and for lowering methanol and formaldehyde emissions at close-coupled locations on a methanol-fueled vehicle. The individual contributions of Pt, Pd and Rh for aged three-way performance indicate significant advantages of using Pd over Pt. A comparison of vehicle system control strategies illustrates that higher system temperatures significantly lower HC emissions, while air/fuel control strategies are most critical in lowering NO x emissions

Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou, E-mail: duyk@suda.edu.cn

2017-07-31

Highlights: • Cross-linked Pt-NiO nanochains using seed-mediated growth method are synthesized. • The as-prepared catalysts exhibit higher electrocatalytic activity than Pt/C for MOR. • The Pt-NiO(1:1 by molar) catalyst shows the best electrocatalytic property towards MOR. - Abstract: A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt{sup 2+} were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt{sup 2+} to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term stability.

Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

International Nuclear Information System (INIS)

Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou

2017-01-01

Highlights: • Cross-linked Pt-NiO nanochains using seed-mediated growth method are synthesized. • The as-prepared catalysts exhibit higher electrocatalytic activity than Pt/C for MOR. • The Pt-NiO(1:1 by molar) catalyst shows the best electrocatalytic property towards MOR. - Abstract: A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt 2+ were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt 2+ to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term stability.

Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

Energy Technology Data Exchange (ETDEWEB)

Du, Lei; Luo, Langli; Feng, Zhenxing; Engelhard, Mark; Xie, Xiaohong; Han, Binghong; Sun, Junming; Zhang, Jianghao; Yin, Geping; Wang, Chongmin; Wang, Yong; Shao, Yuyan

2017-09-01

Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhancing reaction kinetics but are limited by their scarce resource. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides etc. are their low electronic conductivity and durability. Herein, we report a highly active (360 mV overpotential at 10 mA cm–2GEO) and durable (no degradation after 20000 cycles) OER catalyst derived from bimetallic metal–organic frameworks (MOFs) precursors. This catalyst consists of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells. The electron-donation/deviation from Fe and tuned electronic structure of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity, whereas N concentration contributes negligibly. We further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by the chemical state of precursors.

Upgrading of the liquid fuel from fast pyrolysis of biomass over MoNi/γ-Al2O3 catalysts

International Nuclear Information System (INIS)

Xu, Ying; Wang, Tiejun; Ma, Longlong; Zhang, Qi; Liang, Wei

2010-01-01

The hydrotreatment of bio-oil, which obtained from fast pyrolysis of pine sawdust, was investigated over MoNi/γ-Al 2 O 3 catalyst under mild conditions (373 K, 3 MPa hydrogen pressure). Acetic acid was taken as a model compound to investigate the effects of Mo promoter contents and reducing temperatures of catalysts on the catalysts activity under the condition of 473 K and 3 MPa hydrogen pressure. X-ray diffraction and temperature programmed reduction showed that the addition of Mo promoter benefited the uniformity of nickel species and inhibited the formation of NiAl 2 O 4 spinel in the catalysts. The GC spectrum of liquid products showed the mechanism of the model reaction. The maximum conversion of acetic acid (33.20%) was attained over 0.06MoNi/γ-Al 2 O 3 catalysts being reduced at 873 K. This catalyst was chosen for the upgrading of raw bio-oil. After the upgrading process, the pH value of the bio-oil increased from 2.33 to 2.77. The water content increased from 35.52 wt.% to 41.55 wt.% and the gross calorific value increased from 13.96 MJ/kg to 14.17 MJ/kg. The hydrogen content in the bio-oil increased from 6.25 wt.% to 6.95 wt.%. The product properties of the upgraded bio-oil, particularly the hydrogen content and the acidity were considerably improved. The results of gas chromatography-mass spectrometry analysis showed that both hydrotreatment and esterification had happened over 0.06MoNi/γ-Al 2 O 3 (873) catalyst during the upgrading process.

Activity of ruthenium, rhodium, iridium-ruthenium and iridium-rhodium adsorbed catalysts in dehydrogenation of formic acid

Energy Technology Data Exchange (ETDEWEB)

Mikhailov, V A; Zubovich, I A [Yaroslavskij Politekhnicheskij Inst. (USSR)

1977-04-01

The activity of Ru-, Rh- (Ir+nRu)- and (Ir+nRn) catalysts on sugar carbon and silicon dioxide in decomposition of HCOOH was studied. The catalyst activity increases in the series IrRh<(Ir+nRh). The highest activity is displayed by (Ir+nRh) catalysts on silicon dioxide. The results obtained point to activity of single centres (Ru)/sub 1/ and (Rh)/sub 1/ in the reaction of dehydration of HCOOH. It is shown that in the course of preparation of (Ir+nRh)- and (Ir+nRu)-catalysts the Ir atoms interact with Ru(Rh), and variable-composition structures are formed.

Pt Single Atoms Embedded in the Surface of Ni Nanocrystals as Highly Active Catalysts for Selective Hydrogenation of Nitro Compounds.

Science.gov (United States)

Peng, Yuhan; Geng, Zhigang; Zhao, Songtao; Wang, Liangbing; Li, Hongliang; Wang, Xu; Zheng, Xusheng; Zhu, Junfa; Li, Zhenyu; Si, Rui; Zeng, Jie

2018-06-13

Single-atom catalysts exhibit high selectivity in hydrogenation due to their isolated active sites, which ensure uniform adsorption configurations of substrate molecules. Compared with the achievement in catalytic selectivity, there is still a long way to go in exploiting the catalytic activity of single-atom catalysts. Herein, we developed highly active and selective catalysts in selective hydrogenation by embedding Pt single atoms in the surface of Ni nanocrystals (denoted as Pt 1 /Ni nanocrystals). During the hydrogenation of 3-nitrostyrene, the TOF numbers based on surface Pt atoms of Pt 1 /Ni nanocrystals reached ∼1800 h -1 under 3 atm of H 2 at 40 °C, much higher than that of Pt single atoms supported on active carbon, TiO 2 , SiO 2 , and ZSM-5. Mechanistic studies reveal that the remarkable activity of Pt 1 /Ni nanocrystals derived from sufficient hydrogen supply because of spontaneous dissociation of H 2 on both Pt and Ni atoms as well as facile diffusion of H atoms on Pt 1 /Ni nanocrystals. Moreover, the ensemble composed of the Pt single atom and nearby Ni atoms in Pt 1 /Ni nanocrystals leads to the adsorption configuration of 3-nitrostyrene favorable for the activation of nitro groups, accounting for the high selectivity for 3-vinylaniline.

Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

Science.gov (United States)

Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou

2017-07-01

A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt2+ were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt2+ to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term stability.

Preparation of ternary Pt/Rh/SnO2 anode catalysts for use in direct ethanol fuel cells and their electrocatalytic activity for ethanol oxidation reaction

Science.gov (United States)

Higuchi, Eiji; Takase, Tomonori; Chiku, Masanobu; Inoue, Hiroshi

2014-10-01

Pt, Rh and SnO2 nanoparticle-loaded carbon black (Pt/Rh/SnO2/CB) catalysts with different contents of Pt and Rh were prepared by the modified Bönnemann method. The mean size and size distribution of Pt, Rh and SnO2 for Pt-71/Rh-4/SnO2/CB (Pt : Rh : Sn = 71 at.%: 4 at.%: 25 at.%) were 3.8 ± 0.7, 3.2 ± 0.7 and 2.6 ± 0.5 nm, respectively, indicating that Pt, Rh and SnO2 were all nanoparticles. The onset potential of ethanol oxidation current for the Pt-65/Rh-10/SnO2/CB and Pt-56/Rh-19/SnO2/CB electrodes was ca. 0.2 V vs. RHE which was ca. 0.2 V less positive than that for the Pt/CB electrode. The oxidation current at 0.6 V for the Pt/Rh/SnO2/CB electrode (ca. 2% h-1) decayed more slowly than that at the Pt/SnO2/CB electrode (ca. 5% h-1), indicating that the former was superior in durability to the latter. The main product of EOR in potentiostatic electrolysis at 0.6 V for the Pt-71/Rh-4/SnO2/CB electrode was acetic acid.

Simultaneous oxidative conversion and co/sub 2/ reforming of methane to syngas over modified Ni/Al/sub 2/O/sub 3/ catalysts

International Nuclear Information System (INIS)

Eli, W.

2013-01-01

A series of Ni/Al/sub 2/O/sub 3/ and modified Ni-M/Al/sub 2/O/sub 3/ (MLa, Na, K, Ca and Ba) catalysts have been prepared and characterized by XRD, BET, XPS, TGA, TEM and SEM. The performance of these catalysts for simultaneous oxidative conversion and CO/sub 2/ reforming of methane to syngas was evaluated using a fixed-bed reactor. The results indicated that the catalytic activity of Ni/Al/sub 2/O/sub 3/ increased with Ni loading, and reached maximum at 12% Ni loading. The La-modified Ni/Al/sub 2/O/sub 3/ exhibited an excellent catalytic activity and stability within 20 h as compared with unmodified and Na-modified ones. It was found that the addition of La decreased the particle size of nickel, thus increased the Ni dispersion accordingly as indicated by the characterization data. The catalytic activity of Na-modified Ni/Al/sub 2/O/sub 3/ decreased obviously only after 6 h of reaction due to aggregation of metallic Ni particles. Hence, it was suggested that the sintering of Ni particles dominated the catalyst deactivation during the catalytic reaction process. (author)

Electrocatalytic glucose oxidation via hybrid nanomaterial catalyst of multi-wall TiO2 nanotubes supported Ni(OH)2 nanoparticles: Optimization of the loading level

International Nuclear Information System (INIS)

Gu, Yingying; Liu, Yicheng; Yang, Haihong; Li, Benqiang; An, Yarui

2015-01-01

Highlights: • Multi-wall TiO 2 nanotube supported Ni(OH) 2 nanoparticles, Ni(OH) 2 /TNTs, was prepared and investigated as anode electro-catalysts for glucose oxidation. • Ni(OH) 2 -24.2%/TNTs obtains the best catalytic activity. • Compared with Ni(OH) 2, the current density of Ni(OH) 2 -24.2%/TNTs increased 5.9 times in 0.1 M NaOH solution. - Abstract: The novel hybrid nanomaterial catalyst of multi-wall TiO 2 nanotube supported Ni(OH) 2 nanoparticles (Ni(OH) 2 /TNTs) was prepared through hydrothermal method and investigated as anode electro-catalysts for glucose oxidation. The nanostructure was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), thermogravimetry-differential thermal analysis (TGA) and nitrogen adsorption-desorption (BET-BJH). The electrochemical performance was measured by a range of electrochemical measurements. Compared with Ni(OH) 2 , the current density of Ni(OH) 2 /TNTs modified GC electrode increased 5.9 times in 0.1 M NaOH solution. The results indicated that the synthesized nanoparticles exhibited good electro-catalytic activity and stability for glucose oxidation. Meanwhile, the hybrid nanomaterial of Ni(OH) 2 /TNTs may be a potential candidate catalyst for direct glucose fuel cell

Core/shell AgNi/PtAgNi nanoparticles as methanol-tolerant oxygen reduction electrocatalysts

International Nuclear Information System (INIS)

Wu, Dengfeng; Cheng, Daojian

2015-01-01

A core/shell AgNi/PtAgNi nanoparticle (NP) was synthesized via a new seed-mediated growth method in organic solvent medium. The as-synthesized AgNi/PtAgNiNP exhibits an AgNi core coated with PtAgNi shell, which was confirmed by transmission electron microscopy (TEM), ultraviolet–visible absorption spectroscopy and X-ray Photoelectron Spectroscopy (XPS). The AgNi/PtAgNiNPs/C catalyst possesses higher oxygen reduction reaction (ORR) activity and better durability compared with the commercial Pt/C catalyst. It is found that the ORR polarization curve of the AgNi/PtAgNiNPs/C catalyst shows an onset potential of 0.91 V vs. RHE, which is superior to the commercial Pt/C (0.88 V vs. RHE). In addition, the AgNi/PtAgNiNPs/C catalyst shows much better durability than the commercial Pt/C catalyst. More interestingly, the AgNi/PtAgNiNPs/C catalyst displays much higher methanol tolerance than the commercial Pt/C catalyst in 0.1 M KOH solution in the presence of 0.5 M methanol. Our results show that core/shell AgNi/PtAgNiNPs possess selective activity for ORR even in the presence of methanol, showing potential application as methanol-tolerant cathode catalysts in direct methanol fuel cells.

Pt/Cr and Pt/Ni catalysts for oxygen reduction reaction: to alloy or not to alloy?

Science.gov (United States)

Escaño, Mary Clare; Gyenge, Elod; Nakanishi, Hiroshi; Kasai, Hideaki

2011-04-01

Bimetallic systems such as Pt-based alloys or non-alloys have exhibited interesting catalytic properties but pose a major challenge of not knowing a priori how the electronic and chemical properties will be modified relative to the parent metals. In this work, we present the origin of the changes in the reactivity of Pt/Cr and Pt/Ni catalysts, which have been of wide interest in fuel cell research. Using spin-polarized density functional theory calculations, we have shown that the modification of Pt surface reactivity in Pt/Ni is purely of geometric origin (strain). We have also found that the Pt-Ni bonding is very weak, which explains the observed instability of Pt-Ni catalysts under electrochemical measurements. On the other hand, Pt/Cr systems are governed by strong ligand effect (metal-metal interaction), which explains the experimentally observed reactivity dependence on the relative composition of the alloying components. The general characteristics of the potential energy curves for O2 dissociative adsorption on the bimetallic systems and the pure Pt clarify why the d-band center still works for Pt/Cr despite the strong Pt-Cr bonding and high spin polarization of Pt d-states. On the basis of the above clarifications, viable Pt-Cr and Pt-Ni structures, which involve nano-sized alloys and non-alloy bulk catalyst, which may strike higher than the currently observed oxidation reduction reaction activity are proposed.

Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

Energy Technology Data Exchange (ETDEWEB)

Du, Lei; Luo, Langli; Feng, Zhenxing; Engelhard, Mark; Xie, Xiaohong; Han, Binghong; Sun, Junming; Zhang, Jianghao; Yin, Geping; Wang, Chongmin; Wang, Yong; Shao, Yuyan

2017-09-01

Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhanced reaction kinetics but are limited by their scarce resource. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides etc. are their low electronic conductivity and poor durability. Here, we report OER catalysts of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells derived from bimetallic metal–organic frameworks (MOFs) precursors. The optimal OER catalyst shows excellent activity (360 mV overpotential at 10 mA cm–2GEO) and durability (no obvious degradation after 20 000 cycles). The electron-donation from Fe and tuned electronic structure of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity. We further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by chemical state of precursors. Severe metal particle growth probably caused by oxidation of carbon shells and encapsulated nanoparticles is believed to the main mechanism for activity degradation in these catalysts.

Heterogeneous hydrogenation of unsaturated compounds with catalyst P-2-Ni with turnover numbers up to 90,000

Energy Technology Data Exchange (ETDEWEB)

Strohmeier, W; Pfoehler, M; Steigerwald, H [Wuerzburg Univ. (Germany, F.R.). Inst. fuer Physikalische Chemie

1977-12-01

Unsaturated compounds are very rapidly hydrogenated with nickel-boride catalyst P-2-Ni without solvent under mild conditions (70-85/sup 0/C and 10 bar). Turnover numbers UZ up to 90,000 and space-time-yields of 7.440 mmol product per l and 1 mgA Nickel in one hour with a mean catalyst activity a = 124 were observed. This hydrogenation catalyst has a power, which is in the same magnitude of very active noble metal catalysts.

Hydrotreating NiMo/sepiolite catalysts: influence of catalyst preparation on activity for HDS, hydrogenation and chain isomerization reactions

International Nuclear Information System (INIS)

Melo, F.V.; Sanz, E.; Corma, A.; Mifsud, A.

1987-01-01

A series of NiMo catalysts supported on a sepiolite: a) in its natural state, b) modified by acid leaching, and c) modified by cation exchange, have been prepared. The preparation variables studied were: Method of metal deposition, amount of active phase, sepiolite pretreatment, and temperature and time of sulfurization. The catalytic activity for HDS, hydrogenation, and cracking-isomerization has been studied by feeding a thiophene-cyclohexene-cyclohexane mixture and carrying out the reaction in the following conditions: 300 0 and 400 0 C reaction temperature, 20 Kg.cm -2 total pressure, and 3 to 1 molar ratio of H 2 to hydrocarbons. An optimium for HDS and hydrogenation activity was found for a 12% wt MoO 3 , and 5% wt NiO, prepared by simultaneous impregnation by the pore volume method at Ph = 5.0. The optimum conditions with these catalysts are 400 0 C and 3 hours of sulfurization. An increase in the acidity of the support produces a decrease of HDS and hydrogenation and an increase of the cracking-isomerization activities. A good correlation between HDS and the concentration of an XNiO.MoO 3 phase is found. The XNiO.MoO 3 phase is completely sulfurized to a modified MoS 2 , while NiMoO 4 and MoO 3 are only slightly sulfurized. 31 refs.; 7 figs.; 1 table

Development of Sulfur and Carbon Tolerant Reforming Alloy Catalysts Aided by Fundamental Atomistics Insights

Energy Technology Data Exchange (ETDEWEB)

Suljo Linic

2006-08-31

Current hydrocarbon reforming catalysts suffer from rapid carbon and sulfur poisoning. Even though there is a tremendous incentive to develop more efficient catalysts, these materials are currently formulated using inefficient trial and error experimental approaches. We have utilized a novel hybrid experimental/theoretical approach, combining quantum Density Functional Theory (DFT) calculations and various state-of-the-art experimental tools, to formulate carbon tolerant reforming catalysts. We have employed DFT calculations to develop molecular insights into the elementary chemical transformations that lead to carbon poisoning of Ni catalysts. Based on the obtained molecular insights, we have identified, using DFT quantum calculation, Sn/Ni alloy as a potential carbon tolerant reforming catalyst. Sn/Ni alloy was synthesized and tested in steam reforming of methane, propane, and isooctane. We demonstrated that the alloy catalyst is carbon-tolerant under nearly stoichiometric steam-to-carbon ratios. Under these conditions, monometallic Ni is rapidly poisoned by sp2 carbon deposits. The research approach is distinguished by a few characteristics: (a) Knowledge-based, bottom-up approach, compared to the traditional trial and error approach, allows for a more efficient and systematic discovery of improved catalysts. (b) The focus is on exploring alloy materials which have been largely unexplored as potential reforming catalysts.

