Session 6: Catalytic hydro-dehalogenation of halon 1211 (CBrClF{sub 2}) over carbon supported Pd-Fe, Pd-Co and Pd-Ni bimetallic catalysts

Energy Technology Data Exchange (ETDEWEB)

Hai, Yu; Kennedy, E.M.; Md Azhar, Uddin; Dlugogorski, B.Z. [Newcastle Univ., Process Safety and Environment Protection Group, School of Engineering, Callaghan, NSW (Australia)

2004-07-01

In the current study, we present the result of our investigation on the hydro-dehalogenation of halon 1211 with hydrogen over carbon supported Pd-Fe, Pd-Co and Pd-Ni bimetallic catalysts. In addition to dissociatively adsorbing hydrogen, Fe, Co and Ni themselves can facilitate cleavage of C-halogen bonds. The effect of the interaction of a second metal (Fe, Co and Ni) with Pd on the conversion of halon 1211 and selectivity to CH{sub 2}F{sub 2} for the catalytic hydro-dehalogenation of halon 1211 is discussed. Activated carbon is chosen as support in order to minimize the interaction of support with the metals. The obtained experimental results show that the introduction of Fe, Co and Ni to Pd catalysts has a significant influence on the catalytic hydro-dehalogenation of halon 1211, especially with respect to the selectivity to CH{sub 2}F{sub 2}. The presence of Fe increases the amount of halon 1211 adsorbed on the surface of catalysts and enhances the cleavage of C-halogen bonds in halon 1211, resulting in a higher halon 1211 conversion level and selectivity to hydrocarbons. Higher selectivity to CHBrF{sub 2} is ascribed to the secondary reaction: CF{sub 2} + HBr {yields} CHBrF{sub 2}. (authors)

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

Directory of Open Access Journals (Sweden)

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.

Newly designed PdRuBi/N-Graphene catalysts with synergistic effects for enhanced ethylene glycol electro-oxidation

International Nuclear Information System (INIS)

Li, Tengfei; Huang, Yiyin; Ding, Kui; Wu, Peng; Abbas, Syed Comail; Ghausi, Muhammad Arsalan; Zhang, Teng; Wang, Yaobing

2016-01-01

Graphical abstract: We rationally design and synthesize a ternary PdRuBi/NG catalyst with significantly enhanced catalytic activity with synergetic effect of Ru and Bi towards ethylene glycol electro-oxidation. - Abstract: Palladium (Pd)-based catalysts are appealing electro-catalysts for alcohol oxidation reaction in fuel cell, but still not efficient as the complicated oxidation process and sluggish kinetic. Here we rationally design and synthesize a PdRuBi/NG tri-metallic catalyst with space synergetic effect for enhanced ethylene glycol electro-oxidation, in which both Ru and Bi in the catalyst are synergistic effective in promoting catalytic activity of Pd catalytic interlayer by electronic effect and surface modification mechanism respectively. It shows 4.2 times higher peak current density towards ethylene glycol electro-oxidation than commercial Pd/C catalyst, and the catalytic durability is also greatly improved.

Systematic Identification of Promoters for Methane Oxidation Catalysts Using Size- and Composition-Controlled Pd-Based Bimetallic Nanocrystals.

Science.gov (United States)

Willis, Joshua J; Goodman, Emmett D; Wu, Liheng; Riscoe, Andrew R; Martins, Pedro; Tassone, Christopher J; Cargnello, Matteo

2017-08-30

Promoters enhance the performance of catalytic active phases by increasing rates, stability, and/or selectivity. The process of identifying promoters is in most cases empirical and relies on testing a broad range of catalysts prepared with the random deposition of active and promoter phases, typically with no fine control over their localization. This issue is particularly relevant in supported bimetallic systems, where two metals are codeposited onto high-surface area materials. We here report the use of colloidal bimetallic nanocrystals to produce catalysts where the active and promoter phases are colocalized to a fine extent. This strategy enables a systematic approach to study the promotional effects of several transition metals on palladium catalysts for methane oxidation. In order to achieve these goals, we demonstrate a single synthetic protocol to obtain uniform palladium-based bimetallic nanocrystals (PdM, M = V, Mn, Fe, Co, Ni, Zn, Sn, and potentially extendable to other metal combinations) with a wide variety of compositions and sizes based on high-temperature thermal decomposition of readily available precursors. Once the nanocrystals are supported onto oxide materials, thermal treatments in air cause segregation of the base metal oxide phase in close proximity to the Pd phase. We demonstrate that some metals (Fe, Co, and Sn) inhibit the sintering of the active Pd metal phase, while others (Ni and Zn) increase its intrinsic activity compared to a monometallic Pd catalyst. This procedure can be generalized to systematically investigate the promotional effects of metal and metal oxide phases for a variety of active metal-promoter combinations and catalytic reactions.

Efficient Pd@MIL-101(Cr) hetero-catalysts for 2-butyne-1,4-diol hydrogenation exhibiting high selectivity

KAUST Repository

Yin, Dongdong; Li, Chuang; Ren, Hangxing; Shekhah, Osama; Liu, Jinxuan; Liang, Changhai

2017-01-01

Pd@MIL-101(Cr) hetero-catalysts have been successfully prepared using the metal-organic chemical vapour deposition (MOCVD) approach, by choosing [Pd(η-CH)(η-CH)] as a volatile precursor, and the hydrothermally stable metal-organic framework, MIL-101

Catalytic reduction of nitrate and nitrite ions by hydrogen : investigation of the reaction mechanism over Pd and Pd-Cu catalysts

NARCIS (Netherlands)

Ilinitch, OM; Nosova, LV; Gorodetskii, VV; Ivanov, VP; Trukhan, SN; Gribov, EN; Bogdanov, SV; Cuperus, FP

2000-01-01

The catalytic behavior of mono- and bimetallic catalysts with Pd and/or Cu supported over gamma-Al2O3 in the reduction of aqueous nitrate and nitrite ions by hydrogen was investigated. The composition of the supported metal catalysts was analysed using secondary ion mass spectroscopy (SIMS) and

From trash to resource: recovered-Pd from spent three-way catalysts as a precursor of an effective photo-catalyst for H 2 production

KAUST Repository

Gombac, V.; Montini, T.; Falqui, Andrea; Loche, D.; Prato, M.; Genovese, Alessandro; Mercuri, M. L.; Serpe, A.; Fornasiero, P.; Deplano, P.

2016-01-01

The successful production of a nanostructured and highly dispersed Pd-TiO2 photo-catalyst, using [Pd(Me2dazdt)2](I3)2 (Me2dazdt = N,N′-dimethyl-perhydrodiazepine-2,3-dithione) salt, obtained through the selective and safe recovery of palladium from model exhaust three-way catalysts (TWCs), is reported here. The photo-catalyst prepared by the impregnation/photo-reduction of palladium on the support showed improved performance in H2 production from methanol and in glycerol photo-reforming compared to reference photo-catalysts obtained from conventional Pd-salts. The reported results represent a case of successful palladium “recovery and re-employment” and thus constitute an example of green chemistry by providing, in one route, the environmentally friendly recovery of a critical metal and its employment in the renewable energy field.

From trash to resource: recovered-Pd from spent three-way catalysts as a precursor of an effective photo-catalyst for H 2 production

KAUST Repository

Gombac, V.

2016-01-06

The successful production of a nanostructured and highly dispersed Pd-TiO2 photo-catalyst, using [Pd(Me2dazdt)2](I3)2 (Me2dazdt = N,N′-dimethyl-perhydrodiazepine-2,3-dithione) salt, obtained through the selective and safe recovery of palladium from model exhaust three-way catalysts (TWCs), is reported here. The photo-catalyst prepared by the impregnation/photo-reduction of palladium on the support showed improved performance in H2 production from methanol and in glycerol photo-reforming compared to reference photo-catalysts obtained from conventional Pd-salts. The reported results represent a case of successful palladium “recovery and re-employment” and thus constitute an example of green chemistry by providing, in one route, the environmentally friendly recovery of a critical metal and its employment in the renewable energy field.

4,6-Dimethyl-dibenzothiophene conversion over Al{sub 2}O{sub 3}-TiO{sub 2}-supported noble metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Nunez, Sara [Departamento de Ingenieria de Procesos e Hidraulica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Vicentina, Iztapalapa, 09340, Mexico, D.F. (Mexico); Escobar, Jose, E-mail: jeaguila@imp.mx [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, 07730, Mexico, D.F. (Mexico); Vazquez, Armando; Reyes, Jose Antonio de los [Departamento de Ingenieria de Procesos e Hidraulica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Vicentina, Iztapalapa, 09340, Mexico, D.F. (Mexico); Hernandez-Barrera, Melissa [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, 07730, Mexico, D.F. (Mexico)

2011-03-15

Research highlights: {yields} Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-TiO{sub 2} (molar ratio Al/Ti = 2, AT2) mixed oxides were pore-filling impregnated to obtain Pd, Pt and Pd-Pt catalysts with {approx}1 wt% nominal metal loading. {yields} Reduced catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS). {yields} In Pd-containing materials, TiO{sub 2} incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts. {yields} Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide. {yields} Yield to different products over various catalysts seemed to be strongly influenced by metallic particles dispersion. - Abstract: Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-TiO{sub 2} (molar ratio Al/Ti = 2, AT2) mixed oxides were synthesized using a low-temperature sol-gel method and were further pore-filling impregnated to obtain Pd and Pt catalysts with {approx}1 wt% nominal metal loading. Simultaneous impregnation was used to prepare bimetallic materials at Pd:Pt = 80:20. Solids characterization was carried out by N{sub 2}-physisorption, high-resolution transmission electron microscopy (HR-TEM and E-FTEM), X-ray diffraction, temperature-programmed reduction and CO-chemisorption. Reduced (350 deg. C, H{sub 2} flow) catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS) (in n-dodecane, at 300 deg. C and 5.5 MPa, batch reactor). In Pd-containing materials, TiO{sub 2} incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts, where bimetallic Pd-Pt with AT2 carrier had the highest organo-S compound conversion. Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide (as compared to alumina-supported ones). Yield to different products over various catalysts seemed to be strongly influenced by

Influence of zeolite structure on the activity and durability of Co-Pd-zeolite catalysts in the reduction of NOx with methane

International Nuclear Information System (INIS)

Pieterse, J.A.Z.; Van den Brink, R.W.; Booneveld, S.; De Bruijn, F.A.

2003-01-01

Selective catalytic reduction of NO with CH 4 was studied over ZSM-5, MOR, FER and BEA zeolite-based cobalt (Co) and palladium (Pd) catalysts in the presence of oxygen and water. As compared to other catalytic systems reported in literature for CH 4 -SCR in the presence of water, zeolite supported Co-Pd combination catalysts are very active and selective. The most active catalysts, based on MOR and ZSM-5, are characterised by well-dispersed Pd ions in the zeolite that activate methane. Wet ion exchange is a good method to achieve high dispersion of Pd provided that it is carried out in a competitive manner. The presence of cobalt (Co 3 O 4 , Co-oxo ions) boosts SCR activity by oxidising NO to NO 2 . The activity of the zeolite-based Co-Pd combination catalysts decreases with prolonged times on stream. The severity of the deactivation was found to be different for different zeolite topologies. The characterisation and evaluation of freshly calcined catalysts and spent catalysts show two things that occur during reaction: (1) zeolite solvated metal cations disappear in favour of (inactive) metal oxides and presumably larger metal entities, i.e. loss of dispersion; (2) loss of crystallinity affiliated with steam-dealumination and the concomitant formation of extra-framework aluminium (EFAL) in the presence of water. Both phenomena strongly depend on the (reaction) temperature. The deactivation of Co-Pd-zeolite resembles the deactivation of Pd-zeolite. Hence, future research could encompass the stabilisation of Pd (cations) in the zeolite pores by exploring additives other than cobalt. For this, detailed understanding on the siting of Pd in zeolites is important

Dissolution of Metal Supported Spent Auto Catalysts in Acids

Directory of Open Access Journals (Sweden)

Fornalczyk A.

2016-03-01

Full Text Available Metal supported auto catalysts, have been used in sports and racing cars initially, but nowadays their application systematically increases. In Metal Substrate (supported Converters (MSC, catalytic functions are performed by the Platinum Group Metals (PGM: Pt, Pd, Rh, similarly to the catalysts on ceramic carriers. The contents of these metals make that spent catalytic converters are valuable source of precious metals. All over the world there are many methods for the metals recovery from the ceramic carriers, however, the issue of platinum recovery from metal supported catalysts has not been studied sufficiently yet. The paper presents preliminary results of dissolution of spent automotive catalyst on a metal carrier by means of acids: H2SO4, HCl, HNO3, H3PO4. The main assumption of the research was the dissolution of base metals (Fe, Cr, Al from metallic carrier of catalyst, avoiding dissolution of PGMs. Dissolution was the most effective when concentrated hydrochloric acid, and 2M sulfuric acid (VI was used. It was observed that the dust, remaining after leaching, contained platinum in the level of 0.8% and 0.7%, respectively.

Influence of Pd-precursor on the acetoxylation activity of Pd-Sb/TiO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Ben-homeid, A. [Benghazi Univ. (Libyan Arab Jamahiriya). Chemistry Dept.; Kalevaru, V.N.; Radnik, J.; Luecke, B.; Martin, A. [Leibniz-Institut fuer Katalyse e.V. an der Universitaet Rostock (Germany)

2013-11-01

The impact of palladium precursors (e.g. chloride-PdCl{sub 2}; acetate-Pd(OAc){sub 2}; nitrate-Pd(NO{sub 3}){sub 2}) on the catalytic properties of Pd-Sb/TiO{sub 2} catalysts used for acetoxylation of toluene has been investigated. The catalysts were characterized by different techniques such as N{sub 2}-adsorption (BET-surface area and pore volume), XRD, TEM, CO-Chemisorption and XPS for better understanding of the catalytic properties of the catalysts. The acetate and nitrate-type precursors exhibited higher surface areas, pore volumes and higher dispersion of Pd, but displayed poor performance compared to chloride precursor. TEM analysis indicated that the size of Pd particles depended upon the nature of Pd-precursor. Among the three, chloride precursor exhibited bigger Pd particles. XPS results revealed that all the fresh catalysts irrespective of Pd-precursor contained Pd in oxidized state (i.e. Pd{sup +2}), while in the spent catalysts such oxidized Pd species were reduced. The catalytic performance was found to depend strongly on the nature of precursor used. Among the three, the catalysts prepared from chloride-type precursor showed much higher overall catalytic activity (68%) than those of nitrate and/or acetate type precursors. Moreover, these two precursors (acetate and nitrate) gave higher total oxidation products due to oxidative decomposition of mainly acetic acid. Furthermore, the catalyst prepared from Cl-precursor revealed easy deactivation due to coke deposition and also due to loss of Pd in the near-surface-region. (orig.)

Methanol steam reforming over Pd/ZnO and Pd/CeO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Ranganathan, Easwar S.; Bej, Shyamal K.; Thompson, Levi T. [University of Michigan, Department of Chemical Engineering, 3026 H.H. Dow Building, 2300 Hayward Avenue, Ann Arbor, MI 48109-2136 (United States)

2005-08-10

The goal of work described in this paper was to better understand the methanol steam reforming (MSR) activity and selectivity patterns of ZnO and CeO{sub 2} supported Pd catalysts. This reaction is being used to produce H{sub 2}-rich gas for a number of applications including hydrogen fuel cells. The Pd/ZnO catalysts had lower MSR rates but were more selective for the production of CO{sub 2} than the Pd/CeO{sub 2} catalysts. The CH{sub 3}OH conversion rates were proportional to the H{sub 2} chemisorption uptake suggesting that the rate determining step was catalyzed by Pd. The corresponding turnover frequencies averaged 0.8+/-0.3s{sup -1} and 0.4+/-0.2s{sup -1} at 230{sup o}C for the Pd/ZnO and Pd/CeO{sub 2} catalysts, respectively. The selectivities are explained based on the reaction pathways, and characteristics of the support. The key surface intermediate appeared to be a formate. The ZnO supported catalysts had a higher density of acidic sites and favored pathways where the intermediate was converted to CO{sub 2} while the CeO{sub 2} supported catalysts had a higher density of basic sites and favored the production of CO.

Catalyst activity or stability: the dilemma in Pd-catalyzed polyketone synthesis.

Science.gov (United States)

Amoroso, Francesco; Zangrando, Ennio; Carfagna, Carla; Müller, Christian; Vogt, Dieter; Hagar, Mohamed; Ragaini, Fabio; Milani, Barbara

2013-10-28

A series of Pd-complexes containing nonsymmetrical bis(aryl-imino)acenaphthene (Ar-BIAN) ligands, characterized by substituents on the meta positions of the aryl rings, have been synthesized, characterized and applied in CO/vinyl arene copolymerization reactions. Crystal structures of two neutral Pd-complexes have been solved allowing comparison of the bonding properties of the ligand. Kinetic and mechanistic investigations on these complexes have been performed. The kinetic investigations indicate that in general ligands with electron-withdrawing substituents give more active, but less stable, catalytic systems, although steric effects also play a role. The good performance observed with nonsymmetrical ligands is at least in part due to a compromise between catalyst activity and lifetime, leading to a higher overall productivity with respect to catalysts based on their symmetrical counterparts. Additionally, careful analysis of the reaction profiles provided information on the catalyst deactivation pathway. The latter begins with the reduction of a Pd(II) Ar-BIAN complex to the corresponding Pd(0) species, a reaction that can be reverted by the action of benzoquinone. Then the ligand is lost, a process that appears to be facilitated by the contemporary coordination of an olefin or a CO molecule. The so formed Pd(0) complex immediately reacts with another molecule of the initial Pd(II) complex to give a Pd(I) dimeric species that irreversibly evolves to metallic palladium. Mechanistic investigations performed on the complex with a nonsymmetrical Ar-BIAN probe evidence that the detected intermediates are characterized by the Pd-C bond trans to the Pd-N bond of the aryl ring bearing electron-withdrawing substituents. In addition, the intermediate resulting from the insertion of 4-methylstyrene into the Pd-acyl bond is a five-member palladacycle and not the open-chain η(3)-allylic species observed for complexes with Ar-BIANs substituted in ortho position.

Optimization of the Pd-Fe-Mo Catalysts for Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells

International Nuclear Information System (INIS)

Lee, Yeayeon; Jang, Jeongseok; Lee, Jin Goo; Jeon, Ok Sung; Kim, Hyeong Su; Hwang, Ho Jung; Shul, Yong Gun

2016-01-01

Highlights: • Pd-Mo-Fe catalysts show high catalytic activity and stability for oxygen-reduction reactions in acid media. • The optimum compositions were 7.5:1.5:1.0 for Pd-Fe-Mo, and the optimum temperatures were 500 °C. • The Pd-Fe-Mo catalysts were successfully applied to the PEMFC cathode, showing ∼500 mA cm −1 at 0.6 V. • The lattice constant was strongly related to the activity and stability of the catalysts for oxygen-reduction reactions. - Abstract: Highly active and durable non-platinum catalysts for oxygen-reduction reaction (ORR) have been developed for energy conversion devices such as proton-exchange membrane fuel cells (PEMFCs). In this study, Pd-Fe-Mo catalyst is reported as a non-platinum catalyst for ORR. The atomic ratio and annealing temperatures are controlled on the catalysts to understand interplay between their physical and chemical properties and electrochemical activities. The Pd-Fe-Mo catalyst optimized with 7.5:1.5:1.0 of the atomic ratio and 500 °C of the annealing temperature shows 32.18 mA mg −1 PGM (PGM: platinum group metal) of the kinetic current density at 0.9 V for ORR, which is comparable to that of commercial Pt/C catalyst. The current density is degraded to 6.20 mA mg −1 PGM after 3000 cycling of cyclic voltammetry, but it is greatly enhanced value compared to other non-platinum catalysts. In actual application to PEMFCs, the 20% Pd-Fe-Mo catalyst supported on carbons exhibits a high performance of 506 mA cm −2 at 0.6 V. The results suggest that the Pd-Fe-Mo catalyst can be a good candidate for non-platinum ORR catalysts.

Alkaline Ionic Liquid Modified Pd/C Catalyst as an Efficient Catalyst for Oxidation of 5-Hydroxymethylfurfural

Directory of Open Access Journals (Sweden)

Zou Bin

2018-01-01

Full Text Available Conversion of HMF into FDCA was carried out by a simple and green process based on alkaline ionic liquid (IL modified Pd/C catalyst (Pd/C-OH−. Alkaline ionic liquids were chosen to optimize Pd/C catalyst for special hydrophilicity and hydrophobicity, redox stability, and unique dissolving abilities for polar compounds. The Pd/C-OH− catalyst was successfully prepared and characterized by SEM, XRD, TG, FT-IR, and CO2-TPD technologies. Loading of alkaline ionic liquid on the surface of Pd/C was 2.54 mmol·g−1. The catalyst showed excellent catalytic activity in the HMF oxidation after optimization of reaction temperature, reaction time, catalyst amount, and solvent. Supported alkaline ionic liquid (IL could be a substitute and promotion for homogeneous base (NaOH. Under optimal reaction conditions, high HMF conversion of 100% and FDCA yield of 82.39% were achieved over Pd/C-OH− catalyst in water at 373 K for 24 h.

Selective hydrodechlorination of 1,2-dichloroethane to ethylene over Pd-Ag/Al_2O_3 catalysts prepared by surface reduction

International Nuclear Information System (INIS)

Han, Yuxiang; Gu, Guangfeng; Sun, Jingya; Wang, Wenjuan; Wan, Haiqin; Xu, Zhaoyi; Zheng, Shourong

2015-01-01

Graphical abstract: - Highlights: • Surface reduction method was used for preparation of Pd-Ag(Cu) bimetallic catalysts. • Hydrodechlorination of 1,2-dichloroethane was investigated for production of ethylene. • Ag(Cu) selectively deposited on Pd surface during surface reduction process. • Ethylene selectivity was enhanced over Pd-Ag(Cu)/Al_2O_3 catalyst prepared by surface reduction. • Isolated Pd site is the key species for ethylene selectivity. - Abstract: Alumina supported Pd-Ag and (Cu) bimetallic catalysts (denoted as sr-Pd-Ag/Al_2O_3 or sr-Pd-Cu/Al_2O_3) with varied Pd/Ag (or Cu) ratios were prepared using the surface reduction method, and the gas-phase catalytic hydrodechlorination of 1,2-dichloroethane over the catalysts were investigated. For comparison, Pd-Ag bimetallic catalysts were prepared by the conventional co-impregnation method (denoted as im-Pd-Ag/Al_2O_3). The catalysts were characterized by N_2 adsorption, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and CO chemisorption. Characterization results indicated that surface reduction led to selective deposition of metallic Ag on the surface of Pd particles, while Pd and Ag just disorderly mixed in the catalyst prepared by impregnation method. Therefore, sr-Pd-Ag/Al_2O_3 exhibited a higher ethylene selectivity than im-Pd-Ag/Al_2O_3 for hydrodechlorination of 1,2-dichloroethane at a similar Ag loading amount. Moreover, among sr-Pd-Ag/Al_2O_3, sr-Pd-Cu/Al_2O_3 and im-Pd-Ag/Al_2O_3 catalysts, the ethylene selectivity decreased over these catalysts following the order: sr-Pd-Ag/Al_2O_3 > sr-Pd-Cu/Al_2O_3 > im-Pd-Ag/Al_2O_3. The present results indicate that surface reduction can be used as a potential method to synthesize catalyst with enhanced ethylene selectivity in hydrodechlorination of 1,2-dichloroethane.

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.

Reductive dechlorination of tetrachlorobisphenol A by Pd/Fe bimetallic catalysts

International Nuclear Information System (INIS)

Huang, Qiang; Liu, Wen; Peng, Ping’an; Huang, Weilin

2013-01-01

Highlights: • TCBPA can be rapidly and completely dechlorinated by Pd/Fe bimetallic catalysts. • The observed rate constants are functions of dosages, initial concentration, Pd coverage and solution pH. • Pd dosage is the major factor in the observed rates of the reaction. • This is the first report investigating the dechlorination of TCBPA by Pd/Fe catalysts. -- Abstract: The Pd/Fe bimetallic catalysts of micron sizes were synthesized and the rates of tetrachlorobisphenol A (TCBPA) degradation were measured under various conditions using a batch reactor system. The results showed that TCBPA was rapidly dechlorinated to tri-, di- and mono-chlorobisphenol A and to bisphenol A (BPA). The observed rate constants (k obs ) were found to increase as functions of the Pd coverage on the Fe particles and the dosages of the catalysts within the reactors. The k obs value decreased as the initial TCBPA concentration increased, suggesting that the TCBPA dechlorination may follow a surface-site limiting Langmuir–Hinshelwood rate model. The weakly acidic solution, especially at or near pH 6.0, also favored the dechlorination of TCBPA. At pH 6.0, Pd coverage of 0.044 wt% and catalyst dosage of 5 g L −1 , TCBPA with an initial concentration of 20 μM was completely transformed within 60 min, and BPA was detected as the major product through the reaction time. Meanwhile, the k obs values measured at constant solution pH correlated linearly with the mass of particle-bound Pd introduced to the reactors, regardless of Pd/Fe catalyst dosage or Pd surface coverage. This study suggested that Pd/Fe catalysts could be potentially employed to rapidly degrade TCBPA in the contaminated environment

Pd nanoparticles Supported on Cellulose as a catalyst for vanillin conversion in aqueous media.

Science.gov (United States)

Li, Dan-Dan; Zhang, Jia-Wei; Cai, Chun

2018-05-17

Palladium nanoparticles were firstly anchored on modified biopolymer as an efficient catalyst for biofuel upgradation. Fluorinated compounds was grafted onto cellulose to obtain amphiphilic supports for on water reactions. Pd catalyst was prepared by straightforward deposition of metal nanoparticles on modified cellulose. The catalyst exhibited excellent catalytic activity and selectivity in hydrodeoxygenation of vanillin (a typical model compound of lignin) to 2-methoxy-4-methylphenol under atmospheric hydrogen pressure in neat water without any other additives under mild conditions.

Aromatization of n-octane over Pd/C catalysts

KAUST Repository

Yin, Mengchen; Natelson, Robert H.; Campos, Andrew A.; Kolar, Praveen; Roberts, William L.

2013-01-01

Gas-phase aromatization of n-octane was investigated using Pd/C catalyst. The objectives were to: (1) determine the effects of temperature (400-600 °C), weight hourly space velocity (WHSV) (0.8-∞), and hydrogen to hydrocarbon molar ratio (MR) (0-6) on conversion, selectivity, and yield (2) compare the activity of Pd/C with Pt/C and Pt/KL catalysts and (3) test the suitability of Pd/C for aromatization of different alkanes including n-hexane, n-heptane, and n-octane. Pd/C exhibited the best aromatization performance, including 54.4% conversion and 31.5% aromatics yield at 500 °C, WHSV = 2 h-1, and a MR of 2. The Pd/C catalyst had higher selectivity towards the preferred aromatics including ethylbenzene and xylenes, whereas Pt/KL had higher selectivity towards benzene and toluene. The results were somewhat consistent with adsorbed n-octane cyclization proceeding mainly through the six-membered ring closure mechanism. In addition, Pd/C was also capable of catalyzing aromatization of n-hexane and n-heptane. © 2012 Elsevier Ltd. All rights reserved.

Part II: Oxidative Thermal Aging of Pd/Al2O3 and Pd/CexOy-ZrO2 in Automotive Three Way Catalysts: The Effects of Fuel Shutoff and Attempted Fuel Rich Regeneration

Directory of Open Access Journals (Sweden)

Qinghe Zheng

2015-10-01

Full Text Available The Pd component in the automotive three way catalyst (TWC experiences deactivation during fuel shutoff, a process employed by automobile companies for enhancing fuel economy when the vehicle is coasting downhill. The process exposes the TWC to a severe oxidative aging environment with the flow of hot (800 °C–1050 °C air. Simulated fuel shutoff aging at 1050 °C leads to Pd metal sintering, the main cause of irreversible deactivation of 3% Pd/Al2O3 and 3% Pd/CexOy-ZrO2 (CZO as model catalysts. The effect on the Rh component was presented in our companion paper Part I. Moderate support sintering and Pd-CexOy interactions were also experienced upon aging, but had a minimal effect on the catalyst activity losses. Cooling in air, following aging, was not able to reverse the metallic Pd sintering by re-dispersing to PdO. Unlike the aged Rh-TWCs (Part I, reduction via in situ steam reforming (SR of exhaust HCs was not effective in reversing the deactivation of aged Pd/Al2O3, but did show a slight recovery of the Pd activity when CZO was the carrier. The Pd+/Pd0 and Ce3+/Ce4+ couples in Pd/CZO are reported to promote the catalytic SR by improving the redox efficiency during the regeneration, while no such promoting effect was observed for Pd/Al2O3. A suggestion is made for improving the catalyst performance.