Oxidative-reforming of model biogas over NiO/Al{sub 2}O{sub 3} catalysts: The influence of the variation of support synthesis conditions

Energy Technology Data Exchange (ETDEWEB)

Asencios, Yvan J.O., E-mail: yvan.jesus@unifesp.br [Departamento de Ciências do Mar, Universidade Federal de São Paulo, Av. Alm. Saldanha da Gama, 89, Ponta da Praia, CEP: 11030-400, Santos-SP (Brazil); Elias, Kariny F.M. [Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense, 400, 13560-970, São Carlos-SP (Brazil); Assaf, Elisabete M., E-mail: eassaf@iqsc.usp.br [Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense, 400, 13560-970, São Carlos-SP (Brazil)

2014-10-30

Graphical abstract: - Highlights: • Precipitation pH and ageing T °C of Al{sub 2}O{sub 3} influenced the performance of Ni/Al{sub 2}O{sub 3}. • Ni catalysts supported on Al{sub 2}O{sub 3} obtained at pH 7 recorded high conversion values. • Catalysts supported on Al{sub 2}O{sub 3} obtained at pH 7 and 80 °C are promissory for reforming of biogas. • Catalysts supported on Al{sub 2}O{sub 3} obtained at pH 6 deactivated readily during reaction. - Abstract: In this study, nickel catalysts (20 wt%) supported on γ-Al{sub 2}O{sub 3} were prepared by the impregnation method. The γ-Al{sub 2}O{sub 3}, was synthesized by precipitation of bayerite gel obtained from aluminum scrap. The synthetic conditions of the bayerite gel varied as follows: precipitation pH ranging from 6 to 7; ageing temperature ranging from 25 to 80 °C, the calcination temperature for all samples was 500 °C. The catalysts and the supports were analyzed by temperature programmed reduction (H{sub 2}-TPR), X-ray diffraction (XRD), physisorption of N{sub 2} (BET), X-ray absorption near-edge structure (XANES) and scanning electron microscopy (SEM). Isopropanol decomposition reactions over the catalysts were carried out to evaluate their acidity. SEM images of the spent catalysts showed that the morphology of the carbon formed during the reaction is of the filamentous type. The TPR analysis of the catalysts showed the presence of NiO species weakly interacted with the support as well as stoichiometric and non-stoichiometric nickel aluminate, the reduction of these species was also observed by XANES analysis. XRD analysis of the fresh catalyst showed peaks assigned to NiO, NiAl{sub 2}O{sub 4} and γ-Al{sub 2}O{sub 3}. The best catalysts (samples NiAl7-25 and NiAl7-80) synthesized in this report showed high stability and high conversion values (CH{sub 4} (70%) and CO{sub 2} (78%)). These catalysts showed better performance than the catalyst supported on commercial γ-Al{sub 2}O{sub 3}, which showed a

Use of Hydrogen Chemisorption and Ethylene Hydrogenation as Predictors for Aqueous Phase Reforming of Lactose over Ni@Pt and Co@Pt Bimetallic Overlayer Catalysts

Energy Technology Data Exchange (ETDEWEB)

Lai, Qinghua; Skoglund, Michael D.; Zhang, Chen; Morris, Allen R.; Holles, Joseph H.

2016-10-20

Overlayer Pt on Ni (Ni@Pt) or Co (Co@Pt) were synthesized and tested for H2 generation from APR of lactose. H2 chemisorption descriptor showed that Ni@Pt and Co@Pt overlayer catalysts had reduced H2 adsorption strength compared to a Pt only catalyst, which agree with computational predictions. The overlayer catalysts also demonstrated lower activity for ethylene hydrogenation than the Pt only catalyst, which likely resulted from decreased H2 binding strength decreasing the surface coverage of H2. XAS results showed that overlayer catalysts exhibited higher white line intensity than the Pt catalyst, which indicates a negative d-band shift for the Pt overlayer, further providing evidence for overlayer formation. Lactose APR studies showed that lactose can be used as feedstock to produce H2 and CO under desirable reaction conditions. The Pt active sites of Ni@Pt and Co@Pt overlayer catalysts showed significantly enhanced H2 production selectivity and activity when compared with that of a Pt only catalyst. The single deposition overlayer with the largest d-band shift showed the highest H2 activity. The results suggest that overlayer formation using directed deposition technique could modify the behavior of the surface metal and ultimately modify the APR activity.

Pyrolysis and gasification of landfilled plastic wastes with Ni-Mg-La/Al2O3 catalyst.

Science.gov (United States)

Kaewpengkrow, Prangtip; Atong, Duangduen; Sricharoenchaikul, Viboon

2012-12-01

Pyrolysis and gasification processes were utilized to study the feasibility of producing fuels from landfilled plastic wastes. These wastes were converted in a gasifier at 700-900 degrees C. The equivalence ratio (ER) was varied from 0.4-0.6 with or without addition ofa Ni-Mg-La/Al2O3 catalyst. The pyrolysis and gasification of plastic wastes without catalyst resulted in relatively low H2, CO and other fuel gas products with methane as the major gaseous species. The highest lower heating value (LHV) was obtained at 800 degrees C and for an ER of 0.4, while the maximum cold gas efficiency occurred at 700 degrees C and for an ER of 0.4. The presence of the Ni-Mg-La/Al2O3 catalyst significantly enhanced H2 and CO production as well as increasing the gas energy content to 15.76-19.26 MJ/m3, which is suitable for further usage as quality fuel gas. A higher temperature resulted in more H2 and CO and other product gas yields, while char and liquid (tars) decreased. The maximum gas yield, gas calorific value and cold gas efficiency were achieved when the Ni-Mg-La/Al2O3 catalyst was used at 900 degrees C. In general, addition of prepared catalyst resulted in greater H2, CO and other light hydrocarbon yields from superior conversion of wastes to these gases. Thus, thermochemical treatment of these problematic wastes using pyrolysis and gasification processes is a very attractive alternative for sustainable waste management.

Hydroconversion of methyl laurate on bifunctional Ni2P/AlMCM-41 catalyst prepared via in situ phosphorization using triphenylphosphine

Science.gov (United States)

Zhao, Sha; Zhang, Zhena; Zhu, Kongying; Chen, Jixiang

2017-05-01

A series of Ni2P/AlMCM-41-x bifunctional catalysts with different Si/Al ratios (x) were synthesized by in situ phosphorization of Ni/AlMCM-41-x with triphenylphosphine (nominal Ni/P ratio of 0.75) at 300 °C on a fixed-bed reactor. For comparison, NiP/AlMCM-41-5-TPR was also prepared by the TPR method from the supported nickel phosphate with the Ni/P ratio of 1.0, during which metallic Ni rather than Ni2P formed. TEM images show that Ni and Ni2P particles uniformly distributed in Ni2P/AlMCM-41-x and NiP/AlMCM-41-5-TPR. The Ni2P/AlMCM-41-x acidity increased with decreasing the Si/Al ratio. In the hydroconversion of methyl laurate, the conversions were close to 100% on all catalysts at 360 °C, 3.0 MPa, methyl laurate WHSV of 2 h-1 and H2/methyl laurate ratio of 25. As to Ni2P/AlMCM-41-x, with decreasing the Si/Al ratio, the total selectivity to C11 and C12 hydrocarbons decreased, while the total selectivity to isoundecane and isododecane (Si-C11+i-C12) firstly increased and then decreased. Ni2P/AlMCM-41-5 gave the largest Si-C11+i-C12 of 43.2%. While NiP/AlMCM-41-5-TPR gave higher Si-C11+i-C12 than Ni2P/AlMCM-41-5, it was more active for the undesired Csbnd C bond cleavage and methanation. We propose that the in-situ phosphorization adopted here is a promising approach to preparing Ni2P-based bifunctional catalysts.

Study to improve the quality of a Mexican straight run gasoil over NiMo/γ-Al2O3 catalysts

International Nuclear Information System (INIS)

Dominguez-Crespo, M.A.; Diaz-Garcia, L.; Arce-Estrada, E.M.; Torres-Huerta, A.M.; Cortez de la Paz, M.T.

2006-01-01

Four NiMo catalyst supported on Al 2 O 3 with different textural properties have been studied in the hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) of a Mexican straight run gasoil (SRGO). All reactions were carried out at three different temperatures 613, 633, and 653 K. Alumina supports were analysed by pyridine FTIR-TPD and nitrogen physisorption in order to determine their surface acidity and textural properties, respectively. TPR studies of the NiMo catalysts were analysed to correlate their hydrogenating properties. Metallic particles were characterized (after sulfidation) using transmission electron microscopy (TEM). Catalytic activities are discussed in relation to the physicochemical properties of NiMo catalysts. The importance of textural properties on coke deposition has been emphasized. The results of catalytic activity of these materials varied depending on dispersed MoS particles and pore distribution in final catalysts. The optimum pore diameter was found around 80 A for HDS and HDN

Study to improve the quality of a Mexican straight run gasoil over NiMo/γ-Al 2O 3 catalysts

Science.gov (United States)

Domínguez-Crespo, M. A.; Díaz-García, L.; Arce-Estrada, E. M.; Torres-Huerta, A. M.; Cortéz-De la Paz, M. T.

2006-11-01

Four NiMo catalyst supported on Al 2O 3 with different textural properties have been studied in the hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) of a Mexican straight run gasoil (SRGO). All reactions were carried out at three different temperatures 613, 633, and 653 K. Alumina supports were analysed by pyridine FTIR-TPD and nitrogen physisorption in order to determine their surface acidity and textural properties, respectively. TPR studies of the NiMo catalysts were analysed to correlate their hydrogenating properties. Metallic particles were characterized (after sulfidation) using transmission electron microscopy (TEM). Catalytic activities are discussed in relation to the physicochemical properties of NiMo catalysts. The importance of textural properties on coke deposition has been emphasized. The results of catalytic activity of these materials varied depending on dispersed MoS particles and pore distribution in final catalysts. The optimum pore diameter was found around 80 Å for HDS and HDN.

Methodology study for the catalyst obtention to low temperature fuel cells (DEFC)

International Nuclear Information System (INIS)

Oliveira, Emilia Lucena de; Korb, Matias De Angelis; Correa, Patricia dos Santos; Radtke, Claudio; Malfatti, Celia de Fraga; Rieder, Ester

2010-01-01

Different methods to elaboration of catalysts in direct ethanol fuel cells (low temperature fuel cells) have been proposed in the literature. The present work aims to study a simplified methodology to obtain Pt-Sn-Ni alloys, used as catalysts in low temperature fuel cells. Impregnation/reduction method was employed to obtain Pt- Sn-Ni alloys supported on carbon, using ethylenoglycol as reductor agent and carbon Vulcan XC72R as support. Different amounts of Pt, Sn e Ni were studied, with the intent to obtain the maximum catalytic effect. The catalysts were obtained in an alkaline range, at 130 deg C, using the proportion ethylenoglycol:water 75/25 v/v. The analytical techniques used in this study was RBS (Rutherford Backscattering Spectroscopy), X Ray Diffraction and Cyclic Voltammetry. (author)

Formation of Multiple-Phase Catalysts for the Hydrogen Storage of Mg Nanoparticles by Adding Flowerlike NiS.

Science.gov (United States)

Xie, Xiubo; Ma, Xiujuan; Liu, Peng; Shang, Jiaxiang; Li, Xingguo; Liu, Tong

2017-02-22

In order to enhance the hydrogen storage properties of Mg, flowerlike NiS particles have been successfully prepared by solvothermal reaction method, and are subsequently ball milled with Mg nanoparticles (NPs) to fabricate Mg-5 wt % NiS nanocomposite. The nanocomposite displays Mg/NiS core/shell structure. The NiS shell decomposes into Ni, MgS and Mg 2 Ni multiple-phases, decorating on the surface of the Mg NPs after the first hydrogen absorption and desorption cycle at 673 K. The Mg-MgS-Mg 2 Ni-Ni nanocomposite shows enhanced hydrogenation and dehydrogenation rates: it can quickly uptake 3.5 wt % H 2 within 10 min at 423 K and release 3.1 wt % H 2 within 10 min at 573 K. The apparent hydrogen absorption and desorption activation energies are decreased to 45.45 and 64.71 kJ mol -1 . The enhanced sorption kinetics of the nanocomposite is attributed to the synergistic catalytic effects of the in situ formed MgS, Ni and Mg 2 Ni multiple-phase catalysts during the hydrogenation/dehydrogenation process, the porthole effects for the volume expansion and microstrain of the phase transformation of Mg 2 Ni and Mg 2 NiH 4 and the reduced hydrogen diffusion distance caused by nanosized Mg. This novel method of in situ producing multiple-phase catalysts gives a new horizon for designing high performance hydrogen storage material.

Thermal conductivity of partially graphitized biocarbon obtained by carbonization of medium-density fiberboard in the presence of a Ni-based catalyst

Science.gov (United States)

Orlova, T. S.; Parfen'eva, L. S.; Smirnov, B. I.; Gutierrez-Pardo, A.; Ramirez-Rico, J.

2016-01-01

The thermal conductivity k and resistivity ρ of biocarbon matrices, prepared by carbonizing medium-density fiberboard at T carb = 850 and 1500°C in the presence of a Ni-based catalyst (samples MDF-C( Ni)) and without a catalyst (samples MDF-C), have been measured for the first time in the temperature range of 5-300 K. X-ray diffraction analysis has revealed that the bulk graphite phase arises only at T carb = 1500°C. It has been shown that the temperature dependences of the thermal conductivity of samples MDFC- 850 and MDF-C-850(Ni) in the range of 80-300 K are to each other and follow the law of k( T) ˜ T 1.65, but the use of the Ni-catalyst leads to an increase in the thermal conductivity by a factor of approximately 1.5, due to the formation of a greater fraction of the nanocrystalline phase in the presence of the Ni-catalyst at T carb = 850°C. In biocarbon MDF-C-1500 prepared without a catalyst, the dependence is k( T) ˜ T 1.65, and it is controlled by the nanocrystalline phase. In MDF-C-1500(Ni), the bulk graphite phase formed increases the thermal conductivity by a factor of 1.5-2 compared to the thermal conductivity of MDF-C-1500 in the entire temperature range of 5-300 K; k( T = 300 K) reaches the values of ˜10 W m-1 K-1, characteristic of biocarbon obtained without a catalyst only at high temperatures of T carb = 2400°C. It has been shown that MDF-C-1500(Ni) in the temperature range of 40‒300 K is characterized by the dependence, k( T) ˜ T 1.3, which can be described in terms of the model of partially graphitized biocarbon as a composite of an amorphous matrix with spherical inclusions of the graphite phase.

Synthesis of Ni2B nanoparticles by RF thermal plasma for fuel cell catalyst

International Nuclear Information System (INIS)

Cheng, Y; Tanaka, M; Watanabe, T; Choi, S Y; Shin, M S; Lee, K H

2014-01-01

The catalyst of Ni 2 B nanoparticles was successfully prepared using nickel and boron as precursors with the quenching gas in radio frequency thermal plasmas. The generating of Ni 2 B needs adequate reaction temperature and boron content in precursors. The quenching gas is beneficial for the synthesis of Ni 2 B in RF thermal plasma. The effect of quenching rate, powder feed rate and boron content in feeding powders on the synthesis of nickel boride nanoparticles was studied in this research. The high mass fraction of 28 % of Ni 2 B nanoparticles can be generated at the fixed initial composition of Ni:B = 2:3. Quenching gas is necessary in the synthesis of Ni 2 B nanoaprticles. In addition, the mass fraction of Ni 2 B increases with the increase of quenching gas flow rate and powder feed rate

Hydrodeoxygenation of bio-derived phenols to hydrocarbons using RANEY Ni and Nafion/SiO2 catalysts.

Science.gov (United States)

Zhao, Chen; Kou, Yuan; Lemonidou, Angeliki A; Li, Xuebing; Lercher, Johannes A

2010-01-21

A simple, green, cost- and energy-efficient route for converting phenolic components in bio-oil to hydrocarbons and methanol has been developed, with nearly 100% yields. In the heterogeneous catalysts, RANEY Ni acts as the hydrogenation catalyst and Nafion/SiO(2) acts as the Brønsted solid acid for hydrolysis and dehydration.