Solvent-free Hydrodeoxygenation of Bio-oil Model Compounds Cyclopentanone and Acetophenone over Flame-made Bimetallic Pt-Pd/ZrO2 Catalysts

Science.gov (United States)

Jiang, Yijiao; Büchel, Robert; Huang, Jun; Krumeich, Frank; Pratsinis, Sotiris E.; Baiker, Alfons

2013-01-01

Bimetallic Pt-Pd/ZrO2 catalysts with different Pt/Pd atomic ratio and homogeneous dispersion of the metal nanoparticles were prepared in a single step by flame-spray pyrolysis. The catalysts show high activity and tuneable product selectivity for the solvent-free hydrodeoxygenation of the bio-oil model compounds cyclopentanone and acetophenone. PMID:22674738

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...

Pd-Au/C catalysts with different alloying degrees for ethanol oxidation in alkaline media

International Nuclear Information System (INIS)

Qin, Yuan-Hang; Li, Yunfeng; Lv, Ren-Liang; Wang, Tie-Lin; Wang, Wei-Guo; Wang, Cun-Wen

2014-01-01

High alloyed Pd-Au/C catalyst is prepared through a rate-limiting strategy in water/ethylene glycol solution. Pd/C and low alloyed Pd-Au/C catalysts are prepared with trisodium citrate and sodium borohydride as stabilizing and reducing agents, respectively. Transmission electron microscopy (TEM) shows that the synthesized Pd(Au) particles are well dispersed on the catalysts. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) show that the high alloyed Pd-Au/C catalyst presents a relatively homogenous structure while the low alloyed Pd-Au/C catalyst presents a Pd-rich shell/Au-rich core structure. Electrochemical characterization shows that the low alloyed Pd-Au/C catalyst exhibits the best catalytic activity for ethanol oxidation reaction (EOR) in alkaline media, which could be attributed to its relatively large exposed Pd surface area as compared with the high alloyed Pd-Au/C catalyst due to its Pd-rich shell structure and its enhanced adsorption of OH ads as compared with Pd/C catalyst due to its core-shell structure

Transformation of Unsaturated Fatty Acids/Esters to Corresponding Keto Fatty Acids/Esters by Aerobic Oxidation with Pd(II)/Lewis Acid Catalyst.

Science.gov (United States)

Senan, Ahmed M; Zhang, Sicheng; Zeng, Miao; Chen, Zhuqi; Yin, Guochuan

2017-08-16

Utilization of renewable biomass to partly replace the fossil resources in industrial applications has attracted attention due to the limited fossil feedstock with the increased environmental concerns. This work introduced a modified Wacker-type oxidation for transformation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, in which Cu 2+ cation was replaced with common nonredox metal ions, that is, a novel Pd(II)/Lewis acid (LA) catalyst. It was found that adding nonredox metal ions can effectively promote Pd(II)-catalyzed oxidation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, even much better than Cu 2+ , and the promotional effect is highly dependent on the Lewis acidity of added nonredox metal ions. The improved catalytic efficiency is attributed to the formation of heterobimetallic Pd(II)/LA species, and the oxidation mechanism of this Pd(II)/LA catalyst is also briefly discussed.

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.

Study of Pd-Sn/Al{sub 2}O{sub 3} catalysts prepared by an oxide colloidal route; Etude de catalyseurs Pd-Sn/Al{sub 2}O{sub 3} prepares par voie colloidale oxyde

Energy Technology Data Exchange (ETDEWEB)

Verdier, St.

2001-09-01

The oxide colloidal route, developed in the laboratory for mono-metallic catalysts, consists in preparing a metallic oxide hydro-sol which leads to the supported catalyst after deposition onto a support and an activation stage. In this work, this method has been adapted to the preparation of alumina supported bimetallic Pd-Sn catalysts to determine its interest for the control of the properties of the bimetallic phase (size, composition and structure). In the preliminary study concerning tin oxide sols, SnO{sub 2} (size=2,3 nm) and Sn{sub 6}O{sub 4}(OH){sub 4} (size = 25 nm) nano-particles were synthesized by neutralization respectively for tin(IV) and tin(H). The control through the pH of the aggregation of the PdO and SnO{sub 2} particles revealed that increasing oxide solubility promotes integral re-dispersion of the oxide particles. To synthesize oxide bimetallic sols, three strategies were defined. Copolymerization (formation of a mixed oxide nano-sol by cross condensation of both metals) does not lead to a mixed oxide Pd-Sn phase. Surface precipitation (neutralization of the second metal in the presence of the first oxide sol) yields nano-particles of both oxides in close interaction. Adsorption (adsorption of the second metal onto the first oxide sol) significantly occurs when contacting tin with a basic PdO sol (hydrolytic adsorption). The characterization and the assessment of the catalytic properties (selective hydrogenation of buta-1,3-diene) of the catalysts prepared by deposition of oxide bimetallic sols showed that the oxide colloidal route allows the control of the properties of the supported bimetallic phase. Moreover, our results display that both Pd-Sn alloy formation and,aggregation of the metallic particles contribute to increase the selectivity for this reaction. (author)

Ultrahigh figure-of-merit for hydrogen generation from sodium borohydride using ternary metal catalysts

Science.gov (United States)

Hu, Lunghao; Ceccato, R.; Raj, R.

We report further increase in the figure-of-merit (FOM) for hydrogen generation from NaBH 4 than reported in an earlier paper [1], where a sub-nanometer layer of metal catalysts are deposited on carbon nanotube paper (CNT paper) that has been functionalized with polymer-derived silicon carbonitride (SiCN) ceramic film. Ternary, Ru-Pd-Pt, instead of the binary Pd-Pt catalyst used earlier, together with a thinner CNT paper is shown to increase the figure-of-merit by up to a factor of six, putting is above any other known catalyst for hydrogen generation from NaBH 4. The catalysts are prepared by first impregnating the functionalized CNT-paper with solutions of the metal salts, followed by reduction in a sodium borohydride solution. The reaction mechanism and the catalyst efficiency are described in terms of an electric charge transfer, whereby the negative charge on the BH 4 - ion is exchanged with hydrogen via the electronically conducting SiCN/CNT substrate [1].

Electrocatalytic Reduction-oxidation of Chlorinated Phenols using a Nanostructured Pd-Fe Modified Graphene Catalyst

International Nuclear Information System (INIS)

Shi, Qin; Wang, Hui; Liu, Shaolei; Pang, Lei; Bian, Zhaoyong

2015-01-01

A Pd-Fe modified graphene (Pd-Fe/G) catalyst was prepared by the Hummers oxidation method and bimetallic co-deposition method. The catalyst was then characterized by various characterization techniques and its electrochemical property toward the electrocatalytic reduction-oxidation of chlorinated phenols was investigated by using cyclic voltammetry and differential pulse voltammetry. The results of the characterization show that the Pd-Fe/G catalyst in which the weight proportion of Pd and Fe is 1:1 has an optimal surface performance. The diameter of the Pd-Fe particles is approximately 5.2 ± 0.3 nm, with a uniform distribution on the supporting graphene. This is smaller than the Pd particles of a Pd-modified graphene (Pd/G) catalyst. The Pd-Fe/G catalyst shows a higher electrocatalytic activity than the Pd/G catalyst for reductive dechlorination when feeding with hydrogen gas. The reductive peak potentials of −0.188 V, −0.836 V and −0.956 V in the DPV curves are attributed to the dechlorination of ortho-Cl, meta-Cl, and para-Cl in 2-chlorophenol, 3-chlorophenol and 4-chlorophenol, respectively. In accordance with an analysis of the frontier orbital theory, the order of ease of dechlorination with Pd-Fe/G catalyst is 2-chlorophenol > 3-chlorophenol > 4-chlorophenol. The Pd-Fe/G catalyst has a greater activity than the Pd/G catalyst in accelerating the two-electron reduction of O_2 to H_2O_2, which is attributed to the higher current of the reduction peak at approximately −0.40 V when feeding with oxygen gas. Therefore, the Pd-Fe/G catalyst exhibits a higher electrocatalytic activity than the Pd/G catalyst for the reductive dechlorination and acceleration of the two-electron reduction of O_2 to H_2O_2.

Exfoliated Pd/HNb{sub 3}O{sub 8} nanosheet as highly efficient bifunctional catalyst for one-pot cascade reaction

Energy Technology Data Exchange (ETDEWEB)

Lee, Nahaeng; Chung, Young-Min, E-mail: ymchung@kunsan.ac.kr

2016-05-01

Graphical abstract: - Highlights: • Ultrathin and highly acidic HNb{sub 3}O{sub 8} nanosheet was prepared by exfoliation of layered niobium oxide. • Pd/HNb{sub 3}O{sub 8} nanosheet showed excellent catalytic performance for one-pot cascade reaction. • The reaction performance of Pd/HNb{sub 3}O{sub 8} nanosheet is 7.1 and 1.2 times higher than that of layered Pd/KNb{sub 3}O{sub 8} or Pd/HNb{sub 3}O{sub 8}, respectively. • Significant promoting effect of support acidity on the reaction performance was observed. - Abstract: Ultrathin two-dimensional metal oxide nanosheets have drawn attention as potential solid acid catalysts owing to their strong acidity, attributed to the bridged OH groups formed on the nanosheets. In this study, a new class of bifunctional acid–metal catalyst was realized by the deposition of Pd on layered niobium oxide (KNb{sub 3}O{sub 8} and HNb{sub 3}O{sub 8}) or its exfoliated nanosheet (Pd/HNb{sub 3}O{sub 8}-NS) and applied to one-pot cascade deacetalization and hydrogenation. It was found that the acid strength of the support exerted a large influence not only on the promotion of the first deacetalization step, but also on the acceleration of the subsequent hydrogenation step. Comparative experiments using a series of Pd/HZSM-5 catalysts with different acidities reconfirmed the crucial role of acid strength on hydrogenation. However, the superior catalytic activity of Pd/HNb{sub 3}O{sub 8}-NS for hydrogenation compared to that of Pd/HZSM-5 of similar acidity suggests a more efficient ensemble effect of the strong acid sites with the nearby metal sites on the nanosheet surface. Among the catalysts used, Pd/HNb{sub 3}O{sub 8}-NS showed the best catalytic performance for one-pot cascade reaction affording the desired product (benzyl alcohol) in approximately 92% yield, which was 7.1 and 1.2 times higher than that of layered Pd/KNb{sub 3}O{sub 8} or Pd/HNb{sub 3}O{sub 8}, respectively. The excellent catalytic performance of Pd/HNb{sub 3

One step bioconversion of waste precious metals into Serratia biofilm-immobilized catalyst for Cr(VI) reduction.

Science.gov (United States)

Yong, P; Liu, W; Zhang, Z; Beauregard, D; Johns, M L; Macaskie, L E

2015-11-01

For reduction of Cr(VI) the Pd-catalyst is excellent but costly. The objectives were to prove the robustness of a Serratia biofilm as a support for biogenic Pd-nanoparticles and to fabricate effective catalyst from precious metal waste. Nanoparticles (NPs) of palladium were immobilized on polyurethane reticulated foam and polypropylene supports via adhesive biofilm of a Serratia sp. The biofilm adhesion and cohesion strength were unaffected by palladization and catalytic biofilm integrity was also shown by magnetic resonance imaging. Biofilm-Pd and mixed precious metals on biofilm (biofilm-PM) reduced 5 mM Cr(VI) to Cr(III) when immobilized in a flow-through column reactor, at respective flow rates of 9 and 6 ml/h. The lower activity of the latter was attributed to fewer, larger, metal deposits on the bacteria. Activity was lost in each case at pH 7 but was restored by washing with 5 mM citrate solution or by exposure of columns to solution at pH 2, suggesting fouling by Cr(III) hydroxide product at neutral pH. A 'one pot' conversion of precious metal waste into new catalyst for waste decontamination was shown in a continuous flow system based on the use of Serratia biofilm to manufacture and support catalytic Pd-nanoparticles.

Mesoporous silica nanoparticle supported PdIr bimetal catalyst for selective hydrogenation, and the significant promotional effect of Ir

Energy Technology Data Exchange (ETDEWEB)

Yang, Hui; Huang, Chao; Yang, Fan [The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641 (China); Yang, Xu [Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou (China); Du, Li [The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641 (China); Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou (China); Liao, Shijun, E-mail: chsjliao@scut.edu.cn [The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641 (China); Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou (China)

2015-12-01

Graphical abstract: A mesoporous silica nanoparticle (MSN) supported bimetal catalyst, PdIr/MSN, was prepared by a facile impregnation and hydrogen reduction method. The strong promotional effect of Ir was observed and thoroughly investigated. At the optimal molar ratio of Ir to Pd (N{sub Ir}/N{sub Pd} = 0.1), the activity of PdIr{sub 0.1}/MSN was up to eight times and 28 times higher than that of monometallic Pd/MSN and Ir/MSN, respectively. The catalysts were characterized comprehensively by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and hydrogen temperature programmed reduction, which revealed that the promotional effect of Ir may be due to the enhanced dispersion of active components on the MSN, and to the intensified Pd–Ir electronic interaction caused by the addition of Ir. - Highlights: • Mesoporous nanoparticles were synthesized and used as support for metal catalyst. • PdIr bimetallic catalyst exhibited significantly improved hydrogenation activity. • The strong promotion of Ir was recognized firstly and investigated intensively. • PdIr exhibits 18 times higher activity than Pd to the hydrogenation of nitrobenzene. - Abstract: A mesoporous silica nanoparticle (MSN) supported bimetal catalyst, PdIr/MSN, was prepared by a facile impregnation and hydrogen reduction method. The strong promotional effect of Ir was observed and thoroughly investigated. At the optimal molar ratio of Ir to Pd (N{sub Ir}/N{sub Pd} = 0.1), the activity of PdIr{sub 0.1}/MSN was up to eight times and 28 times higher than that of monometallic Pd/MSN and Ir/MSN, respectively. The catalysts were characterized comprehensively by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and hydrogen temperature programmed reduction, which revealed that the promotional effect of Ir may be due to the enhanced dispersion of active components on the MSN, and to the intensified Pd–Ir electronic interaction

Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes

Directory of Open Access Journals (Sweden)

Luis M. Rivera Gavidia

2017-05-01

Full Text Available Direct methanol fuel cells (DMFCs are electrochemical devices that efficiently produce electricity and are characterized by a large flexibility for portable applications and high energy density. Methanol crossover is one of the main obstacles for DMFC commercialization, forcing the search for highly electro-active and methanol tolerant cathodes. In the present work, carbon-supported Pd and PdFe catalysts were synthesized using a sodium borohydride reduction method and physico-chemically characterized using transmission electron microscopy (TEM and X-ray techniques such as photoelectron spectroscopy (XPS, diffraction (XRD and energy dispersive spectroscopy (EDX. The catalysts were investigated as DMFC cathodes operating at different methanol concentrations (up to 10 M and temperatures (60 °C and 90 °C. The cell based on PdFe/C cathode presented the best performance, achieving a maximum power density of 37.5 mW·cm−2 at 90 °C with 10 M methanol, higher than supported Pd and Pt commercial catalysts, demonstrating that Fe addition yields structural changes to Pd crystal lattice that reduce the crossover effects in DMFC operation.

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.

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.

Selective hydrogenation of 4-isobutylacetophenone over a sodium-promoted Pd/C catalyst

International Nuclear Information System (INIS)

Cho, Hong-Baek; Lee, Bae Uk; Nakayama, Tadachika; Park, Yeung-Ho; Ryu, Chung-Han

2013-01-01

The effect of sodium promotion on the selective hydrogenation of 4-isobutylacetophenone, 4-IBAP, was investigated over a Pd/C catalyst. A precipitation and deposition method was used to prepare the catalyst, and sodium was promoted on the Pd/C catalyst via post-impregnation while varying the sodium content. The sodium-promoted Pd/C catalyst resulted in a significantly improved yield greater than 96% of the desired product, 1-(4-isobutylphenyl) ethanol (4-IBPE), compared with the non-patented literature results under a mild hydrogenation condition. A detailed hydrogenation network over the Pd/C catalyst was suggested. The reaction mechanism for the yield and selectivity enhancement of 4-IBPE induced-by the promoted Pd/C was elucidated in relation to the geometric and electronic effects of reactant molecules in the microporous support depending on the reaction steps

Enhanced Activity and Selectivity of Carbon Nanofiber Supported Pd Catalysts for Nitrite Reduction

KAUST Repository

Shuai, Danmeng; Choe, Jong Kwon; Shapley, John R.; Werth, Charles J.

2012-01-01

Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment. © 2012 American Chemical Society.

Enhanced Activity and Selectivity of Carbon Nanofiber Supported Pd Catalysts for Nitrite Reduction

KAUST Repository

Shuai, Danmeng

2012-03-06

Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment. © 2012 American Chemical Society.

Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane.

Science.gov (United States)

Zhang, Sheng; Kang, Peng; Bakir, Mohammed; Lapides, Alexander M; Dares, Christopher J; Meyer, Thomas J

2015-12-29

Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world's continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd-H sites and Cu-CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices.

Scalable synthesis of palladium nanoparticle catalysts by atomic layer deposition

International Nuclear Information System (INIS)

Liang Xinhua; Lyon, Lauren B.; Jiang Yingbing; Weimer, Alan W.

2012-01-01

Atomic layer deposition (ALD) was used to produce Pd/Al 2 O 3 catalysts using sequential exposures of Pd(II) hexafluoroacetylacetonate and formalin at 200 °C in a fluidized bed reactor. The ALD-prepared Pd/alumina catalysts were characterized by various methods including hydrogen chemisorption, XPS, and TEM, and compared with a commercially available 1 wt% Pd/alumina catalyst, which was also characterized. The content of Pd on alumina support and the size of Pd nanoparticles can be controlled by the number of ALD-coating cycles and the dose time of the Pd precursor. One layer of organic component from the Pd precursor remained on the Pd particle surface. The ALD 0.9 wt% Pd/alumina had greater active metal surface area and percent metal dispersion than the commercial 1 wt% Pd/alumina catalyst. The ALD and commercial catalysts were subjected to catalytic testing to determine their relative activities for glucose oxidation to gluconic acid in aqueous solution. The ALD 0.9 wt% Pd/alumina catalyst had comparable activity as compared to the commercial 1 wt% Pd catalyst. No noticeable amount of Pd leaching was observed for the ALD-prepared catalysts during the vigorously stirred reaction.

Wire gauze and cordierite supported noble metal catalysts for passive autocatalytic recombiner

International Nuclear Information System (INIS)

Sanap, Kiran K.; Varma, S.; Waghmode, S.B.; Bharadwaj, S.R.

2015-01-01

Highlights: • Synthesis by electroless deposition method and chemical reduction route. • Particle size of 0.1–0.5 μm & 3.5–5 nm for Pt–Pd/Wg & Pt–Pd/Cord catalysts. • Active for H_2 and O_2 reaction with initial H_2 concentration of 1.5 to 7% in air. • Active in presence of different contaminants like CO_2, CH_4, CO & relative humidity. • Enhanced resistance of Pt–Pd/Cord catalyst towards the poisoning of CO. - Abstract: Hydrogen released in nuclear reactor containment under severe accident scenario poses a threat to containment and hence needs to be regulated by catalytic recombination. Mixed noble metal catalysts with platinum–palladium supported on stainless steel wire gauze and cordierite support have been developed for this purpose. The developed catalysts have been found to be highly efficient for removal of hydrogen concentration in the range of 1.5 to 7.0% v/v in air. Though both the catalysts exhibit similar kinetics for lower hydrogen concentration, cordierite supported catalysts exhibits better kinetic rate at higher hydrogen concentration. The performances of these catalysts in presence of various probable catalytic poison like carbon monoxide and catalytic inhibitors like moisture, carbon dioxide, and hydrocarbons provide data for use of these catalysts under the actual scenario. Compared to stainless steel wire gauze supported catalyst, the cordierite based catalyst are found to exhibit enhanced resistance towards carbon monoxide and limited temperature rise for safer application at higher hydrogen concentrations.

Effect of the dispersants on Pd species and catalytic activity of supported palladium catalyst

Energy Technology Data Exchange (ETDEWEB)

Hu, Yue [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Yang, Xiaojun, E-mail: 10100201@wit.edu.cn [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Cao, Shuo, E-mail: cao23@email.sc.edu [North America R& D Center, Clariant BU Catalysts, Louisville, 40209, KY (United States); Zhou, Jie [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Wu, Yuanxin [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Han, Jinyu [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Yan, Zhiguo [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Zheng, Mingming [Oil Crops Research Institute, Chinese Academy of Agricultural Sciences, Hubei Key Laboratory of Oilcrops Lipid Chemistry and Nutrition, Wuhan 430062 (China)

2017-04-01

Highlights: • Polyvinyl alcohol (PVA) inhibited the sintering and reduction of Pd nanoparticles. • Activity was improved for supported Pd catalysts with PVA modified method. • PVA modified method minimized the catalyst deactivation. • This work provides an insight of the regeneration strategies for Pd catalysts. - Abstract: A series of supported palladium catalysts has been prepared through the precipitation method and the reduction method, using polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) as dispersants. The effects of the dispersants on the properties of catalysts were evaluated and the catalytic performance of the new materials was investigated for the oxidative carbonylation of phenol to diphenyl carbonate (DPC). The catalysts as prepared were also characterized by the X-ray diffraction (XRD), transmission electron microscope (TEM), Brunner-Emmet-Teller (BET) measurements and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the addition of the dispersants had no effect on the crystal phase of the catalysts. However, the dispersion of Pd particles was improved when the dispersants were used. Moreover, the particle sizes of Pd nanoparticles modified by PVA were smaller than those modified by PVP. The catalysts prepared using the dispersants gave better yields of DPC than the catalysts prepared without the dispersants. The highest yield of DPC was 17.9% with the PVA-Red catalyst. The characterization results for the used catalysts showed that the Pd species in the PVA-Red catalyst remained mostly divalent and the lattice oxygen species were consumed during the reaction, which could lead to the higher catalytic activity of the PVA-Red catalyst. The experimental results confirm that PVA effectively inhibited the sintering and reduction of active Pd species in the oxidative carbonylation of phenol.

Improvement of sulfur resistance of Pd/Ce-Zr-Al-O catalysts for CO oxidation

Science.gov (United States)

Shin, Haebin; Baek, Minsung; Ro, Youngsoo; Song, Changyeol; Lee, Kwan-Young; Song, In Kyu

2018-01-01

Two kinds of mesoporous ceria-zirconia-alumina supports were prepared by a single-step epoxide-driven sol-gel method (SGCZA) and by a co-precipitation method (PCZA). Palladium catalysts supported on these materials were then prepared by a wet impregnation method (Pd/SGCZA and Pd/PCZA). The prepared catalysts were applied to the CO oxidation reaction before and after sulfur aging. XRD and N2 adsorption-desorption analyses revealed that these two catalysts retained different physicochemical properties. Pd/SGCZA had higher surface area and larger pore volume than Pd/PCZA before and after sulfur aging. TPR (Temperature-programmed reduction), CO chemisorption, FT-IR, and XPS analyses showed that the catalysts were differently influenced by sulfur species. Pd/SGCZA formed less sulfate and retained higher palladium dispersion than Pd/PCZA after sulfur aging. In the CO oxidation, Pd/PCZA showed better activity than Pd/SGCZA before sulfur aging. However, Pd/SGCZA showed higher CO conversion than Pd/PCZA after sulfur aging. We concluded that Pd/SGCZA was less poisoned by sulfur species than Pd/PCZA.

Promising SiC support for Pd catalyst in selective hydrogenation of acetylene to ethylene

Science.gov (United States)

Guo, Zhanglong; Liu, Yuefeng; Liu, Yan; Chu, Wei

2018-06-01

In this study, SiC supported Pd nanoparticles were found to be an efficient catalyst in acetylene selective hydrogenation reaction. The ethylene selectivity can be about 20% higher than that on Pd/TiO2 catalyst at the same acetylene conversion at 90%. Moreover, Pd/SiC catalyst showed a stable catalytic life at 65 °C with 80% ethylene selectivity. With the detailed characterization using temperature-programmed reduction (H2-TPR), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption/desorption analysis, CO-chemisorption and thermo-gravimetric analysis (TGA), it was found that SiC owns a lower surface area (22.9 m2/g) and a broad distribution of meso-/macro-porosity (from 5 to 65 nm), which enhanced the mass transfer during the chemical process at high reaction rate and decreased the residence time of ethylene on catalyst surface. Importantly, SiC support has the high thermal conductivity, which favored the rapid temperature homogenization through the catalyst bed and inhabited the over-hydrogenation of acetylene. The surface electronic density of Pd on Pd/SiC catalyst was higher than that on Pd/TiO2, which could promote desorption of ethylene from surface of the catalyst. TGA results confirmed a much less coke deposition on Pd/SiC catalyst.

Nanoporous PdCo Catalyst for Microfuel Cells: Electrodeposition and Dealloying

Directory of Open Access Journals (Sweden)

Satoshi Tominaka

2011-01-01

Full Text Available PdCo alloy is a promising catalyst for oxygen reduction reaction of direct methanol fuel cells because of its high activity and the tolerance to methanol. We have applied this catalyst in order to realize on-chip fuel cell which is a membraneless design. The novel design made the fuel cells to be flexible and integratable with other microdevices. Here, we summarize our recent research on the synthesis of nanostructured PdCo catalyst by electrochemical methods, which enable us to deposit the alloy onto microelectrodes of the on-chip fuel cells. First, the electrodeposition of PdCo is discussed in detail, and then, dealloying for introducing nanopores into the electrodeposits is described. Finally, electrochemical response and activities are fully discussed.

Monometallic Pd and Pt and Bimetallic Pd-Pt/Al2O3-TiO2 for the HDS of DBT: Effect of the Pd and Pt Incorporation Method

Directory of Open Access Journals (Sweden)

Reynaldo Martínez Guerrero

2014-01-01

Full Text Available The effect of the preparation method of monometallic Pd and Pt and bimetallic Pd-Pt/Al2O3-TiO2 catalysts on the hydrodesulfurization (HDS of dibenzothiophene (DBT was investigated in this study. The synthesis was accomplished using three methods: (A impregnation, (B metal organic chemical vapor deposition (MOCVD, and (C impregnation-MOCVD. The bimetallic Pd-Pt catalyst prepared by the impregnation-MOCVD method was most active for the HDS of DBT compared to those prepared by the single impregnation or MOCVD method due to the synergetic effect between both noble metals. The greater selectivity toward biphenyl indicated that this bimetallic Pd-Pt catalyst preferentially removes sulfur via the direct desulfurization mechanism. However, the bimetallic Pd-Pt catalyst prepared using the single MOCVD method did not produce any cyclohexylbenzene, which is most likely associated with the hydrogenation/dehydrogenation sites.

Electrochemical characterization of nano-sized Pd-based catalysts as cathode materials in direct methanol fuel cells.

Science.gov (United States)

Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

2011-01-01

To improve the catalytic activity of palladium (Pd) as a cathode catalyst in direct methanol fuel cells (DMFCs), we prepared palladium-titanium oxide (Pd-TiO2) catalysts which the Pd and TiO2 nanoparticles were simultaneously impregnated on carbon. We selected Pd and TiO2 as catalytic materials because of their electrochemical stability in acid solution. The crystal structure and the loading amount of Pd and TiO2 on carbon were characterized by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis (EDX). The electrochemical characterization of Pd-TiO2/C catalysts for the oxygen reduction reaction was carried out in half and single cell systems. The catalytic activities of the Pd-TiO2 catalysts were strongly influenced by the TiO2 content. In the single cell test, the Pd-TiO2 catalysts showed very comparable performance to the Pt catalyst.

Designing Pd-based supported bimetallic catalysts for environmental applications

OpenAIRE

Nowicka, Ewa; Meenakshisundaram, Sankar

2018-01-01

Supported bimetallic nanoparticulate catalysts are an important class of heterogeneous catalysts for many reactions including selective oxidation, hydrogenation/hydrogenolysis, reforming, biomass conversion reactions, and many more. The activity, selectivity, and stability of these catalysts depend on their structural features including particle size, composition, and morphology. In this review, we present important structural features relevant to supported bimetallic catalysts focusing on Pd...

Syngas Conversion to Gasoline-Range Hydrocarbons over Pd/ZnO/Al2O3 and ZSM-5 Composite Catalyst System

Energy Technology Data Exchange (ETDEWEB)

Dagle, Robert A.; Lizarazo Adarme, Jair A.; Lebarbier, Vanessa MC; Gray, Michel J.; White, James F.; King, David L.; Palo, Daniel R.

2014-07-01

A composite Pd/ZnO/Al2O3-HZSM-5 (Si/Al=40) catalytic system was evaluated for the synthesis of gasoline-range hydrocarbons directly from synthesis gas. Bifunctional catalyst comprising PdZn metal and acid sites present the required catalytically active sites necessary for the methanol synthesis, methanol dehydration, and methanol-to-gasoline reactions. This system provides a unique catalytic pathway for the production of liquid hydrocarbons directly from syngas. However, selectivity control is difficult and poses many challenges. The composite catalytic system was evaluated under various process conditions. Investigated were the effects of temperature (310-375oC), pressure (300-1000 psig), time-on-stream (50 hrs), and gas-hour space velocity (740-2970 hr-1), using a H2/CO molar syngas ratio of 2.0. By operating at the lower end of the temperature range investigated, liquid hydrocarbon formation was favored, as was decreased amounts of undesirable light hydrocarbons. However, lower operating temperatures also facilitated undesirable CO2 formation via the water-gas shift reaction. Higher operating pressures slightly favored liquid synthesis. Operating at relatively low pressures (e.g. 300 psig) was made possible, whereas for methanol synthesis alone higher pressure are usually required to achieve similar conversion levels (e.g. 1000 psig). Thermodynamic constraints on methanol synthesis are eased by pushing the equilibrium through hydrocarbon formation. Catalytic performance was also evaluated by altering Pd and Zn composition of the Pd/ZnO/Al2O3 catalyst. Of the catalysts and conditions tested, selectivity toward liquid hydrocarbon was highest when using a 5% Pd metal loading and Pd/Zn molar ratio of 0.25 and mixed with HZMS-5, operating at 310oC and 300 psig, CO conversion was 43 % and selectivity (carbon weight basis) to hydrocarbons was 49 wt. %. Of the hydrocarbon fraction, 44wt. % was in the C5-C12 liquid product range and consisted primarily of aromatic

Hydrogen storage in Pd nanocrystals covered with a metal-organic framework

Science.gov (United States)

Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M.; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

2014-08-01

Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

Oxidation of tritium in packed bed of noble metal catalyst for detritiation from system gases

International Nuclear Information System (INIS)

Nishikawa, Masabumi; Takeishi, Toshiharu; Munakata, Kenzo; Kotoh, Kenji; Enoeda, Mikio

1985-01-01

Catalytic oxidation rates of tritium in the bed of the noble metal catalysts are obtained and compared with the oxidation rates observed for the packed bed of spongy copper oxide or hopcalites. Use of Pt- or Pd-aluminia catalysts is recommended in this study because they give effective oxidation rates of tritium in the ambient temperature range. The adsorption performance of tritiated water in the catalyst bed is also discussed. (orig.)

Practical chemical analysis of Pt and Pd based heterogeneous catalysts with hard X-ray photoelectron spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Yoshikawa, H., E-mail: YOSHIKAWA.Hideki@nims.go.jp [National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Matolínová, I.; Matolín, V. [Charles University in Prague, Faculty of Mathematics and Physics, V Holešovičkách 2, 18000 Prague 8 (Czech Republic)

2013-10-15

Highlights: •Hard X-ray photoelectron spectroscopy (HAXPES) enables interface analysis of catalyst. •HAXPES enables overall analysis of porous film of Pt-doped CeO{sub 2} and related catalyst. •HAXPES enables analysis of trace elements for Pd and Pt{sub 3}Ni nanoparticle catalysts. -- Abstract: Interfacial properties including configuration, porosity, chemical states, and atomic diffusion greatly affect the performance of supported heterogeneous catalysts. Hard X-ray photoelectron spectroscopy (HAXPES) can be used to analyze the interfaces of heterogeneous catalysts because of its large information depth of more than 20 nm. We use HAXPES to examine Pt-doped CeO{sub 2} and related thin film catalysts evaporated on Si, carbon, and carbon nanotube substrates, because Pt-doped CeO{sub 2} has great potential as a noble metal-based heterogeneous catalyst for fuel cells. The HAXPES measurements clarify that the dopant material, substrate material, and surface pretreatment of substrate are important parameters that affect the interfacial properties of Pt-doped CeO{sub 2} and related thin film catalysts. Another advantage of HAXPES measurement of heterogeneous catalysts is that it can be used for chemical analysis of trace elements by detecting photoelectrons from deep core levels, which have large photoionization cross-sections in the hard X-ray region. We use HAXPES for chemical analysis of trace elements in Pd nanoparticle catalysts immobilized on sulfur-terminated substrates and Pt{sub 3}Ni nanoparticle catalysts enveloped by dendrimer molecules.

Bi-modified Pd/C catalyst via irreversible adsorption and its catalytic activity for ethanol oxidation in alkaline medium

International Nuclear Information System (INIS)

Cai, Jindi; Huang, Yiyin; Guo, Yonglang

2013-01-01

Highlights: • Pd-Bi/C catalysts were easily prepared by irreversible adsorption of Bi on Pd/C surface. • The adsorption of Bi increases the oxygen-containing species obviously on Pd-Bi/C surface. • Only a little amount of Bi on Pd-Bi/C can play a significant role in ethanol oxidation reaction (EOR). • Current density of EOR on Pd-Bi/C (20:1) is 2.4 times higher than that on Pd/C. • Anti-poisoning ability and durability of Pd-Bi/C (20:1) is greatly enhanced. -- Abstract: A facile approach to promote ethanol electro-oxidation on Pd-based catalysts is presented by the modification of Bi on Pd/C catalyst via irreversible adsorption. X-ray diffraction (XRD), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) measurements show that the modification of Bi has no significant effect on the Pd morphology and particle size distribution. Bi(III) and Pd(0) are the dominant forms in Pd-Bi/C catalyst. Electrochemical tests show that the modification of the appropriate amount of Bi on Pd/C catalyst can remarkably enhance activity toward ethanol oxidation reaction (EOR) up to about 2.4 times higher compared to Pd/C catalyst. The Pd-Bi/C (20:1) catalyst exhibits excellent stability and enhances CO tolerance. The enhanced electrochemical performance of Pd-Bi/C catalyst is attributed to the electronic effect and the bifunctional mechanism. The high exchange current density and the low apparent activation energy on Pd-Bi/C (20:1) catalyst reveal its faster kinetics and higher intrinsic activity compared to Pd/C catalyst

Selective Synthesis of Gasoline-Ranged Hydrocarbons from Syngas over Hybrid Catalyst Consisting of Metal-Loaded ZSM-5 Coupled with Copper-Zinc Oxide

Directory of Open Access Journals (Sweden)

Ting Ma

2014-04-01

Full Text Available The conversion of syngas (CO + H2 to gasoline-ranged hydrocarbons was carried out using a hybrid catalyst consisting of metal-loaded ZSM-5 coupled with Cu-ZnO in a near-critical n-hexane solvent. Methanol was synthesized from syngas over Cu-ZnO; subsequently, was converted to hydrocarbons through the formation of dimethyl ether (DME over the metal-loaded ZSM-5. When 0.5 wt% Pd/ZSM-5 and 5 wt% Cu/ZSM-5 among the metal-loaded ZSM-5 catalysts with Pd, Co, Fe or Cu were employed as a portion of the hybrid catalyst, the gasoline-ranged hydrocarbons were selectively produced (the gasoline-ranged hydrocarbons in all hydrocarbons: 59% for the hybrid catalyst with Pd/ZSM-5 and 64% for that with Cu/ZSM-5 with a similar CO conversion during the reaction. An increase in the Cu loading on ZSM-5 resulted in increasing the yield of the gasoline-ranged hydrocarbons, and in decreasing the yield of DME. Furthermore, the hybrid catalyst with Cu/ZSM-5 exhibited no deactivation for 30 h of the reaction. It was revealed that a hybrid catalyst containing Cu/ZSM-5 was efficient in the selective synthesis of gasoline-ranged hydrocarbons from syngas via methanol in the near-critical n-hexane fluid.

Effect of chlorine on performance of Pd catalysts prepared via colloidal immobilization

NARCIS (Netherlands)

Zhao, Yingnan; Liang, Wanwei; Li, Yongdan; Lefferts, Leon

2017-01-01

This contribution shows the effect of residual chlorine on the catalytic performance of a Pd-based catalyst in the hydrogenation of nitrite for cleaning of drinking water. The catalyst was prepared via immobilization a colloidal Pd nanoparticles using activated carbon as support. Different amount of

Efficient Catalytic Reduction of Hexavalent Chromium With Pd-decorated Carbon Nanotubes

Energy Technology Data Exchange (ETDEWEB)

Kim, Ji Dang; Choi, Hyun Chul [Chonnam National University, Gwangju (Korea, Republic of)

2016-05-15

Heavy metal pollution is currently a serious environmental issue. Chromium (Cr) and chromium compounds are commonly found in wastewater discharged by various industries such as wood preservation, leather tanning, electroplating, metal finishing, and the production of chemicals. Pd nanoparticles can easily be introduced into CNTs by performing DCC-activated amidation. Our TEM and XRD results indicate that well-dispersed metallic Pd nanoparticles are anchored on the surface of the amidated CNTs. The XPS results suggest that the Pd content of the sample is approximately 9.8 atomic %. In comparison with the commercial Pd catalyst, the prepared Pd-CNTs were demonstrated to exhibit good catalytic activity in the reduction of 4-NP by NaBH4. Moreover, the Pd-CNT catalyst can easily be separated by performing a simple filtration and reused over at least 10 cycles. This Pd-CNT catalyst is therefore believed to have significant potential for use as a reusable catalyst in the reduction of Cr(Vi)

Enhancing the biofuel upgrade performance for Pd nanoparticles via increasing the support hydrophilicity of metal-organic frameworks.

Science.gov (United States)

Sun, Qi; Chen, Meng; Aguila, Briana; Nguyen, Nicholas; Ma, Shengqian

2017-09-08

In this work, the influence of the hydrophilic/hydrophobic nature of metal-organic framework (MOF) materials on the catalytic performance of supported Pd nanoparticles for biofuel upgrade was studied. We show that the introduction of hydrophilic groups on a MOF can greatly enhance the performance of the resultant catalyst. Specifically, Pd nanoparticles supported on MIL-101-SO 3 Na with superhydrophilicity (Pd/MIL-101-SO 3 Na) far outperforms pristine MIL-101 and the benchmark catalyst Pd/C in the hydrodeoxygenation reaction of vanillin, a model component of pyrolysis oil derived from the lignin fraction. This is attributed to a favorable mode of adsorption of the highly water soluble reactants on the more hydrophilic support in the vicinity of the catalytically active Pd nanoparticles, thereby promoting their transformation.

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

A Phenomenological Study on the Synergistic Role of Precious Metals in the Steam Reforming of Logistic Fuels on Bimetal-Supported Catalysts

Directory of Open Access Journals (Sweden)

Abdul-Majeed Azad

2011-01-01

Full Text Available Fuel processors are required to convert sulfur-laden logistic fuels into hydrogen-rich reformate and deliver to the fuel cell stack with little or no sulfur. Since sulfur poisons and deactivates the reforming catalyst, robust sulfur-tolerant catalysts ought to be developed. In this paper, the development, characterization and evaluation of a series of reforming catalysts containing two noble metals (with total metal loading not exceeding 1 weight percent supported on nanoscale ceria for the steam-reforming of kerosene is reported. Due to inherent synergy, a bimetallic catalyst is superior to its monometallic analog, for the same level of loading. The choice of noble metal combination in the bimetallic formulations plays a vital and meaningful role in their performance. Presence of ruthenium and/or rhodium in formulations containing palladium showed improved sulfur tolerance and significant enhancement in their catalytic activity and stability. Rhodium was responsible for higher hydrogen yields in the logistic fuel reformate. Duration of steady hydrogen production was higher in the case of RhPd (75 h than for RuPd (68 h; hydrogen generation was stable over the longest period (88 h with RuRh containing no Pd. A mechanistic correlation between the characteristic role of precious metals in the presence of each other is discussed.

Permanganate oxidation of sulfur compounds to prevent poisoning of Pd catalysts in water treatment processes.

Science.gov (United States)

Angeles-Wedler, Dalia; Mackenzie, Katrin; Kopinke, Frank-Dieter

2008-08-01

The practical application of Pd-catalyzed water treatment processes is impeded by catalyst poisoning by reduced sulfur compounds (RSCs). In this study, the potential of permanganate as a selective oxidant for the removal of microbially generated RSCs in water and as a regeneration agent for S-poisoned catalysts was evaluated. Hydrodechlorination using Pd/Al2O3 was carried out as a probe reaction in permanganate-pretreated water. The activity of the Pd catalysts in the successfully pretreated reaction medium was similar to that in deionized water. The catalyst showed no deactivation behavior in the presence of permanganate at a concentration level or = 0.08 mM, a significant but temporary inhibition of the catalytic dechlorination was observed. Unprotected Pd/Al2O3, which had been completely poisoned by sulfide, was reactivated by a combined treatment with permanganate and hydrazine. However, the anthropogenic water pollutants thiophene and carbon disulfide were resistant against permanganate. Together with the preoxidation of catalyst poisons, hydrophobic protection of the catalysts was studied. Pd/zeolite and various hydrophobically coated catalysts showed a higher stability against ionic poisons and permanganate than the uncoated catalyst. By means of a combination of oxidative water pretreatment and hydrophobic catalyst protection, we provide a new tool to harness the potential of Pd-catalyzed hydrodehalogenation for the treatment of real waters.

Pd enhanced WC catalyst to promote heterogeneous methane combustion

International Nuclear Information System (INIS)

Terracciano, Anthony Carmine; De Oliveira, Samuel; Siddhanti, Deepti; Blair, Richard; Vasu, Subith S.; Orlovskaya, Nina

2017-01-01

Highlights: • Pd enhanced WC catalyst particles were synthesized via mechanochemical alloying. • Catalyst was characterized by XRD, XRF, SEM, and EDS. • Catalyst was deposited on porous ZrO_2 and evaluated in heterogeneous combustion. • During combustion temperature profiles and spectral emissions were collected. - Abstract: The efficiency of combustion for low cost heat production could be greatly enhanced if an active and low cost catalyst would be used to facilitate the chemical reactions occurring during combustor operation. Within this work an experimental study of palladium (Pd) enhanced tungsten carbide (WC) catalyst, synthesized via high energy ball milling and deposited by dip coating onto a magnesia partially stabilized zirconia (MgO-ZrO_2) porous matrix of 10 ppin was evaluated in heterogeneous methane combustion. The synthesized powder was characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) coupled with Energy Dispersive Spectroscopy (EDS) analysis, as well as by X-ray Fluorescence (XRF); and the morphology of the deposited WC-Pd coating was also characterized using SEM and EDS. Performance evaluation of the heterogeneous combustor with WC-Pd coated MgO-ZrO_2 porous media was conducted at constant air flow rate and various equivalence ratios of methane/air gaseous mixtures, while monitoring axial temperature profiles within the combustion chamber using thermocouples, as well as thermal radiative and acoustic emissions from the combustor exhaust using an externally placed CCD camera and a microphone. It was found that there is a strong dependence of flame position and maximum temperature on equivalence ratio (φ) over the range of 0.47 ± 0.02 ⩽ φ ⩽ 0.75 ± 0.02. Additionally it was found that over the same equivalence ratio range, there is a characteristic 4 peak acoustic signature between 200 and 500 Hz. It was found that at higher equivalence ratios 0.51 ± 0.02 ⩽ φ ⩽ 0.75 ± 0.02 the performance of combustor

Effects of metal composition and ratio on peptide-templated multimetallic PdPt nanomaterials

International Nuclear Information System (INIS)

Merrill, Nicholas A.; Nitka, Tadeusz T.; McKee, Erik M.; Merino, Kyle C.; Drummy, Lawrence F.

2017-01-01

It can be difficult to simultaneously control the size, composition, and morphology of metal nanomaterials under benign aqueous conditions. For this, bioinspired approaches have become increasingly popular due to their ability to stabilize a wide array of metal catalysts under ambient conditions. In this regard, we used the R5 peptide as a three-dimensional template for formation of PdPt bimetallic nanomaterials. Monometallic Pd and Pt nanomaterials have been shown to be highly reactive toward a variety of catalytic processes, but by forming bimetallic species, increased catalytic activity may be realized. The optimal metal-to-metal ratio was determined by varying the Pd:Pt ratio to obtain the largest increase in catalytic activity. To better understand the morphology and the local atomic structure of the materials, the bimetallic PdPt nanomaterials were extensively studied by transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and pair distribution function analysis. The resulting PdPt materials were determined to form multicomponent nanostructures where the Pt component demonstrated varying degrees of oxidation based upon the Pd:Pt ratio. To test the catalytic reactivity of the materials, olefin hydrogenation was conducted, which indicated a slight catalytic enhancement for the multicomponent materials. Finally, these results suggest a strong correlation between the metal ratio and the stabilizing biotemplate in controlling the final materials morphology, composition, and the interactions between the two metal species.

Effects of Metal Composition and Ratio on Peptide-Templated Multimetallic PdPt Nanomaterials

Energy Technology Data Exchange (ETDEWEB)

Merrill, Nicholas A.; Nitka, Tadeusz T.; McKee, Erik M.; Merino, Kyle C.; Drummy, Lawrence F.; Lee, Sungsik; Reinhart, Benjamin; Ren, Yang; Munro, Catherine J.; Pylypenko, Svitlana; Frenkel, Anatoly I.; Bedford, Nicholas M.; Knecht, Marc R.

2017-02-22

It can be difficult to simultaneously control the size, composition, and morphology of metal nanomaterials under benign aqueous conditions. For this, bio-inspired approaches have become increasing popular due to their ability to stabilize a wide array of metal catalysts under ambient conditions. In this regard, we used the R5 peptide as a 3D template for the formation of PdPt bimetallic nanomaterials. Monometallic Pd and Pt nanomaterials have been shown to be highly reactive towards a variety of catalytic processes, but by forming bimetallic species, increased catalytic activity may be realized. The optimal metal-to-metal ratio was determined by varying the Pd:Pt ratio to obtain the largest increase in catalytic activity. To better understand the morphology and the local atomic structure of the materials, the bimetallic PdPt nanomaterials were extensively studied using transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and pair distribution function analysis. The resulting PdPt materials were determined to form multicomponent nanostructures where the Pt component demonstrated varying degrees of oxidation based upon the Pd:Pt ratio. To test the catalytic reactivity of the materials, olefin hydrogenation was conducted which indicated a slight catalytic enhancement for the multicomponent materials. These results suggest a strong correlation between the metal ratio and the stabilizing biotemplate in controlling the final materials morphology, composition, and the interactions between the two metal species.

Pt-Pd bimetallic nanoparticles on MWCNTs: catalyst for hydrogen peroxide electrosynthesis

Energy Technology Data Exchange (ETDEWEB)

Felix-Navarro, R. M., E-mail: moi6salazar@hotmail.com; Beltran-Gastelum, M.; Salazar-Gastelum, M. I.; Silva-Carrillo, C.; Reynoso-Soto, E. A.; Perez-Sicairos, S.; Lin, S. W. [Centro de Graduados e Investigacion, Instituto Tecnologico de Tijuana (Mexico); Paraguay-Delgado, F. [Centro de Investigacion en Materiales Avanzados (Mexico); Alonso-Nunez, G. [Centro de Nanociencias y Nanotecnologia (Mexico)

2013-08-15

Bimetallic nanoparticles of Pt-Pd were deposited by the microemulsion method on a multiwall carbon nanotube (MWCNTs) to obtain a Pt-Pd/MWCNTs for electrocatalytic reduction of O{sub 2} to H{sub 2}O{sub 2}. The activity and selectivity of the catalyst was determined qualitatively by the rotating disk electrode method in acidic medium. The catalyst was spray-coated onto a reticulated vitreous carbon substrate and quantitatively was tested in bulk electrolysis for 20 min under potentiostatic conditions (0.5 V vs Ag/AgCl) in a 0.5 M H{sub 2}SO{sub 4} electrolyte using dissolved O{sub 2}. The bulk electrolysis experiments show that the Pt-Pd/MWCNTs catalyst is more efficient for H{sub 2}O{sub 2} electrogeneration than a MWCNTs catalyst. Nitrobenzene degradation by electrogenerated H{sub 2}O{sub 2} alone and Electro-Fenton process were also tested. Our results show that both processes decompose nitrobenzene, but the Electro-Fenton process does it more efficiently. The prepared nanoparticulated catalyst shows a great potential in environmental applications.

Pd nanoparticles supported on three-dimensional graphene aerogels as highly efficient catalysts for methanol electrooxidation

International Nuclear Information System (INIS)

Liu, Mingrui; Peng, Cheng; Yang, Wenke; Guo, Jiaojiao; Zheng, Yixiong; Chen, Peiqin; Huang, Tingting; Xu, Jing

2015-01-01

Well-dispersed Pd nanoparticles supported on three-dimensional graphene aerogels (Pd/3DGA) were successfully prepared via a facile and efficient hydrothermal method without surfactant and template. The morphology and structure of the as-prepared Pd/3DGA nanocomposites were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). SEM showed that the Pd nanoparticles with a small average diameter and narrow size distribution were uniformly deposited on the surface of the self-assembled three-dimensional graphene aerogels. Raman spectra revealed the surface properties of 3DGA and its interaction with metallic nanoparticles. Cyclic voltammetric (CV) and chronoamperometric (CA) experiments further exhibited its superior catalytic activity and stability for the electro-oxidation of methanol in alkaline media, making it a promising anodic catalyst for direct alkaline alcohol fuel cells (DAAFCs).

Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

Energy Technology Data Exchange (ETDEWEB)

Coan, Patrick D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Ellis, Lucas D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Griffin, Michael B. [National Bioenergy Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Schwartz, Daniel K. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Medlin, J. Will [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States

2018-03-01

Cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al2O3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivity for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al2O3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.

Evaluation of functionalized silica's for the adsorptive recovery of homogeneous catalysts through interaction with the metal centre

NARCIS (Netherlands)

Djekic, T.; Ham, van der A.G.J.; Haan, de A.B.

2007-01-01

The goal of this paper is the evaluation of functionalized silica's for the recovery of homogeneous catalysts by adsorption via its metal centre. As model catalysts, we selected bis(triphenylphosphine)cobalt(II)dichloride (CoCl2(PPh3)2), bis(triphenylphosphine)palladium(II)dichloride (PdCl2(PPh3)2)

Combinatorial computational chemistry approach to the design of metal catalysts for deNOx

International Nuclear Information System (INIS)

Endou, Akira; Jung, Changho; Kusagaya, Tomonori; Kubo, Momoji; Selvam, Parasuraman; Miyamoto, Akira

2004-01-01

Combinatorial chemistry is an efficient technique for the synthesis and screening of a large number of compounds. Recently, we introduced the combinatorial approach to computational chemistry for catalyst design and proposed a new method called ''combinatorial computational chemistry''. In the present study, we have applied this combinatorial computational chemistry approach to the design of precious metal catalysts for deNO x . As the first step of the screening of the metal catalysts, we studied Rh, Pd, Ag, Ir, Pt, and Au clusters regarding the adsorption properties towards NO molecule. It was demonstrated that the energetically most stable adsorption state of NO on Ir model cluster, which was irrespective of both the shape and number of atoms including the model clusters

Chitosan supported bimetallic Pd/Co nanoparticles as a heterogeneous catalyst for the reduction of nitroaromatics to amines

Directory of Open Access Journals (Sweden)

Sajjad Keshipour

2017-01-01

Full Text Available A new bimetallic nanocomposite of chitosan was prepared. Pd and Co nanoparticles were deposited on chitosan to produce a new heterogeneous recyclable catalyst for use in the bimetallic catalytic reduction reaction. The catalyst was characterized with common analysis methods for nanocomposites including Energy Dispersive X-Ray Spectroscopy, X-Ray Diffraction pattern, Thermal Gravimetric Analysis, Flame Atomic Absorption Spectroscopy and Scanning Electron Microscopy, and applied in the reduction reaction of nitroaromatics using NaBH4 at room temperature. The bimetallic system gave good results compared to each of the applied metals. Various aromatic amines and diamines were used in the reduction reaction. The aromatic amines were obtained as the sole product of the reduction reaction with 15 mol% Pd and 12 mol% Co during 2h. This reaction had some advantages such as mild reaction conditions, high yield, green solvent, and a recyclable catalyst. Also, the recovered catalyst was applicable in the reduction reaction without a significant decrease in the activity for up to six times.

Preparation of Pd/γ- Al2O3 catalyst utilized in chemisorption of hydrogen isotopes

International Nuclear Information System (INIS)

David, Elena; Stefanescu, Doina; Stanciu, V.

1997-01-01

Separation and hydrogen isotope determination require packings with special properties, utilizable in separation columns. Consequently, such packings as catalysts using γ-aluminia and metallic palladium active component as holder were obtained. The γ-aluminia used as holder has been prepared starting from λ salts, easy soluble in water, such as Al 2 (NO 3 ) 3 ·9H 2 O, at a preset (6.2-6.4) controlled pH. At a first stage the Al(OH) 3 results which by calcination at controlled temperature transforms in γ-Al 2O3 . On this holder, in which the specific surface and porosity has been determined, metallic palladium has been deposed, using for impregnation a 2% PdCl 2 solution. The content of deposed palladium was determined as the difference between the content in the initial solution and solution remaining after holder impregnation. This content has been determined by atomic absorption and is within 0.5 - 1.2% Pd. After impregnation the catalyst has been dried, then granulated at the 0.16 mm size and activated by hydrogen at a flow rate of 300 vol H 2 /volume

On the metal-support synergy for selective gas-phase ethanol oxidation over MgCuCr2O4 supported metal nanoparticle catalysts

NARCIS (Netherlands)

Liu, P.; Zhu, X.; Yang, S.; Li, T.; Hensen, E.J.M.

2015-01-01

Achieving high yields in the production of bulk chemicals is an important goal for the chemical industry. We investigated the influence of the metal on the catalytic performance of M/MgCuCr2O4 (M = Cu, Ag, Pd, Pt, Au) catalysts to better understand the metal-support synergy for the aerobic oxidation

Hydrodeoxygenation of phenol over Pd catalysts by in-situ generated hydrogen from aqueous reforming of formic acid

DEFF Research Database (Denmark)

Zeng, Ying; Wang, Ze; Lin, Weigang

2016-01-01

Hydrodeoxygenation of phenol, as model compound of bio-oil, was investigated over Pd catalysts, using formic acid as a hydrogen donor. The order of activity for deoxygenation of phenol with Pd catalysts was found to be: Pd/SiO2 > Pd/MCM-41 > Pd/CA > Pd/Al2O3 > Pd/HY approximate to Pd/ZrO2 ≈ Pd...

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.

Pd-bound functionalized mesoporous silica as active catalyst for Suzuki coupling reaction: Effect of OAcˉ, PPh3 and Clˉ ligands on catalytic activity

Science.gov (United States)

Das, Trisha; Uyama, Hiroshi; Nandi, Mahasweta

2018-04-01

Three new palladium catalysts, PdCat-I, PdCat-II and PdCat-III, immobilized over heterogeneous silica support have been synthesized using different ligands attached to the palladium precursor. The ligands that have been used in this study are acetate, triphenylphosphine and chloride in PdCat-I, PdCat-II and PdCat-III, respectively. The ligands have different effect on stability of the compounds and impart different oxidation states to the metal center. The materials have been characterized by powder X-ray diffraction, nitrogen adsorption-desorption studies, transmission electron microscopy, thermal analysis, and different spectroscopic techniques. The Pd-content of the samples have been determined by ICP-AES analysis. The materials have been used as catalysts for Suzuki coupling reaction of aryl halides with phenylboronic acid under mild conditions. A comparative study has been carried out to ascertain the effect of the nature of different ligands on the outcome of the catalytic reactions. Products have been identified and estimated by 1H NMR and gas chromatography. The results show that the best yields are obtained with the catalyst containing triphenylphosphine as the ligand in methanol. Such type of work to study the effect of ligand on Suzuki coupling reaction over functionalized mesoporous silica heterogeneous catalysts have not been carried out so far.

Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH 3 ) 4 ](ReO 4 ) 2 on γ-Al 2 O 3

Energy Technology Data Exchange (ETDEWEB)

Thompson, Simon T.; Lamb, H. Henry

2017-06-01

The double complex salt [Pd(NH3)4](ReO4)2 was employed as precursor of supported bimetallic catalysts for selective hydrogenation of furfural. Direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 in flowing H2 at 400 °C yields bimetallic nanoparticles 1–2 nm in size that exhibit significant interaction between the metals, as evidenced by temperature-programmed hydride decomposition (complete suppression of β-PdHx formation), extended X-ray absorption fine structure spectroscopy at the Pd K and Re LIII edges (PdRe distance = 2.72 Å), and scanning transmission electron microscopy with energy dispersive X-ray analysis. In contrast, calcination of [Pd(NH3)4](ReO4)2 on γ-Al2O3 at 350 °C in air and subsequent reduction in H2 at 400 °C results in metal segregation and formation of large (>50 nm) supported Pd particles; Re species cover the Pd particles and γ-Al2O3 support. A PdRe 1:2 catalyst prepared by sequential impregnation and calcination using HReO4 and [Pd(NH3)4](NO3)2 has a similar morphology. The catalyst derived by direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 exhibits remarkably high activity for selective hydrogenation of furfural to furfuryl alcohol (FAL) at 150 °C and 1 atm. Suppression of H2 chemisorption via elimination of Pd threefold sites, as evidenced by CO diffuse-reflectance infrared Fourier transform spectroscopy, correlates with increased FAL selectivity.