Hydrocracking of α-Cellulose Using Co, Ni, and Pd Supported on Mordenite Catalysts

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Wega Trisunaryanti

2018-02-01

Full Text Available Hydrocracking of α-cellulose has been conducted in a semi-batch reactor at 400, 450, and 500 °C with hydrogen flow (30 mL/min. for 4 h. Mordenite (MOR and Co, Ni and Pd metal supported on the MOR were used as solid catalysts. The catalysts were characterized using X-ray Diffractometer (XRD, Fourier Transform Infrared (FTIR spectroscopy, and Scanning Electron Microscopy (SEM to evaluate the physical-chemical properties. Energy Dispersive X-ray (EDX and Inductively Coupled Plasma (ICP were used to analyze the amount of metal impregnated on the catalysts. The liquid product was analyzed using Gas Chromatograph-Mass Spectroscopy (GC-MS. Thermal hydrocracking was also conducted at 450 °C with the amount of liquid product was 37.86 wt.%. The highest liquid conversion obtained by mordenite catalyst was 94.66 wt.% at 450 °C and the highest liquid conversion (98.08 wt.% was reached by Pd/MOR catalyst at 400 °C.

Development of Cu and Ni catalysts supported on ZrO2 for the generation of H2 by means of the reaction of reformed methanol in atmosphere oxidizer

International Nuclear Information System (INIS)

Lopez C, P.

2012-01-01

ZrO 2 was prepared by the sol-gel method and calcined at 450 C. The prepared zirconia was impregnated with an aqueous solution of Cu(CH 3 CO 2 ) 2 ·H 2 O or NiNO 3 ·6H 2 O at an appropriate concentration to yield 3 wt % of copper or nickel, respectively, in the mono metallic catalysts. Three bimetallic samples were prepared at 80% Cu and 20% Ni respectively to obtain 3 wt % of total metallic phase. Surface area of the Cu-Ni base catalysts supported on ZrO 2 oxide showed differences as a function of the metal addition. Between them, the Cu/ZrO 2 catalyst had the lowest surface area than other catalysts. X-ray diffraction patterns of the bimetallic catalysts did not show diffraction peaks of the Cu, Ni or bimetallic Cu-Ni alloys. In addition, TPR profiles of the bimetallic catalysts had the lowest reduction temperature compared with the mono metallic samples. The reactivity of the catalysts in the range of 250-350 C showed that the samples prepared by successive impregnation had the highest catalytic activity than the other catalysts studied. Also the selectivity for H 2 production was higher for these catalysts. This finding was associated to the presence of the bimetallic Cu-Ni nanoparticles, as was evidenced by Tem-EDX analysis. (Author)

Low-Temperature Catalytic Performance of Ni-Cu/Al2O3 Catalysts for Gasoline Reforming to Produce Hydrogen Applied in Spark Ignition Engines

Directory of Open Access Journals (Sweden)

Le Anh Tuan

2016-03-01

Full Text Available The performance of Ni-Cu/Al2O3 catalysts for steam reforming (SR of gasoline to produce a hydrogen-rich gas mixture applied in a spark ignition (SI engine was investigated at relatively low temperature. The structural and morphological features and catalysis activity were observed by X-ray diffractometry (XRD, scanning electron microscopy (SEM, and temperature programmed reduction (TPR. The results showed that the addition of copper improved the dispersion of nickel and therefore facilitated the reduction of Ni at low temperature. The highest hydrogen selectivity of 70.6% is observed over the Ni-Cu/Al2O3 catalysts at a steam/carbon ratio of 0.9. With Cu promotion, a gasoline conversion of 42.6% can be achieved at 550 °C, while with both Mo and Ce promotion, the gasoline conversions were 31.7% and 28.3%, respectively, higher than with the conventional Ni catalyst. On the other hand, initial durability testing showed that the conversion of gasoline over Ni-Cu/Al2O3 catalysts slightly decreased after 30 h reaction time.

An anodic alumina supported Ni-Pt bimetallic plate-type catalysts for multi-reforming of methane, kerosene and ethanol

KAUST Repository

Zhou, Lu; Guo, Yu; Kameyama, Hideo; Basset, Jean-Marie

2014-01-01

. The prepared Ni-Pt catalyst showed excellent performance during steam reforming of methane, kerosene and ethanol under both 3000 h stationary and 500-time daily start-up and shut-down operation modes. Self-activation ability of this catalyst was evidenced

The atomistic origin of the extraordinary oxygen reduction activity of Pt3Ni7 fuel cell catalysts.

Science.gov (United States)

Fortunelli, Alessandro; Goddard Iii, William A; Sementa, Luca; Barcaro, Giovanni; Negreiros, Fabio R; Jaramillo-Botero, Andrés

2015-07-01

Recently Debe et al. reported that Pt 3 Ni 7 leads to extraordinary Oxygen Reduction Reaction (ORR) activity. However, several reports show that hardly any Ni remains in the layers of the catalysts close to the surface ("Pt-skin effect"). This paradox that Ni is essential to the high catalytic activity with the peak ORR activity at Pt 3 Ni 7 while little or no Ni remains close to the surface is explained here using large-scale first-principles-based simulations. We make the radical assumption that processing Pt-Ni catalysts under ORR conditions would leach out all Ni accessible to the solvent. To simulate this process we use the ReaxFF reactive force field, starting with random alloy particles ranging from 50% Ni to 90% Ni and containing up to ∼300 000 atoms, deleting the Ni atoms, and equilibrating the resulting structures. We find that the Pt 3 Ni 7 case and a final particle radius around 7.5 nm lead to internal voids in communication with the exterior, doubling the external surface footprint, in fair agreement with experiment. Then we examine the surface character of these nanoporous systems and find that a prominent feature in the surface of the de-alloyed particles is a rhombic structure involving 4 surface atoms which is crystalline-like but under-coordinated. Using density-functional theory, we calculate the energy barriers of ORR steps on Pt nanoporous catalysts, focusing on the O ad -hydration reaction (O ad + H 2 O ad → OH ad + OH ad ) but including the barriers of O 2 dissociation (O 2ad → O ad + O ad ) and water formation (OH ad + H ad → H 2 O ad ). We find that the reaction barrier for the O ad -hydration rate-determining-step is reduced significantly on the de-alloyed surface sites compared to Pt(111). Moreover we find that these active sites are prevalent on the surface of particles de-alloyed from a Pt-Ni 30 : 70 initial composition. These simulations explain the peak in surface reactivity at Pt 3 Ni 7 , and provide a rational guide to

Synthesis and characterization of Fe–Ni/ɣ-Al2O3 egg-shell catalyst for H2 generation by ammonia decomposition

DEFF Research Database (Denmark)

Silva, Hugo José Lopes; Nielsen, Morten Godtfred; Fiordaliso, Elisabetta Maria

2015-01-01

The Fe–Ni alloyed nanoparticles are a promising alternative to expensive ruthenium-based catalysts for a real-scale application of hydrogen generation by ammonia decomposition. In practical applications, millimeter-sized extrudates are used as catalyst supports, where the spatial distribution...... of the active phase should match with the type of reaction. In this work, a novel synthesis route was developed for the preparation of a Fe–Ni/ɣ-Al2O3 egg-shell catalyst. Egg-shell is a preferred profile considering the highly endothermic nature of ammonia decomposition reaction. The high viscosity of glycerol...... using focused ion bean (FIB) milling allowed to acquire high resolution images of the Ni and Fe nanoparticles on ɣ-Al2O3, which is particularly challenging due to the crystalline nature of this support. Distinct regions of the egg-shell catalyst were analyzed through scanning TEM (STEM) and TEM...

Oxidant-free Rh(III)-catalyzed direct C-H olefination of arenes with allyl acetates.

Science.gov (United States)

Feng, Chao; Feng, Daming; Loh, Teck-Peng

2013-07-19

Rh(III)-catalyzed direct olefination of arenes with allyl acetate via C-H bond activation is described using N,N-disubstituted aminocarbonyl as the directing group. The catalyst undergoes a redox neutral process, and high to excellent yields of trans-products are obtained. This protocol exhibits a wide spectrum of functionality compatibility because of the simple reaction conditions employed and provides a highly effective synthetic method in the realm of C-H olefination.

Study of polyoxide catalysts of methane combustion on Mn, Cu, Ni, rare earth elements, alkaline earth elements base by the X-ray fluorescence analysis method

International Nuclear Information System (INIS)

Grigor'eva, V.P.; Popova, N.M.; Zheksenbaeva, Z.T.; Sass, A.S.; Salakhova, R.Kh.; Dosumov, K.D.

2002-01-01

The results of X-ray fluorescence analysis of polyoxide catalysts on of Mn, Cu, Ni, rare earth elements, alkaline earth elements base supported on 2 % Ce/θ-Al 2 O 3 are presented. This polyoxide catalysts are using for deep methane oxidation. DRON-4-7 X-ray diffractometers was applied for the analysis. It was found, that oxides in Ni-Cu-Cr catalysts after long time heating up to 1200 deg. C have been interacted with catalyst supports with Ni(Cu)Al 2 O 3 aluminates formation and due to its decomposition transformation degree of CH 4 to CO 2 are reduced. Activity of MnBaSrCeLa catalysts after heating up to 1200 deg. C does not changed

Rh promoted La0.75Sr0.25(Fe0.8Co0.2)1−xGaxO3-δ perovskite catalysts: Characterization and catalytic performance for methane partial oxidation to synthesis gas

International Nuclear Information System (INIS)

Palcheva, R.; Olsbye, U.; Palcut, M.; Rauwel, P.; Tyuliev, G.; Velinov, N.; Fjellvåg, H.H.

2015-01-01

Graphical abstract: - Highlights: • Perovskites type-oxide La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ (x = 0.1, 0.25, 0.4) prepared by the sol–gel citrate method. • Bulk and surface analysis to determine catalysts composition evolution. • Anaerobic catalytic partial oxidation of methane to syngas at 600 °C in a pulse apparatus over Rh promoted perovskites. • The catalysts showed high stability and selectivity. - Abstract: Synthesis gas production via selective oxidation of methane at 600 °C in a pulse reaction over La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ (x = 0.1, 0.25, 0.4) perovskite-supported rhodium catalysts, was investigated. The perovskite oxides were prepared by sol–gel citrate method and characterized by X-ray Diffraction (XRD), Moessbauer Spectroscopy (MS), Temperature Programmed Reduction (TPR-H 2 ), X-ray Photoelectron Spectroscopy (XPS) and High Resolution Transmission Electron Microscopy (HRTEM). According to XRD analysis, the synthesized samples were a single perovskite phase. The perovskite structure of Ga substituted samples remained stable after TPR-H 2 , as confirmed by XRD. Data of MS identified Fe 3+ ions in two distinctive coordination environments, and Fe 4+ ions. The Rh 2 O 3 thin overlayer was detected by the HRTEM for the Rh impregnated perovskite oxides. During the interaction of methane with oxidized perovskite-supported Rh (0.5 wt.%) catalysts, besides CO, H 2 , and surface carbon, CO 2 and H 2 O were formed. The Rh perovskite catalyst with x = 0.25 gallium exhibits the highest catalytic activity of 83% at 600 °C. The CO selectivity was affected by the reducibility of La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ perovskite materials.

Two 3D structured Co-Ni bimetallic oxides as cathode catalysts for high-performance alkaline direct methanol fuel cells

Science.gov (United States)

Liu, Yan; Shu, Chengyong; Fang, Yuan; Chen, Yuanzhen; Liu, Yongning

2017-09-01

Two NiCo2O4 bimetallic oxides were synthesized via a facile hydrothermal method. SEM and TEM observations show that these materials have three-dimensional (3D) dandelion-like (DL) and flower-like (FL) morphologies. Their large specific surface areas (90.68 and 19.8 m2·g-1) and porous structures provide many active sites and effective transport pathways for the oxygen reduction reaction (ORR). Electrochemical measurements with a rotating ring-disc electrode (RRDE) indicate that the electron transfer numbers of the NiCo2O4-DL and NiCo2O4-FL catalysts for ORR in an alkaline solution are 3.97 and 3.91, respectively. Fuel cells were assembled with the bimetallic oxides, PtRu/C and a polymer fiber membrane (PFM) as cathode catalysts, anode catalyst and electrolyte film, respectively. For NiCo2O4-DL, the peak power density reaches up to 73.5 mW·cm-2 at 26 °C, which is the highest room-temperature value reported to date. The high catalytic activity of NiCo2O4 is mainly attributed to the presence of many Co3+ cations that directly donate electrons to O2 to reduce it via a more efficient and effective route. Furthermore, the catalytic performance of NiCo2O4-DL is superior to that of NiCo2O4-FL because it has a higher specific surface area and is less crystalline.

Syngas Production from CO2 Reforming and CO2-steam Reforming of Methane over Ni/Ce-SBA-15 Catalyst

Science.gov (United States)

Tan, J. S.; Danh, H. T.; Singh, S.; Truong, Q. D.; Setiabudi, H. D.; Vo, D.-V. N.

2017-06-01

This study compares the catalytic performance of mesoporous 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane reactions in syngas production. The catalytic performance of 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane was evaluated in a temperature-controlled tubular fixed-bed reactor at stoichiometric feed composition, 1023 K and atmospheric pressure for 12 h on-stream with gas hourly space velocity (GHSV) of 36 L gcat -1 h-1. The 10 Ni/Ce-SBA-15 catalyst possessed a high specific BET surface area and average pore volume of 595.04 m2 g-1. The XRD measurement revealed the presence of NiO phase with crystallite dimension of about 13.60 nm whilst H2-TPR result indicates that NiO phase was completely reduced to metallic Ni0 phase at temperature beyond 800 K and the reduction temperature relied on different degrees of metal-support interaction associated with the location and size of NiO particles. The catalytic reactivity was significantly enhanced with increasing H2O/CO2 feed ratio. Interestingly, the H2/CO ratio for CO2-steam reforming of methane varied between 1 and 3 indicated the occurrence of parallel reactions, i.e., CH4 steam reforming giving a H2/CO of 3 whilst reverse water-gas shift (RWGS) reaction consuming H2 to produce CO gaseous product.

Direct production of carbon nanofibers decorated with Cu2O by thermal chemical vapor deposition on Ni catalyst electroplated on a copper substrate

Directory of Open Access Journals (Sweden)

MA Vesaghi

2012-12-01

Full Text Available  Carbon nanofibers (CNFs decorated with Cu2O particles were grown on a Ni catalyst layer deposited on a Cu substrate by thermal. chemical vapor deposition from liquid petroleum gas. Ni catalyst nanoparticles with different sizes were produced in an electroplating system at 35˚C. These nanoparticles provide the nucleation sites for CNF growth, removing the need for a buffer layer. High temperature surface segregation of the Cu substrate into the Ni catalyst layer and its exposition to O2 at atmospheric environment, during the CNFs growth, lead to the production of CNFs decorated with Cu2O particles. The surface morphology of the Ni catalyst films and grown CNFs over it was studied by scanning electron microscopy. Transmission electron microscopy and Raman spectroscopy revealed the formation of CNFs. The selected area electron diffraction pattern and electron diffraction studies show that these CNFs were decorated with Cu2O nanoparticles.

Oxidation of CO and Methanol on Pd-Ni Catalysts Supported on Different Chemically-Treated Carbon Nanofibers

Directory of Open Access Journals (Sweden)

Juan Carlos Calderón

2016-10-01

Full Text Available In this work, palladium-nickel nanoparticles supported on carbon nanofibers were synthesized, with metal contents close to 25 wt % and Pd:Ni atomic ratios near to 1:2. These catalysts were previously studied in order to determine their activity toward the oxygen reduction reaction. Before the deposition of metals, the carbon nanofibers were chemically treated in order to generate oxygen and nitrogen groups on their surface. Transmission electron microscopy analysis (TEM images revealed particle diameters between 3 and 4 nm, overcoming the sizes observed for the nanoparticles supported on carbon black (catalyst Pd-Ni CB 1:2. From the CO oxidation at different temperatures, the activation energy Eact for this reaction was determined. These values indicated a high tolerance of the catalysts toward the CO poisoning, especially in the case of the catalysts supported on the non-chemically treated carbon nanofibers. On the other hand, apparent activation energy Eap for the methanol oxidation was also determined finding—as a rate determining step—the COads diffusion to the OHads for the catalysts supported on carbon nanofibers. The results here presented showed that the surface functional groups only play a role in the obtaining of lower particle sizes, which is an important factor in the obtaining of low CO oxidation activation energies.

New catalysts for exhaust gas cleaning

Energy Technology Data Exchange (ETDEWEB)

Haerkoenen, M [Kemira Metalkat Oy, Oulu (Finland)

1997-12-31

Major challenge for future catalyst systems was to develop thermally more stable washcoats for close coupled operating conditions and for engines operating under high speed and load conditions. To design these future emission systems extensive research and development was undertaken to develop methods to disperse and stabilize the key catalytic materials for operation at much higher temperatures. Second priority was to design catalysts that are more effective under low temperature exhaust conditions and have improved oxygen storage properties in the washcoats. Incorporating new materials and modified preparation technology a new generation of metallic catalyst formulations emerged, those being trimetallic K6 (Pt:Pd:Rh and bimetallic K7) (Pd+Pd:Rh). The target was to combine the best property of Pt:Rh (good NO{sub x} reduction) with that of the good HC oxidation activity of Pd and to ensure that precious metal/support interactions were positively maintained. Both K6 and K7 concepts contain special catalyst structures with optimized washcoat performance which can be brick converter configuration. Improvement in light-off, thermal stability and transient performance with these new catalyst formulations have clearly been shown in both laboratory and vehicle testing. (author) (20 refs.)

New catalysts for exhaust gas cleaning

Energy Technology Data Exchange (ETDEWEB)

Haerkoenen, M. [Kemira Metalkat Oy, Oulu (Finland)

1996-12-31

Major challenge for future catalyst systems was to develop thermally more stable washcoats for close coupled operating conditions and for engines operating under high speed and load conditions. To design these future emission systems extensive research and development was undertaken to develop methods to disperse and stabilize the key catalytic materials for operation at much higher temperatures. Second priority was to design catalysts that are more effective under low temperature exhaust conditions and have improved oxygen storage properties in the washcoats. Incorporating new materials and modified preparation technology a new generation of metallic catalyst formulations emerged, those being trimetallic K6 (Pt:Pd:Rh and bimetallic K7) (Pd+Pd:Rh). The target was to combine the best property of Pt:Rh (good NO{sub x} reduction) with that of the good HC oxidation activity of Pd and to ensure that precious metal/support interactions were positively maintained. Both K6 and K7 concepts contain special catalyst structures with optimized washcoat performance which can be brick converter configuration. Improvement in light-off, thermal stability and transient performance with these new catalyst formulations have clearly been shown in both laboratory and vehicle testing. (author) (20 refs.)

MECHANISTIC KINETIC MODELS FOR STEAM REFORMING OF CONCENTRATED CRUDE ETHANOL ON NI/AL2O3 CATALYST

Directory of Open Access Journals (Sweden)

O. A. OLAFADEHAN

2015-05-01

Full Text Available Mechanistic kinetic models were postulated for the catalytic steam reforming of concentrated crude ethanol on a Ni-based commercial catalyst at atmosphere pressure in the temperature range of 673-863 K, and at different catalyst weight to the crude ethanol molar flow rate ratio (in the range 0.9645-9.6451 kg catalyst h/kg mole crude ethanol in a stainless steel packed bed tubular microreactor. The models were based on Langmuir-Hinshelwood-Hougen-Watson (LHHW and Eley-Rideal (ER mechanisms. The optimization routine of Nelder-Mead simplex algorithm was used to estimate the inherent kinetic parameters in the proposed models. The selection of the best kinetic model amongst the rival kinetic models was based on physicochemical, statistical and thermodynamic scrutinies. The rate determining step for the steam reforming of concentrated crude ethanol on Ni/Al2O3 catalyst was found to be surface reaction between chemisorbed CH3O and O when hydrogen and oxygen were adsorbed as monomolecular species on the catalyst surface. Excellent agreement was obtained between the experimental rate of reaction and conversion of crude ethanol, and the simulated results, with ADD% being ±0.46.

Effects of impregnation methods and drying conditions on quinoline hydrodenitrogenation over Ni-W based catalysts

Energy Technology Data Exchange (ETDEWEB)

Guo, Fang; Qiu, Zegang; Zhao, Liangfu; Xiang, Hongwei [Institute of Coal Chemistry, Chinese Academy of Sciences (China); Guo, Shaoqing [Taiyuan University of Science and Technology (China)

2014-04-15

The effects of impregnation methods (co-impregnation and sequential impregnation) and drying conditions (air and vacuum) on the structure and catalytic behavior of MCM-41 supported Ni-W catalysts were investigated. The catalysts were characterized by powder X-ray diffraction (XRD) analysis, Fourier-transform infrared spectroscopy (FT-IR), diffuse reflectance UV-Vis absorbance spectroscopy (DRS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and pyridine adsorbed infrared spectroscopy (Py-IR) techniques. They were tested for hydrodenitrogenation (HDN) of quinoline at temperatures of 300-400 deg C. The HDN results showed that the catalysts prepared by co-impregnation were more active than the catalysts prepared by sequential impregnation and the catalysts prepared by drying under vacuum were more active than the catalysts dried in air. Characterization revealed that the co-impregnation method and drying under vacuum promoted the dispersion of W, the formation of the active phases, and the formation of acidic sites on the catalysts. (author)

Rhodium (II) carbene C-H insertion in water and catalyst reuse

International Nuclear Information System (INIS)

Candeias, Nuno R.; Gois, Pedro M.P.; Afonso, Carlos A.M.

2007-01-01

A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II) catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonyl acetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh 2 (OAc) 4 . The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization. (author)

Gram-Scale Synthesis of Highly Active and Durable Octahedral PtNi Nanoparticle Catalysts for Proton Exchange Membrane Fuel Cell

DEFF Research Database (Denmark)

Choi, Juhyuk; Jang, Jue-Hyuk; Roh, Chi-Woo

2018-01-01

for the commercialization of PEMFCs. In this study, we focus on gram-scale synthesis of octahedral PtNi nanoparticles with Pt overlayers (PtNi@Pt) supported on the carbon, resulting in enhanced catalytic activity and durability. Such PtNi@Pt catalysts show high mass activity (1.24 A mgPt−1) at 0.9 V (vs RHE) for the ORR......Proton exchange membrane fuel cells (PEMFC) are regarded as a promising renewable energy source for a future hydrogen energy society. However, highly active and durable catalysts are required for the PEMFCs because of their intrinsic high overpotential at the cathode and operation under the acidic...... condition for oxygen reduction reaction (ORR). Since the discovery of the exceptionally high surface activity of Pt3Ni(111), the octahedral PtNi nanoparticles have been synthesized and tested. Nonetheless, their milligram-scale synthesis method and poor durability make them unsuitable...

Directly observing catalytic intermediates of methane dry reforming (MDR) on model Ni(111) catalyst via in operando surface techniques

Science.gov (United States)

Yuan, Kaidi

In this work, near ambient pressure x-ray photoelectron spectroscopy was used to trace the in operando catalytic intermediates of methane dry reforming on model Ni(111) catalyst. The following reactive carbon intermediates have been characterized from dissociation of CH4: *CH, *C1 (Ni3C), *Cn (n≥2) and clock-reconstructed Ni2C. They can develop into inert graphene, and the conditions for this transition have been explored. One the other hand, the oxygen intermediates from CO2 dissociation were also studied, which play an important role on restraining graphene growth. Their dynamic coverage decreases with increasing temperature, which is suggested the fundamental mechanism of regional carbon overspill and causes irreversible graphene formation. Therefore, solutions based on Ni-O stabilization were proposed in developing coking resisting catalysts.

Upgrading of the liquid fuel from fast pyrolysis of biomass over MoNi/{gamma}-Al{sub 2}O{sub 3} catalysts

Energy Technology Data Exchange (ETDEWEB)

Xu, Ying; Liang, Wei [Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, Guangdong (China); Graduate School of the Chinese Academy of Sciences, Beijing (China); Wang, Tiejun; Ma, Longlong; Zhang, Qi [Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, Guangdong (China); Key Laboratory of Renewable Energy and Gas Hydrate, Chinese Academy of Sciences, Guangzhou, Guangdong (China)

2010-09-15

The hydrotreatment of bio-oil, which obtained from fast pyrolysis of pine sawdust, was investigated over MoNi/{gamma}-Al{sub 2}O{sub 3} catalyst under mild conditions (373 K, 3 MPa hydrogen pressure). Acetic acid was taken as a model compound to investigate the effects of Mo promoter contents and reducing temperatures of catalysts on the catalysts activity under the condition of 473 K and 3 MPa hydrogen pressure. X-ray diffraction and temperature programmed reduction showed that the addition of Mo promoter benefited the uniformity of nickel species and inhibited the formation of NiAl{sub 2}O{sub 4} spinel in the catalysts. The GC spectrum of liquid products showed the mechanism of the model reaction. The maximum conversion of acetic acid (33.20%) was attained over 0.06MoNi/{gamma}-Al{sub 2}O{sub 3} catalysts being reduced at 873 K. This catalyst was chosen for the upgrading of raw bio-oil. After the upgrading process, the pH value of the bio-oil increased from 2.33 to 2.77. The water content increased from 35.52 wt.% to 41.55 wt.% and the gross calorific value increased from 13.96 MJ/kg to 14.17 MJ/kg. The hydrogen content in the bio-oil increased from 6.25 wt.% to 6.95 wt.%. The product properties of the upgraded bio-oil, particularly the hydrogen content and the acidity were considerably improved. The results of gas chromatography-mass spectrometry analysis showed that both hydrotreatment and esterification had happened over 0.06MoNi/{gamma}-Al{sub 2}O{sub 3} (873) catalyst during the upgrading process. (author)

Hydroconversion of Waste Cooking Oil into Green Biofuel over Hierarchical USY-Supported NiMo Catalyst: A Comparative Study of Desilication and Dealumination

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Zongwei Zhang

2017-09-01

Full Text Available The hydroconversion of waste cooking oil into hydrocarbon fuel was investigated over the hierarchical USY zeolite-supported NiMo catalysts which were prepared by dealumination ((NH42SiF6/desilication (NaOH. The physical and acidity properties of the hierarchical catalysts were characterized by X-ray diffraction (XRD, the Brunauer-Emmett-Teller (BET infrared spectroscopy of adsorbed pyridine (Py-IR, ammonia temperature-programmed desorption (NH3-TPD, and H2 temperature-programmed reduction (H2-TPR. The Brønsted/Lewis (B/L acid distribution was little affected by dealumination and the acid density decreased significantly. However, the highly-desilicated catalysts decreased the B/L ratio obviously. Therefore, many more Mo species in the NiMoO4− and MoO3 phases were produced in the AHFS-treated catalysts, while more high-valence-state Mo species in the NiMoO4− phase were formed in the NaOH-treated catalysts. The AHFS-treated catalysts showed higher catalytic activity and better DCO2 selectivity and selective cracking for jet fuel. The 42.3% selectivity of jet fuel and 13.5% selectivity of jet-range aromatics was achieved over the 8 wt % (NH42SiF6-treated catalyst with 67% DCO2 selectivity.

Very large refrigerant capacity at room temperature with reproducible magnetocaloric effect in Fe0.975Ni0.025Rh

International Nuclear Information System (INIS)

Manekar, Meghmalhar; Roy, S B

2011-01-01

We present the results of magnetocaloric effect (MCE) measurements on Fe 0.975 Ni 0.025 Rh. The MCE is estimated using both the isothermal field-dependent magnetization and the temperature-dependent magnetization in constant magnetic fields. We find a very large effective refrigerant capacity of nearly 492.8 J kg -1 , with the hot end at about 307 K, which is reproducible over many field cycles. We compare this refrigerant capacity with those of two well known systems, namely Gd 5 Ge 1.9 Si 2 Fe 0.1 and MnFeP 0.45 As 0.55 , which show a large MCE near room temperature, and also with our earlier results on the parent Fe-Rh alloy. The large effective refrigerant capacity in our sample is one of the largest achieved yet at room temperature with a significant improvement over the parent Fe-Rh system. (fast track communication)

Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst

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Istadi Istadi

2011-11-01

Full Text Available Major problem in CO2 reforming of methane (CORM process is coke formation which is a carbonaceous residue that can physically cover active sites of a catalyst surface and leads to catalyst deactivation. A key to develop a more coke-resistant catalyst lies in a better understanding of the methane reforming mechanism at a molecular level. Therefore, this paper is aimed to simulate a micro-kinetic approach in order to calculate coking rate in CORM reaction. Rates of encapsulating and filamentous carbon formation are also included. The simulation results show that the studied catalyst has a high activity, and the rate of carbon formation is relatively low. This micro-kinetic modeling approach can be used as a tool to better understand the catalyst deactivation phenomena in reaction via carbon deposition. Copyright © 2011 BCREC UNDIP. All rights reserved.(Received: 10th May 2011; Revised: 16th August 2011; Accepted: 27th August 2011[How to Cite: I. Istadi, D.D. Anggoro, N.A.S. Amin, and D.H.W. Ling. (2011. Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 129-136. doi:10.9767/bcrec.6.2.1213.129-136][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.2.1213.129-136 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/1213 ] | View in  |  

Synergy in Lignin Upgrading by a Combination of Cu-Based Mixed Oxide and Ni-Phosphide Catalysts in Supercritical Ethanol.

Science.gov (United States)

Korányi, Tamás I; Huang, Xiaoming; Coumans, Alessandro E; Hensen, Emiel J M

2017-04-03

The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu-Mg-Al oxide (CuMgAlO x ) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e. Ni/SiO 2 , Ni 2 P/SiO 2 , and Ni/ASA (ASA = amorphous silica alumina), with the aim of combining lignin depolymerization and HDO in a single reaction step. While the silica-supported catalysts were themselves hardly active in lignin upgrading, Ni/ASA displayed comparable lignin monomer yield as CuMgAlO x . A drawback of using an acidic support is extensive dehydration of the ethanol solvent. Instead, combining CuMgAlO x with Ni/SiO 2 and especially Ni 2 P/SiO 2 proved to be effective in increasing the lignin monomer yield, while at the same time reducing the oxygen content of the products. With Ni 2 P/SiO 2 , the lignin monomer yield was 53 wt %, leading to nearly complete deoxygenation of the aromatic products.

Synthesis of renewable diesel through hydrodeoxygenation reaction from nyamplung oil (Calophyllum Inophyllum oil) using NiMo/Z and NiMo/C catalysts with rapid heating and cooling method

Science.gov (United States)

Susanto, B. H.; Prakasa, M. B.; Shahab, M. H.

2016-11-01

The synthesis of metal nanocrystal was conducted by modification preparation from simple heating method which heating and cooling process run rapidly. The result of NiMo/Z 575 °C characterizations are 33.73 m2/gram surface area and 31.80 nm crystal size. By used NiMo/C 700 °C catalyst for 30 minutes which had surface area of 263.21 m2/gram, had 31.77 nm crystal size, and good morphology, obtained catalyst with high activity, selectivity, and stability. After catalyst activated, synthesis of renewable diesel performed in hydrogenation reactor at 375 °C, 12 bar, and 800 rpm. The result of conversion was 81.99%, yield was 68.08%, and selectivity was 84.54%.

Hydrodeoxygenation of Methyl Laurate over Ni Catalysts Supported on Hierarchical HZSM-5 Zeolite

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Nana Li

2017-12-01

Full Text Available The hierarchical HZSM-5 zeolite was prepared successfully by a simple NaOH treatment method. The concentration of NaOH solution was carefully tuned to optimal the zeolite acidity and pore structure. Under NaOH treatment conditions, a large number of mesopores, which interconnected with the retained micropores, were created to facilitate mass transfer performance. There are very good correlations between the decline of the relative zeolite crystallinity and the loss of micropores volume. The Ni nanoclusters were uniformly confined in the mesopores of hierarchical HZSM-5 by the excessive impregnation method. The direct deoxygenation in N2 and hydrodeoxygenation in H2 of the methyl laurate were compared respectively over the Ni/HZSM-5 catalysts. In the N2 atmosphere, the deoxygenation rate of the methyl laurate on the Ni/HZSM-5 catalyst is relatively slow. In the presence of H2, the synergistic effect between the hydrogenation function of the metal and the acid function of the zeolite supports can make the deoxygenation level more obvious. The yield of hydrocarbon products gradually reached the maximum with the appropriate treatment concentration of 1M NaOH, which could be attributed to the improved mass transfer in the hierarchical HZSM-5 supports.

Enhancement of Glycerol Steam Reforming Activity and Thermal Stability by Incorporating CeO2 and TiO2 in Ni- and Co-MCM-41 Catalysts

Science.gov (United States)

Dade, William N.

Hydrogen (H2) has many applications in industry with current focus shifted to production of hydrocarbon fuels and valuable oxygenates using the Fischer-Tropsch technology and direct use in proton exchange membrane fuel cell (PEMFC). Hydrogen is generally produced via steam reforming of natural gas or alcohols like methanol and ethanol. Glycerol, a by-product of biodiesel production process, is currently considered to be one of the most attractive sources of sustainable H2 due to its high H/C ratio and bio-based origin. Ni and Co based catalysts have been reported to be active in glycerol steam reforming (GSR); however, deactivation of the catalysts by carbon deposition and sintering under GSR operating conditions is a major challenge. In this study, a series of catalysts containing Ni and Co nanoparticles incorporated in CeO2 and TiO2 modified high surface area MCM-41 have been synthesized using one-pot method. The catalysts are tested for GSR (at H2O/Glycerol mole ratio of 12 and GHSV of 2200 h-1) to study the effect of support modification and reaction temperature (450 - 700 °C) on the product selectivity and long term stability. GSR results revealed that all the catalysts performed significantly well exhibiting over 85% glycerol conversion at 650 °C except Ni catalysts that showed better low temperature activities. Deactivation studies of the catalysts conducted at 650 °C indicated that the Ni-TiO2-MCM-41 and Ni-CeO 2-MCM-41 were resistant to deactivation with ˜100% glycerol conversion for 40 h. In contrast, Co-TiO2-MCM-41 perform poorly as the catalyst rapidly deactivated after 12 h to yield ˜20% glycerol conversion after 40 h. The WAXRD and TGA-DSC analyses of spent catalysts showed a significant amount of coke deposition that might explain catalysts deactivation. The flattening shape of the original BET type IV isotherm with drastic reduction of catalyst surface area can also be responsible for observed drop in catalysts activities.