A novel method for synthesis of phosphomolybdic acid-modified Pd/C catalysts for oxygen reduction reaction

Science.gov (United States)

Zhu, Mingyuan; Gao, Xiaoling; Luo, Guangqin; Dai, Bin

2013-03-01

This manuscript reports a convenient method for immobilizing phosphomolybdic acid (HPMo) on polyaniline (PAN-) functionalized carbon supports. The obtained HPMo-PAN-C sample is used as the support to prepare a Pd/HPMo-PAN-C catalyst. The samples are characterized by Fourier transform infrared spectroscopy, transmission electron microscopy and X-ray diffraction analysis. The results suggest that HPMo retains its Keggin structure and that the presence of HPMo reduces the average particle size of the Pd nano-particles in the obtained Pd/HPMo-PAN-C catalyst. Electro-chemical measurements in 0.5 M HClO4 solution reveal that the Pd/HPMo-PAN-C catalyst has higher catalytic activity for oxygen reduction reactions than does a Pd/C catalyst prepared using a similar procedure. The stability of the Pd/HPMo-PAN-C catalyst is evaluated by multiple-cycle voltammetry techniques; the mass catalytic activity decreases by only 10% after 100 scanning cycles.

Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

Energy Technology Data Exchange (ETDEWEB)

Eraenen, K; Kumar, N; Lindfors, L E [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

1997-12-31

Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

Energy Technology Data Exchange (ETDEWEB)

Eraenen, K.; Kumar, N.; Lindfors, L.E. [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

1996-12-31

Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

Process for Making a Noble Metal on Tin Oxide Catalyst

Science.gov (United States)

Davis, Patricia; Miller, Irvin; Upchurch, Billy

2010-01-01

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

Design of Pd/PANI/Pd sandwich-structured nanotube array catalysts with special shape effects and synergistic effects for ethanol electrooxidation.

Science.gov (United States)

Wang, An-Liang; Xu, Han; Feng, Jin-Xian; Ding, Liang-Xin; Tong, Ye-Xiang; Li, Gao-Ren

2013-07-24

Low cost, high activity, and long-term durability are the main requirements for commercializing fuel cell electrocatalysts. Despite tremendous efforts, developing non-Pt anode electrocatalysts with high activity and long-term durability at low cost remains a significant technical challenge. Here we report a new type of hybrid Pd/PANI/Pd sandwich-structured nanotube array (SNTA) to exploit shape effects and synergistic effects of Pd-PANI composites for the oxidation of small organic molecules for direct alcohol fuel cells. These synthesized Pd/PANI/Pd SNTAs exhibit significantly improved electrocatalytic activity and durability compared with Pd NTAs and commercial Pd/C catalysts. The unique SNTAs provide fast transport and short diffusion paths for electroactive species and high utilization rate of catalysts. Besides the merits of nanotube arrays, the improved electrocatalytic activity and durability are especially attributed to the special Pd/PANI/Pd sandwich-like nanostructures, which results in electron delocalization between Pd d orbitals and PANI π-conjugated ligands and in electron transfer from Pd to PANI.

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.

Nanoparticular metal oxide/anatase catalysts

DEFF Research Database (Denmark)

2010-01-01

The present invention concerns a method of preparation of nanoparticular metal oxide catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular metal oxide catalyst precursors comprising combustible crystallization seeds upon which...... the catalyst metai oxide is co-precipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step. The present invention also concerns processes wherein the nanoparticular metal oxide catalysts of the invention are used, such as SCR (deNOx) reactions...

Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

KAUST Repository

Al-Shareef, Reem A.; Harb, Moussab; Saih, Youssef; Ould-Chikh, Samy; Roldan, Manuel A.; Anjum, Dalaver H.; Guyonnet, Elodie Bile; Candy, Jean-Pierre; Jan, Deng-Yang; Abdo, Suheil F.; Aguilar-Tapia, Antonio; Proux, Olivier; Hazemann, Jean-Louis; Basset, Jean-Marie

2018-01-01

Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

KAUST Repository

Alshareef, Reem Abdul aziz Hamed

2018-04-25

Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

Catalytic Oxidation of Propene over Pd Catalysts Supported on CeO2, TiO2, Al2O3 and M/Al2O3 Oxides (M = Ce, Ti, Fe, Mn

Directory of Open Access Journals (Sweden)

Sonia Gil

2015-04-01

Full Text Available In the following work, the catalytic behavior of Pd catalysts prepared using different oxides as support (Al2O3, CeO2 and TiO2 in the catalytic combustion of propene, in low concentration in excess of oxygen, to mimic the conditions of catalytic decomposition of a volatile organic compound of hydrocarbon-type is reported. In addition, the influence of different promoters (Ce, Ti, Fe and Mn when added to a Pd/Al2O3 catalyst was analyzed. Catalysts were prepared by the impregnation method and were characterized by ICP-OES, N2 adsorption, temperature-programmed reduction, temperature-programmed oxidation, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. Catalyst prepared using CeO2 as the support was less easily reducible, due to the stabilization effect of CeO2 over the palladium oxides. Small PdO particles and, therefore, high Pd dispersion were observed for all of the catalysts, as confirmed by XRD and TEM. The addition of Ce to the Pd/Al2O3 catalysts increased the metal-support interaction and the formation of highly-dispersed Pd species. The addition of Ce and Fe improved the catalytic behavior of the Pd/Al2O3 catalyst; however, the addition of Mn and Ti decreased the catalytic activity in the propene oxidation. Pd/TiO2 showed the highest catalytic activity, probably due to the high capacity of this catalyst to reoxidize Pd into PdO, as has been found in the temperature-programmed oxidation (TPO experiments.

Novel palladium-lead (Pd-Pb/C) bimetallic catalysts for electrooxidation of ethanol in alkaline media

Energy Technology Data Exchange (ETDEWEB)

Wang, Yi; Nguyen, Truong Son; Wang, Xin [School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Liu, Xuewei [School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 639798 (Singapore)

2010-05-01

Carbon-supported bimetallic palladium-lead (Pd-Pb/C) catalysts with different amounts of lead are prepared using a co-reduction method. The catalysts are characterized by various techniques, which reveal the formation of an alloy nanoparticle structure. The electrochemical activities of the catalysts towards ethanol oxidation in alkaline media are examined by cyclic voltammetry, linear sweep voltammetry and chronoamperometry methods. The results show that the Pd-Pb(4:1)/C catalyst exhibits a better catalytic activity than the Pd/C catalyst. From carbon monoxide (CO) stripping results, the addition of lead also facilitates the oxidative removal of adsorbed CO. The promoting effect of lead is explained by a bi-functional mechanism and d-band theory. (author)

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.

Evaluation of functionalized silica¿s for the adsorptive recovery of homogenous catalysts through interaction with the metal centre

NARCIS (Netherlands)

Djekic, T.; van der Ham, Aloysius G.J.; de Haan, A.B.

2007-01-01

The goal of this paper is the evaluation of functionalized silica's for the recovery of homogeneous catalysts by adsorption via its metal centre. As model catalysts, we selected bis(triphenylphosphine)cobalt(II)dichloride (CoCl2(PPh3)2), bis(triphenylphosphine)palladium(II)dichloride (PdCl2(PPh3)2)

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.)

Synthesis and characterization of bimetallic Pd-Ni catalysts in a CeO_2 matrix for the generation of H_2 by the reforming reaction of methanol

International Nuclear Information System (INIS)

Contreras C, R.

2016-01-01

The hydrothermal method was used for the synthesis of CeO_2 nano rods using Ce(NO_3)_3·6H_2O and NH_4OH. The catalytic support was calcined at 700 degrees Celsius. The synthesis of CeO_2 nano rods were impregnated with an aqueous solution of Ni(NO_3)_2·6H_2O by an incipient wetness impregnation method at an appropriate concentration to yield 5 and 15% of Ni in the catalysts. Then 0.5% of Pd was impregnated using PdCl_2. The samples obtained were calcined at 400 and reduced at 450 degrees Celsius. The catalytic materials were characterized by: temperature programmed reduction (TPR), Scanning Electron Microscopy (Sem) , surface area and X-ray diffraction (XRD) . Sem results showed that the CeO_2 is formed by nano rods and in lesser proportion semi spherical particles. Bet surface area of the catalysts decreases with Ni loading onto the CeO_2 nano rods. Pd O and Ni O were reduced at low and high temperature as was observed by TPR. The CeO_2 one-dimensional nano rods showed a highly crystalline structure with sharp diffraction peaks, with a typical fluorite structure (cubic structure of the CeO_2) and characteristic peaks corresponding to metallic Ni. No diffraction peaks of Pd were found. This is due to the low concentration of this metal in the catalyst. These catalysts showed high activity and selectivity to H_2 at maximum reaction temperature. According to the results of activity and selectivity, the catalysts with Pd-Ni are an alternative for the H_2 production in auto thermal reforming reaction of methanol. (Author)

Mesoporous metal catalysts formed by ultrasound

Energy Technology Data Exchange (ETDEWEB)

Schaeferhans, Jana; Pazos Perez, Nicolas; Andreeva, Daria [Physikalische Chemie II, Universitaet Bayreuth (Germany)

2010-07-01

We study the ultrasound-driven formation of mesoporous metal sponges. The collapse of acoustic cavitations leads to very high temperatures and pressures on very short scales. Therefore, structures may be formed and quenched far from equilibrium. Mechanism of metal modification by ultrasound is complex and involves a variety of aspects. We propose that modification of metal particles and formation of mesoporous inner structures can be achieved due to thermal etching of metals by ultrasound stimulated high speed jets of liquid. Simultaneously, oxidation of metal surfaces by free radicals produced in water during cavitation stabilizes developed metal structures. Duration and intensity of the ultrasonication treatment is able to control the structure and morphology of metal sponges. We expect that this approach to the formation of nanoscale composite sponges is universal and opens perspective for a whole new class of catalytic materials that can be prepared in a one-step process. The developed method makes it possible to control the sponge morphology and can be used for formation of modern types of catalysts. For example, the sonication technique allows to combine the fabrication of mesoporous support and distribution of metal (Cu, Pd, Au, Pt etc.) nanoparticles in its pores into a single step.

Highly active carbon supported ternary PdSnPtx (x=0.1-0.7) catalysts for ethanol electro-oxidation in alkaline and acid media.

Science.gov (United States)

Wang, Xiaoguang; Zhu, Fuchun; He, Yongwei; Wang, Mei; Zhang, Zhonghua; Ma, Zizai; Li, Ruixue

2016-04-15

A series of trimetallic PdSnPtx (x=0.1-0.7)/C catalysts with varied Pt content have been synthesized by co-reduction method using NaBH4 as a reducing agent. These catalysts were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and chronoamperometry (CA). The electrochemical results show that, after adding a minor amount of Pt dopant, the resultant PdSnPtx/C demonstrated more superior catalytic performance toward ethanol oxidation as compared with that of mono-/bi-metallic Pd/C or PdSn/C in alkaline solution and the PdSnPt0.2/C with optimal molar ratio reached the best. In acid solution, the PdSnPt0.2/C also depicted a superior catalytic activity relative to the commercial Pt/C catalyst. The possible enhanced synergistic effect between Pd, Sn/Sn(O) and Pt in an alloyed state should be responsible for the as-revealed superior ethanol electro-oxidation performance based upon the beneficial electronic effect and bi-functional mechanism. It implies the trimetallic PdSnPt0.2/C with a low Pt content has a promising prospect as anodic electrocatalyst in fields of alkali- and acid-type direct ethanol fuel cells. Copyright © 2016 Elsevier Inc. All rights reserved.

Metal-support interaction: The key factor governing activity of Pd/SnO2 catalyst for denitration of ground water

Directory of Open Access Journals (Sweden)

Bošković Goran C.

2008-01-01

Full Text Available Two mesoporous nanocristalline Pd/SnO2 catalysts were prepared by modified solgel technique differing in the pH conditions (pH = 2 and 9.5 of the synthesis of their supports. Samples achieved different activity and selectivity in water denitration reaction using hydrogen. XPS results of reduced samples indicate a strong interaction between the Pd and the Sn possibly as a result of electron shift from Sn to Pd. The solid solution of Pd2+ and SnO2 is formed by taking O from the surface of the support. In such a way some SnO2-X species may stay onto the surface and be responsible for its pronounced activity.

Self-regenerative function of the intelligent automotive catalyst

International Nuclear Information System (INIS)

Tanaka, Hirohisa; Nishihata, Yasuo

2007-01-01

Intelligent catalyst, in which noble metals are used as an active part of automotive catalyst, has been considered for keeping up their sufficient activity. The noble metals have a function of cleaning up the exhaust gas as well as that of self-regeneration. In 2002, a Pd system has been put to practical use, and continuously Rh and Pt systems have been commercialized. Now the catalyst has been used in more than three million vehicles. In this report, the atomic level mechanism of the catalyst and its self-regeneration function getting from analyses using synchrotron radiation are introduced. By the analysis using the Spring-8, the mechanism of keeping the active state of the Pd Perovskite Oxide without degradation was identified. The DXAFS (Dispersive X-ray Absorption Fine Structure) analysis in the ESRF (European Synchrotron Radiation Facility) made clear the self-regeneration mechanism of the Pd Perovskite Oxide. This knowledge could lead to the practical development of the Rh and Pt systems. The catalyst technology is counted on balancing resources of the noble metal and environmental sustainability. (A.H.)

Catalytic Hydrodechlorination of Trichlorobenzenes with Pd(PhenCl2 as Catalyst Precursor

Directory of Open Access Journals (Sweden)

Guanlin Zhang

2015-01-01

Full Text Available We reported the catalytic hydrodechlorination (HDC of trichlorobenzenes by an organometallic compound Pd(PhenCl2 as a catalyst precursor. The catalyst precursor was prepared by chemical coordination reaction and characterized by FTIR and 1H NMR techniques. The HDC performance of Pd(PhenCl2 as catalyst precursor was evaluated on 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes (TCBs. All TCBs could be converted to dechlorination products with high conversion. Products distribution was closely related with the substrate structures and C-Cl bond energies. A reasonable reaction mechanism was also proposed.

Development and Comparison of the Substrate Scope of Pd-Catalysts for the Aerobic Oxidation of Alcohols

Science.gov (United States)

Schultz, Mitchell J.; Hamilton, Steven S.; Jensen, David R.; Sigman, Matthew S.

2009-01-01

Three catalysts for aerobic oxidation of alcohols are discussed and the effectiveness of each is evaluated for allylic, benzylic, aliphatic, and functionalized alcohols. Additionally, chiral nonracemic substrates as well as chemoselective and diastereoselective oxidations are investigated. In this study, the most convenient system for the Pd-catalyzed aerobic oxidation of alcohols is Pd(OAc)2 in combination with triethylamine. This system functions effectively for the majority of alcohols tested and uses mild conditions (3 to 5 mol % of catalyst, room temperature). Pd(IiPr)(OAc)2(H2O) (1) also successfully oxidizes the majority of alcohols evaluated. This system has the advantage of significantly lowering catalyst loadings but requires higher temperatures (0.1 to 1 mol % of catalyst, 60 °C). A new catalyst is also disclosed, Pd(IiPr)(OPiv)2 (2). This catalyst operates under very mild conditions (1 mol %, room temperature, and air as the O2 source) but with a more limited substrate scope. PMID:15844968

Hydrothermal Method Using DMF as a Reducing Agent for the Fabrication of PdAg Nanochain Catalysts towards Ethanol Electrooxidation

Directory of Open Access Journals (Sweden)

Yue Feng

2016-07-01

Full Text Available In this article, we developed a facile one-step hydrothermal method using dimethyl formamide (DMF as a reducing agent for the fabrication of PdAg catalyst. The scanning electron microscope (SEM and transmission electron microscopy (TEM images have shown that the as-synthesized PdAg catalyst had a nanochain structure. The energy-dispersive X-ray analyzer (EDX spectrum presented the actual molar ratio of Pd and Ag in the PdAg alloy. Traditional electrochemical measurements, such as cyclic voltammetry (CV, chronoamperometry (CA and electrochemical impedance spectrometry (EIS, were performed using a CHI 760D electrochemical analyzer to characterize the electrochemical properties of the as-synthesized catalyst. The results have shown that the PdAg catalyst with a nanochain structure displays higher catalytic activity and stability than pure Pd and commercial Pd/C catalysts.

High stability and high activity Pd/ITO-CNTs electrocatalyst for direct formic acid fuel cell

International Nuclear Information System (INIS)

Qu, Wei-Li; Gu, Da-Ming; Wang, Zhen-Bo; Zhang, Jing-Jia

2014-01-01

Graphical abstract: The addition of ITO in Pd/CNTs catalyst significantly improves the activity and stability of catalyst for formic acid electrooxidation due to excellent stability and high electrical conductivity of ITO, and metal-support interaction between Pd nanoparticles and ITO. - Highlights: • Pd catalyst with ITO and CNTs as a mixture support for DFAFC was first prepared by microwave-assisted polyol process. • The activity and stability of Pd/ITO-CNTs catalyst is significantly higher than those of Pd/CNTs. • When ITO content is 50% of ITO/CNTs support mass, Pd/ITO-CNTs exhibits the best performance. - Abstract: Indium tin oxide (ITO) and carbon nanotube hybrid has been explored as a support for Pd catalyst. Pd/ITO-CNTs catalysts with different ITO contents were prepared by the microwave-assisted polyol process. The as-prepared Pd/ITO-CNTs catalysts were characterized by X-ray diffraction (XRD), energy dispersive analysis of X-ray (EDAX), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), and electrochemical measurements in this work. The TEM results show that Pd particle size distribution in the Pd/ITO-CNTs catalyst is more uniform than that in Pd/CNTs, indicating that the ITO can promote the dispersion of Pd nanoparticles. It is found that there is metal-support interaction between Pd nanoparticles and ITO in the Pd/ITO-CNTs catalyst through XPS test. The results of electrochemical tests prove that the Pd/ITO-CNTs catalysts exhibit higher electro-catalytic activity and stability than Pd/CNTs toward formic acid electrooxidation. When the ITO content is 50% of ITO-CNTs support mass, the Pd/ITO-CNTs catalyst has the best catalytic performance for formic acid electrooxidation. The peak current density of formic acid electrooxidation on the Pd/ITO-CNTs50% electrode is 1.53 times as high as that on Pd/CNTs, 2.31 times higher than that on Pd/ITO. The results of aging

A facile self-assembly approach to prepare palladium/carbon nanotubes catalyst for the electro-oxidation of ethanol

Science.gov (United States)

Wen, Cuilian; Zhang, Xinyuan; Wei, Ying; Zhang, Teng; Chen, Changxin

2018-02-01

A facile self-assembly approach is reported to prepare palladium/carbon nanotubes (Pd/CNTs) catalyst for the electro-oxidation of ethanol. In this method, the Pd-oleate/CNTs was decomposed into the Pd/CNTs at an optimal temperature of 195 °C in air, in which no inert gas is needed for the thermal decomposition process due to the low temperature used and the decomposed products are also environmental friendly. The prepared Pd/CNTs catalyst has a high metallic Pd0 content and the Pd particles in the catalyst are disperse, uniform-sized with an average size of ˜2.1 nm, and evenly distributed on the CNTs. By employing our strategy, the problems including the exfoliation of the metal particles from the CNTs and the aggregation of the metal particles can be solved. Comparing with the commercial Pd/C one, the prepared Pd/CNTs catalyst exhibits a much higher electrochemical activity and stability for the electro-oxidation of ethanol in the direct ethanol fuel cells.

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.

PdZnAl Catalysts for the Reactions of Water-Gas-Shift, Methanol Steam Reforming, and Reverse-Water-Gas-Shift

Energy Technology Data Exchange (ETDEWEB)

Dagle, Robert A.; Platon, Alexandru; Datye, Abhaya K.; Vohs, John M.; Wang, Yong; Palo, Daniel R.

2008-03-07

Pd/ZnO/Al2O3 catalysts were studied for water-gas-shift (WGS), methanol steam reforming, and reverse-water-gas-shift (RWGS) reactions. WGS activity was found to be dependent on the Pd:Zn ratio with a maximum activity obtained at approximately 0.50, which was comparable to that of a commercial Pt-based catalyst. The catalyst stability was demonstrated for 100 hours time-on-stream at a temperature of 3600C without evidence of metal sintering. WGS reaction rates were approximately 1st order with respect to CO concentration, and kinetic parameters were determined to be Ea = 58.3 kJ mol-1 and k0 = 6.1x107 min-1. During methanol steam reforming, the CO selectivities were observed to be lower than the calculated equilibrium values over a range of temperatures and steam/carbon ratios studied while the reaction rate constants were approximately of the same magnitude for both WGS and methanol steam reforming. These results indicate that although Pd/ZnO/Al2O3 are active WGS catalysts, WGS is not involved in methanol steam reforming. RWGS rate constants are on the order of about 20 times lower than that of methanol steam reforming, suggesting that RWGS reaction could be one of the sources for small amount of CO formation in methanol steam reforming.

Hybrid NiCoOx adjacent to Pd nanoparticles as a synergistic electrocatalyst for ethanol oxidation

Science.gov (United States)

Wang, Wei; Yang, Yan; Liu, Yanqin; Zhang, Zhe; Dong, Wenkui; Lei, Ziqiang

2015-01-01

To improve the electrocatalytic activity of Pd for ethanol oxidation, hybrid NiCoOx adjacent to Pd catalyst (Pd-NiCoOx/C) is successfully synthesized. Physical characterization shows NiCoOx is closely adjacent to Pd nanoparticles in Pd-NiCoOx/C catalyst, which leads to Strong Metal-Support Interactions (SMSI) between the NiCoOx and Pd nanoparticles, in favor of the electrocatalytic properties. The Pd-NiCoOx/C catalyst is estimated to own larger electrochemically active surface area than Pd/C and Pd-NiO/C catalysts. Moreover, compared to Pd/C catalyst, the onset potential of Pd-NiCoOx/C catalyst is negative 40 mV for ethanol oxidation. Noticeably, the current density of Pd-NiCoOx/C catalyst is 2.05 and 1.43 times higher contrasted to Pd/C and Pd-NiO/C catalysts accordingly. Importantly, the Pd-NiCoOx/C catalyst exhibits better stability during ethanol oxidation, which is a promising electrocatalyst for application in direct alkaline alcohol fuel cells.

Application of a mixed metal oxide catalyst to a metallic substrate

Science.gov (United States)

Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

2009-01-01

A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

Electrochemical characterization of Pt-Ru-Pd catalysts for methanol oxidation reaction in direct methanol fuel cells.

Science.gov (United States)

Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

2011-01-01

PtRuPd nanoparticles on carbon black were prepared and characterized as electrocatalysts for methanol oxidation reaction in direct methanol fuel cells. Nano-sized Pd (2-4 nm) particles were deposited on Pt/C and PtRu/C (commercial products) by a simple chemical reduction process. The structural and physical information of the PtRuPd/C were confirmed by TEM and XRD, and their electrocatalytic activities were measured by cyclic voltammetry and linear sweep voltammetry. The catalysts containing Pd showed higher electrocatalytic activity for methanol oxidation reaction than the other catalysts. This might be attributed to an increase in the electrochemical surface area of Pt, which is caused by the addition of Pd; this results in increased catalyst utilization.

A palladium-doped ceria@carbon core-sheath nanowire network: a promising catalyst support for alcohol electrooxidation reactions

Science.gov (United States)

Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi

2015-08-01

A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique interconnected one-dimensional core-sheath structure is revealed to facilitate immobilization of the metal catalysts, leading to the improved durability. This core-sheath nanowire network opens up a new strategy for catalyst performance optimization for next-generation fuel cells.A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique

Novel non-platinum metal catalyst material

DEFF Research Database (Denmark)

2014-01-01

The present invention relates to a novel non-platinum metal catalyst material for use in low temperature fuel cells and electrolysers and to fuel cells and electrolysers comprising the novel non-platinum metal catalyst material. The present invention also relates to a novel method for synthesizing...... the novel non-platinum metal catalyst material....

Preparation and characterization of Pd doped ceria–ZnO nanocomposite catalyst for methyl tert-butyl ether (MTBE) photodegradation

International Nuclear Information System (INIS)

Seddigi, Zaki S.; Bumajdad, Ali; Ansari, Shahid P.; Ahmed, Saleh A.; Danish, Ekram Y.; Yarkandi, Naeema H.; Ahmed, Shakeel

2014-01-01

Highlights: • Novel Pd supported ceria–ZnO photocatalysts were prepared with different amounts of palladium. • The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. • Near complete removal of MTBE was achieved using 1% Pd doped ceria–ZnO catalyst and UV irradiation. • Highest rate constant was obtained in case of 1% Pd doped ceria–ZnO catalyst. • Shape and size of pores are important factors for high photoactivity of catalyst. -- Abstract: A series of binary oxide catalysts (ceria–ZnO) were prepared and doped with different amounts of palladium in the range of 0.5%–1.5%. The prepared catalysts were characterized by SEM, TEM, XRD and XPS, as well as by N 2 sorptiometry study. The XPS results confirmed the structure of the Pd CeO 2−x -ZnO. The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. These photocatalyst efficiently degrade a 100 ppm aqueous solution of MTBE upon UV irradiation for 5 h in the presence of 100 mg of each of these photocatalysts. The removal of 99.6% of the MTBE was achieved with the ceria–ZnO catalyst doped with 1% Pd. In addition to the Pd loading, the N 2 sorptiometry study introduced other factors that might affect the catalytic efficiency is the catalyst average pore sizes. The photoreaction was determined to be a first order reaction

Preparation and characterization of Pd doped ceria–ZnO nanocomposite catalyst for methyl tert-butyl ether (MTBE) photodegradation

Energy Technology Data Exchange (ETDEWEB)

Seddigi, Zaki S. [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Bumajdad, Ali [Chemistry Department, Faculty of Science, Kuwait University (Kuwait); Ansari, Shahid P. [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Ahmed, Saleh A., E-mail: saleh_63@hotmail.com [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Danish, Ekram Y. [Chemistry Department, King Abdulaziz University, Jeddah (Saudi Arabia); Yarkandi, Naeema H. [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Ahmed, Shakeel [Center for Refining and Petrochemicals, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia)

2014-01-15

Highlights: • Novel Pd supported ceria–ZnO photocatalysts were prepared with different amounts of palladium. • The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. • Near complete removal of MTBE was achieved using 1% Pd doped ceria–ZnO catalyst and UV irradiation. • Highest rate constant was obtained in case of 1% Pd doped ceria–ZnO catalyst. • Shape and size of pores are important factors for high photoactivity of catalyst. -- Abstract: A series of binary oxide catalysts (ceria–ZnO) were prepared and doped with different amounts of palladium in the range of 0.5%–1.5%. The prepared catalysts were characterized by SEM, TEM, XRD and XPS, as well as by N{sub 2} sorptiometry study. The XPS results confirmed the structure of the Pd CeO{sub 2−x}-ZnO. The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. These photocatalyst efficiently degrade a 100 ppm aqueous solution of MTBE upon UV irradiation for 5 h in the presence of 100 mg of each of these photocatalysts. The removal of 99.6% of the MTBE was achieved with the ceria–ZnO catalyst doped with 1% Pd. In addition to the Pd loading, the N{sub 2} sorptiometry study introduced other factors that might affect the catalytic efficiency is the catalyst average pore sizes. The photoreaction was determined to be a first order reaction.

Influence of Multi-Valency, Electrostatics and Molecular Recognition on the Adsorption of Transition Metal Complexes on Metal Oxides: A Molecular Approach to Catalyst Synthesis

Energy Technology Data Exchange (ETDEWEB)

Rioux, Robert M. [Pennsylvania State Univ., University Park, PA (United States)

2017-03-31

In this work, we have primarily utilized isothermal titration calorimetry (ITC) and complimentary catalyst characterization techniques to study and assess the impact of solution conditions (i.e., solid-liquid) interface on the synthesis of heterogeneous and electro-catalysts. Isothermal titration calorimetry is well-known technique from biochemistry/physics, but has been applied to a far lesser extent to characterize buried solid-liquid interfaces in materials science. We demonstrate the utility and unique information provided by ITC for two distinct catalytic systems. We explored the thermodynamics associated catalyst synthesis for two systems: (i) ion-exchange or strong electrostatic adsorption for Pt and Pd salts on silica and alumina materials (ii) adsorption to provide covalent attachment of metal and metal-oxo clusters to Dion-Jacobsen perovskite materials.

Reverse Topotactic Transformation of a Cu–Zn–Al Catalyst during Wet Pd Impregnation : Relevance for the Performance in Methanol Synthesis from CO2/H2 Mixtures

NARCIS (Netherlands)

Fierro, J.L.G.; López Granados, M.; Melián-Cabrera, I.

2002-01-01

The effect of palladium metal on the performance of a CuO–ZnO–Al2O3 catalyst is studied for methanol synthesis by hydrogenation of carbon dioxide. The dramatic decrease in the methanol yield (in mol CH3OH/h · gcat) seen for the Pd-containing catalysts is discussed in terms of formation,

Study of (La, Ce)(Pd, Mn, Fe, Co) O3-Perovskite catalysts characterization with nanoparticles produced by compressor and vacuum until 20/000 km and comparison with imported catalyst of Iran Khodro

International Nuclear Information System (INIS)

Khanfekr, A.; Arzani, K.; Nemati, A.; Hossaini, M.

2009-01-01

(La,Ce)(Pd,Mn,Fe,Co)O 3 - Perovskite catalyst was prepared by the citrate route and deposited on ceramic monoliths via dip coating procedure by compressor and vacuum method. The catalyst was applied on Rd car with XU7 motors model and the amount of emission was monitored with vehicle emission test systems in Sapco Company after 10000 and 20/000 Km. The results indicate low emission in catalyst with vacuum method and were compared with the imported catalyst with noble metals such as Palladium, Platinum and Rhodium by Iran Khodro Company b ased on the Euro III standards . The catalysts were characterized by specific surface area measurements, scanning electron microscopy, X-ray diffraction, line scan and map. In the results indicated in the home made sample, the amount of carbon monoxide, nitrogen oxides and hydrocarbons were lower than imported catalyst with Iran Khodro company with nobel metals. The illustration shows Nano Particles size on coat. The microstructure evaluation showed that the improved properties can he related to the existence of nano particles on coating.

Pd/NbOPO₄ multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans.

Science.gov (United States)

Xia, Qi-Neng; Cuan, Qian; Liu, Xiao-Hui; Gong, Xue-Qing; Lu, Guan-Zhong; Wang, Yan-Qin

2014-09-08

Great efforts have been made to convert renewable biomass into transportation fuels. Herein, we report the novel properties of NbO(x)-based catalysts in the hydrodeoxygenation of furan-derived adducts to liquid alkanes. Excellent activity and stability were observed with almost no decrease in octane yield (>90% throughout) in a 256 h time-on-stream test. Experimental and theoretical studies showed that NbO(x) species play the key role in C-O bond cleavage. As a multifunctional catalyst, Pd/NbOPO4 plays three roles in the conversion of aldol adducts into alkanes: 1) The noble metal (in this case Pd) is the active center for hydrogenation; 2) NbO(x) species help to cleave the C-O bond, especially of the tetrahydrofuran ring; and 3) a niobium-based solid acid catalyzes the dehydration, thus enabling the quantitative conversion of furan-derived adducts into alkanes under mild conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved ethanol electrooxidation performance by shortening Pd-Ni active site distance in Pd-Ni-P nanocatalysts

Science.gov (United States)

Chen, Lin; Lu, Lilin; Zhu, Hengli; Chen, Yueguang; Huang, Yu; Li, Yadong; Wang, Leyu

2017-01-01

Incorporating oxophilic metals into noble metal-based catalysts represents an emerging strategy to improve the catalytic performance of electrocatalysts in fuel cells. However, effects of the distance between the noble metal and oxophilic metal active sites on the catalytic performance have rarely been investigated. Herein, we report on ultrasmall (~5 nm) Pd-Ni-P ternary nanoparticles for ethanol electrooxidation. The activity is improved up to 4.95 A per mgPd, which is 6.88 times higher than commercial Pd/C (0.72 A per mgPd), by shortening the distance between Pd and Ni active sites, achieved through shape transformation from Pd/Ni-P heterodimers into Pd-Ni-P nanoparticles and tuning the Ni/Pd atomic ratio to 1:1. Density functional theory calculations reveal that the improved activity and stability stems from the promoted production of free OH radicals (on Ni active sites) which facilitate the oxidative removal of carbonaceous poison and combination with CH3CO radicals on adjacent Pd active sites.

Active sites and mechanisms for H2O2 decomposition over Pd catalysts

Science.gov (United States)

Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

2016-01-01

A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

Selective hydrodeoxygenation of cyclic vicinal diols to cyclic alcohols over tungsten oxide-palladium catalysts.

Science.gov (United States)

Amada, Yasushi; Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

2014-08-01

Hydrodeoxygenation of cyclic vicinal diols such as 1,4-anhydroerythritol was conducted over catalysts containing both a noble metal and a group 5-7 transition-metal oxide. The combination of Pd and WOx allowed the removal of one of the two OH groups selectively. 3-Hydroxytetrahydrofuran was obtained from 1,4-anhydroerythritol in 72 and 74% yield over WOx -Pd/C and WOx -Pd/ZrO2 , respectively. The WOx -Pd/ZrO2 catalyst was reusable without significant loss of activity if the catalyst was calcined as a method of regeneration. Characterization of WOx -Pd/C with temperature-programmed reduction, X-ray diffraction, and transmission electron microscopy/energy-dispersive X-ray spectroscopy suggested that Pd metal particles approximately 9 nm in size were formed on amorphous tungsten oxide particles. A reaction mechanism was proposed on the basis of kinetics, reaction results with tungsten oxides under an atmosphere of Ar, and density functional theory calculations. A tetravalent tungsten center (W(IV) ) was formed by reduction of WO3 with the Pd catalyst and H2 , and this center served as the reductant for partial hydrodeoxygenation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rare earth metals for automotive exhaust catalysts

International Nuclear Information System (INIS)

Shinjoh, Hirohumi

2006-01-01

The usage of rare earth metals for automotive exhaust catalysts is demonstrated in this paper. Rare earth metals have been widely used in automotive catalysts. In particular, three-way catalysts require the use of ceria compounds as oxygen storage materials, and lanthana as both a stabilizer of alumina and a promoter. The application for diesel catalysts is also illustrated. Effects of inclusion of rare earth metals in automotive catalysts are discussed

Ni-Pd-Al2O3 catalyst supported on reticulated ceramic foam for dry methane reforming

Directory of Open Access Journals (Sweden)

Vesna Nikolić

2015-03-01

Full Text Available In the present study, Ni-Pd/Al2O3 catalyst supported on α-Al2O3 based foam was prepared and evaluated in the dry methane reforming process. Corresponding metal chlorides were deposited to the foam surface by impregnation of the foam with ultrasonically aerosolized salt solutions at 473 K and drying at that temperature. Calcination step was excluded and the catalyst was reduced at very low temperature – 533 K. The reforming experiment lasted for 3 h, with standing time of 1 h at the following temperatures: 873, 973 and 1023 K. Conclusions on selectivity, catalytic activity and stability were reached on the basis of CO and H2 yields.

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

Formic Acid Oxidation over Hierarchical Porous Carbon Containing PtPd Catalysts

Directory of Open Access Journals (Sweden)

Elena Pastor

2013-10-01

Full Text Available The use of high surface monolithic carbon as support for catalysts offers important advantage, such as elimination of the ohmic drop originated in the interparticle contact and improved mass transport by ad-hoc pore design. Moreover, the approach discussed here has the advantage that it allows the synthesis of materials having a multimodal porous size distribution, with each pore size contributing to the desired properties. On the other hand, the monolithic nature of the porous support also imposes new challenges for metal loading. In this work, the use of Hierarchical Porous Carbon (HPC as support for PtPd nanoparticles was explored. Three hierarchical porous carbon samples (denoted as HPC-300, HPC-400 and HPC-500 with main pore size around 300, 400 and 500 nm respectively, are used as porous support. PtPd nanoparticles were loaded by impregnation and subsequent chemical reduction with NaBH4. The resulting material was characterized by EDX, XRD and conventional electrochemical techniques. The catalytic activity toward formic acid and methanol electrooxidation was evaluated by electrochemical methods, and the results compared with commercial carbon supported PtPd. The Hierarchical Porous Carbon support discussed here seems to be promising for use in DFAFC anodes.

The Role of Mg(OH)2 in the So-Called "Base-Free" Oxidation of Glycerol with AuPd Catalysts.

Science.gov (United States)

Fu, Jile; He, Qian; Miedziak, Peter J; Brett, Gemma L; Huang, Xiaoyang; Pattisson, Samuel; Douthwaite, Mark; Hutchings, Graham J

2018-02-16

Mg(OH) 2 - and Mg(OH) 2 -containing materials can provide excellent performance as supports for AuPd nanoparticles for the oxidation of glycerol in the absence of base, which is considered to be a result of additional basic sites on the surface of the support. However, its influence on the reaction solution is not generally discussed. In this paper, we examine the relationship between the basic Mg(OH) 2 support and AuPd nanoparticles in detail using four types of catalyst. For these reactions, the physical interaction between Mg(OH) 2 and AuPd was adjusted. It was found that the activity of the AuPd nanoparticles increased with the amount of Mg(OH) 2 added under base-free conditions, regardless of its interaction with the noble metals. In order to investigate how Mg(OH) 2 affected the glycerol oxidation, detailed information about the performance of AuPd/Mg(OH) 2 , physically mixed (AuPd/C+Mg(OH) 2 ) and (AuPd/C+NaHCO 3 ) was obtained and compared. Furthermore, NaOH and Mg(OH) 2 were added during the reaction using AuPd/C. All these results indicate that the distinctive and outstanding performance of Mg(OH) 2 supported catalysts in base-free condition is in fact directly related to its ability to affect the pH during the reaction and as such, assists with the initial activation of the primary alcohol, which is considered to be the rate determining step in the reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Morphological Effect of Pd Catalyst on Ethanol Electro-Oxidation Reaction

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Rosalba Fuentes Ramírez

2012-09-01

Full Text Available In the present study, three different structures with preferentially exposed crystal faces were supported on commercial carbon black by the polyol method (nanoparticles (NP/C, nanobars (NB/C and nanorods (NR/C. The electrocatalysts were characterized by XRD, TEM, TGA and cyclic voltammetry at three different ethanol concentrations. Considerable differences were found in terms of catalytic electroactivity. At all ethanol concentrations, the trend observed for the ethanol oxidation peak potential was preserved as follows: NB/C < NP/C< NR/C < commercial Pd/C. This result indicates that, from a thermodynamics point of view, the NB/C catalyst enclosed by Pd(100 facets presented the highest activity with respect to ethanol electro-oxidation among all of the catalysts studied.

Hollow Pd/MOF Nanosphere with Double Shells as Multifunctional Catalyst for Hydrogenation Reaction.

Science.gov (United States)

Wan, Mingming; Zhang, Xinlu; Li, Meiyan; Chen, Bo; Yin, Jie; Jin, Haichao; Lin, Lin; Chen, Chao; Zhang, Ning

2017-10-01

A new type of hollow nanostructure featured double metal-organic frameworks shells with metal nanoparticles (MNPs) is designed and fabricated by the methods of ship in a bottle and bottle around the ship. The nanostructure material, hereinafter denoted as Void@HKUST-1/Pd@ZIF-8, is confirmed by the analyses of photograph, transmission electron microscopy, scanning electron microscopy, powder X-ray diffraction, inductively coupled plasma, and N 2 sorption. It possesses various multifunctionally structural characteristics such as hollow cavity which can improve mass transfer, the adjacent of the inner HKUST-1 shell to the void which enables the matrix of the shell to host and well disperse MNPs, and an outer ZIF-8 shell which acts as protective layer against the leaching of MNPs and a sieve to guarantee molecular-size selectivity. This makes the material eligible candidates for the heterogeneous catalyst. As a proof of concept, the liquid-phase hydrogenation of olefins with different molecular sizes as a model reaction is employed. It demonstrates the efficient catalytic activity and size-selectivity of Void@HKUST-1/Pd@ZIF-8. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogenolysis of α-methylbenzyl alcohol to ethylbenzene over Pd/C catalyst

Science.gov (United States)

Feng, J.; Zhong, Y. H.; Dai, S. H.

2018-01-01

The hydrogenolysis of α-methylbenzyl alcohol (MBA) to ethylbenzene (EB) over Pd/C catalyst was studied. The XRD and TEM results show that Pd nanoparticles are well dispersed on the carbon support with good crystallinity. There is no 1-cyclohexylethanol or ethylcyclohexane in the products, indicating that Pd/C is excellent for inhibiting the hydrogenation of the aromatic ring. Alcohol solvents are beneficial to increase the catalytic activity because of their strong polarity and good solubility.

CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO₂ Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al₂O₃.

Science.gov (United States)

Goto, Tomoyo; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

2015-12-15

The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO₂ and Pt/α-Al₂O₃ catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO₂, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H₂, while H₂ combustion was activated by repeated exposure to H₂ gas during the periodic gas test. Selective CO sensing of the micro-TGS against H₂ was attempted using a double catalyst structure with 0.3-30 wt% Pt/α-Al₂O₃ as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al₂O₃ catalyst, by cancelling out the combustion heat from the AuPtPd/SnO₂ catalyst. In addition, the AuPtPd/SnO₂ and 0.3 wt% Pt/α-Al₂O₃ double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H₂.

Process Intensification of Alkynol Semihydrogenation in a Tube Reactor Coated with a Pd/ZnO Catalyst

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Nikolay Cherkasov

2017-11-01

Full Text Available Semihydrogenation of 2-methyl-3-butyn-2-ol (MBY was studied in a 5 m tube reactor wall-coated with a 5 wt% Pd/ZnO catalyst. The system allowed for the excellent selectivity towards the intermediate alkene of 97.8 ± 0.2% at an ambient H2 pressure and a MBY conversion below 90%. The maximum alkene yield reached 94.6% under solvent-free conditions and 96.0% in a 30 vol % MBY aqueous solution. The reactor stability was studied for 80 h on stream with a deactivation rate of only 0.07% per hour. Such a low deactivation rate provides a continuous operation of one month with only a two-fold decrease in catalyst activity and a metal leaching below 1 parts per billion (ppb. The excellent turn-over numbers (TON of above 105 illustrates a very efficient utilisation of the noble metal inside catalyst-coated tube reactors. When compared to batch operation at 70 °C, the reaction rate in flow reactor can be increased by eight times at a higher reaction temperature, keeping the same product decomposition of about 1% in both cases.

Study on the correlation between the surface active species of Pd/cordierite monolithic catalyst and its catalytic activity

International Nuclear Information System (INIS)

Liao, Hengcheng; Zuo, Peiyuan; Liu, Miaomiao

2016-01-01

Two Pd-loading routes and three Pd-precursor matters were adopted to prepare Pd/(Ce,Y)O_2/γ-Al_2O_3/cordierite monolithic catalyst. The surface active species on the catalyst were characterized by XPS, and its catalytic activity for methane combustion was tested, and the dynamics of the catalytic combustion reaction was also discussed. Pd-loading route and Pd-precursor mass have a significant influence on the catalytic activity and surface active species. The sol dipping method is more advanced than the aqueous solution impregnating method. PN-sol catalyst, by sol dipping combined with Pd(NO_3)_2-precursor, has the best catalytic activity. The physical reason is the unique active Pd phase coexisting with active PdO phase on the surface, and thus the Pd3d_5_/_2 binding energy of surface species and apparent activation energy of combustion reaction are considerably decreased. The catalytic activity index, Pd3d_5_/_2 binding energy and apparent activation energy are highly tied each other with exponential relations.

Bimetallic magnetic PtPd-nanoparticles as efficient catalyst for PAH removal from liquid media

Science.gov (United States)

Zanato, A. F. S.; Silva, V. C.; Lima, D. A.; Jacinto, M. J.

2017-11-01

Monometallic Pd- and bimetallic PtPd-nanoparticles supported on a mesoporous magnetic magnetite@silica matrix resembling a core-shell structure (Fe3O4@mSiO2) have been fabricated. The material was characterized by transmission electron microscope (TEM), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectra (XPS), energy dispersive spectroscopy (EDS) and inductively coupled plasma mass spectrometry (ICP-MS). The catalysts were applied in the removal of anthracene from liquid phase via catalytic hydrogenation. It was found that anthracene as a model compound could be completely converted into the partially hydrogenated species by the monometallic and bimetallic solids. However, during the recycling study the bimetallic material (Fe3O4@mSiO2PtPd-) showed an enhanced activity towards anthracene removal compared with the monometallic materials. A single portion of the PtPd-based catalyst can be used up to 11 times in the hydrogenation of anthracene under mild conditions (6 atm of H2, 75 °C, 20 min). Thanks to the presence of a dense magnetic core, the catalysts were capable of responding to an applied external magnetic field and once the reaction was completed, catalyst/product separation was straightforward.

Enhanced catalytic performance of Pd catalyst for formic acid electrooxidation in ionic liquid aqueous solution

Science.gov (United States)

Feng, Yuan-Yuan; Yin, Qian-Ying; Lu, Guo-Ping; Yang, Hai-Fang; Zhu, Xiao; Kong, De-Sheng; You, Jin-Mao

2014-12-01

A protic ionic liquid (IL), n-butylammonium nitrate (N4NO3), is prepared and employed as the electrolyte for formic acid electrooxidation reaction (FAOR) on Pd catalysts. The oxidation peak potential of FAOR in the IL solution shows about a 200 mV negative shift as compared with those in traditional H2SO4/HClO4 electrolytes, suggesting that FAOR can be more easily carried out on Pd catalysts in IL media. The catalytic properties of Pd toward FAOR are not only dependent on the concentration of IL, as a consequence of the varied electronic conductivity of the IL solution, but also on the high potential limit of the cyclic voltammograms. When the Pd catalyst is cycled up to 1.0 V (vs. SCE), which induces a significant oxidation of Pd, it shows ca. 4.0 times higher activity than that not subjected to the Pd oxidation (up to 0.6 V). The Pd oxides, which are more easily formed in IL solution than in traditional H2SO4/HClO4 electrolytes, may play a crucial role in increasing the catalytic activities of Pd toward FAOR. Our work would shed new light on the mechanism of FAOR and highlight the potential applications of IL as green and environment-friendly electrolytes in fuel cells and other technologies.

Screening the best catalyst with group 9, 10 and 11 metals monolayer loading on NbC(001) from first-principles study

Science.gov (United States)

Kan, Dongxiao; Zhang, Xilin; Zhang, Yanxing; Yang, Zongxian

2018-02-01

The supported catalysts have received great attentions due to their high catalytic activity, low cost and good stability. Here we report the stability, wetting ability, corrosion resistance and catalytic activity of the supported catalysts with group 9, 10 and 11 metals (M = Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au) monolayers (ML) deposited on NbC(001), denoted as MML/NbC(001). The PdML/NbC(001) and PtML/NbC(001) are testified as the most stable and active ones with the former even better on the whole. The catalytic activities toward oxygen reduction reactions (ORR) are clarified by the dissociation and the change in Gibbs free energies for the elementary reaction steps of O2 on PdML/NbC(001).

Effect of the Pd/MWCNTs anode catalysts preparation methods on their morphology and activity in a direct formic acid fuel cell

Energy Technology Data Exchange (ETDEWEB)

Lesiak, B., E-mail: blesiak-orlowska@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa (Poland); Mazurkiewicz, M.; Malolepszy, A. [Faculty of Chemical and Process Engineering, Warsaw University of Technology, Waryńskiego 1, 00-645 Warszawa (Poland); Stobinski, L. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa (Poland); Faculty of Chemical and Process Engineering, Warsaw University of Technology, Waryńskiego 1, 00-645 Warszawa (Poland); Mierzwa, B.; Mikolajczuk-Zychora, A.; Juchniewicz, K.; Borodzinski, A. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa (Poland); Zemek, J.; Jiricek, P. [Institute of Physics, Academy of Sciences of the Czech Republic, 162-53 Prague 6, Cukrovarnicka 10 (Czech Republic)

2016-11-30

Highlights: • Catalysts properties studied by XRD, STEM, XPS methods. • Differences in Pd particle size, content of Pd, functional groups, PdC{sub x.}. • Catalytic activity studied in a Direct Formic Acid Fuel Cell. • Highest activity–catalyst prepared using a strong reducing agent (NaBH{sub 4}). - Abstract: Impact of Pd/MWCNTs catalysts preparation method on the catalysts morphology and activity in a formic acid electrooxidation reaction was investigated. Three reduction methods of Pd precursor involving reduction in a high pressure microwave reactor (Pd1), reduction with NaBH{sub 4} (Pd2) and microwave-assisted polyol method (Pd3) were used in this paper. Crystallites size and morphology were studied using the scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), whereas elemental composition, Pd chemical state and functional groups content by the X-ray photoelectron spectroscopy (XPS). The prepared catalysts were tested in a direct formic acid fuel cell (DFAFC) as an anode material. The catalytic activity was correlated with a mean fraction of the total Pd atoms exposed at the surface (FE). The value of FE was calculated from the crystallites size distribution determined by the STEM measurements. Non-linear dependence of a current density versus FE, approaching the maximum at FE≈0.25 suggests that the catalytic process proceeded at Pd nanocrystallites faces, with inactive edges and corners. Pd2 catalyst exhibited highest activity due to its smallest Pd crystallites (3.2 nm), however the absence of Pd crystallites aggregation and low content of carbon in PdC{sub x} phase, i.e. x = 4 at.% may also affect the observed.

Effect of the Pd/MWCNTs anode catalysts preparation methods on their morphology and activity in a direct formic acid fuel cell

International Nuclear Information System (INIS)

Lesiak, B.; Mazurkiewicz, M.; Malolepszy, A.; Stobinski, L.; Mierzwa, B.; Mikolajczuk-Zychora, A.; Juchniewicz, K.; Borodzinski, A.; Zemek, J.; Jiricek, P.

2016-01-01

Highlights: • Catalysts properties studied by XRD, STEM, XPS methods. • Differences in Pd particle size, content of Pd, functional groups, PdC x. . • Catalytic activity studied in a Direct Formic Acid Fuel Cell. • Highest activity–catalyst prepared using a strong reducing agent (NaBH 4 ). - Abstract: Impact of Pd/MWCNTs catalysts preparation method on the catalysts morphology and activity in a formic acid electrooxidation reaction was investigated. Three reduction methods of Pd precursor involving reduction in a high pressure microwave reactor (Pd1), reduction with NaBH 4 (Pd2) and microwave-assisted polyol method (Pd3) were used in this paper. Crystallites size and morphology were studied using the scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), whereas elemental composition, Pd chemical state and functional groups content by the X-ray photoelectron spectroscopy (XPS). The prepared catalysts were tested in a direct formic acid fuel cell (DFAFC) as an anode material. The catalytic activity was correlated with a mean fraction of the total Pd atoms exposed at the surface (FE). The value of FE was calculated from the crystallites size distribution determined by the STEM measurements. Non-linear dependence of a current density versus FE, approaching the maximum at FE≈0.25 suggests that the catalytic process proceeded at Pd nanocrystallites faces, with inactive edges and corners. Pd2 catalyst exhibited highest activity due to its smallest Pd crystallites (3.2 nm), however the absence of Pd crystallites aggregation and low content of carbon in PdC x phase, i.e. x = 4 at.% may also affect the observed.

Synthesis of Hydrocarbons from H2-Deficient Syngas in Fischer-Tropsch Synthesis over Co-Based Catalyst Coupled with Fe-Based Catalyst as Water-Gas Shift Reaction

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Ting Ma

2015-01-01

Full Text Available The effects of metal species in an Fe-based catalyst on structural properties were investigated through the synthesis of Fe-based catalysts containing various metal species such, as Mn, Zr, and Ce. The addition of the metal species to the Fe-based catalyst resulted in high dispersions of the Fe species and high surface areas due to the formation of mesoporous voids about 2–4 nm surrounded by the catalyst particles. The metal-added Fe-based catalysts were employed together with Co-loaded beta zeolite for the synthesis of hydrocarbons from syngas with a lower H2/CO ratio of 1 than the stoichiometric H2/CO ratio of 2 for the Fischer-Tropsch synthesis (FTS. Among the catalysts, the Mn-added Fe-based catalyst exhibited a high activity for the water-gas shift (WGS reaction with a comparative durability, leading to the enhancement of the CO hydrogenation in the FTS in comparison with Co-loaded beta zeolite alone. Furthermore, the loading of Pd on the Mn-added Fe-based catalyst enhanced the catalytic durability due to the hydrogenation of carbonaceous species by the hydrogen activated over Pd.

Synthesis, characterization and catalytic activity of CoFe{sub 2}O{sub 4}-APTES-Pd magnetic recyclable catalyst

Energy Technology Data Exchange (ETDEWEB)

Demirelli, M. [Department of Chemistry, Faculty of Arts and Sciences, Yıldız Teknik University Davutpaşa Campus, Esenler, İstanbul (Turkey); Department of Chemistry, Faculty of Arts and Sciences, Fatih University, B. Cekmece, İstanbul 34500 (Turkey); Karaoğlu, E., E-mail: ebubekirkaraoglu@gmail.com [Department of Chemistry, Faculty of Arts and Sciences, Fatih University, B. Cekmece, İstanbul 34500 (Turkey); Department of Medical Biochemistry, Faculty of Medicine, Sakarya University, Korucuk, Sakarya (Turkey); Baykal, A. [Department of Chemistry, Faculty of Arts and Sciences, Fatih University, B. Cekmece, İstanbul 34500 (Turkey); Sözeri, H.; Uysal, E. [TUBITAK-UME, National Metrology Institute, PO Box 54, 41470 Gebze, Kocaeli (Turkey)

2014-01-05

Highlights: • CoFe{sub 2}O{sub 4}-APTES-Pd (0) nanocomposite, as effective catalysts for reduction reactions. • It could be reused several times without significant loss in hydrogenation reaction. • So far, CoFe{sub 2}O{sub 4}-APTES-Pd (0) nanocomposite have not been synthesized. • CoFe{sub 2}O{sub 4}-APTES-Pd (0) nanocomposite was confirmed by XRD, FT-IR. • Pd containing nanoparticles embedded in organic surfactant observed by TEM. -- Abstract: A new magnetically recyclable catalyst, CoFe{sub 2}O{sub 4}-APTES-Pd(0) nanocomposite, as highly effective catalysts for reduction reactions in liquid phase was fabricated and characterized. The reduction of Pd{sup 2+} was accomplished with sodium borohydride (NaBH{sub 4}). The chemical characterization of the product was done with X-ray diffractometry, infrared spectroscopy, transmission electron microscopy, UV–Vis spectroscopy and inductively coupled plasma. It was found that the combination of CoFe{sub 2}O{sub 4} and 3-aminopropyltriethoxysilane (APTES) could give rise to structurally stable catalytic sites. Furthermore, the high magnetization CoFe{sub 2}O{sub 4}-APTES-Pd(0) catalyst can be recovered by magnet and reused for ten runs for hydrogenation reaction of 4-nitro aniline, 1,3 dinitro and cyclohexanone. The catalyst was easily isolated from the reaction mixture by a magnetic bar and reused at least 10 times without significant degradation in the activity which shows the indicative of a potential applications of these catalysts in industry.

Bi-metallic catalysts, methods of making, and uses thereof

KAUST Repository

Basset, Jean-Marie

2017-01-19

Provided herein are bi-metallic catalysts, methods of making, and uses thereof. In some embodiments, the bi-metallic catalyst contains two different metal catalysts that can be used in hydrocarbon metathesis reactions, in some embodiments, the methods of making the bi-metallic catalysts can include two steps utilizing a surface organometallic chemistry approach in which the two different metal catalysts are sequentially grafted onto a support.

Bi-metallic catalysts, methods of making, and uses thereof

KAUST Repository

Basset, Jean-Marie; Samantaray, Manoja K.; Dey, Raju; Abou-Hamad, Edy; Kavitake, Santosh

2017-01-01

Provided herein are bi-metallic catalysts, methods of making, and uses thereof. In some embodiments, the bi-metallic catalyst contains two different metal catalysts that can be used in hydrocarbon metathesis reactions, in some embodiments, the methods of making the bi-metallic catalysts can include two steps utilizing a surface organometallic chemistry approach in which the two different metal catalysts are sequentially grafted onto a support.

Predicting catalyst-support interactions between metal nanoparticles and amorphous silica supports

Science.gov (United States)

Ewing, Christopher S.; Veser, Götz; McCarthy, Joseph J.; Lambrecht, Daniel S.; Johnson, J. Karl

2016-10-01

Metal-support interactions significantly affect the stability and activity of supported catalytic nanoparticles (NPs), yet there is no simple and reliable method for estimating NP-support interactions, especially for amorphous supports. We present an approach for rapid prediction of catalyst-support interactions between Pt NPs and amorphous silica supports for NPs of various sizes and shapes. We use density functional theory calculations of 13 atom Pt clusters on model amorphous silica supports to determine linear correlations relating catalyst properties to NP-support interactions. We show that these correlations can be combined with fast discrete element method simulations to predict adhesion energy and NP net charge for NPs of larger sizes and different shapes. Furthermore, we demonstrate that this approach can be successfully transferred to Pd, Au, Ni, and Fe NPs. This approach can be used to quickly screen stability and net charge transfer and leads to a better fundamental understanding of catalyst-support interactions.

Water-dispersable hybrid Au-Pd nanoparticles as catalysts in ethanol oxidation, aqueous phase Suzuki-Miyaura and Heck reactions

KAUST Repository

Song, Hyon Min

2012-01-01

The catalytic activities of water-dispersable Au@Pd core-shell nanoparticles (NPs) and Au-Pd alloy NPs were examined. There is growing interest in Au-Pd hybridized NPs in a supported matrix or non-supported forms as catalysts in various reactions that are not limited to conventional Pd-related reactions. Four different Au@Pd core-shell NPs in this study were prepared at room temperature with help from the emulsion phase surrounding the Au core NPs. Au-Pd alloy NPs were prepared over 90 °C, and underwent phase transfer to aqueous medium for their catalytic use. Au@Pd core-shell NPs show catalytic activity in ethanol oxidation reactions as electrocatalysts, and both core-shell and alloy NPs are good to excellent catalysts in various Suzuki-Miyaura and Heck reactions as heterogeneous catalysts. Specifically, Au@Pd core-shell NPs with sharp branched arms show the highest yield in the reactions tested in this study. A relatively small amount (0.25 mol%) was used throughout the catalytic reactions. © 2012 The Royal Society of Chemistry.