Microstructural study of Ni/γ-Al2O3 catalyst: addition effects of CeO2 on carbon dioxide reforming of methane

International Nuclear Information System (INIS)

Valentini, Antoninho; Probst, Luiz Fernando Dias; Carreno, Neftali L. V.; Leite, Edson R.; Pontes, Fenelon M.; Longo, Elson; Schreiner, Wido H.; Lisboa-Filho, Paulo N.

2003-01-01

The carbon dioxide reforming of methane was carried out over nickel catalysts supported on the γ-Al 2 O 3 /CeO 2 system prepared by wet impregnation. With the increase of the Co2 weight in the catalyst, a higher stability was observed in the catalytic activity, together with an excellent resistance to carbon deposition and a better Ni dispersion. The catalysts were characterized by means of surface area measurements, TPR, H 2 chemisorption, XRD, SEM, EDX, XPS and TEM. An interaction between Ni and CeO 2 was observed to the Ni/CeO 2 sample after activation in a H 2 atmosphere above 300 deg C. Such behavior has a significantly influence on the catalytic activity. (author)

Origin of low temperature deactivation of Ni5Ga3 nanoparticles as catalyst for methanol synthesis

DEFF Research Database (Denmark)

Gardini, Diego; Sharafutdinov, Irek; Damsgaard, Christian Danvad

that the highest methanol yield is obtained with a Ni5Ga3 alloy exposed to a 25% CO2 – 75% H2 reaction mixture at 210 °C [2]. Under these experimental conditions, the catalyst is found to lose 35% of its activity after 20 hours of continuous testing at both 1 and 5 Bars. Although in situ XRD and EXAFS studies [3......In an effort to find alternative energy sources capable to compete with fossil fuels, methanol synthesis could represent a realistic solution to store “green” hydrogen produced from electrolysis or photo-induced water splitting. Recently, density functional theory (DFT) calculations [1] proposed Ni......-Ga alloys as active catalysts for methanol production from syngas mixtures and Ni-Ga nanoparticles supported on highly porous silica have been prepared using an incipient wetness impregnation technique from a solution of nickel and gallium nitrates [2]. Tests conducted in a fixed-bed reactor showed...

Conversion of furan derivatives for preparation of biofuels over Ni-Cu/C catalyst

DEFF Research Database (Denmark)

Fu, Zhaolin; Wang, Z.; Lin, Weigang

2017-01-01

Conversions of furfural and 5-hydroxymethylfurfural as model components in bio-oil were investigated over Ni-Cu/C catalyst with formic acid as hydrogen donor in isopropanol solvent to produce biofuels. The effects of reaction temperature, feed ratio, and reaction time were studied. A high yield...... of 2-methylfuran up to 91 mol% was obtained from furfural in 8 h at 200°C, and under same conditions 80 mol% yield of 2,5-dimethylfuran could also be obtained from 5-hydroxymethylfurfural in 6 h. The results verified the catalyst performance and the availability of the reaction conditions for producing...

Promotion Effect of CaO Modification on Mesoporous Al2O3-Supported Ni Catalysts for CO2 Methanation

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Wen Yang

2016-01-01

Full Text Available The catalysts Ni/Al2O3 and CaO modified Ni/Al2O3 were prepared by impregnation method and applied for methanation of CO2. The catalysts were characterized by N2 adsorption/desorption, temperature-programmed reduction of H2 (H2-TPR, X-ray diffraction (XRD, and temperature-programmed desorption of CO2 and H2 (CO2-TPD and H2-TPD techniques, respectively. TPR and XRD results indicated that CaO can effectively restrain the growth of NiO nanoparticles, improve the dispersion of NiO, and weaken the interaction between NiO and Al2O3. CO2-TPD and H2-TPD results suggested that CaO can change the environment surrounding of CO2 and H2 adsorption and thus the reactants on the Ni atoms can be activated more easily. The modified Ni/Al2O3 showed better catalytic activity than pure Ni/Al2O3. Ni/CaO-Al2O3 showed high CO2 conversion especially at low temperatures compared to Ni/Al2O3, and the selectivity to CH4 was very close to 1. The high CO2 conversion over Ni/CaO-Al2O3 was mainly caused by the surface coverage by CO2-derived species on CaO-Al2O3 surface.

Hydrogenation of Levulinic Acid over Nickel Catalysts Supported on Aluminum Oxide to Prepare γ-Valerolactone

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Jie Fu

2015-12-01

Full Text Available Four types of nickel catalysts supported on aluminum oxide (Ni/Al2O3 with different nickel loadings were synthesized using the co-precipitation method and were used for the hydrogenation of levulinic acid (LA to prepare γ-valerolactone (GVL. The synthesized Ni/Al2O3 catalysts exhibited excellent catalytic activity in dioxane, and the activity of the catalysts was excellent even after being used four times in dioxane. The catalytic activity in dioxane as a solvent was found to be superior to the activity in water. Nitrogen physisorption, X-ray diffraction, and transmission electron microscopy were employed to characterize the fresh and used catalysts. The effects of the nickel loading, temperature, hydrogen pressure, and substrate/catalyst ratio on the catalytic activity were investigated.

Influences of doping Cr/Fe/Ta on the performance of Ni/CeO{sub 2} catalyst under microwave irradiation in dry reforming of CH{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Odedairo, Taiwo [School of Chemical Engineering, The University of Queensland, St Lucia, Brisbane (Australia); Ma, Jun [School of Engineering, University of South Australia, Mawson Lakes, SA (Australia); Chen, Jiuling, E-mail: cjlchen@yahoo.com [School of Chemical Engineering, The University of Queensland, St Lucia, Brisbane (Australia); Wang, Shaobin [Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA 6845 (Australia); Zhu, Zhonghua, E-mail: z.zhu@uq.edu.au [School of Chemical Engineering, The University of Queensland, St Lucia, Brisbane (Australia)

2016-01-15

The structure of Ni/CeO{sub 2} catalyst with doping of Cr, Fe and Ta was investigated with XRD, N{sub 2} physisorption, XPS and HRTEM and the catalytic activity of the catalysts under microwave irradiation in dry reforming of methane was tested in a microwave reactor. The results show that the introduction of Cr and Ta to Ni/CeO{sub 2} can enhance the interaction between Ni and the support/promoter and inhibit the enlargement of NiO particles during the synthesis. The CH{sub 4} conversions in dry reforming on the catalysts follow the order: Ni/CeO{sub 2}<2Fe–Ni<2Ta–Ni<2Cr–Ni. The superior performance of 2Ta–Ni and 2Cr–Ni may be attributed to the locally-heated Ni particles caused by the strong microwave absorption of the in-situ grown graphene attached on them under microwave irradiation. - Highlights: • The influences of doping Cr, Fe and Ta on Ni/CeO{sub 2} were investigated. • The catalytic performances before and after doping were investigated. • The in-situ grown graphene can promote the conversion of reactants.

Activity of PtSnRh/C nanoparticles for the electrooxidation of C1 and C2 alcohols

International Nuclear Information System (INIS)

Teran, Freddy E.; Santos, Deise M.; Ribeiro, Josimar; Kokoh, Kouakou B.

2012-01-01

A systematic investigation of alcohol adsorption and oxidation on binary and ternary electrocatalysts in acid medium was performed. Binary (PtRh) and ternary (PtRhSn) were prepared by the Pechini modified method on carbon Vulcan XC-72, and different nominal compositions were characterized by energy dispersive X-ray and X-ray diffraction (XRD) techniques. The XRD results showed that the Pt 80 Rh 20 /C and Pt 70 Sn 10 Rh 20 /C electrocatalysts consisted of the Pt displaced phase, suggesting the formation of a solid solution between the metals Pt/Rh and Pt/Sn. Electrochemical investigations on these different electrode materials were carried out as a function of the electrocatalyst composition, in acid medium (0.5 mol dm −3 H 2 SO 4 ), and in the absence and presence of different alcohols (methanol, ethanol and ethylene glycol). The electrochemical results obtained at room temperature have shown that the Pt 70 Sn 10 Rh 20 /C catalyst display better catalytic activity for alcohol oxidation compared with the binary catalyst. In situ reflectance infrared spectroscopy measurements have shown that the oxidation of alcohols mentioned produced CO 2 at low potentials indicating that the materials synthesized could be used as efficient anodes in the fuel cell applications. - Highlights: ► Pt-based catalysts were synthesized by thermal decomposition polymeric precursors. ► Pt 70 Sn 10 Rh 20 /C displays better catalytic activity for the oxidation of alcohols. ► The co-catalysts tin and rhodium promote the removal of CO to CO 2 at low potentials. ► Ethylene glycol is oxidizing strongly to CO 2 at low potentials. ► Pt 70 Sn 10 Rh 20 /C catalyst is an efficient anode material for a direct alcohol fuel cell.

Cuboid Ni2 P as a Bifunctional Catalyst for Efficient Hydrogen Generation from Hydrolysis of Ammonia Borane and Electrocatalytic Hydrogen Evolution.

Science.gov (United States)

Du, Yeshuang; Liu, Chao; Cheng, Gongzhen; Luo, Wei

2017-11-16

The design of high-performance catalysts for hydrogen generation is highly desirable for the upcoming hydrogen economy. Herein, we report the colloidal synthesis of nanocuboid Ni 2 P by the thermal decomposition of nickel chloride hexahydrate (NiCl 2 ⋅6 H 2 O) and trioctylphosphine. The obtained nanocuboid Ni 2 P was characterized by using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy. For the first time, the as-synthesized nanocuboid Ni 2 P is used as a bifunctional catalyst for hydrogen generation from the hydrolysis of ammonia borane and electrocatalytic hydrogen evolution. Owing to the strong synergistic electronic effect between Ni and P, the as-synthesized Ni 2 P exhibits catalytic performance that is superior to its counterpart without P doping. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of transition metal-doped Ni(211) for CO dissociation: Insights from DFT calculations

Energy Technology Data Exchange (ETDEWEB)

Yang, Kuiwei; Zhang, Minhua [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China)

2017-03-31

Highlights: • Doping the step edge of Ni(211) with Fe or Ru observably enhances CO dissociation. • Rh doping is unfavorable for CO activation both kinetically and thermodynamically. • Two neat linear relations are proposed besides the Brønsted–Evans–Polanyi relation. • The differences of CO adsorption are rationalized via the Blyholder model. - Abstract: Density functional theory slab calculations were performed to investigate the adsorption and dissociation of CO over pure and M-doped Ni(211) (M = Fe, Co, Ru and Rh) with the aim to elucidate the effect of transition metal doping for CO activation. Doping the step edge of Ni(211) with Fe, Co and Ru is found to enhance the binding of CO in the initial state (IS) (in the sequence by the improvement degree: Fe > Ru > Co) as well as the co-adsorption of C and O in the final state (FS) (Ru > Fe > Co). In contrast, Rh doping is unfavorable both in the IS and in the FS. Analysis of the overall potential energy surfaces (PES) suggests CO dissociation is facilitated by Fe, Ru and Co doping both kinetically and thermodynamically, wherein Fe and Ru behave extraordinary. Interestingly, Fe substitute is slightly superior to Ru in kinetics whereas the contrary is the case in thermodynamics. Rh doping elevates the energy height from 0.97 eV on Ni(211) to 1.32 eV and releases 0.39 eV less heat relative to Ni(211), again manifesting a negative effect. Besides the classical Brønsted–Evans–Polanyi relationship, we put forward another two neat linear relations, which can well describe the feature of CO dissociation. The differences of CO adsorption and activation in the IS over pure and doped Ni(211) surfaces are rationalized via electronic structure analysis. The findings presented herein are expected to provide theoretical guidance for catalyst design and optimization in relevant processes.

Influence of Solvent on Liquid Phase Hydrodeoxygenation of Furfural-Acetone Condensation Adduct using Ni/Al2O3-ZrO2 Catalysts

Science.gov (United States)

Ulfa, S. M.; Mahfud, A.; Nabilah, S.; Rahman, M. F.

2017-02-01

Influence of water and acidic protic solvent on hydrodeoxygenation (HDO) of the furfural-acetone adduct (FAA) over Ni/Al2O3-ZrO2 (NiAZ) catalysts were investigated. The HDO of FAA was carried out in a batch reactor at 150°C for 8 hours. The NiAZ catalysts were home-made catalysts which were prepared by wet impregnation method with 10 and 20% nickel loading. The HDO reaction of FAA using 10NiAZ in water at 150°C gave alkane and oxygenated hydrocarbons at 31.41% with selectivity over tridecane (C13) in 6.67%. On the other hand, a reaction using acetic acid:water (1:19 v/v) in similar reaction condition gave only oxygenated compounds and hydrocracking product (C8-C10). The formation of tridecane (C13) was proposed by hydrogenation of C=O and C=C followed by decarboxylation without hydrocracking process. The presence of water facilitated decarboxylation mechanism by stabilized dehydrogenated derivatives of FAA.

High-Performance Rh ₂ P Electrocatalyst for Efficient Water Splitting

Energy Technology Data Exchange (ETDEWEB)

Duan, Haohong [Department; Chemistry; Li, Dongguo [Materials; Tang, Yan [Department; amp, Molecular; He, Yang [Department; Ji, Shufang [Department; Wang, Rongyue [Materials; Lv, Haifeng [Materials; Lopes, Pietro P. [Materials; Paulikas, Arvydas P. [Materials; Li, Haoyi [Department; amp, Molecular; Mao, Scott X. [Department; Wang, Chongmin [Environmental; Markovic, Nenad M. [Materials; Li, Jun [Department; amp, Molecular; Stamenkovic, Vojislav R. [Materials; Li, Yadong [Department

2017-04-05

The search for active, stable, and cost-efficient electrocatalysts for hydrogen production via water splitting could make a substantial impact on energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high-surface-area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction and oxygen evolution reaction compared to Rh/C and Pt/C catalysts. The atomic structure of the Rh2P NCs was directly observed by annular dark-field scanning transmission electron microscopy, which revealed a phosphorus-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorus plays a crucial role in determining the robust catalyst properties.

Catalisadores Ni/Al2O3 promovidos com molibdênio para a reação de reforma a vapor de metano Mo-Ni/AL2O3 catalysts for the methane steam reforming reaction

Directory of Open Access Journals (Sweden)

Silvia Sálua Maluf

2003-03-01

Full Text Available Mo-promoted Ni/Al2O3 catalysts for the methane steam reforming reaction were studied in this work. The Ni/Al2O3 catalysts were prepared by precipitation and molibdenum was added by impregnation up to 2%wt. The solids were tested using a micro-reactor under two H2Ov/C conditions and were characterized by ICP-OES, XRD, N2 adsoption, H2 chemisorption and TPR. NiO and NiAl2O4 phases were observed and the metallic area decreased with the increase of the Mo content. From the catalytic tests high stability was verified for H2Ov/C=4.0. On the other hand, only the catalyst containing 0,05% Mo stayed stable during 30 hours of the test at H2Ov/C=2.0.

High efficient conversion of furfural to 2-methylfuran over Ni-Cu/Al2O3 catalyst with formic acid as a hydrogen donor

DEFF Research Database (Denmark)

Fu, Zhaolin; Wang, Ze; Lin, Weigang

2017-01-01

Conversion of furfural to 2-methylfuran over Cu/Al2O3, Ni/Al2O3 and Ni-Cu/Al2O3 catalysts were investigated with formic acid as a hydrogen donor. Ni/Al2O3 showed a high catalytic activity but a moderate selectivity to 2-methylfuran. Contrarily, Cu/Al2O3 showed a low catalytic activity but a high...... selectivity for carbonyl reduction. Over the bimetallic catalysts Ni-10%Cu/Al2O3, by increasing Ni content, more furfural was converted with the reduction of carbonyl primarily. The effect of reaction solvent and the fraction of formic acid were also studied. The result showed that isopropanol solvent could...

Efficient Photocatalytic Degradation of Malachite Green in Seawater by the Hybrid of Zinc-Oxide Nanorods Grown on Three-Dimensional (3D Reduced Graphene Oxide(RGO/Ni Foam

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Qing Wang

2018-06-01

Full Text Available A hybrid of ZnO nanorods grown onto three-dimensional (3D reduced graphene oxide (RGO@Ni foam (ZnO/RGO@NF is synthesized by a facile hydrothermal method. The as-prepared hybrid material is physically characterized by SEM, XRD, Raman, and X-ray photoelectron spectroscopy (XPS. When the as-prepared 3D hybrid is investigated as a photocatalyst, it demonstrates significant high photocatalytic activity for the degradation of methylene blue (MB, rhodamine (RhB, and mixed MB/RhB as organic dye pollutants. In addition, the practical application and the durability of the as-prepared catalyst to degradation of malachite green (MG in seawater are firstly assessed in a continuous flow system. The catalyst shows a high degradation efficiency and stable photocatalytic activity for 5 h continuous operation, which should be a promising catalyst for the degradation of organic dyes in seawater.

The effect of noble metals on catalytic methanation reaction over supported Mn/Ni oxide based catalysts

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Wan Azelee Wan Abu Bakar

2015-09-01

Full Text Available Carbon dioxide (CO2 in sour natural gas can be removed using green technology via catalytic methanation reaction by converting CO2 to methane (CH4 gas. Using waste to wealth concept, production of CH4 would increase as well as creating environmental friendly approach for the purification of natural gas. In this research, a series of alumina supported manganese–nickel oxide based catalysts doped with noble metals such as ruthenium and palladium were prepared by wetness impregnation method. The prepared catalysts were run catalytic screening process using in-house built micro reactor coupled with Fourier Transform Infra Red (FTIR spectroscopy to study the percentage CO2 conversion and CH4 formation analyzed by GC. Ru/Mn/Ni(5:35:60/Al2O3 calcined at 1000 °C was found to be the potential catalyst which gave 99.74% of CO2 conversion and 72.36% of CH4 formation at 400 °C reaction temperature. XRD diffractogram illustrated that the supported catalyst was in polycrystalline with some amorphous state at 1000 °C calcination temperature with the presence of NiO as active site. According to FESEM micrographs, both fresh and used catalysts displayed spherical shape with small particle sizes in agglomerated and aggregated mixture. Nitrogen Adsorption analysis revealed that both catalysts were in mesoporous structures with BET surface area in the range of 46–60 m2/g. All the impurities have been removed at 1000 °C calcination temperature as presented by FTIR, TGA–DTA and EDX data.

Analysis and removal of heteroatom containing species in coal liquid distillate over NiMo catalysts

Energy Technology Data Exchange (ETDEWEB)

S.D. Sumbogo Murtia; Ki-Hyouk Choi; Kinya Sakanishi; Osamu Okuma; Yozo Korai; Isao Mochida [Kyushu University, Fukuoka (Japan). Institute for Materials Chemistry and Engineering

2005-02-01

Heteroatom containing molecules in South Banko coal liquid (SBCL) distillate were identified with a gas chromatograph equipped with an atomic emission detector (GC-AED). Thiophenes and benzothiophenes were found to be the major sulfur compounds. Pyridines, anilines, and phenols were the major nitrogen and oxygen compounds, respectively. Reactivities of heteroatom containing species in hydrotreatment over conventional NiMoS/Al{sub 2}O{sub 3}, NiMoS/Al{sub 2}O{sub 3}-SiO{sub 2} catalysts were very different according to their cyclic structure as well as the kind of heteroatom in the species. The sulfur species were completely desulfurized over the catalysts examined in the present study by 60 min at 360{degree}C under initial hydrogen pressure of 5 MPa. However, hydrodenitrogenation was more difficult than hydrodesulfurization even at 450{degree}C. Anilines were found the most refractory ones among the nitrogen species. Hydrodeoxygenation of SBCL was also difficult in the hydrotreatment conditions examined in the present study. Dibenzofuran was the most refractory molecule among the oxygen species. A two-stage reaction configuration at 340 and 360{degree}C improved HDN and HDO reactivities, although the conversions were still insufficient. Increasing the acidity of the support as well as the loading of the metals on the NiMoS/Al{sub 2}O{sub 3} catalysts improved very much the heteroatom reduction to achieve complete removal of nitrogen by two-stage reaction configuration at 340-360{degree}C and oxygen at 360{degree}C, respectively. The addition of H{sub 2}S in the reaction atmosphere inhibited the HDN reaction but increased markedly the HDO conversion. The acidic support increased the activity in hydrotreatment through enhancing the hydrogenation activity, while H{sub 2}S maintained the catalyst in a sufficiently sulfided state. 19 refs., 4 figs., 8 tabs.

Transformation of Sodium Bicarbonate and CO2 into Sodium Formate over NiPd Nanoparticle Catalyst

Science.gov (United States)

Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

2013-09-01

The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

Hydrogenation/Deoxygenation (H/D Reaction of Furfural-Acetone Condensation Product using Ni/Al2O3-ZrO2 Catalyst

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Adam Mahfud

2016-08-01

Full Text Available The catalytic hydrogenation/deoxygenation (H/D reaction was carried out using Ni/Al2O3-ZrO2 catalyst. The 10% (wt/wt of Ni were impregnated on Al2O3-ZrO2 (10NiAZ by wet impregnation method followed by calcination and reduction. X-Ray diffraction analysis showed that Nideposited on the surface, with specific surface areas (SBET was 48.616 m2/g. Catalyst performance were evaluated for H/D reaction over furfural-acetone condensation products, mixture of 2-(4-furyl-3-buten-2-on and 1,5-bis-(furan-2-yl-pentan-3-one. The reaction was carried out in a batch, performed at 150°C for 8 hours. The H/D reaction gave alkane derivatives C8 and C10 by hydrogenation process followed by ring opening of furan in 15.2% yield. While, oxygenated product C10-C13 were also detected in 17.2% yield. The increasing of pore volume of 10NiAZ might enhance catalyst activity over H/D reaction. The alkene C=C bond was easy to hydrogenated under this condition by the lower bond energy gap.

Synergetic effects leading to coke-resistant NiCo bimetallic catalysts for dry reforming of methane

KAUST Repository

Li, Lidong; Anjum, Dalaver; Zhu, Haibo; Saih, Youssef; Laveille, Paco; D'Souza, Lawrence; Basset, Jean-Marie

2015-01-01

A new dry reforming of methane catalyst comprised of NiCo bimetallic nanoparticles and a Mgx(Al)O support that exhibits high coke resistance and long-term on-stream stability is reported. The structural characterization by XRD, TEM, temperature

Carbon-embedded Ni nanocatalysts derived from MOFs by a sacrificial template method for efficient hydrogenation of furfural to tetrahydrofurfuryl alcohol.

Science.gov (United States)

Su, Yanping; Chen, Chun; Zhu, Xiaoguang; Zhang, Yong; Gong, Wanbing; Zhang, Haimin; Zhao, Huijun; Wang, Guozhong

2017-05-16

We report a fast and simple method for the synthesis of Ni-based metal-organic-frameworks (Ni-MOFs). Due to the existence of nickel ions and an organic ligand, the MOFs are employed as a sacrificial template for the facile preparation of carbon-embedded Ni (Ni/C) catalysts by a direct thermal decomposition method. The obtained Ni/C catalysts exhibit excellent catalytic activity for selectively transforming furfural (FAL) to tetrahydrofurfuryl alcohol (THFOL) due to the Ni nanoparticles (NPs) embedded uniformly in the ligand-derived carbon. The exemplified results illustrate that the catalytic performance of the Ni/C catalyst is greatly affected by the calcination conditions (temperature and time), composition of the Ni-MOF precursor and the catalysis conditions. The conversion of FAL and selectivity of THFOL both reached 100% under the conditions of 120 °C, 1 MPa H 2 pressure and 120 min of hydrogenation over the Ni/C-500 catalyst, derived from the pyrolysis of Ni-MOFs (Ni : BTC mole ratio of 1.0) at 500 °C for 120 min, which exhibits an average nanoparticle size of ∼14 nm and uniform dispersion, and the highest BET surface area (∼92 m 2 g -1 ) among all investigated Ni/C catalysts. This facilely prepared heterogeneous catalyst would be very promising for the replacement of noble metal catalysts for the efficient catalytic conversion of biomass-derived feedstocks into value-added chemicals.

CO and ethanol electro-oxidation on Pt-Rh/C

OpenAIRE

Calderón-Cárdenas, Alfredo; Ortiz-Restrepo, John E.; Mancilla-Valencia, Nelson D.; Torres-Rodriguez, Gerardo A.; Lima, Fabio H. B.; Bolaños-Rivera, Alberto; Gonzalez, Ernesto R.; Lizcano-Valbuena, William H.

2014-01-01

In this work we studied the effect of the composition and thermal treatment in H2 of Pt-Rh/C materials with atomic ratios close to Pt:Rh 3:1, 1:1 and 1:3 and metal loading of 40 wt. %, for the COads and ethanol oxidation. Catalysts were prepared by chemical reduction with formic acid and physically characterized by energy dispersive X-rays spectroscopy (EDX), electron backscattering (EBS) and transmission electron microscopy (TEM), showing Pt:Rh ratios close to the nominals values, similar av...

Rh(I)-Catalyzed Arylation of Heterocycles via C-H Bond Activation: Expanded Scope Through Mechanistic Insight

Energy Technology Data Exchange (ETDEWEB)

Lewis, Jared; Berman, Ashley; Bergman, Robert; Ellman, Jonathan

2007-07-18

A practical, functional group tolerant method for the Rh-catalyzed direct arylation of a variety of pharmaceutically important azoles with aryl bromides is described. Many of the successful azole and aryl bromide coupling partners are not compatible with methods for the direct arylation of heterocycles using Pd(0) or Cu(I) catalysts. The readily prepared, low molecular weight ligand, Z-1-tert-butyl-2,3,6,7-tetrahydrophosphepine, which coordinates to Rh in a bidentate P-olefin fashion to provide a highly active yet thermally stable arylation catalyst, is essential to the success of this method. By using the tetrafluoroborate salt of the corresponding phosphonium, the reactions can be assembled outside of a glove box without purification of reagents or solvent. The reactions are also conducted in THF or dioxane, which greatly simplifies product isolation relative to most other methods for direct arylation of azoles employing high-boiling amide solvents. The reactions are performed with heating in a microwave reactor to obtain excellent product yields in two hours.

Syngas Production from Catalytic CO2 Reforming of CH4 over CaFe2O4 Supported Ni and Co Catalysts: Full Factorial Design Screening

Directory of Open Access Journals (Sweden)

M. Anwar Hossain

2018-01-01

Full Text Available In this study, the potential of dry reforming reaction over CaFe2O4 supported Ni and Co catalysts were investigated. The Co/CaFe2O4 and Ni/CaFe2O4 catalysts were synthesized using wet impregnation method by varying the metal loading from 5-15 %. The synthesized catalysts were tested in methane dry reforming reaction at atmospheric pressure and reaction temperature ranged 700-800 oC. The catalytic performance of the catalysts based on the initial screening is ranked as 5%Co/CaFe2O4 < 10%Co/CaFe2O4 < 5%Ni/CaFe2O4 < 10%Ni/CaFe2O4 according to their performance. The Ni/CaFe2O4 catalyst was selected for further investigation using full factorial design of experiment. The interaction effects of three factors namely metal loading (5-15 %, feed ratio (0.4-1.0, and reaction temperature (700-800 oC were evaluated on the catalytic activity in terms of CH4 and CO2 conversion as well as H2 and CO yield. The interaction between the factors showed significant effects on the catalyst performance at metal loading, feed ratio and reaction temperature of 15 %, 1.0, and 800 oC. respectively. The 15 wt% Ni/CaFe2O4 was subsequently characterized by Thermogravimetric (TGA, X-ray Diffraction (XRD, Field Emission Scanning Electron Microscopy (FESEM, Energy Dispersive X-ray Spectroscopy (EDX, X-ray Photoelectron Spectroscopy (XPS, N2-physisorption, Temperature Programmed Desorption (TPD-NH3, TPD-CO2, and Fourier Transform Infra Red (FTIR to ascertain its physiochemical properties.  This study demonstrated that the CaFe2O4 supported Ni catalyst has a good potential to be used for syngas production via methane dry reforming. Copyright © 2018 BCREC Group. All rights reserved Received: 5th May 2017; Revised: 8th August 2017; Accepted: 9th August 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Hossain, M.A., Ayodele, B.V., Cheng, C.K., Khan, M.R. (2018. Syngas Production from Catalytic CO2 Reforming of CH4 over CaFe2O4 Supported

NO reduction by CO over noble-metal catalysts under cycled feedstreams

International Nuclear Information System (INIS)

Muraki, H.; Fujitani, Y.

1986-01-01

The reduction of NO with CO was studied over α-Al/sub 2/O/sub 3/-supported Pt, Pd, Rh, Ru, and Ir catalysts. The activities were measured by using cycled feeds and steady noncycled feed. The activity sequence of the catalysts tested was Rh > Ru > Ir > Pd > Pt. The activities of Pt and Pd catalysts were increased under the cycled feed. The periodic operation effect on the Pt catalyst was more predominant than that on the Pd catalyst. The order of periodic operation effect corresponded to the order of their susceptibility to CO self-poisoning

Heterogenization of Homogeneous Catalysts: the Effect of the Support

Energy Technology Data Exchange (ETDEWEB)

Earl, W.L.; Ott, K.C.; Hall, K.A.; de Rege, F.M.; Morita, D.K.; Tumas, W.; Brown, G.H.; Broene, R.D.

1999-06-29

We have studied the influence of placing a soluble, homogeneous catalyst onto a solid support. We determined that such a 'heterogenized' homogeneous catalyst can have improved activity and selectivity for the asymmetric hydrogenation of enamides to amino acid derivatives. The route of heterogenization of RhDuPhos(COD){sup +} cations occurs via electrostatic interactions with anions that are capable of strong hydrogen bonding to silica surfaces. This is a novel approach to supported catalysis. Supported RhDuPhos(COD){sup +} is a recyclable, non-leaching catalyst in non-polar media. This is one of the few heterogenized catalysts that exhibits improved catalytic performance as compared to its homogeneous analog.

Comparison of P-containing {gamma}-Al{sub 2}O{sub 3} supported Ni-Mo bimetallic carbide, nitride and sulfide catalysts for HDN and HDS of gas oils derived from Athabasca bitumen

Energy Technology Data Exchange (ETDEWEB)

Sundaramurthy, V.; Dalai, A.K. [Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon, SK (Canada); Adjaye, J. [Syncrude Edmonton Research Centre, Edmonton, AB (Canada)

2006-09-01

Phosphorus containing {gamma}-Al{sub 2}O{sub 3} supported bimetallic Ni-Mo carbide, nitride and sulfide catalysts have been synthesized from an oxide precursor containing 12.73wt.% Mo, 2.54wt.% Ni and 2.38wt.% P and characterized by elemental analysis, pulsed CO chemisorption, surface area measurements, X-ray diffraction, temperature-programmed reduction and DRIFT spectroscopy of CO adsorption. DRIFT spectroscopy of adsorbed CO on activated catalysts showed that carbide and nitride catalysts have surface exposed sites of Mo{sup o+} (0Ni-Mo carbide, nitride and sulfide catalysts were compared against commercial Ni-Mo/Al{sub 2}O{sub 3} catalyst in a trickle bed reactor using light gas oil and heavy gas oil derived from Athabasca bitumen in the temperature range 340-370 and 375-400{sup o}C respectively at 8.8MPa. The gradual transformation of Ni-Mo carbide and nitride phases into Ni-Mo sulfide phases was observed during precoking period, and the formed Ni-Mo sulfide phases enhanced the HDN and HDS activities of carbide and nitride catalysts. The {gamma}-Al{sub 2}O{sub 3} supported Ni-Mo bimetallic sulfide catalyst was found to be more active for HDN and HDS of light gas oil and heavy gas oil than the corresponding carbide and nitride catalysts on the basis of unit weight. (author)

The thermal stability and catalytic performance of Ce-Zr promoted Rh-Pd/γ-Al2O3 automotive catalysts

International Nuclear Information System (INIS)

Wu Xiaodong; Xu Luhua; Weng Duan

2004-01-01

The noble metals (Rh, Pd) supported on alumina promoted with Ce-Zr mixed oxides were investigated as catalysts under diverse oxidants/reductants ratios of simulated automotive exhaust feed gas. Aging test was performed in air at 1000 deg. C for 20 h. Both fresh and aged catalysts, as well as alumina-supported Ce-Zr mixed powders, were characterized by means of X-ray diffraction (XRD), scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) and X-ray photoelectron spectroscopy (XPS). The results confirmed the oxygen storage capacity of Ce-Zr mixed oxides favored CO, C 3 H 8 and NO conversions in stationary versus dynamic stoichiometric operation. The accelerated aging of the systems produced inconspicuous effect on the phase structure, specific surface area and chemical state of these samples. Accordingly, the aged samples still showed low light-off temperature and broad λ-window, which suggested the relative low relevance of the thermal degradation on the overall catalytic performance of the system

Employment of an ion implantation technique for catalyst coating on various substrates

International Nuclear Information System (INIS)

Bannikov, M.G.; Chattha, J.A.; Zlobin, V.N.; Vasilve, I.P.; Cherkasov, J.A.; Gawrilenko, P.N.