Tsuji-Trost N-allylation with allylic acetates using cellulose-Pd catalyst

Science.gov (United States)

Allylic amines are synthesized using heterogeneous cellulose-Pd catalyst via N-allylation of amines; aliphatic and benzyl amines undergo facile reaction with substituted and unsubstituted allyl acetates in high yields.

Size-dependent effects in supported highly dispersed Fe2O3 catalysts, doped with Pt and Pd

International Nuclear Information System (INIS)

Cherkezova-Zheleva, Zara; Shopska, Maya; Mitov, Ivan; Kadinov, Georgi

2010-01-01

Series of Fe and Fe–Me (Me = Pt or Pd) catalyst supported on γ-Al 2 O 3 , TiO 2 (anatase) or diatomite were prepared by the incipient wetness impregnation method. The metal loading was 8 wt.% Fe and 0.7 wt.% noble metal. The preparation and pretreatment conditions of all studied samples were kept to be the same. X-ray diffraction, Moessbauer spectroscopy, X-ray photoelectron spectroscopy and temperature-programmed reduction are used for characterization of the supports and the samples at different steps during their treatment and catalytic tests. The catalytic activity of the samples was tested in the reaction of total benzene oxidation. The physicochemical and catalytic properties of the obtained materials are compared with respect of the different chemical composition, dispersion of used carriers and of the supported phases. Samples with the same composition prepared by mechanical mixing are studied as catalysts for comparison and for clearing up the presence of size-dependent effect, also.

Preparation of Mesoporous Silica-Supported Palladium Catalysts for Biofuel Upgrade

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Ling Fei

2012-01-01

Full Text Available We report the preparation of two hydrocracking catalysts Pd/CoMoO4/silica and Pd/CNTs/CoMoO4/silica (CNTs, carbon nanotubes. The structure, morphologies, composition, and thermal stability of catalysts were studied by X-ray diffraction (XRD, scanning electron microscopy (SEM, Raman spectroscopy, transmission electron microscopy (TEM, energy-dispersive X-ray (EDX, and thermogravimetric analysis (TGA. The catalyst activity was measured in a Parr reactor with camelina fatty acid methyl esters (FAMEs as the feed. The analysis shows that the palladium nanoparticles have been incorporated onto mesoporous silica in Pd/CoMoO4/silica or on the CNTs surface in Pd/CNTs/CoMoO4/silica catalysts. The different combinations of metals and supports have selective control cracking on heavy hydrocarbons.

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.

Methane oxidation over noble metal catalysts as related to controlling natural gas vehicle exhaust emissions

International Nuclear Information System (INIS)

Oh, S.H.; Mitchell, P.J.; Siewert, R.M.

1992-01-01

Natural gas has considerable potential as an alternative automotive fuel. This paper reports on methane, the principal hydrocarbon species in natural-gas engine exhaust, which has extremely low photochemical reactivity but is a powerful greenhouse gas. Therefore, exhaust emissions of unburned methane from natural-gas vehicles are of particular concern. This laboratory reactor study evaluates noble metal catalysts for their potential in the catalytic removal of methane from natural-gas vehicle exhaust. Temperature run-up experiments show that the methane oxidation activity decreases in the order Pd/Al 2 O 3 > Rh/Al 2 O 3 > Pt/Al 2 O 3 . Also, for all the noble metal catalysts studied, methane conversion can be maximized by controlling the O 2 concentration of the feedstream at a point somewhat rich (reducing) of stoichiometry

Energy conversion using Pt-Pd/C anode catalyst in direct 2-propanol fuel cell

Directory of Open Access Journals (Sweden)

S. S. Mahapatra

2016-06-01

Full Text Available The Pt-Pd/C electrocatalyst was synthesized on graphite substrate by the electrochemical codeposition technique. The Physico-chemical characterization of the catalyst was done by SEM, XRD and EDX. The electrochemical characterization of the Pt-Pd/C catalyst for 2-propanol electro-oxidation was studied over a range of 2-propanol concentrations in alkaline medium using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The activity of 2-propanol oxidation increased with the increase of 2-propanol concentration, at 2-propanol concentration greater than 1.0 M, no change in the oxidation peak current density is because of excess 2-propanol at the electrode surface and/or depletion of OH− at the electrode surface. The Pt-Pd/C catalyst shows good stability and the low value of charge transfer resistance. The enhanced electrocatalytic activity of the electrodes is ascribed to the synergistic effect of higher electrochemical surface area, preferred OH− adsorption and ad-atom contribution on the alloyed surface.

The application of aberration-corrected electron microscopy to the characterization of gold-based catalysts

Science.gov (United States)

Herzing, Andrew A.

prepared using more traditional methods. The combination of STEM-HAADF imaging and XEDS mapping has been used to characterize these catalysts and a strong correlation between the catalytic activity and the enhanced degree of metal dispersion over the support is demonstrated. Thirdly, a systematic series of Au-Pd/Al2O3 catalysts has been studied in order to characterize the effects of various heat treatments on the development of core-shell morphologies within the bi-metallic particles and its subsequent effect on their catalytic performance for H2O 2 synthesis. STEM-XEDS spectrum imaging was employed in order to determine the degree of alloying and segregation behavior within the individual Au-Pd particles as a function of calcination/reduction temperature. It was found that the as prepared catalyst contained homogeneous Au-Pd alloy particles and that a Pd-rich shell/Au-rich core morphology gradually developed upon calcination. Subsequent reduction of the catalyst caused a large fraction of the particles to invert and form Pd-rich core/Au-rich shell structures. These changes are related to both the activity and stability of the catalyst. Finally, the washing of activated carbon support materials in acid was found to be extremely beneficial for producing Au-Pd catalysts for the direct synthesis of H2O2. STEM-HAADF imaging revealed that the acid-washing treatment increased the dispersion of the metal on the carbon supports. Aberration-corrected STEM-XEDS spectrum imaging demonstrated a strong size dependence of the Au-Pd particle composition. Crucially, the acid-washing pre-treatment enhanced the alloying of Au and Pd by suppressing the formation of large (> 25 nm) Au-rich particles. In summary, the application of aberration-corrected HAADF imaging and STEM-XEDS spectrum imaging to the characterization of Au-based catalysts has enhanced the understanding of the structural and chemical features that determine their catalytic behavior. Specifically, they have allowed us to

Quasi-zero-dimensional cobalt-doped CeO2 dots on Pd catalysts for alcohol electro-oxidation with enhanced poisoning-tolerance.

Science.gov (United States)

Tan, Qiang; Zhu, Haiyan; Guo, Shengwu; Chen, Yuanzhen; Jiang, Tao; Shu, Chengyong; Chong, Shaokun; Hultman, Benjamin; Liu, Yongning; Wu, Gang

2017-08-31

Deactivation of an anode catalyst resulting from the poisoning of CO ad -like intermediates is one of the major problems for methanol and ethanol electro-oxidation reactions (MOR & EOR), and remains a grand challenge towards achieving high performance for direct alcohol fuel cells (DAFCs). Herein, we report a new approach for the preparation of ultrafine cobalt-doped CeO 2 dots (Co-CeO 2 , d = 3.6 nm), which can be an effective anti-poisoning promoter for Pd catalysts towards MOR and EOR in alkaline media. Compared to Pd/CeO 2 and pure Pd, the hybrid Pd/Co-CeO 2 nanocomposite catalyst exhibited a much enhanced activity and remarkable anti-poisoning ability for both MOR and EOR. The nanocomposite catalyst showed much higher mass activity (4×) than a state-of-the-art PtRu catalyst. The promotional mechanism was elucidated using extensive characterization and density-functional theory (DFT). A bifunctional effect of the Co-CeO 2 dots was discovered to be due to (i) an enhanced electronic interaction between Co-CeO 2 and Pd dots and (ii) the increased oxygen storage capacity of Co-CeO 2 dots to facilitate the oxidation of CO ad . Therefore, the Pd/Co-CeO 2 nanocomposite appears to be a promising catalyst for advanced DAFCs with low cost and high performance.

Surface structure and reaction property of CuCl2-PdCl2 bimetallic catalyst in methanol oxycarbonylation: A DFT approach

International Nuclear Information System (INIS)

Meng, Qingsen; Wang, Shengping; Shen, Yongli; Yan, Bing; Wu, Yuanxin; Ma, Xinbin

2014-01-01

Surface structure of CuCl 2 -PdCl 2 bimetallic catalyst (Wacker-type catalyst) was built employing density functional theory (DFT) calculations, and the reaction mechanism of methanol oxycarbonylation over the CuCl 2 -PdCl 2 surfaces was also investigated. On the CuCl 2 -PdCl 2 surface, the active site for methanol oxidation was confirmed as Cu-Cl-Cu (Pd). Comparing with pure CuCl 2 surface, the introduction of Pd atom causes the electron repopulation on the surface and lowers the energy barrier for methanol oxidation, but the number of the active site decreases with the increasing of Pd doping volume. Agreed with previous experimental results, the Pd site is most favorable for the CO insertion, indicated by the lowest activation barrier for the formation of COOCH 3 on Pd atom. The lowest energy barrier for the formation of DMC appears when COOCH 3 species adsorbed on Pd atom and methoxyl adsorbed on Cu atoms, which is 0.42 eV. Finally, the reconstruction of the unsaturated surface is a spontaneous and exothermic process. Comparing with other surfaces, the rate-limiting step, methanol oxidation, on CuCl 2 -PdCl 2 surface with Pd/Cu = 1:17 has the lowest energy barrier, which is agreed with the experimental observation that PdCl 2 -CuCl 2 catalyst with Pd/Cu = 1:20 has the favorable activity. The adsorbed methoxyl will further lower the activation barrier of methanol oxidation, which is agreed with experimental observation that the Wacker-type catalysts have an induction period in the methanol oxidative carbonylation system.

Effect of the nanosized TiO2 particles in Pd/C catalysts as cathode materials in direct methanol fuel cells.

Science.gov (United States)

Choi, Mahnsoo; Han, Choonsoo; Kim, In-Tae; Lee, Ji-Jung; Lee, Hong-Ki; Shim, Joongpyo

2011-07-01

Pd-TiO2/C catalysts were prepared by impregnating titanium dioxide (TiO2) on carbon-supported Pd (Pd/C) for use as the catalyst for the oxygen reduction reaction (ORR) in direct methanol fuel cells (DMFCs). Transmission electron microscope (TEM), scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses were carried to confirm the distribution, morphology and structure of Pd and TiO2 on the carbon support. In fuel cell test, we confirmed that the addition of TiO2 nanoparticles make the improved catalytic activity of oxygen reduction. The electrochemical characterization of the Pd-TiO2/C catalyst for the ORR was carried out by cyclic voltammetry (CV) in the voltage window of 0.04 V to 1.2 V with scan rate of 25 mV/s. With the increase in the crystallite size of TiO2, the peak potential for OH(ads) desorption on the surface of Pd particle shifted to higher potential. This implies that TiO2 might affect the adsorption and desorption of oxygen molecules on Pd catalyst. The performance of Pd-TiO2/C as a cathode material was found to be similar to or better performance than that of Pt/C.

Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation

Science.gov (United States)

Zhang, Ke; Bin, Duan; Yang, Beibei; Wang, Caiqin; Ren, Fangfang; Du, Yukou

2015-07-01

Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly

Magnetically Separable Fe3O4@DOPA-Pd: A Heterogeneous Catalyst for Aqueous Heck Reaction

Science.gov (United States)

Magnetically separable Fe3O4@DOPA-Pd catalyst has been synthesized via anchoring of palladium over dopamine-coated magnetite via non-covalent interaction and the catalyst is utilized for expeditious Heck coupling in aqueous media.

Catalytic reduction of NOx with H2/CO/CH4 over PdMOR catalysts

International Nuclear Information System (INIS)

Pieterse, Johannis A.Z.; Booneveld, Saskia

2007-01-01

Conversion of NO x with reducing agents H 2 , CO and CH 4 , with and without O 2 , H 2 O, and CO 2 were studied with catalysts based on MOR zeolite loaded with palladium and cerium. The catalysts reached high NO x to N 2 conversion with H 2 and CO (>90% conversion and N 2 selectivity) range under lean conditions. The formation of N 2 O is absent in the presence of both H 2 and CO together with oxygen in the feed, which will be the case in lean engine exhaust. PdMOR shows synergic co-operation between H 2 and CO at 450-500 K. The positive effect of cerium is significant in the case of H 2 and CH 4 reducing agent but is less obvious with H 2 /CO mixture and under lean conditions. Cerium lowers the reducibility of Pd species in the zeolite micropores. The catalysts showed excellent stability at temperatures up to 673 K in a feed with 2500 ppm CH 4 , 500 ppm NO, 5% O 2 , 10% H 2 O (0-1% H 2 ), N 2 balance but deactivation is noticed at higher temperatures. Combining results of the present study with those of previous studies it shows that the PdMOR-based catalysts are good catalysts for NO x reduction with H 2 , CO, hydrocarbons, alcohols and aldehydes under lean conditions at temperatures up to 673 K. (author)

Investigation of Supported Pd-Based Electrocatalysts for the Oxygen Reduction Reaction: Performance, Durability and Methanol Tolerance

Directory of Open Access Journals (Sweden)

Carmelo Lo Vecchio

2015-11-01

Full Text Available Next generation cathode catalysts for direct methanol fuel cells (DMFCs must have high catalytic activity for the oxygen reduction reaction (ORR, a lower cost than benchmark Pt catalysts, and high stability and high tolerance to permeated methanol. In this study, palladium catalysts supported on titanium suboxides (Pd/TinO2n–1 were prepared by the sulphite complex route. The aim was to improve methanol tolerance and lower the cost associated with the noble metal while enhancing the stability through the use of titanium-based support; 30% Pd/Ketjenblack (Pd/KB and 30% Pd/Vulcan (Pd/Vul were also synthesized for comparison, using the same methodology. The catalysts were ex-situ characterized by physico-chemical analysis and investigated for the ORR to evaluate their activity, stability, and methanol tolerance properties. The Pd/KB catalyst showed the highest activity towards the ORR in perchloric acid solution. All Pd-based catalysts showed suitable tolerance to methanol poisoning, leading to higher ORR activity than a benchmark Pt/C catalyst in the presence of low methanol concentration. Among them, the Pd/TinO2n–1 catalyst showed a very promising stability compared to carbon-supported Pd samples in an accelerated degradation test of 1000 potential cycles. These results indicate good perspectives for the application of Pd/TinO2n–1 catalysts in DMFC cathodes.

Catalysis mechanism of Pd-promoted γ-alumina in the thermal decomposition of methane to hydrogen: A density functional theory study

Energy Technology Data Exchange (ETDEWEB)

Salam, M. Abdus; Abdullah, Bawadi, E-mail: bawadi_abdullah@utp.edu.my

2017-02-15

Thermo-catalytic methane decomposition to elemental hydrogen mechanism in transitional metals (Pd, Ni & Mo) promoted Al{sub 2}O{sub 3} (001) catalyst have been studied using the density functional theory (DFT). Decomposition reactions are spontaneous and favourable above 775 K for all promoter. Pd-promoted Al{sub 2}O{sub 3} (001) catalyst demonstrates a breakthrough decomposition activity in hydrogen production as compared to Ni− and Mo-promoted Al{sub 2}O{sub 3} (001) catalysts. The activation energy (E{sub a}) range of the catalysis for Pd promoted Al{sub 2}O{sub 3} (001) catalysts is 0.003–0.34 eV. Whereas, Ni and Mo promoted Al{sub 2}O{sub 3} (001) catalysts display activation energy E{sub a} in the range of 0.63–1.15 eV and 0.04–5.98 eV, respectively. Pd-promoted catalyst also shows a higher adsorption energy (−0.68 eV) and reactivity than that of Ni and Mo promoted Al{sub 2}O{sub 3} (001) catalysts. The rates of successive decomposition of methane are found to be 16.15 × 10{sup 12}, 15.95 × 10{sup 12} and 16.09 × 10{sup 12} s{sup −1} for the promoter of Pd, Ni and Mo, respectively. Pd promoted Al{sub 2}O{sub 3} (001) catalyst reduces the methane decomposition temperature (775 K) and deactivation rate significantly. The catalytic conditions and catalyst is promising in producing hydrogen to support hydrogen economy. - Highlights: • Transition metals (Pd, Ni & Mo) promoted γ-alumina catalysts are designed successfully. • Pd-promoted catalyst showed breakthrough activity in methane decomposition to hydrogen. • DFT study explored the catalysis mechanism of methane decomposition at atomic level. • Pd-promoted catalyst reduced temperature and activation barrier of methane decomposition reaction significantly.

Catalysis mechanism of Pd-promoted γ-alumina in the thermal decomposition of methane to hydrogen: A density functional theory study

International Nuclear Information System (INIS)

Salam, M. Abdus; Abdullah, Bawadi

2017-01-01

Thermo-catalytic methane decomposition to elemental hydrogen mechanism in transitional metals (Pd, Ni & Mo) promoted Al_2O_3 (001) catalyst have been studied using the density functional theory (DFT). Decomposition reactions are spontaneous and favourable above 775 K for all promoter. Pd-promoted Al_2O_3 (001) catalyst demonstrates a breakthrough decomposition activity in hydrogen production as compared to Ni− and Mo-promoted Al_2O_3 (001) catalysts. The activation energy (E_a) range of the catalysis for Pd promoted Al_2O_3 (001) catalysts is 0.003–0.34 eV. Whereas, Ni and Mo promoted Al_2O_3 (001) catalysts display activation energy E_a in the range of 0.63–1.15 eV and 0.04–5.98 eV, respectively. Pd-promoted catalyst also shows a higher adsorption energy (−0.68 eV) and reactivity than that of Ni and Mo promoted Al_2O_3 (001) catalysts. The rates of successive decomposition of methane are found to be 16.15 × 10"1"2, 15.95 × 10"1"2 and 16.09 × 10"1"2 s"−"1 for the promoter of Pd, Ni and Mo, respectively. Pd promoted Al_2O_3 (001) catalyst reduces the methane decomposition temperature (775 K) and deactivation rate significantly. The catalytic conditions and catalyst is promising in producing hydrogen to support hydrogen economy. - Highlights: • Transition metals (Pd, Ni & Mo) promoted γ-alumina catalysts are designed successfully. • Pd-promoted catalyst showed breakthrough activity in methane decomposition to hydrogen. • DFT study explored the catalysis mechanism of methane decomposition at atomic level. • Pd-promoted catalyst reduced temperature and activation barrier of methane decomposition reaction significantly.

The Complete Oxidation of Ethanol at Low Temperature over a Novel Pd-Ce/γ-Al2O3-TiO2 Catalyst

International Nuclear Information System (INIS)

Wang, Yanping; Zhao, Jinshuang; Wang, Xiaoli; Li, Zhe; Liu, Pengfei

2013-01-01

Pd-Ce/γ-Al 2 O 3 -TiO 2 catalysts were prepared by combined sol.gel and impregnation methods. Transmission electron microscopy, X-ray diffraction, H 2 -temperature-programmed reduction, O 2 -temperature-programmed desorption, and ethanol oxidation experiments were conducted to determine the properties of the catalysts. Addition of an optimal amount of Ce improved the performance of the Pd/γ-Al 2 O 3 -TiO 2 catalyst in promoting the complete oxidation of ethanol. The catalyst with 1% Ce exhibited the highest activity, and catalyzed complete oxidation of ethanol at 175 .deg. C; its selectivity to CO 2 reached 87%. Characterization results show that addition of appropriate amount of Ce could enrich the PdO species, and weaken the Pd-O bonds, thus enhancing oxidation ability of the catalyst. Meanwhile, the introduction of CeO 2 could make PdO better dispersed on γ-Al 2 O 3 -TiO 2 , which is beneficial for the improvement of the catalytic oxidation activity

Recovery of high-purity metallic Pd from Pd(II)-sorbed biosorbents by incineration.

Science.gov (United States)

Won, Sung Wook; Lim, Areum; Yun, Yeoung-Sang

2013-06-01

This work reports a direct way to recover metallic palladium with high purity from Pd(II)-sorbed polyethylenimine-modified Corynebacterium glutamicum biosorbent using a combined method of biosorption and incineration. This study is focused on the incineration part which affects the purity of recovered Pd. The incineration temperature and the amount of Pd loaded on the biosorbent were considered as major factors in the incineration process, and their effects were examined. The results showed that both factors significantly affected the enhancement of the recovery efficiency and purity of the recovered Pd. SEM-EDX and XRD analyses were used to confirm that Pd phase existed in the ash. As a result, the recovered Pd was changed from PdO to zero-valent Pd as the incineration temperature was increased from 600 to 900°C. Almost 100% pure metallic Pd was recovered with recovery efficiency above 99.0% under the conditions of 900°C and 136.9 mg/g. Copyright © 2013 Elsevier Ltd. All rights reserved.

An investigation of the activity and stability of Pd and Pd-Zr modified Y-zeolite catalysts for the removal of PAH, CO, CH4 and NOx emissions

International Nuclear Information System (INIS)

Klingstedt, F.; Kalantar Neyestanaki, A.; Lindfors, L.-E.; Salmi, T.; Heikkila, T.; Laine, E.

2003-01-01

Pd-Y- and Pd-Zr-Y-zeolite catalysts were prepared by the ion-exchange of parent NH 3 -Y-zeolite, thermally pre-treated Y-zeolite and hydrothermally pre-treated Y-zeolite. The activity of the catalysts was studied in conversion of gas mixtures simulating the flue gases from the combustion of biofuels and natural gas driven vehicles (NGVs) at temperature ranges of 120-800C. The effect of sulphur-poisoning was examined by the addition of 5ppm SO 2 into the feed gas mixtures. High activity in the removal of the model pollutants was obtained over the fresh catalysts. De-activation was observed as a result of catalyst ageing in the reactants' flow (800C, 6h) or steam treatment (850C, 12vol.% H 2 O, 16h). The de-activation was attributed to the de-alumination as well as to the migration of Pd 2+ cations. The catalysts were characterised by XRD, SEM-EDXA, N 2 -physisorption, O 2 /SO 2 /NH 3 /naphthalene-TPD, XRF and DCP

Isotopic exchange between deuterium and neohexane on supported platinum and palladium catalysts

International Nuclear Information System (INIS)

Eskinazi, V.

1979-01-01

The isotopic exchange reaction between neohexane and deuterium on supported Pt/SiO 2 and Pd/SiO 2 catalysts has been investigated in the temperature range 86.5 to 110 0 C. Rates of exchange were studied as functions of percentage of metal atoms exposed, the conditions of catalyst pretreatment, and the reaction temperature. The rates of exchange were not strongly dependent upon percentage exposed; however, the relative yields of d 1 through d 5 in the ethyl moiety or neohexane were dependent on the percentage metal atoms exposed. The Pt/SiO 2 catalysts were found to be more active for exchange than the Pd/SiO 2 catalysts by an order of magnitude. Both the turnover frequencies and the exchange pattern were observed to be influenced by the pretreatment of the catalyst. Maxima in the exchange pattern occurred at d 3 and d 5 in the case of Pt/SiO 2 and at d 5 only in the case of the Pd/SiO 2 catalysts. In order to account for the d 3 maximum observed for Pt catalysts, some extension of the Horiuti-Polanyi mechanism is required. Mechanisms by which the d 3 species might be formed are proposed and discussed. On Pd/SiO 2 catalysts exchange occurs preferentially in the ethyl substituent of the quaternary carbon atom rather than on the three methyl substituents of the quaternary carbon atom. Such preference is not observed on Pt/SiO 2 catalysts; in fact, in some cases, this preference is reversed. Whenever exchange occurs in the three methyl substituents, mostly the d 1 product is obtained. For Pt/SiO 2 catalysts, the exchange pattern appears to be influenced by steric effects, but the data suggest that factors other than steric effects are important on Pd

Catalyst for automotive emissions control in next generation. Relation of the intelligent property to its structure

CERN Document Server

Mizuki, J; Tanaka, H

2003-01-01

We use X-ray diffraction and absorption to show that the perovskite-based Pd catalyst retains its high metal dispersion owing to structural responses to the fluctuations in exhaust-gas composition that occur in state-of-the-art petrol engines. We find that as the catalyst is cycled between oxidative and reductive atmospheres typically encountered in exhaust gas, Pd reversibly moves into and out of the perovskite lattice. This movement appears to suppress the growth of metallic Pd particles, and hence explains the retention of high catalytic activity. (J.P.N.)

Size-dependent effects in supported highly dispersed Fe{sub 2}O{sub 3} catalysts, doped with Pt and Pd

Energy Technology Data Exchange (ETDEWEB)

Cherkezova-Zheleva, Zara; Shopska, Maya, E-mail: shopska@ic.bas.bg; Mitov, Ivan; Kadinov, Georgi [Bulgarian Academy of Sciences, Institute of Catalysis (Bulgaria)

2010-06-15

Series of Fe and Fe-Me (Me = Pt or Pd) catalyst supported on {gamma}-Al{sub 2}O{sub 3}, TiO{sub 2} (anatase) or diatomite were prepared by the incipient wetness impregnation method. The metal loading was 8 wt.% Fe and 0.7 wt.% noble metal. The preparation and pretreatment conditions of all studied samples were kept to be the same. X-ray diffraction, Moessbauer spectroscopy, X-ray photoelectron spectroscopy and temperature-programmed reduction are used for characterization of the supports and the samples at different steps during their treatment and catalytic tests. The catalytic activity of the samples was tested in the reaction of total benzene oxidation. The physicochemical and catalytic properties of the obtained materials are compared with respect of the different chemical composition, dispersion of used carriers and of the supported phases. Samples with the same composition prepared by mechanical mixing are studied as catalysts for comparison and for clearing up the presence of size-dependent effect, also.

Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

KAUST Repository

Wang, Liang

2018-04-04

Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

KAUST Repository

Wang, Liang; Guan, Erjia; Zhang, Jian; Yang, Junhao; Zhu, Yihan; Han, Yu; Yang, Ming; Cen, Cheng; Fu, Gang; Gates, Bruce C.; Xiao, Feng-Shou

2018-01-01

Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO2 Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al2O3

Science.gov (United States)

Goto, Tomoyo; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

2015-01-01

The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO2 and Pt/α-Al2O3 catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO2, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H2, while H2 combustion was activated by repeated exposure to H2 gas during the periodic gas test. Selective CO sensing of the micro-TGS against H2 was attempted using a double catalyst structure with 0.3–30 wt% Pt/α-Al2O3 as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al2O3 catalyst, by cancelling out the combustion heat from the AuPtPd/SnO2 catalyst. In addition, the AuPtPd/SnO2 and 0.3 wt% Pt/α-Al2O3 double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H2. PMID:26694397

Catalyst synthesis PD/SiO2 and PD/C by irradiation microwave method

International Nuclear Information System (INIS)

Sant'Anna, L.S.; Franceschi, E.; Egues, S.; Santos, M.L.; Dariva, C.; Borges, G.R.

2016-01-01

The synthesis of nanoparticulate materials has been developed over the years, in order to propose new routes or routes more efficient in the process. The application of microwave irradiation applied in this work allowed to show that metal catalysts may be generated in a faster reaction time compared to conventional mechanical agitation techniques. Catalysts using palladium acetate (OAc) 2 supported on charcoal and commercial silica were synthesized. The solvent used for the preparation was 40 ml of ethanol at a temperature of 100 ° C and 300 W power. The synthesis time was 2 to 5 minutes. The synthesized material was calcined and characterized by ICP, XRD, TEM and BET obtained metal content ranged from 1.1 to 4.1% of the metal support. The particle size was between 7 and 9 nm. The surface areas of the carriers were reduced on its surface due to the metal impregnation. (author)

Determination of palladium content in palladium-alumina/palladium-silica/palladium-tin oxide catalyst for nuclear reactor applications

International Nuclear Information System (INIS)

Sharma, P.K.; Bassan, M.K.T.; Avhad, D.K.; Singhal, R.K.

2012-01-01

Alumina and silica act as support for finely divided palladium metal powder in synthesis of catalyst. These catalyst (Pd-Al 2 O 3 , Pd-SiO 2 and Pd-SnO 2 ) used in nuclear power reactor (moderator cover gas system) for the conversion of hydrogen. In Indian nuclear power programme these catalyst are regularly used in Kaiga 1 and 2 and Rajasthan atomic power plant 3 and 4. The performance of the catalyst, solely depends on the concentration of palladium, which is the active component in this catalyst composition. Therefore it is highly desirable to have rouged analytical methodology for the accurate estimation of palladium. Leaching of Pd from the bulk matrix is tedious due to the less reactive nature of Pd therefore complete solubilization of the matrix is carried out by fusion method

Enhanced performance of a novel anodic PdAu/VGCNF catalyst for electro-oxidation in a glycerol fuel cell.