2001-01-01

Catalysts are widely used in the chemical industry as well as in the production of vehicle catalytic converters. Precious metals are employed increasingly as catalytic materials. Traditional methods of coating, such as impregnation, are thought to reduce the porosity and specific area of catalyst thus reducing the catalytic efficiency. Apart from that, impregnation technology leads to the high expense of precious metals. To reduce the content of noble metals in catalysts the ion implantation method of coating has been investigated. Several samples of catalysts on various substrates were prepared by ion implantation technique and tested. New catalysts have shown high nitric oxides (NO/sub x/) and carbon monoxide (CO) conversion efficiency, with the content of noble metals reduced substantially. Experiment has also shown that specific area of substrates coated by an ion implantation had not decreased. Schematic of an ion implanter and experimental results are provided. (author)

Development of Fe-Ni/YSZ-GDC electro-catalysts for application as SOFC anodes. XRD and TPR characterization, and evaluation in ethanol steam reforming reaction

Energy Technology Data Exchange (ETDEWEB)

Paz Fiuza, Raigenis da; Silva, Marcos Aurelio da; Boaventura, Jaime Soares [UFBA, Salvador, Bahia (Brazil). Energy and Materials Science Group

2010-07-01

Electro-catalysts based on Fe-Ni alloys were prepared using physical mixture and modified Pechini methods; they were supported on a composite of Yttria Stabilized Zirconia (YSZ) and Gadolinia Doped Ceria (GDC). The composites had compositions of 35% metal load and 65% support (70% wt. YSZ and 30% wt. GDC mixture) (cermets). The samples were characterized by Temperature-Programmed Reduction (TPR) and X-Ray Diffraction (XRD) and evaluated in ethanol steam reforming at 650 C for six hours and in the temperature range 300 - 900 C. The XRD results showed that the bimetallic sample calcined at 800 C formed a mixed oxide (NiFe{sub 2}O{sub 4}) in spinel structure; after reducing the sample in hydrogen, Ni-Fe alloys were formed. The presence of Ni decreased the final reduction temperature of the NiFe{sub 2}O{sub 4} species. The addition of Fe to Ni anchored to YSZ-GDC increased the hydrogen production and inhibits the carbon deposition. The bimetallic 30Fe5Ni samples reached an ethanol conversion of about 95%, and a hydrogen yield up to 48% at 750 C. In general, the ethanol conversion and hydrogen production were independent of the metal content in the electro-catalyst. However, the substitution of Ni for Fe significantly reduced the carbon deposition on the electro-catalyst: 74, 31 and 9 wt. % in the 35Ni, 20Fe15Ni, and 30Fe5Ni samples, respectively. (orig.)

Ni/SiO2 Catalyst Prepared with Nickel Nitrate Precursor for Combination of CO2 Reforming and Partial Oxidation of Methane: Characterization and Deactivation Mechanism Investigation

Directory of Open Access Journals (Sweden)

Sufang He

2015-01-01

Full Text Available The performance of Ni/SiO2 catalyst in the process of combination of CO2 reforming and partial oxidation of methane to produce syngas was studied. The Ni/SiO2 catalysts were prepared by using incipient wetness impregnation method with nickel nitrate as a precursor and characterized by FT-IR, TG-DTA, UV-Raman, XRD, TEM, and H2-TPR. The metal nickel particles with the average size of 37.5 nm were highly dispersed over the catalyst, while the interaction between nickel particles and SiO2 support is relatively weak. The weak NiO-SiO2 interaction disappeared after repeating oxidation-reduction-oxidation in the fluidized bed reactor at 700°C, which resulted in the sintering of metal nickel particles. As a result, a rapid deactivation of the Ni/SiO2 catalysts was observed in 2.5 h reaction on stream.

Synergistically Enhanced Electrochemical Performance of Ni3S4-PtX (X = Fe, Ni) Heteronanorods as Heterogeneous Catalysts in Dye-Sensitized Solar Cells.

Science.gov (United States)

Huang, Shoushuang; Ma, Dui; Hu, ZhangJun; He, Qingquan; Zai, Jiantao; Chen, Dayong; Sun, Huai; Chen, Zhiwen; Qiao, Qiquan; Wu, Minghong; Qian, Xuefeng

2017-08-23

Platinum (Pt)-based alloys are considerably promising electrocatalysts for the reduction of I - /I 3 - and Co 2+ /Co 3+ redox couples in dye-sensitized solar cells (DSSCs). However, it is still challenging to minimize the dosage of Pt to achieve comparable or even higher catalytic efficiency. Here, by taking full advantages of the Mott-Schottky (M-S) effect at the metal-semiconductor interface, we successfully strategize a low-Pt-based M-S catalyst with enhanced electrocatalytic performance and stability for the large-scale application of DSSCs. The optimized M-S electrocatalyst of Ni 3 S 4 -Pt 2 X 1 (X = Fe, Ni) heteronanorods is constructed by rationally controlling the ratio of Pt to transition metal in the hybrids. It was found that the electrons transferred from Ni 3 S 4 to Pt 2 X 1 at their interface under the Mott-Schottky effect result in the concentration of electrons onto Pt 2 X 1 domains, which subsequently accelerates the regeneration of both I - /I 3 - and Co 2+ /Co 3+ redox shuttles in DSSCs. As a result, the DSSC with Ni 3 S 4 -Pt 2 Fe 1 manifests an impressive power conversion efficiency (PCE) of 8.79% and 5.56% for iodine and cobalt-based electrolyte under AM1.5G illumination, respectively. These PCEs are obviously superior over those with Ni 3 S 4 -Pt, PtFe, Ni 3 S 4 , and pristine Pt electrodes. The strategy reported here is able to be further expanded to fabricate other low-Pt-alloyed M-S catalysts for wider applications in the fields of photocatalysis, water splitting, and heterojunction solar cells.

Transformation of Sodium Bicarbonate and CO2 into Sodium Formate over NiPd Nanoparticle Catalyst

Directory of Open Access Journals (Sweden)

Mengnan eWang

2013-09-01

Full Text Available The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs. Ni NPs and eight NiM (M stands for a second metal NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

Co-Processing of Jatropha-Derived Bio-Oil with Petroleum Distillates over Mesoporous CoMo and NiMo Sulfide Catalysts

Directory of Open Access Journals (Sweden)

Shih-Yuan Chen

2018-02-01

Full Text Available The co-processing of an unconventional type of Jatropha bio-oil with petroleum distillates over mesoporous alumina-supported CoMo and NiMo sulfide catalysts (denoted CoMo/γ-Al2O3 and NiMo/γ-Al2O3 was studied. Either a stainless-steel high-pressure batch-type reactor or an up-flow fixed-bed reaction system was used under severe reaction conditions (330–350 °C and 5–7 MPa, similar to the conditions of the conventional diesel hydrodesulfurization (HDS process. To understand the catalytic performance of the mesoporous sulfide catalysts for co-processing, we prepared two series of oil feedstocks. First, model diesel oils, consisting of hydrocarbons and model molecules with various heteroatoms (sulfur, oxygen, and nitrogen were used for the study of the reaction mechanisms. Secondly, low-grade oil feedstocks, which were prepared by dissolving of an unconventional type of Jatropha bio-oil (ca. 10 wt % in the petroleum distillates, were used to study the practical application of the catalysts. Surface characterization by gas sorption, spectroscopy, and electron microscopy indicated that the CoMo/γ-Al2O3 sulfide catalyst, which has a larger number of acidic sites and coordinatively unsaturated sites (CUS on the mesoporous alumina framework, was associated with small Co-incorporated MoS2-like slabs with high stacking numbers and many active sites at the edges and corners. In contrast, the NiMo/γ-Al2O3 sulfide catalyst, which had a lower number of acidic sites and CUS on mesoporous alumina framework, was associated with large Ni-incorporated MoS2-like slabs with smaller stacking numbers, yielding more active sites at the brims and corresponding to high hydrogenation (HYD activity. Concerning the catalytic performance, the mesoporous CoMo/γ-Al2O3 sulfide catalyst with large CUS number was highly active for the conventional diesel HDS process; unfortunately, it was deactivated when oxygen- and nitrogen-containing model molecules or Jatropha bio

XRD (X-Ray Diffraction) and nitrogen adsorption characterization of Ni-Pt/mordenite catalysts; Caracterizacao por EDX (Espectrometria de Raios-X), DRX (Difracao de Raios-X) e adsorcao de nitrogenio de catalisadores Ni/Pt/mordenita visando sua aplicacao na isomerizacao de n-hexano

Energy Technology Data Exchange (ETDEWEB)

Martins, Geovana do Socorro V.; Sousa, Bianca V.; Rodrigues, Meiry Glaucia F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil)

2008-07-01

The search for molecules of high octane arose great interest in the isomerization processes. Catalysts to the zeolite base have been wide developed for the n-paraffins isomerization. In this work, bimetallic bifunctional catalysts supported on Mordenite zeolite were prepared samples containing 60Pt40Ni (wt.%) metal (Pt). The catalysts were obtained by competitive ion exchange using aqueous solutions of [Pt(NH{sub 3}){sub 4}]Cl{sub 2} and Ni(NH{sub 3}){sub 6}]Cl{sub 2} complexes. The EDS characterization analyses showed incorporation of the nickel and platinum mordenite zeolite. The diffractograms showed competitive ion exchange and calcination processes did not provoke appreciable changes in the zeolitic support framework. The peaks attributed to nickel and platinum oxides was possible to observe in the bimetallic catalysts 60Ni40Pt/MOR. The results of the N{sub 2} physical adsorption of the 60Ni40Pt/MOR showed that it did not have modification in the superficial area of the catalysts. (author)

Acetylene and carbon monoxide oxidation over a Pt/Rh/CeO2/γ-Al2O3 automotive exhaust gas catalyst: kinetic modelling of transient experiments

NARCIS (Netherlands)

Harmsen, J.M.A.; Hoebink, J.H.B.J.; Schouten, J.C.

2001-01-01

The transient kinetics of acetylene (C2H2) conversion by oxygen over a commercial Pt/Rh/CeO2/¿-Al2O3 three-way catalyst have been modelled. Experiments to validate the model were carried out in a fixed-bed reactor with two separate inlets, enabling alternate feeding of acetylene and oxygen.

Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements.

Science.gov (United States)

Back, Seoin; Lim, Juhyung; Kim, Na-Young; Kim, Yong-Hyun; Jung, Yousung

2017-02-01

A single-atom catalyst (SAC) has an electronic structure that is very different from its bulk counterparts, and has shown an unexpectedly high specific activity with a significant reduction in noble metal usage for CO oxidation, fuel cell and hydrogen evolution applications, although physical origins of such performance enhancements are still poorly understood. Herein, by means of density functional theory (DFT) calculations, we for the first time investigate the great potential of single atom catalysts for CO 2 electroreduction applications. In particular, we study a single transition metal atom anchored on defective graphene with single or double vacancies, denoted M@sv-Gr or M@dv-Gr, where M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh or Ru, as a CO 2 reduction catalyst. Many SACs are indeed shown to be highly selective for the CO 2 reduction reaction over a competitive H 2 evolution reaction due to favorable adsorption of carboxyl (*COOH) or formate (*OCHO) over hydrogen (*H) on the catalysts. On the basis of free energy profiles, we identified several promising candidate materials for different products; Ni@dv-Gr (limiting potential U L = -0.41 V) and Pt@dv-Gr (-0.27 V) for CH 3 OH production, and Os@dv-Gr (-0.52 V) and Ru@dv-Gr (-0.52 V) for CH 4 production. In particular, the Pt@dv-Gr catalyst shows remarkable reduction in the limiting potential for CH 3 OH production compared to any existing catalysts, synthesized or predicted. To understand the origin of the activity enhancement of SACs, we find that the lack of an atomic ensemble for adsorbate binding and the unique electronic structure of the single atom catalysts as well as orbital interaction play an important role, contributing to binding energies of SACs that deviate considerably from the conventional scaling relation of bulk transition metals.

Activity of PtSnRh/C nanoparticles for the electrooxidation of C1 and C2 alcohols

Energy Technology Data Exchange (ETDEWEB)

Teran, Freddy E. [Universite de Poitiers, IC2MP UMR CNRS 7285, ' Equipe E-lyse' , 4 rue Michel Brunet-B27, BP 633, 86022 Poitiers cedex (France); Santos, Deise M. [Departamento de Quimica, CCE-UFES, Av. Fernando Ferrari, 514, Goiabeiras-Vitoria, ES (Brazil); Ribeiro, Josimar, E-mail: josimar.ribeiro@ufes.br [Universite de Poitiers, IC2MP UMR CNRS 7285, ' Equipe E-lyse' , 4 rue Michel Brunet-B27, BP 633, 86022 Poitiers cedex (France); Departamento de Quimica, CCE-UFES, Av. Fernando Ferrari, 514, Goiabeiras-Vitoria, ES (Brazil); Kokoh, Kouakou B. [Universite de Poitiers, IC2MP UMR CNRS 7285, ' Equipe E-lyse' , 4 rue Michel Brunet-B27, BP 633, 86022 Poitiers cedex (France)

2012-07-01

A systematic investigation of alcohol adsorption and oxidation on binary and ternary electrocatalysts in acid medium was performed. Binary (PtRh) and ternary (PtRhSn) were prepared by the Pechini modified method on carbon Vulcan XC-72, and different nominal compositions were characterized by energy dispersive X-ray and X-ray diffraction (XRD) techniques. The XRD results showed that the Pt{sub 80}Rh{sub 20}/C and Pt{sub 70}Sn{sub 10}Rh{sub 20}/C electrocatalysts consisted of the Pt displaced phase, suggesting the formation of a solid solution between the metals Pt/Rh and Pt/Sn. Electrochemical investigations on these different electrode materials were carried out as a function of the electrocatalyst composition, in acid medium (0.5 mol dm{sup -3} H{sub 2}SO{sub 4}), and in the absence and presence of different alcohols (methanol, ethanol and ethylene glycol). The electrochemical results obtained at room temperature have shown that the Pt{sub 70}Sn{sub 10}Rh{sub 20}/C catalyst display better catalytic activity for alcohol oxidation compared with the binary catalyst. In situ reflectance infrared spectroscopy measurements have shown that the oxidation of alcohols mentioned produced CO{sub 2} at low potentials indicating that the materials synthesized could be used as efficient anodes in the fuel cell applications. - Highlights: Black-Right-Pointing-Pointer Pt-based catalysts were synthesized by thermal decomposition polymeric precursors. Black-Right-Pointing-Pointer Pt{sub 70}Sn{sub 10}Rh{sub 20}/C displays better catalytic activity for the oxidation of alcohols. Black-Right-Pointing-Pointer The co-catalysts tin and rhodium promote the removal of CO to CO{sub 2} at low potentials. Black-Right-Pointing-Pointer Ethylene glycol is oxidizing strongly to CO{sub 2} at low potentials. Black-Right-Pointing-Pointer Pt{sub 70}Sn{sub 10}Rh{sub 20}/C catalyst is an efficient anode material for a direct alcohol fuel cell.

Synthesis of Green Diesel From Waste Cooking Oil Through Hydrodeoxygenation Technology With NiMo/γ-Al2O3 Catalysts

Directory of Open Access Journals (Sweden)

Heriyanto Heri

2018-01-01

Full Text Available Hydrodeoxygenation (HDO of waste cooking oil (WCO and trapped grease over sulfide catalysts was examined to produce high quality transportation fuel from low-grade resources. The hydrodeoxygenation of waste cooking oils was carried out in a high pressure of 30 and 60 bar and high temperature of 300 – 400 °C in a batch reactor autoclave. NiMo/γ-Al2O3 catalyst was prepared and for the first time tested in hydroprocessing of waste cooking oil. The content of NiMo/γ-Al2O3 in each catalyst was about wCo 5 wt.%. A maximum of 77,97 % green diesel yield was achieved at nearly complete conversion of waste cooking oil using NiMo/γ-Al2O3 at temperature of 400°C, pressure 60 bar and 4 hours of reaction time. The oxygen content was decreased from 14,25 wt.% to 13,35 wt.%, at temperature of 400°C, pressure of 30 bar and 1 hour of reaction time. The Hydrodeoxygenation process was much influenced by temperature, pressure, and time.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

Science.gov (United States)

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-07-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

Deoxygenation of palm kernel oil to jet fuel-like hydrocarbons using Ni-MoS_2/γ-Al_2O_3 catalysts

International Nuclear Information System (INIS)

Itthibenchapong, Vorranutch; Srifa, Atthapon; Kaewmeesri, Rungnapa; Kidkhunthod, Pinit; Faungnawakij, Kajornsak

2017-01-01

Highlights: • The Ni-MoS_2/γ-Al_2O_3 catalysts synthesized using thiourea solution processing. • The Ni-MoS_2 showed semi-amorphous crystallinity with crystallite size of 5–10 nm. • The Ni K-edge XANES and EXAFS indicated the Ni substitution in MoS_2 structure. • A high yield of jet fuel-like hydrocarbon (>90%) from the palm kernel oil feedstock. • The HDO pathway was highly selective, while the DCO_2 and DCO pathways were minor. - Abstract: In the current study, palm kernel oil was used as a renewable feedstock for production of jet fuel-like hydrocarbons via the deoxygenation over the Ni-MoS_2/γ-Al_2O_3 catalyst. The dominant C12 fatty acid content in palm kernel oil makes it promising for jet fuel application. Synthesized by a liquid processing method with thiourea organosulfur agent, the catalyst revealed MoS_2 structure with low stacking, while Ni substitution in the MoS_2 structure and interaction with the Al_2O_3 support were determined based on the Ni K-edge XANES and EXAFS results. A high hydrodeoxygenation (HDO) activity, which as the major pathway in the deoxygenation, was observed upon application of a H_2 pressure of 30–50 bar over Ni-MoS_2/γ-Al_2O_3. The optimum product yield of approximately 92% was obtained mainly from the HDO pathway (∼60%) with 58% selectivity to C10–C12 jet fuel hydrocarbons. The flow property of the jet fuel-like hydrocarbons was more desirable than those obtained from palm olein oil-derived fuel.