Science.gov (United States)

Yahya, N; Kamarudin, S K; Karim, N A; Masdar, M S; Loh, K S

2017-11-25

This study presents a novel anodic PdAu/VGCNF catalyst for electro-oxidation in a glycerol fuel cell. The reaction conditions are critical issues affecting the glycerol electro-oxidation performance. This study presents the effects of catalyst loading, temperature, and electrolyte concentration. The glycerol oxidation performance of the PdAu/VGCNF catalyst on the anode side is tested via cyclic voltammetry with a 3 mm 2 active area. The morphology and physical properties of the catalyst are examined using X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. Then, optimization is carried out using the response surface method with central composite experimental design. The current density is experimentally obtained as a response variable from a set of experimental laboratory tests. The catalyst loading, temperature, and NaOH concentration are taken as independent parameters, which were evaluated previously in the screening experiments. The highest current density of 158.34 mAcm -2 is obtained under the optimal conditions of 3.0 M NaOH concentration, 60 °C temperature and 12 wt.% catalyst loading. These results prove that PdAu-VGCNF is a potential anodic catalyst for glycerol fuel cells.

Comparison of Tungsten and Molybdenum Carbide Catalysts for the Hydrodeoxygenation of Oleic Acid

NARCIS (Netherlands)

Hollak, S.A.W.; Gosselink, R.J.A.; Es, van D.S.; Bitter, J.H.

2013-01-01

Group 6 (W, Mo) metal carbide catalysts are promising alternatives to hydrodesulfurization (NiMo, CoMo) catalysts and group 10 (Pd) type catalysts in the deoxygenation of vegetable fats/oils. Herein, we report a comparison of carbon nanofiber-supported W2C and Mo2C catalysts on activity,

Carbon nanotube-supported Au-Pd alloy with cooperative effect of metal nanoparticles and organic ketone/quinone groups as a highly efficient catalyst for aerobic oxidation of amines.

Science.gov (United States)

Deng, Weiping; Chen, Jiashu; Kang, Jincan; Zhang, Qinghong; Wang, Ye

2016-05-21

Functionalised carbon nanotube (CNT)-supported Au-Pd alloy nanoparticles were highly efficient catalysts for the aerobic oxidation of amines. We achieved the highest turnover frequencies (>1000 h(-1)) for the oxidative homocoupling of benzylamine and the oxidative dehydrogenation of dibenzylamine. We discovered a cooperative effect between Au-Pd nanoparticles and ketone/quinone groups on CNTs.

Highly reusability surface loaded metal particles magnetic catalyst microspheres (MCM-MPs) for treatment of dye-contaminated water

International Nuclear Information System (INIS)

Liu, Ying; Zhang, Kun; Yin, Xiaoshuang; Yang, Wenzhong; Zhu, Hongjun

2016-01-01

The metal-deposited magnetic catalyst microspheres (MCM-MPs) were successfully synthesized by one facile, high yield and controllable approach. Here, the bare magnetic microspheres were firstly synthesized according to the solvothermal method. Then silica shell were coated on the surface of the magnetic microspheres via sol–gel method, and subsequently with surface modifying with amino in the purpose to form SiO_2–NH_2 shell. Thus, metal particles were easily adsorbed into the SiO_2–NH_2 shell and in-situ reduced by NaBH_4 solution. All the obtained products (MCM-Cu, MCM-Ag, MCM-Pd) which were monodisperse and constitutionally stable were exhibited high magnetization and excellent catalytic activity towards dyes solution reduction. The catalytic rate ratio of MCM-Pd: MCM-Cu: MCM-Ag could be 10:3:1. Besides, some special coordination compound Cu_2(OH)_3Br had been generated in the in-situ reduced process of MCM-Cu, which produced superior cyclical stability (>20 times) than that of MCM-Ag and MCM-Pd. In all, those highly reusability and great catalytic efficiency of MCM-MPs show promising and great potential for treatment of dye-contaminated water. - Graphical abstract: Surface loaded metal particles magnetic catalyst microspheres MCM-MPs for rapid decolorizing dye-contaminated water: Synthesis, characterization and possible mechanisms. - Highlights: • A simple and high yield synthetic method for fabricate multi MCM-MPs is proposed with adequately optimize. • The highest reusability of MCM-Cu is attribute to the coordination compounds Cu_2(OH)_3Br. • MCM-MPs show excellent catalytic properties under different situations for various dyes • The catalytic mechanism of MCM-MPs is presented.

Catalytic oxidation of dichloromethane over sol-gel oxides supported Pd or Ni

International Nuclear Information System (INIS)

Martinez; Leidy Marcela; Montes, Consuelo

2004-01-01

Several supported Pd or Ni catalysts were synthesized by the sol-gel method using y-alumina, silica, sulfated zirconium and sulfated titanium as carriers. The resulting catalysts were characterized by XRD and nitrogen adsorption, and evaluated in the catalytic oxidation of dichloromethane. The effect of different parameters were determined, i.e. method of synthesis, temperature and the type of support. The durability of the best catalyst (0,5% Pd impregnated over sulfated titanium) was tested between 300 degrades Celsius and 350 degrades Celsius during 48 h. Under the conditions of this study, impregnated catalysts exhibited higher activity than those prepared by cogelation. Pd loaded catalysts showed higher conversion into CO 2 and HCl. Catalyst activity also increased with increasing temperature. Y-Alumina and sulfated titanium showed good activity but the formation of CO is favored instead of CO 2 . Therefore, bifunctional catalysts, i.e. containing metallic and acid sites appear to be required for the decomposition of methylene chloride into CO 2 and HCI

Water-dispersable hybrid Au-Pd nanoparticles as catalysts in ethanol oxidation, aqueous phase Suzuki-Miyaura and Heck reactions

KAUST Repository

Song, Hyon Min; Moosa, Basem; Khashab, Niveen M.

2012-01-01

The catalytic activities of water-dispersable Au@Pd core-shell nanoparticles (NPs) and Au-Pd alloy NPs were examined. There is growing interest in Au-Pd hybridized NPs in a supported matrix or non-supported forms as catalysts in various reactions

Effect of Ni and noble metals (Ru, Pd and Pt) on performance of bifunctional MoP/SiO2 for hydroconversion of methyl laurate

Science.gov (United States)

Nie, Ziyang; Zhang, Zhena; Chen, Jixiang

2017-10-01

SiO2 supported bifunctional MoP catalysts modified with different metal promoters (Ni, Ru, Pd, Pt), where Mo/Ni and Mo/M(M = Ru, Pd and Pt) atomic ratios was respectively 10 and 40, were prepared by TPR method from the phosphate precursors. It was found that the introduction of metal promoters facilitated the reduction of phosphate precursor and enhanced the dispersion of MoP. However, the MoP catalyst acidity was scarcely influenced by the small amount of metal promoters. In the hydroconversion of methyl laurate, the promoters enhanced the MoP catalyst activity for conversion of methyl laurate and hydrogenation of alkenes (intermediate), but reduced isomerization ability. Among the promoters, Ru was an optimum to decrease selectivity to alkenes while maintain high selectivity to iso-alkanes, and Mo40RuP showed better stability than MoP. At 380 °C and 3.0 MPa, the conversion of methyl laurate, the total selectivity to C11 and C12 hydrocarbons and the selectivity to iso-alkanes maintained at 100%, ∼94% and ∼30% on Mo40RuP during 102 h, respectively. The good stability of Mo40RuP is ascribed to that the presence of Ru prevented the sintering of MoP particles and suppressed carbon deposition.

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.

Synthesis and characterization of bimetallic Pd-Ni catalysts in a CeO{sub 2} matrix for the generation of H{sub 2} by the reforming reaction of methanol; Sintesis y caracterizacion de catalizadores bimetalicos Pd-Ni en una matriz de CeO{sub 2} para la generacion de H{sub 2} mediante la reaccion de reformado de metanol

Energy Technology Data Exchange (ETDEWEB)

Contreras C, R.

2016-07-01

The hydrothermal method was used for the synthesis of CeO{sub 2} nano rods using Ce(NO{sub 3}){sub 3}·6H{sub 2}O and NH{sub 4}OH. The catalytic support was calcined at 700 degrees Celsius. The synthesis of CeO{sub 2} nano rods were impregnated with an aqueous solution of Ni(NO{sub 3}){sub 2}·6H{sub 2}O by an incipient wetness impregnation method at an appropriate concentration to yield 5 and 15% of Ni in the catalysts. Then 0.5% of Pd was impregnated using PdCl{sub 2}. The samples obtained were calcined at 400 and reduced at 450 degrees Celsius. The catalytic materials were characterized by: temperature programmed reduction (TPR), Scanning Electron Microscopy (Sem) , surface area and X-ray diffraction (XRD) . Sem results showed that the CeO{sub 2} is formed by nano rods and in lesser proportion semi spherical particles. Bet surface area of the catalysts decreases with Ni loading onto the CeO{sub 2} nano rods. Pd O and Ni O were reduced at low and high temperature as was observed by TPR. The CeO{sub 2} one-dimensional nano rods showed a highly crystalline structure with sharp diffraction peaks, with a typical fluorite structure (cubic structure of the CeO{sub 2}) and characteristic peaks corresponding to metallic Ni. No diffraction peaks of Pd were found. This is due to the low concentration of this metal in the catalyst. These catalysts showed high activity and selectivity to H{sub 2} at maximum reaction temperature. According to the results of activity and selectivity, the catalysts with Pd-Ni are an alternative for the H{sub 2} production in auto thermal reforming reaction of methanol. (Author)

Surfactant-controlled synthesis of Pd/Ce0.6Zr0.4O2 catalyst for NO reduction by CO with excess oxygen

International Nuclear Information System (INIS)

Chen, L.F.; Gonzalez, G.; Wang, J.A.; Norena, L.E.; Toledo, A.; Castillo, S.; Moran-Pineda, M.

2005-01-01

For the first time, this work reports a surfactant-controlled synthetic method to obtain a nanophase of mesoporous ceria-zirconia solid solution containing cationic defects in the crystalline structure. The incorporation of a cationic surfactant (myristyltrimethylammonium bromide) into the ceria-zirconia solid network not only controlled the pore diameter distribution but also induced creation of the lattice defect. Ceria-zirconia solid solution showed crystal microstrain and structural distortion that varied with the calcination temperature. Compared to pure ceria, the addition of zirconium to the ceria promoted the bulk oxygen reducibility and enhanced the thermal stability of the solid. Hydrogen could be stored into or released from the PdO/Ce 0.6 Zr 0.4 O 2 catalyst during the TPR procedure, which is associated to the formation/decomposition of a PdH x phase, due to the hydrogen dissociation catalyzed by metallic Pd. At cool start of reaction, NO reduction by CO with excess oxygen over the Pd/Ce 0.6 Zr 0.4 O 2 catalyst showed selectivity around 100% to N 2 . A competition between NO reduction by CO and CO oxidation by O 2 was observed: at reaction temperatures below 200 deg. C, NO inhibited CO oxidation activity; however, at reaction temperatures above 200 deg. C, high activity of CO oxidation resulted in an inhibition effect on NO reduction

Hydrogen Production on Ag-Pd/TiO2 Bimetallic Catalysts: Is there a Combined Effect of Surface Plasmon Resonance with Schottky Mechanism on the Photo-Catalytic Activity?

KAUST Repository

Nadeem, Muhammad A.; Al-Oufi, Maher; Wahab, Ahmed K.; Anjum, Dalaver H.; Idriss, Hicham

2017-01-01

Despite many observations that plasmonics can enhance photocatalytic reactions, their relative role in the overall reaction rate is not thoroughly investigated. Here we report that silver nanoparticles contribution in the reaction rate by its plasmonic effect is negligible when compared to that of Pd (Schottky effect). To conduct the study a series of Ag−Pd/TiO2 catalysts have been prepared, characterized and tested for H2 production from water in the presence of an organic sacrificial agent. Pd was chosen as a standard high work function metal needed for the Schottky junction to pump away electrons from the conduction band of the semiconductor and Ag (whose work function is ca. 1 eV lower than that of Pd) for its high plasmonic resonance response at the edge of the bandgap of TiO2. While H2 production rates showed linear dependency on plasmonic response of Ag in the Pd−Ag series, the system performed less than that of pure Pd. In other words, the plasmonic contribution of Ag in the Ag−Pd/TiO2 catalyst for hydrogen production, while confirmed using different excitation energies, is small. Therefore, the “possible” synergistic effect of plasmonic (in the case of Ag) and Schottky-mechanism (in the case of Pd) is minor when compared to that of Schottky-effect alone.

Hydrogen Production on Ag-Pd/TiO2 Bimetallic Catalysts: Is there a Combined Effect of Surface Plasmon Resonance with Schottky Mechanism on the Photo-Catalytic Activity?

KAUST Repository

Nadeem, Muhammad A.

2017-03-28

Despite many observations that plasmonics can enhance photocatalytic reactions, their relative role in the overall reaction rate is not thoroughly investigated. Here we report that silver nanoparticles contribution in the reaction rate by its plasmonic effect is negligible when compared to that of Pd (Schottky effect). To conduct the study a series of Ag−Pd/TiO2 catalysts have been prepared, characterized and tested for H2 production from water in the presence of an organic sacrificial agent. Pd was chosen as a standard high work function metal needed for the Schottky junction to pump away electrons from the conduction band of the semiconductor and Ag (whose work function is ca. 1 eV lower than that of Pd) for its high plasmonic resonance response at the edge of the bandgap of TiO2. While H2 production rates showed linear dependency on plasmonic response of Ag in the Pd−Ag series, the system performed less than that of pure Pd. In other words, the plasmonic contribution of Ag in the Ag−Pd/TiO2 catalyst for hydrogen production, while confirmed using different excitation energies, is small. Therefore, the “possible” synergistic effect of plasmonic (in the case of Ag) and Schottky-mechanism (in the case of Pd) is minor when compared to that of Schottky-effect alone.

Ag1 Pd1 Nanoparticles-Reduced Graphene Oxide as a Highly Efficient and Recyclable Catalyst for Direct Aryl C-H Olefination.

Science.gov (United States)

Hu, Qiyan; Liu, Xiaowang; Wang, Guoliang; Wang, Feifan; Li, Qian; Zhang, Wu

2017-12-14

The efficient and selective palladium-catalyzed activation of C-H bonds is of great importance for the construction of diverse bioactive molecules. Despite significant progress, the inability to recycle palladium catalysts and the need for additives impedes the practical applications of these reactions. Ag 1 Pd 1 nanoparticles-reduced graphene oxide (Ag 1 Pd 1 -rGO) was used as highly efficient and recyclable catalyst for the chelation-assisted ortho C-H bond olefination of amides with acrylates in good yields with a broad substrate scope. The catalyst can be recovered and reused at least 5 times without losing activity. A synergistic effect between the Ag and Pd atoms on the catalytic activity was found, and a plausible mechanism for the AgPd-rGO catalyzed C-H olefination is proposed. These findings suggest that the search for such Pd-based bimetallic alloy nanoparticles is a new method towards the development of superior recyclable catalysts for direct aryl C-H functionalization under mild conditions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gasification of carbon deposits on catalysts and metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Figueiredo, J L

1986-10-01

'Coke' deposited on catalysts and reactor surfaces includes a variety of carbons of different structures and origins, their reactivities being conveniently assessed by Temperature Programmed Reaction (TPR). The gasification of carbon deposits obtained in the laboratory under well controlled conditions, and the regeneration of coked catalysts from petroleum refining processes are reviewed and discussed. Filamentary carbon deposits, containing dispersed metal particles, behave as supported metal catalysts during gasification, and show high reactivities. Pyrolytic and acid catalysis carbons are less reactive on their own, as the gasification is not catalysed; however, metal components of the catalyst or metal impurities deposited on the surface may enhance gasification. 26 refs., 8 figs., 2 tabs.

Recovery of Platinum Group Metals from Spent Catalysts Using Iron Chloride Vapor Treatment

Science.gov (United States)

Taninouchi, Yu-ki; Okabe, Toru H.

2018-05-01

The recovery of platinum group metals (PGMs) from spent automobile catalysts is a difficult process because of their relatively low contents in the scrap. In this study, to improve the efficiency of the existing recycling techniques, a novel physical concentration method involving treatment with FeCl2 vapor has been examined. The reactions occurring between typical catalyst components and FeCl2 vapor are discussed from the thermodynamic point of view, and the validity of the proposed technique was experimentally verified. The obtained results indicate that the vapor treatment at around 1200 K (927 °C) can effectively alloy PGMs (Pt, Pd, and Rh) with Fe, resulting in the formation of a ferromagnetic alloy. It was also confirmed that cordierite and alumina (the major catalyst components) remained unreacted after the vapor treatment, while ceria species were converted into oxychlorides. The samples simulating the automobile catalyst were also subjected to magnetic separation after the treatment with FeCl2 vapor; as a result, PGMs were successfully extracted and concentrated in the form of a magnetic powder. Thus, the FeCl2 vapor treatment followed by magnetic separation can be utilized for recovering PGMs directly from spent catalysts as an effective pretreatment for the currently used recycling methods.

Platinum and palladium nano-structured catalysts for polymer electrolyte fuel cells and direct methanol fuel cells.

Science.gov (United States)

Long, Nguyen Viet; Thi, Cao Minh; Yong, Yang; Nogami, Masayuki; Ohtaki, Michitaka

2013-07-01

In this review, we present the synthesis and characterization of Pt, Pd, Pt based bimetallic and multi-metallic nanoparticles with mixture, alloy and core-shell structure for nano-catalysis, energy conversion, and fuel cells. Here, Pt and Pd nanoparticles with modified nanostructures can be controllably synthesized via chemistry and physics for their uses as electro-catalysts. The cheap base metal catalysts can be studied in the relationship of crystal structure, size, morphology, shape, and composition for new catalysts with low cost. Thus, Pt based alloy and core-shell catalysts can be prepared with the thin Pt and Pt-Pd shell, which are proposed in low and high temperature proton exchange membrane fuel cells (PEMFCs), and direct methanol fuel cells (DMFCs). We also present the survey of the preparation of Pt and Pd based catalysts for the better catalytic activity, high durability, and stability. The structural transformations, quantum-size effects, and characterization of Pt and Pd based catalysts in the size ranges of 30 nm (1-30 nm) are presented in electro-catalysis. In the size range of 10 nm (1-10 nm), the pure Pt catalyst shows very large surface area for electro-catalysis. To achieve homogeneous size distribution, the shaped synthesis of the polyhedral Pt nanoparticles is presented. The new concept of shaping specific shapes and morphologies in the entire nano-scale from nano to micro, such as polyhedral, cube, octahedra, tetrahedra, bar, rod, and others of the nanoparticles is proposed, especially for noble and cheap metals. The uniform Pt based nanosystems of surface structure, internal structure, shape, and morphology in the nanosized ranges are very crucial to next fuel cells. Finally, the modifications of Pt and Pd based catalysts of alloy, core-shell, and mixture structures lead to find high catalytic activity, durability, and stability for nano-catalysis, energy conversion, fuel cells, especially the next large-scale commercialization of next

Recycling of platinum group metals from the automotive catalysts

International Nuclear Information System (INIS)

Benevit, Mariana; Petter, Patricia Melo Halmenschlager; Veit, Hugo Marcelo

2014-01-01

Currently it is very important to use alternative sources of raw material for obtaining metals, avoiding the traditional mining. This work aims to characterize and evaluate the recoverability of platinum group metals present in automotive catalysts. Thus, the catalysts were divided into two groups: the first was catalysts used in 1.0 cars and the second was catalyst used in 2.0 cars. DRX and FRX techniques and chemical analysis performed by ICP/OES was used to characterized these materials. The results showed that there is a significant amount of platinum group elements in catalyst waste, which can be separated and reused. In the next step, hydro and pyrometallurgical routes, for metals extraction from catalyst waste, will be studied. (author)

HZSM-5 CATALYST FOR CRACKING PALM OIL TO BIODIESEL: A COMPARATIVE STUDY WITH AND WITHOUT PT AND PD IMPREGNATION

Directory of Open Access Journals (Sweden)

Agus Budianto

2014-05-01

Full Text Available The Needs of healthy environment and green energy poses a great demand for alternative energy. Biofuel is one of the alternative energy products that are environmentally friendly. Biofuel can be made from plant oils, especially palm oil. Cracking of palm oil into biofuel is constrained by the availability of catalysts. Moreover the available catalyst still gives a low yield. This research aims to study the effect of Pt and Pd impregnation into HZSM-5 catalyst on the catalytic properties. Another aim is to obtain the operating conditions of the catalytic cracking process of palm oil into biofuel which gives the highest yield and selectivity, especially for biodiesel and biogasoline fractions. Catalytic cracking process was carried out in a micro fixed bed reactor with diameter of 1 cm and length of 16 cm. The reactor was filled with a catalyst. The results of the study successfully prove that Pt and Pd impregnated into HZSM-5 catalyst can increase the yield and selectivity of biodiesel. Pd and Pt are highly recommended to increase the yield and selectivity of biodiesel.

Surface structure and reaction property of CuCl{sub 2}-PdCl{sub 2} bimetallic catalyst in methanol oxycarbonylation: A DFT approach

Energy Technology Data Exchange (ETDEWEB)

Meng, Qingsen [Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Wang, Shengping, E-mail: spwang@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Shen, Yongli; Yan, Bing [Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Wu, Yuanxin [School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430073 (China); Ma, Xinbin [Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

2014-02-15

Surface structure of CuCl{sub 2}-PdCl{sub 2} bimetallic catalyst (Wacker-type catalyst) was built employing density functional theory (DFT) calculations, and the reaction mechanism of methanol oxycarbonylation over the CuCl{sub 2}-PdCl{sub 2} surfaces was also investigated. On the CuCl{sub 2}-PdCl{sub 2} surface, the active site for methanol oxidation was confirmed as Cu-Cl-Cu (Pd). Comparing with pure CuCl{sub 2} surface, the introduction of Pd atom causes the electron repopulation on the surface and lowers the energy barrier for methanol oxidation, but the number of the active site decreases with the increasing of Pd doping volume. Agreed with previous experimental results, the Pd site is most favorable for the CO insertion, indicated by the lowest activation barrier for the formation of COOCH{sub 3} on Pd atom. The lowest energy barrier for the formation of DMC appears when COOCH{sub 3} species adsorbed on Pd atom and methoxyl adsorbed on Cu atoms, which is 0.42 eV. Finally, the reconstruction of the unsaturated surface is a spontaneous and exothermic process. Comparing with other surfaces, the rate-limiting step, methanol oxidation, on CuCl{sub 2}-PdCl{sub 2} surface with Pd/Cu = 1:17 has the lowest energy barrier, which is agreed with the experimental observation that PdCl{sub 2}-CuCl{sub 2} catalyst with Pd/Cu = 1:20 has the favorable activity. The adsorbed methoxyl will further lower the activation barrier of methanol oxidation, which is agreed with experimental observation that the Wacker-type catalysts have an induction period in the methanol oxidative carbonylation system.

Efficiency of bimetallic PtPd on polydopamine modified on various carbon supports for alcohol oxidations

Science.gov (United States)

Pinithchaisakula, A.; Ounnunkad, K.; Themsirimongkon, S.; Promsawan, N.; Waenkaew, P.; Saipanya, S.

2017-02-01

In this work, the preparation, characterization, and electrocatalytic analysis of the catalysts on various carbon substrates for direct alcohol fuel cells were studied. Selected carbons were modified with/without polydopamine (labelled as PDA-C and C) and further metal electrodeposited incorporated onto the glassy carbon (labelled as 5Pt1Pd/PDA-C and 5Pt1Pd/C). Four various carbon materials were used e.g. graphite (G), carbon nanotube (CNT), graphene (GP) and graphene oxide (GO) and the carbons were modified with PDA denoted as PDA-G, PDA-CNT, PDA-GP and PDA-GO, respectively. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) experimental observation showed narrow size distribution of metal anchored on the PDA-C and C materials. Chemical compositions and oxidation states of the catalysts were determined by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX). The catalytic performances for small organic electro-oxidation (e.g. methanol and ethanol) were measured by cyclic voltammetry (CV). Among different PDA-C and C catalysts, monometallic Pt showed less activity than the bimetallic catalysts. Among catalysts with PDA, the 5Pt1Pd/PDA-GO catalyst facilitated methanol and ethanol oxidations with high oxidation currents and If/Ib value and stability with low potentials while among catalysts without PDA, the 5Pt1Pd/CNT provides highest activity and stability. It was found that the catalysts with PDA provided high activity and stability than the catalysts without PDA. The improved catalytic performance of the prepared catalysts could be related to the higher active surface area from polymer modification and bimetallic catalyst system in the catalyst composites.

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.

Fast microwave-assisted solvothermal synthesis of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated MWCNTs: Pd-based bimetallic catalysts for ethanol oxidation in alkaline medium

CSIR Research Space (South Africa)

Ramulifho, T

2012-01-01

Full Text Available The preparation of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated multi-walled carbon nanotubes (SF-MWCNTs) using a very rapid microwave-assisted solvothermal strategy has been described. Electrocatalytic behaviour of the SF...

Preparation and characterization of micro-arc-induced Pd/TM(TM = Ni, Co and Ti) catalysts and comparison of their electrocatalytic activities toward ethanol oxidation

International Nuclear Information System (INIS)

Wang, Xiaoguang; Ma, Guanshui; Zhu, Fuchun; Lin, Naiming; Tang, Bin; Zhang, Zhonghua

2013-01-01

Using the electro-spark deposition technique, a novel kind of Pd/TM (TM = Ni, Co and Ti) electrode was successfully prepared by arc-depositing Pd on the transition metal substrates. The structure, morphology and chemical composition of the arc-deposited films were investigated using thin-film X-ray diffraction (TF-XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). The results show that, a coarsening topographical morphology can be obtained, being composed of numerous craters/spots with sizes ranging from nano-scales to several microns. The electrochemical measurements indicate that the arc-deposited Pd/TM electrodes exhibit distinct electrochemical behaviors and the catalytic activity toward ethanol electro-oxidation reaction (EOR) is highly dependent upon the nature of substrate. Among the Pd/TM electrodes investigated, the arc-deposited Pd/Co reveals the best activity and superior poisoning tolerance towards ethanol oxidation and will find promising applications as a candidate for the anode catalyst of direct ethanol fuel cells (DEFCs)

Magnetic Pd-Fe{sub 3}O{sub 4} heterodimer nanocrystals as recoverable catalysts for ligand-free hiyama cross-coupling reactions

Energy Technology Data Exchange (ETDEWEB)

Lee, Woong Sup; Byun, Sang Moon; Kwon, Jung Min; Kim, B. Moon [Dept. of Chemistry, College of Natural Sciences, Seoul National University, Seoul (Korea, Republic of)

2016-12-15

Ligand-free Hiyama cross-coupling reaction was achieved through the use of Pd-Fe{sub 3}O{sub 4} heterodimeric nanocrystals (1 mol% in Pd) as recyclable catalysts. The nanocrystal catalysts exhibited good activities accommodating a variety of substrates including aryl bromides and iodides with substituents of varying electronic and steric properties. Furthermore, the nanocrystal catalyst could be conveniently recovered with the aid of an external magnet and recycled five times without the loss of catalytic activity to a considerable degree.

Improving the electrocatalytic properties of Pd-based catalyst for direct alcohol fuel cells: effect of solid solution.

Science.gov (United States)

Wen, Cuilian; Wei, Ying; Tang, Dian; Sa, Baisheng; Zhang, Teng; Chen, Changxin

2017-07-07

The tolerance of the electrode against the CO species absorbed upon the surface presents the biggest dilemma of the alcohol fuel cells. Here we report for the first time that the inclusion of (Zr, Ce)O 2 solid solution as the supporting material can significantly improve the anti-CO-poisoning as well as the activity of Pd/C catalyst for ethylene glycol electro-oxidation in KOH medium. In particular, the physical origin of the improved electrocatalytic properties has been unraveled by first principle calculations. The 3D stereoscopic Pd cluster on the surface of (Zr, Ce)O 2 solid solution leads to weaker Pd-C bonding and smaller CO desorption driving force. These results support that the Pd/ZrO 2 -CeO 2 /C composite catalyst could be used as a promising effective candidate for direct alcohol fuel cells application.

Catalytic activity of bimetal-containing Co,Pd systems in the oxidation of carbon monoxide

Science.gov (United States)

Oleksenko, L. P.; Lutsenko, L. V.

2013-02-01

The catalytic activity of low-percentage Co,Pd systems on ZSM-5, ERI, SiO2, and Al2O3 supports in the oxidation of CO was studied. The activity of bimetal-containing catalysts was shown to depend on the nature of the catalyst and the amount and ratio of their active components. According to the results of thermoprogrammed reduction with H2 (H2 TPR) and X-ray photoelectron spectroscopy (XPS) data, the metals are distributed as isolated cations or Coδ+-O-Pdδ+ clusters with cobalt and palladium cations surrounded by off-lattice oxygen in Co,Pd systems. The 0.8% Co,0.5% Pd-ZSM-5 bimetal catalysts were found to be more active due to the presence of clusters.