A Synthetic Pseudo-Rh: NOx Reduction Activity and Electronic Structure of Pd-Ru Solid-solution Alloy Nanoparticles

Science.gov (United States)

Sato, Katsutoshi; Tomonaga, Hiroyuki; Yamamoto, Tomokazu; Matsumura, Syo; Zulkifli, Nor Diana Binti; Ishimoto, Takayoshi; Koyama, Michihisa; Kusada, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Nagaoka, Katsutoshi

2016-06-01

Rh is one of the most important noble metals for industrial applications. A major fraction of Rh is used as a catalyst for emission control in automotive catalytic converters because of its unparalleled activity toward NOx reduction. However, Rh is a rare and extremely expensive element; thus, the development of Rh alternative composed of abundant elements is desirable. Pd and Ru are located at the right and left of Rh in the periodic table, respectively, nevertheless this combination of elements is immiscible in the bulk state. Here, we report a Pd-Ru solid-solution-alloy nanoparticle (PdxRu1-x NP) catalyst exhibiting better NOx reduction activity than Rh. Theoretical calculations show that the electronic structure of Pd0.5Ru0.5 is similar to that of Rh, indicating that Pd0.5Ru0.5 can be regarded as a pseudo-Rh. Pd0.5Ru0.5 exhibits better activity than natural Rh, which implies promising applications not only for exhaust-gas cleaning but also for various chemical reactions.

Effect of Y{sub 2}O{sub 3} addition to Rh/Al{sub 2}O{sub 3} catalysts on the autothermal reforming of methane; Efeito da adicao de Y{sub 2}O{sub 3} a catalisadores de Rh/Al{sub 2}O{sub 3} na reforma autotermica do metano

Energy Technology Data Exchange (ETDEWEB)

Ribeiro, Vanessa Monteiro; Cardoso, Gabriel Alexandre Lima; Coutinho, Ana Carla da S. Lomba S.; Passos, Fabio Barboza [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Engenharia Quimica e de Petroleo. Lab. de Reatores, Cinetica e Catalise (RECAT)]. E-mail: vanessafisqui@yahoo.com.br

2008-07-01

In this work, the effect of the addition of Y{sub 2}O{sub 3} (with 2%, 5% and 10% weight content) on Rh/{alpha}-Al{sub 2}O{sub 3} catalysts in the autothermal reforming reaction of methane to the production of hydrogen for fuel cells was investigated. The catalysts were characterized by the following techniques: N{sub 2} adsorption, H{sub 2} chemisorption, X-ray diffraction (XRD) and cyclohexane dehydrogenation reaction. The catalysts were also evaluated in the reaction of autothermal reforming. The catalyst with higher Y{sub 2}O{sub 3} content showed the best results both in the cyclohexane dehydrogenation rate and in the conversion of methane. (author)

Produção de hidrogênio a partir da reforma a vapor de etanol utilizando catalisadores Cu/Ni/gama-Al2o3 Hydrogen production by ethanol steam reforming using Cu/Ni/gamma-Al2o3 catalysts

Directory of Open Access Journals (Sweden)

Thaísa A. Maia

2007-04-01

Full Text Available Cu/Ni/gamma-Al2O3 catalysts were prepared by an impregnation method with 2.5 or 5% wt of copper and 5 or 15% wt of nickel and applied in ethanol steam reforming. The catalysts were characterized by atomic absorption spectrophotometry, X-ray diffraction, temperature programmed reduction with hydrogen and nitrogen adsorption. The samples showed low crystallinity, with the presence of CuO and NiO, both as crystallites and in dispersed phase, as well as of NiO-Al2O3. The catalytic tests carried out at 400 ºC, with a 3:1 water/ethanol molar ratio, indicated the 5Cu/5Ni/Al2O3 catalyst as the most active for hydrogen production, with a hydrogen yield of 77% and ethanol conversion of 98%.

Pt-Ni and Pt-Co Catalyst Synthesis Route for Fuel Cell Applications

Science.gov (United States)

Firdosy, Samad A.; Ravi, Vilupanur A.; Valdez, Thomas I.; Kisor, Adam; Narayan, Sri R.

2013-01-01

Oxygen reduction reactions (ORRs) at the cathode are the rate-limiting step in fuel cell performance. The ORR is 100 times slower than the corresponding hydrogen oxidation at the anode. Speeding up the reaction at the cathode will improve fuel cell efficiency. The cathode material is generally Pt powder painted onto a substrate (e.g., graphite paper). Recent efforts in the fuel cell area have focused on replacing Pt with Pt-X alloys (where X = Co, Ni, Zr, etc.) in order to (a) reduce cost, and (b) increase ORR rates. One of these strategies is to increase ORR rates by reducing the powder size, which would result in an increase in the surface area, thereby facilitating faster reaction rates. In this work, a process has been developed that creates Pt-Ni or Pt-Co alloys that are finely divided (on the nano scale) and provide equivalent performance at lower Pt loadings. Lower Pt loadings will translate to lower cost. Precursor salts of the metals are dissolved in water and mixed. Next, the salt mixtures are dried on a hot plate. Finally, the dried salt mixture is heattreated in a furnace under flowing reducing gas. The catalyst powder is then used to fabricate a membrane electrode assembly (MEA) for electrochemical performance testing. The Pt- Co catalyst-based MEA showed comparable performance to an MEA fabri cated using a standard Pt black fuel cell catalyst. The main objective of this program has been to increase the overall efficiencies of fuel cell systems to support power for manned lunar bases. This work may also have an impact on terrestrial programs, possibly to support the effort to develop a carbon-free energy source. This catalyst can be used to fabricate high-efficiency fuel cell units that can be used in space as regenerative fuel cell systems, and terrestrially as primary fuel cells. Terrestrially, this technology will become increasingly important when transition to a hydrogen economy occurs.

The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins

Directory of Open Access Journals (Sweden)

Sondre H. Hopen Eliasson

2017-12-01

Full Text Available Linear alpha olefins (LAOs are key commodity chemicals and petrochemical intermediates that are currently produced from fossil resources. Fatty acids are the obvious renewable starting material for LAOs, which can be obtained via transition-metal-catalyzed decarbonylative dehydration. However, even the best catalysts that have been obtained to date, which are based on palladium, are not active and stable enough for industrial use. To provide insight for design of better catalysts, we here present the first computationally derived mechanism for another attractive transition-metal for this reaction, rhodium. By comparing the calculated mechanisms and free energy profiles for the two metals, Pd and Rh, we single out important factors for a facile, low-barrier reaction and for a stable catalyst. While the olefin formation is rate limiting for both of the metals, the rate-determining intermediate for Rh is, in contrast to Pd, the starting complex, (PPh32Rh(COCl. This complex largely draws its stability from the strength of the Rh(I–CO bond. CO is a much less suitable ligand for the high-oxidation state Rh(III. However, for steric reasons, rhodium dissociates a bulkier triphenylphosphine and keeps the carbonyl during the oxidative addition, which is less favorable than for Pd. When compared to Pd, which dissociates two phosphine ligands at the start of the reaction, the catalytic activity of Rh also appears to be hampered by its preference for high coordination numbers. The remaining ancillary ligands leave less space for the metal to mediate the reaction.

The Effect of Annealing Temperature on Nickel on Reduced Graphene Oxide Catalysts on Urea Electrooxidation

International Nuclear Information System (INIS)

Glass, Dean E.; Galvan, Vicente; Prakash, G.K. Surya

2017-01-01

Highlights: •Nickel was reduced on graphene oxide and annealed under argon from 300 to 700 °C. •Nickel was oxidized from the removal of oxygen groups on the graphene oxide. •Higher annealed catalysts displayed decreased urea electrooxidation currents. •Micro direct urea/hydrogen peroxide fuel cells were employed for the first time. •Ni/rGO catalysts displayed enhanced fuel cell performance than the bare nickel. -- Abstract: The annealing temperature effects on nickel on reduced graphene oxide (Ni/rGO) catalysts for urea electrooxidation were investigated. Nickel chloride was directly reduced in an aqueous solution of graphene oxide (GO) followed by annealing under argon at 300, 400, 500, 600, and 700 °C, respectively. X-ray Diffraction (XRD) patterns revealed an increase in the crystallite size of the nickel nanoparticles while the Raman spectra displayed an increase in the graphitic disorder of the reduced graphene oxide at higher annealing temperatures due to the removal of oxygen functional groups. The Ni/rGO catalysts annealed at higher temperatures displayed oxidized nickel surface characteristics from the Ni 2p X-ray Photoelectron Spectra (XPS) due to the oxidation of the nickel from the oxygen functional groups in the graphitic lattice. In the half-cell testing, the onset potential of urea electrooxidation decreased while the urea electrooxidation currents decreased as the annealing temperature was increased. The nickel catalyst annealed at 700 °C displayed a 31% decrease in peak power density while the catalyst annealed at 300 °C displayed a 13% increase compared with the unannealed Ni/rGO catalyst in the micro direct urea/hydrogen peroxide fuel cells tests.

Preparation of a Ni-MgO-Al2O3 catalyst with high activity and resistance to potassium poisoning during direct internal reforming of methane in molten carbonate fuel cells

Science.gov (United States)

Jang, Won-Jun; Jung, You-Shick; Shim, Jae-Oh; Roh, Hyun-Seog; Yoon, Wang Lai

2018-02-01

Steam reforming of methane (SRM) is conducted using a series of Ni-MgO-Al2O3 catalysts for direct internal reforming (DIR) in molten carbonate fuel cells (MCFCs). Ni-MgO-Al2O3 catalysts are prepared by the homogeneous precipitation method with a variety of MgO loading amounts ranging from 3 to 15 wt%. In addition, each precursor concentrations are systemically changed (Ni: 1.2-4.8 mol L-1; Mg: 0.3-1.2 mol L-1; Al: 0.4-1.6 mol L-1) at the optimized composition (10 wt% MgO). The effects of MgO loading and precursor concentration on the catalytic performance and resistance against poisoning of the catalyst by potassium (K) are investigated. The Ni-MgO-Al2O3 catalyst with 10 wt% MgO and the original precursor concentration (Ni: 1.2 mol L-1; Mg: 0.3 mol L-1; Al: 0.4 mol L-1) exhibits the highest CH4 conversion and resistance against K poisoning even at the extremely high gas space velocity (GHSV) of 1,512,000 h-1. Excellent SRM performance of the Ni-MgO-Al2O3 catalyst is attributed to strong metal (Ni) to alumina support interaction (SMSI) when magnesium oxide (MgO) is co-precipitated with the Ni-Al2O3. The enhanced interaction of the Ni with MgO-Al2O3 support is found to protect the active Ni species against K poisoning.

Catalytic technology in the energy/environment field. Utilization of catalyst in coal pyrolysis and gasification processes; Energy kankyo bun`ya ni okeru shokubai gijutsu. Sekitan no netsubunkai oyobi gas ka ni okeru shokubai no riyo

Energy Technology Data Exchange (ETDEWEB)

Otsuka, Y. [Tohoku University, Institute for Chemical Reaction Science (Japan)

1998-05-20

This review article focuses on the utilization of several catalysts during coal pyrolysis and gasification. In situ or off line catalytic upgrading of volatile matters during pyrolysis of low rank coals is carried out in pressurized H2 with different reactors to produce BTX (benzene, toluene and xylene). When NiSO4 and Ni(OH)2 are used in the hydropyrolysis of Australian brown coal using an entrained bed reactor with two separated reaction zones, BTX yield reaches 18-23%. MS-13X zeolite and USY zeolite mixed with Al2O3 are effective for producing BTX with powder-particle fluidized bed and two-stage reactors, respectively. Catalytic gasification is described from a standpoint of direct production of SNG(CH4) from coal and steam. When K2CO3 and Ni are compared for this purpose, Ni catalyst is more suitable at low temperatures of 500-600degC, where CH4 formation is thermodynamically favorable. Fe and Ca catalysts can successfully be prepared from inexpensive raw materials and are rather active for steam gasification at {>=}700degC. The use of upgrading and gasification catalysts is discussed in terms of preparation, performance, life and recovery. 27 refs., 6 figs., 2 tabs.

Synthesis and characterization of Ni-CeO{sub 2} catalysts by the hydrothermal method; Sintesis y caracterizacion de catalizadores de Ni-CeO{sub 2} por el metodo hidrotermal

Energy Technology Data Exchange (ETDEWEB)

Lazcano O, I.

2013-07-01

At the present time the necessity exists to reduce the level of atmospheric pollutants, because these are the main originators of such problems as: the greenhouse effect, acid rain, global heating, among others and that are affecting the human being seriously. In this context, is necessary to look for new solutions that contribute to the improvement of the problems without appealing to limitations in the energy production, because this would imply a non only delay in the economic development, but also in the cultural, technological and of research in our country. An alternative for the energy solution is the use of renewable fuels, because they will decrease the production costs with the time, as well as to diminish the dependence of the fossil fuels, contributing this way to the improvement of the environment quality. The use of the hydrogen as an alternating fuel to the petroleum, is intends as energy solution. The objective of the present work is to develop Ni-CeO{sub 2} catalysts through the hydrothermal method for the hydrogen production starting from the partial oxidation reaction of methanol for the clean fuel generation that does not produce polluting emissions to the environment. As well as, to determine the importance of the metallic load in the catalytic activity for which catalysts to 1 and 2% in weight of Ni were prepared. To achieve these objective different techniques were used to characterize the prepared catalysts, as: Temperature Programmed Reduction to evidence the metal-support interaction, Scanning Electron Microscopy (Sem) to determine the morphology of the catalysts, Surface Area (Bet) with respect to the adsorption-desorption of N{sub 2} and X-Rays Diffraction (XRD) to know the crystalline structure of the catalysts. Also the catalytic properties (activity and selectivity) were studied under the reaction: CH{sub 3}OH + 1/2 O{sub 2} obtaining as products to the CO{sub 2} + 2H{sub 2}, with the help of the multi-tasks equipment Rig-100 that

Structure and coke preventing characteristics of Ca-Ni-Mo/Al sub 2 O sub 3 catalyst for hydrogenation of brown coal liquid bottoms. Kattan ekikaabura suisokayo Ca-Ni-Mo/Al sub 2 O sub 3 shokubai no kozo to tansoshitsu seisei yokusei sayo

Energy Technology Data Exchange (ETDEWEB)

Kimura, T. (Cosmo Oil Co. Ltd., Tokyo (Japan)); Kaneko, T.; Kageyama, Y. (Mitsubishi Kasei Corp., Tokyo (Japan). Research Center); Kawai, S. (Nippon Brown Coal Liquefaction Co. Ltd., Tokyo (Japan))

1990-09-01

Operating a 50 t/d fixed bed pilot plant, hydroprocessing of de-ashed coal liquid bottoms (DAO) derived from Victorial Brown coal liquefaction has been carried out in Australia using a newly developed Ca-Ni-Mo/Al {sub 2} O {sub 3} catalyst. This catalyst has a great advantage compared with conventional molybdenum catalysts in that there is less coke formation using this catalyst as indicated by 5,000 h runs in a 0.1 t/d bench scale plant. In this paper, the catalyst active center and the role of Ca in the Ca-Ni-Mo/Al {sub 2} O {sub 3} catalyst were analyzed using Raman, TPS-XPS, EXAFS and AES methods. Molybdenum is loaded as CaMoO {sub 4} and X-ray diffraction data. But the oxide is changed to MoS {sub 2} after sulfiding treatment. Data of the Mo-S bond obtained from EXAFS analysis indicated that MoS {sub 2} has a tendency to pile up on the Ca-Ni-Mo/Al {sub 2} O {sub 3} catalyst. 20 refs., 12 figs., 5 tabs.

Chemical waves in the O2 + H2 reaction on a Rh(111) surface alloyed with nickel. II. Photoelectron spectroscopy and microscopy

Science.gov (United States)

Smolinsky, Tim; Homann, Mathias; von Boehn, Bernhard; Gregoratti, Luca; Amati, Matteo; Al-Hada, Mohamed; Sezen, Hikmet; Imbihl, Ronald

2018-04-01

Chemical waves in the H2 + O2 reaction on a Rh(111) surface alloyed with Ni [ΘNi chemical attraction between O and Ni, has been explained with a phase separation of the oxygen covered Rh(111)/Ni surface into a 3D-Ni oxide and into a Ni poor metallic phase. Macroscopic NiO islands (≈1 μm size) formed under reaction conditions have been identified as 2D-Ni oxide. Titration experiments of the oxygen covered Rh(111)/Ni surface with H2 demonstrated that the reactivity of oxygen is decreased by an order of magnitude through the addition of 0.6 ML Ni. An excitation mechanism is proposed in which the periodic formation and reduction of NiO modulate the catalytic activity.

Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane

KAUST Repository

Zhu, Haibo

2015-03-05

The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (T<400°C), nanostructured Ni-Nb oxide composites. These new materials efficiently catalyzed the oxidative dehydrogenation (ODH) of ethane to ethylene at a relatively low temperature (T<300°C). These catalysts appear to be much more stable than the corresponding composites prepared by other chemical methods; more than 90% of their original intrinsic activity was retained after 50h with time on-stream. Furthermore, the stability was much less affected by the Nb content than in composites prepared by classical "wet" syntheses. These materials, obtained in a solvent-free way, are thus promising green and sustainable alternatives to the current Ni-Nb candidates for the low-temperature ODH of ethane.

Deoxygenation of methyl laurate over Ni based catalysts: Influence of supports