Highly reusability surface loaded metal particles magnetic catalyst microspheres (MCM-MPs) for treatment of dye-contaminated water

Energy Technology Data Exchange (ETDEWEB)

Liu, Ying; Zhang, Kun, E-mail: kun4219@njtech.edu.cn; Yin, Xiaoshuang; Yang, Wenzhong; Zhu, Hongjun

2016-04-01

The metal-deposited magnetic catalyst microspheres (MCM-MPs) were successfully synthesized by one facile, high yield and controllable approach. Here, the bare magnetic microspheres were firstly synthesized according to the solvothermal method. Then silica shell were coated on the surface of the magnetic microspheres via sol–gel method, and subsequently with surface modifying with amino in the purpose to form SiO{sub 2}–NH{sub 2} shell. Thus, metal particles were easily adsorbed into the SiO{sub 2}–NH{sub 2} shell and in-situ reduced by NaBH{sub 4} solution. All the obtained products (MCM-Cu, MCM-Ag, MCM-Pd) which were monodisperse and constitutionally stable were exhibited high magnetization and excellent catalytic activity towards dyes solution reduction. The catalytic rate ratio of MCM-Pd: MCM-Cu: MCM-Ag could be 10:3:1. Besides, some special coordination compound Cu{sub 2}(OH){sub 3}Br had been generated in the in-situ reduced process of MCM-Cu, which produced superior cyclical stability (>20 times) than that of MCM-Ag and MCM-Pd. In all, those highly reusability and great catalytic efficiency of MCM-MPs show promising and great potential for treatment of dye-contaminated water. - Graphical abstract: Surface loaded metal particles magnetic catalyst microspheres MCM-MPs for rapid decolorizing dye-contaminated water: Synthesis, characterization and possible mechanisms. - Highlights: • A simple and high yield synthetic method for fabricate multi MCM-MPs is proposed with adequately optimize. • The highest reusability of MCM-Cu is attribute to the coordination compounds Cu{sub 2}(OH){sub 3}Br. • MCM-MPs show excellent catalytic properties under different situations for various dyes • The catalytic mechanism of MCM-MPs is presented.

Pd-catalysts for DFAFC prepared by magnetron sputtering

Czech Academy of Sciences Publication Activity Database

Bieloshapka, Igor; Jiříček, Petr; Vorokhta, M.; Tomšík, Elena; Rednyk, A.; Perekrestov, R.; Jurek, Karel; Ukraintsev, Egor; Hruška, Karel; Romanyuk, Olexandr; Lesiak, B.

2017-01-01

Roč. 419, Oct (2017), s. 838-846 ISSN 0169-4332 R&D Projects: GA ČR(CZ) GBP108/12/G108; GA MŠk LM2015088 Institutional support: RVO:68378271 ; RVO:61389013 Keywords : Pd catalyst * formic acid fuel cell * magnetron sputtering * DFAFC * surface morphology Subject RIV: BM - Solid Matter Physics ; Magnetism; BM - Solid Matter Physics ; Magnetism (UMCH-V) OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.); Condensed matter physics (including formerly solid state physics, supercond.) (UMCH-V) Impact factor: 3.387, year: 2016

Potential of Transition Metal Atoms Embedded in Buckled Monolayer g-C3N4 as Single-Atom Catalysts

KAUST Repository

Li, Shu-Long; Kan, Xiang; Yin, Hui; Gan, Li-Yong; Schwingenschlö gl, Udo; Zhao, Yong

2017-01-01

We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C3N4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C3N4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C3N4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C3N4 gives rise to promising single-atom catalysts at low temperature.

Potential of Transition Metal Atoms Embedded in Buckled Monolayer g-C3N4 as Single-Atom Catalysts

KAUST Repository

Li, Shu-Long

2017-10-27

We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C3N4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C3N4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C3N4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C3N4 gives rise to promising single-atom catalysts at low temperature.

MOF-derived Cu-Pd/nanoporous carbon composite as an efficient catalyst for hydrogen evolution reaction: A comparison between hydrothermal and electrochemical synthesis

Science.gov (United States)

Mandegarzad, Sakineh; Raoof, Jahan Bakhsh; Hosseini, Sayed Reza; Ojani, Reza

2018-04-01

In this study, a novel catalyst based on Cu-Pd bimetallic nanoparticles supported on nanoporous carbon composite (NPCC) is successfully fabricated through three-step process and used as an electrocatalyst towards hydrogen evolution reaction (HER). At the first step, MOF-199 is synthesized via two distinct strategies; (1) hydrothermal (HT) and (2) electrochemical (EC). Next, the synthesized MOF-199 is used as a template in order to prepare Cu/NPCC by direct carbonization under N2 atmosphere followed by galvanic replacement reaction of Cu metals by PdII ions. All the prepared materials are characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and nitrogen adsorption/desorption measurements. The effect of synthesis method of MOF-199 on the electrocatalytic activity of the final product towards HER is investigated. The electrochemical measurements indicate that Cu-Pd/NPCC derived from the MOF prepared by EC method (Cu-Pd/NPCC/EC) exhibits an enhanced catalytic activity towards HER in H2SO4 solution than the Cu-Pd/NPCC/HT. This improvement may be attributed to using of supporting electrolyte in the preparation of Cu-Pd/NPCC/EC.

Selective hydrogenation of phenol to cyclohexanone over Pd@CN (N-doped porous carbon): Role of catalyst reduction method

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Hu, Shuo; Yang, Guangxin; Jiang, Hong; Liu, Yefei; Chen, Rizhi

2018-03-01

Selective phenol hydrogenation is a green and sustainable technology to produce cyclohexanone. The work focused on investigating the role of catalyst reduction method in the liquid-phase phenol hydrogenation to cyclohexanone over Pd@CN (N-doped porous carbon). A series of reduction methods including flowing hydrogen reduction, in-situ reaction reduction and liquid-phase reduction were designed and performed. The results highlighted that the reduction method significantly affected the catalytic performance of Pd@CN in the liquid-phase hydrogenation of phenol to cyclohexanone, and the liquid-phase reduction with the addition of appropriate amount of phenol was highly efficient to improve the catalytic activity of Pd@CN. The influence mechanism was explored by a series of characterizations. The results of TEM, XPS and CO chemisorption confirmed that the reduction method mainly affected the size, surface composition and dispersion of Pd in the CN material. The addition of phenol during the liquid-phase reduction could inhibit the aggregation of Pd NPs and promote the reduction of Pd (2+), and then improved the catalytic activity of Pd@CN. The work would aid the development of high-performance Pd@CN catalysts for selective phenol hydrogenation.

Effect of preparation method on the surface characteristics and activity of the Pd/OMS-2 catalysts for the oxidation of carbon monoxide, toluene, and ethyl acetate

Science.gov (United States)

Liu, Lisha; Song, Yong; Fu, Zhidan; Ye, Qing; Cheng, Shuiyuan; Kang, Tianfang; Dai, Hongxing

2017-02-01

The cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2)-supported Pd (0.5 wt% Pd/OMS-2-DP, 0.5 wt% Pd/OMS-2-PI, and 0.5 wt% Pd/OMS-2-EX) catalysts were prepared by the deposition-precipitation, pre-incorporation, and ion-exchanging strategies, respectively. It is shown that the preparation method exerted an important effect on the physicochemical property of the sample. Among the OMS-2-supported Pd catalysts, 0.5 wt% Pd/OMS-2-DP possessed the highest surface (Mn2+ + Mn3+)/Mn4+ atomic ratio and the highest surface Pd loading and acid sites. The 0.5 wt% Pd/OMS-2 catalysts outperformed the Pd-free counterpart, among which 0.5 wt% Pd/OMS-2-DP presented the best catalytic activity (T50% and T90% were 25 and 55 °C for CO oxidation, 240 and 285 °C for toluene oxidation, and 160 and 200 °C for ethyl acetate oxidation, respectively). We believe that the high Pd surface loading, high surface atomic ratio of (Mn2+ + Mn3+)/Mn4+, and good low-temperature reducibility, good oxygen mobility, and high acidity were responsible for the excellent performance of the 0.5 wt% Pd/OMS-2-DP catalyst.

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry.

Science.gov (United States)

Hiebler, Katharina; Lichtenegger, Georg J; Maier, Manuel C; Park, Eun Sung; Gonzales-Groom, Renie; Binks, Bernard P; Gruber-Woelfler, Heidrun

2018-01-01

Within the "compartmentalised smart factory" approach of the ONE-FLOW project the implementation of different catalysts in "compartments" provided by Pickering emulsions and their application in continuous flow is targeted. We present here the development of heterogeneous Pd catalysts that are ready to be used in combination with biocatalysts for catalytic cascade synthesis of active pharmaceutical ingredients (APIs). In particular, we focus on the application of the catalytic systems for Suzuki-Miyaura cross-coupling reactions, which is the key step in the synthesis of the targeted APIs valsartan and sacubitril. An immobilised enzyme will accomplish the final product formation via hydrolysis. In order to create a large interfacial area for the catalytic reactions and to keep the reagents separated until required, the catalyst particles are used to stabilise Pickering emulsions of oil and water. A set of Ce-Sn-Pd oxides with the molecular formula Ce 0.99- x Sn x Pd 0.01 O 2-δ ( x = 0-0.99) has been prepared utilising a simple single-step solution combustion method. The high applicability of the catalysts for different functional groups and their minimal leaching behaviour is demonstrated with various Suzuki-Miyaura cross-coupling reactions in batch as well as in continuous flow employing the so-called "plug & play reactor". Finally, we demonstrate the use of these particles as the sole emulsifier of oil-water emulsions for a range of oils.

Design of supported bi-metallic nanoparticles based on Platinum and Palladium using Surface Organometallic Chemistry (SOMC)

KAUST Repository

Al-Shareef, Reem A.

2017-11-01

Well-defined silica supported bimetallic catalysts Pt100-x Pdx (where x is the molar ratio of Pd) are prepared by Surface Organometallic Chemistry (SOMC) via controlled decomposition of Pd2(allyl)2Cl2 on Pt/SiO2. For comparison purposes, Pt100-x Pdx bimetallic catalysts is also prepared by ion-exchange (IE). According to the results of STEM, XAS and H2 chemisorption, all bimetallic nanoparticles, prepared using neither SOMC nor IE, produce discrete formation of monometallic species (either Pt or Pd). Most catalysts exhibit a narrow particle size distribution with an average diameter ranging from 1 to 3 nm for samples prepared by IE and from 2 to 5 nm for the ones synthesized by SOMC. For all catalysts investigated in the present work, iso-butane reaction with hydrogen under differential conditions (conversions below 5%) leads to the formation of methane and propane (hydrogenolysis), n-butane (isomerization), and traces of iso-butylene (dehydrogenation). The total rate of reaction decreases with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate (expressed as moles converted per total surface metal per second) of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the results suggest a selective coverage of Pt (100) surface by a Pd layer, followed by a buildup of Pd overcoat onto a Pd layer assuming that each metal keeps its intrinsic catalytic properties. There is no mutual electronic charge transfer between the two metals (DFT). For the PtPd catalysts prepared by IE, the catalytic behavior cannot simply be explained by a surface coverage of highly active Pt metal by less active Pd (not observed), suggesting there is formation of a surface alloy between Pt and Pd collaborated by EXAFS and DFT. The catalytic results are explained by a simple structure activity relationship based on the previously proposed mechanism of C-H bond and C-C Bond activation and cleavage for iso-butane hydrogenolysis

Brazing of Cu with Pd-based metallic glass filler

Energy Technology Data Exchange (ETDEWEB)

Terajima, Takeshi [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan)], E-mail: terajima@jwri.osaka-u.ac.jp; Nakata, Kazuhiro [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Matsumoto, Yuji [Materials and Structures Laboratory, Tokyo Institute of Technology (Japan); Zhang, Wei; Kimura, Hisamichi; Inoue, Akihisa [Institute for Materials Research, Tohoku University (Japan)

2008-02-25

Metallic glass has several unique properties, including high mechanical strength, small solidification shrinkage, small elastic modulus and supercooling state, all of which are well suited as a residual stress buffer for metal and ceramic joining. In the present preliminary study, we demonstrated brazing of Cu rods with Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} metallic glass filler. The brazing was carried out at 873 K for 1 min in a vacuum atmosphere (1 x 10{sup -3} Pa), and then the specimens were quenched at the rate of 30 K/s by blowing He. The metallic glass brazing of Cu using Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler was successful, with the exception that several voids remained in the filler. According to micro-focused X-ray diffraction, no diffraction patterns were observed at both the center of the Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler and the Cu/Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} interface. The result showed that the Cu specimens were joined with Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler in the glassy state. The tensile fracture strength of the brazed specimens ranged from 20 to 250 MPa. The crack extension from the voids in the Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler may have caused the results to be uneven and very low compared to the strength of Pd-based bulk metallic glass.

Nitrite reduction mechanism on a Pd surface.

Science.gov (United States)

Shin, Hyeyoung; Jung, Sungyoon; Bae, Sungjun; Lee, Woojin; Kim, Hyungjun

2014-11-04

Nitrate (NO3-) is one of the most harmful contaminants in the groundwater, and it causes various health problems. Bimetallic catalysts, usually palladium (Pd) coupled with secondary metallic catalyst, are found to properly treat nitrate-containing wastewaters; however, the selectivity toward N2 production over ammonia (NH3) production still requires further improvement. Because the N2 selectivity is determined at the nitrite (NO2-) reduction step on the Pd surface, which occurs after NO3- is decomposed into NO2- on the secondary metallic catalyst, we here performed density functional theory (DFT) calculations and experiments to investigate the NO2- reduction pathway on the Pd surface activated by hydrogen. Based on extensive DFT calculations on the relative energetics among ∼100 possible intermediates, we found that NO2- is easily reduced to NO* on the Pd surface, followed by either sequential hydrogenation steps to yield NH3 or a decomposition step to N* and O* (an adsorbate on Pd is denoted using an asterisk). Based on the calculated high migration barrier of N*, we further discussed that the direct combination of two N* to yield N2 is kinetically less favorable than the combination of a highly mobile H* with N* to yield NH3. Instead, the reduction of NO2- in the vicinity of the N* can yield N2O* that can be preferentially transformed into N2 via diverse reaction pathways. Our DFT results suggest that enhancing the likelihood of N* encountering NO2- in the solution phase before combination with surface H* is important for maximizing the N2 selectivity. This is further supported by our experiments on NO2- reduction by Pd/TiO2, showing that both a decreased H2 flow rate and an increased NO2- concentration increased the N2 selectivity (78.6-93.6% and 57.8-90.9%, respectively).

Direct synthesis of iso-butane from synthesis gas or CO2 over CuZnZrAl/Pd-β hybrid catalyst

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Congming Li

2017-12-01

Full Text Available The effect of various factors on the catalytic performance of iso-butane formation over CuZnZrAl/Pd-β hybrid catalyst via synthesis gas or CO2 hydrogenation has been deeply investigated in this work. It was interesting to note that the iso-butane/n-butane ratio value was much higher than that of thermodynamic equilibrium (about 1/1, whose value was directly related to the reaction condition using this hybrid catalyst. In order to further clearly clarify this finding, various experimental reaction factors were selected to investigate the formation of iso-butane. The results revealed that increasing temperature, H2/COx, CO2/COx, and/or Pd loading possessed an inhibiting effect on the iso-butane yield. High selectivity of iso-butane could be achieved by increasing the reaction pressure, W/F and the weight ratio of CuZnZrAl methanol catalyst to Pd-β catalyst. It is also noted that the addition of water seriously suppressed the reaction activity, resulting in the low ratio of iso-butane/n-butane. A possible reaction route was elucidated based on the latest results. This might shed light on the development of a high efficient catalyst for iso-butane production from synthesis gas or CO2 hydrogenation. Keywords: Iso-butane, Synthesis gas, CO2, CuZnZrAl/Pd-β hybrid catalyst

Highly active Pd–In/mesoporous alumina catalyst for nitrate reduction

Energy Technology Data Exchange (ETDEWEB)

Gao, Zhenwei; Zhang, Yonggang; Li, Deyi [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Werth, Charles J. [Civil, Architectural and Environmental Engineering, University of Texas at Austin, 301 East Dean Keeton St., Stop C1786, Austin, TX 78712 (United States); Zhang, Yalei, E-mail: zhangyalei2003@163.com [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Zhou, Xuefei, E-mail: zhouxuefei@tongji.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China)

2015-04-09

Highlights: • Pd–In nanoparticles (6–7 nm) uniformly form in the mesopores of alumina (4 nm). • Pd–In nanoparticles aggregation is prevented during the synthesis process. • The reduction rate of nitrate is efficient by using the obtained catalyst. • The selectivity toward N{sub 2} is ideal by using the obtained catalyst. - Abstract: The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd–In/Al{sub 2}O{sub 3} with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO{sub 2}-buffered water and under continuous H{sub 2} as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd–In ratio of 4, with a first-order rate constant (k{sub obs} = 0.241 L min{sup −1} g{sub cata}{sup −1}) that was 1.3× higher than that of conventional Pd–In/Al{sub 2}O{sub 3} (5 wt% Pd; 0.19 L min{sup −1} g{sub cata}{sup −1}). The Pd–In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate.

High-pressure phase transition of alkali metal-transition metal deuteride Li2PdD2

Science.gov (United States)

Yao, Yansun; Stavrou, Elissaios; Goncharov, Alexander F.; Majumdar, Arnab; Wang, Hui; Prakapenka, Vitali B.; Epshteyn, Albert; Purdy, Andrew P.

2017-06-01

A combined theoretical and experimental study of lithium palladium deuteride (Li2PdD2) subjected to pressures up to 50 GPa reveals one structural phase transition near 10 GPa, detected by synchrotron powder x-ray diffraction, and metadynamics simulations. The ambient-pressure tetragonal phase of Li2PdD2 transforms into a monoclinic C2/m phase that is distinct from all known structures of alkali metal-transition metal hydrides/deuterides. The structure of the high-pressure phase was characterized using ab initio computational techniques and from refinement of the powder x-ray diffraction data. In the high-pressure phase, the PdD2 complexes lose molecular integrity and are fused to extended [PdD2]∞ chains. The discovered phase transition and new structure are relevant to the possible hydrogen storage application of Li2PdD2 and alkali metal-transition metal hydrides in general.

Diatomite-supported Pd-M (M=Cu, Co, Ni) bimetal nanocatalysts for selective hydrogenation of long-chain aliphatic esters.

Science.gov (United States)

Huang, Changliang; Zhang, Hongye; Zhao, Yanfei; Chen, Sha; Liu, Zhimin

2012-11-15

Diatomite supported Pd-M (M=Cu, Co, Ni) bimetal nanocatalysts with various metal compositions were prepared and characterized by means of X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. It was demonstrated that the metal nanoparticles were uniformly distributed on the support, and their size was centered around 8 nm with a relatively narrow size distribution. The catalysts were used to catalyze hydrogenation of long-chain aliphatic esters, including methyl palmitate, methyl stearate, and methyl laurate. It was indicated that the all diatomite-supported Pd-based bimetal catalysts were active to the selective hydrogenation of long-chain esters to corresponding alcohols at 270°C, originated from the synergistic effect between the metal particles and the diatomite support. For the selective hydrogenation of methyl palmitate, Pd-Cu/diatomite with metal loading of 1% and Pd/Cu=3 displayed the highest performance, giving a 1-hexadecanol yield of 82.9% at the substrate conversion of 98.8%. Copyright © 2012 Elsevier Inc. All rights reserved.

Comparative Study on The Photocatalytic Hydrogen Production from Methanol over Cu-, Pd-, Co- and Au-Loaded TiO2

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Udani P.P.C.

2015-09-01

Full Text Available Photocatalytic hydrogen production from a methanol-water solution was investigated in a semi-continuous reactor over different metal-loaded TiO2 catalysts under UltraViolet (UV light irradiation. The catalysts were mainly prepared by the incipient wetness impregnation method by varying the metal weight ratio in the range of 1-10 wt%. The effects of metal loading and H2 pre-treatment on the photocatalytic activity were investigated. In addition, the activity of the catalysts was also compared with a reference Au-TiO2 catalyst from the World Gold Council (WGC. The photocatalysts were characterized by using X-Ray Diffraction (XRD and N2 physisorption before and after the activity measurements. The photocatalytic activity decreased in the order of Pd > Au > Cu > Co in the comparative study of Cu-TiO2, Co-TiO2, Au-TiO2 and Pd-TiO2. Optimum hydrogen evolution was achieved with 5 wt% Pd-TiO2 and 5 wt% Cu-TiO2.

Catalytic Dehydration of Glycerol to Acrolein over a Catalyst of Pd/LaY Zeolite and Comparison with the Chemical Equilibrium

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Israel Pala Rosas

2017-02-01

Full Text Available Glycerol dehydration to acrolein was studied with three catalysts using zeolite-Y. This zeolite in its protonic form (HY, with La (LaY and Pd with La (Pd/LaY, was characterized by X-ray diffraction (XRD, Fourier-transform-infrared spectroscopy (FTIR with pyridine, BET, Scanning Electron Microscope (SEM–Energy-Dispersive Spectroscopy X-ray (EDS and the catalytic activity tests were carried out under H2 atmosphere. It was found that La ions exchanged in the zeolite-Y resulted in the improvement of both glycerol conversion and yield to acrolein, also a relatively constant glycerol conversion was achieved up to three hours, due to the presence of Pd on the catalyst and H2 in the feed. The comparison of the calculated and experimental yields obtained from the catalytic tests of the Pd/LaY catalyst indicates a greater activity for the reaction to acrolein than for the reaction to acetol. The calculated equilibrium yields of the dehydration reaction from glycerol to acrolein, acetol, ethanal, methanol, and water and the experimental yields of a Pd/LaY catalyst were compared. Thermodynamically, a complete conversion of glycerol can be achieved since the general system remains exothermic and promotes the path to acetol below 480 K. Above this temperature the system consumes energy and favors the production of acrolein, reaching its maximum concentration at 600 K.

Palladium Loaded on Magnetic Nanoparticles as Efficient and Recyclable Catalyst for the Suzuki- Miyaura Reaction

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H. Khojasteh

2015-07-01

Full Text Available Palladium is the best metal catalyst for Suzuki cross coupling reaction for synthesize of unsymmetrical biaryl compounds. But its high cost limits its application in wide scale. Using of nanoscale particles as active catalytic cites is a good approach for reducing needed noble metal. By loading precious nanoparticles on magnetic nanocores as a support, recycling and reusing of catalyst will be possible. Magnetic nanoparticles have super paramagnetic feature and applying an external magnetic field can collect the supported catalyst from reaction milieu simply. In this work new palladium catalyst immobilized on modified magnetic nanoparticles containing NNO donor atoms were synthesized. Then the catalyst characterized by FT-IR spectroscopy, thermogravimetric analysis, X-ray diffraction and ICP. Prepared catalyst showed high activity in the Suzuki– Miyaura cross-coupling reaction of phenylboronic acid with aryl halides. Activity, Pd loading, reusability and Pd leaching of catalyst were studied. Results showed that the supported catalyst has the advantage to be completely recoverable with the simple application of an external magnetic field.

Preparation and characterization of Pd{sub x}Ag{sub y}/C electrocatalysts for ethanol electrooxidation reaction in alkaline media

Energy Technology Data Exchange (ETDEWEB)

Li Guanglan [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Jiang Luhua [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Jiang Qian [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Wang Suli [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Sun Gongquan, E-mail: gqsun@dicp.ac.cn [Direct Alcohol Fuel Cell Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

2011-09-01

Highlights: {center_dot} The effects of Pd or PdAg particle size and PdAg alloy degrees on the EOR activity are investigated. {center_dot} The Pd lattice constant of the PdAg increases with increasing the Ag content. {center_dot} The EOR activity of the PdAg/C presents a 'volcano' plot with increasing the Pd lattice constant. {center_dot} The optimal Pd/Ag atomic ratio locates between 2/1 and 3/1. {center_dot} The EOR activity of the PdAg/C increases with increasing the PdAg particle size from 3.4 to 5.2 nm. - Abstract: Carbon-supported bimetallic PdAg catalysts with Pd/Ag atomic ratios varying from 4/1 to 1/2 were prepared by an impregnation-reduction method. The impregnated black mixture was treated in H{sub 2}/N{sub 2} atmosphere at a temperature varying from 180 to 500 deg. C. The obtained Pd{sub x}Ag{sub y}/C catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry (CV) and chronoamperometry (CA). XRD results show that the lattice constant of Pd is dilated, suggesting the formation of PdAg alloy. The lattice constant of Pd for the Pd{sub x}Ag{sub y}/C-500 (reduced at 500 deg. C by H{sub 2}) increases linearly and the average metal particle size decreases slightly from 6.8 to 5.1 nm with increasing Ag fractions from 20% to 67% in the PdAg composition. For Pd{sub x}Ag{sub y}/C catalysts with a certain specific Pd/Ag atomic ratio, e.g., Pd{sub 2}Ag{sub 1}/C, the dilated lattice constant of Pd is independent of the reducing temperature, indicating the alloy degree for the Pd{sub 2}Ag{sub 1}/C-t catalysts is comparable. The average metal particle size for the Pd{sub 2}Ag{sub 1}/C-t catalysts increases from 3.4 to 5.2 nm with H{sub 2} reduction temperature increasing from 180 to 500 deg. C. The potentiodynamic measurements on ethanol electrooxidation reaction (EOR) show that the catalytic activities for the Pd{sub x}Ag{sub y}/C-t catalysts toward the EOR are improved by alloying Pd with Ag. At

Catalytic reduction of 4-nitrophenol over Ni-Pd nanodimers supported on nitrogen-doped reduced graphene oxide

Energy Technology Data Exchange (ETDEWEB)

Liu, Lijun, E-mail: liulj@wtu.edu.cn [College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, People' s Republic of China (China); Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Chen, Ruifen; Liu, Weikai [College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, People' s Republic of China (China); Wu, Jiamin [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Gao, Di, E-mail: gaod@pitt.edu [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States)

2016-12-15

Catalytic reduction of toxic 4-nitrophenol to 4-aminophenol over magnetically recoverable nanocatalysts has attracted much attention. Herein, we report a Ni-Pd/NrGO catalyst through the growth of Ni-Pd nanodimers (NDs) on nitrogen-doped reduced graphene oxide (NrGO). The Ni-Pd NDs show a heterogeneous nanostructure with Ni and Pd subparts contacting with each other, remarkably different from the frequently-observed core/shell nanoparticles (NPs) or nanoalloy. The formation of Ni-Pd NDs follows an initial deposition of Pd NPs on the graphene and in-situ catalytic generation of Ni subparts over the newly-generated Pd NPs. The resulting Ni-Pd/NrGO exhibits a superior catalytic activity towards the reduction of 4-nitrophenol at room temperature with a high rate constant (3400 s{sup -1} g{sup -1}) and a low activated energy (29.1 kJ mol{sup -1}) as compared to unsupported Ni-Pd NDs and supported monometallic catalysts. The conversion rate of 4-NP is calculated to be 99.5% and the percent yield (%) of 4-AP is as high as 99.1%. A synergistic catalysis mechanism is rationally proposed, which is ascribed to the electronic modification of Ni-Pd metals due to the strong metal/support interaction (SMSI) effect as well as the electron transfer between Ni and Pd. The hybrid catalyst shows soft ferromagnetic properties and can be magnetically separated and recycled without obvious loss of activity.

TiO2 Nanorods Decorated with Pd Nanoparticles for Enhanced Liquefied Petroleum Gas Sensing Performance.

Science.gov (United States)

Dhawale, Dattatray S; Gujar, Tanaji P; Lokhande, Chandrakant D

2017-08-15

Development of highly sensitive and selective semiconductor-based metal oxide sensor devices to detect toxic, explosive, flammable, and pollutant gases is still a challenging research topic. In the present work, we systematically enhanced the liquefied petroleum gas (LPG) sensing performance of chemical bath deposited TiO 2 nanorods by decorating Pd nanoparticle catalyst. Surface morphology with elemental mapping, crystal structure, composition and oxidation states, and surface area measurements of pristine TiO 2 and Pd:TiO 2 nanorods was examined by high resolution transmission electron microscopy with energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and nitrogen adsorption-desorption characterization techniques. LPG sensing performance of pristine TiO 2 and Pd:TiO 2 nanorods was investigated in different LPG concentration and operating temperature ranges. The LPG response of 21% for pristine TiO 2 nanorods is enhanced to 49% after Pd catalyst decoration with reasonably fast response and recovery times. Further, the sensor exhibited long-term stability, which could be due to the strong metal support (Pd:TiO 2 ) interaction and catalytic properties offered by the Pd nanoparticle catalyst. The work described herein demonstrates a general and scalable approach that provides a promising route for rational design of variety of sensor devices for LPG detection.

Reductive dechlorination of trichloroacetic acid (TCAA) by electrochemical process over Pd-In/Al_2O_3 catalyst

International Nuclear Information System (INIS)

Liu, Yanzhen; Mao, Ran; Tong, Yating; Lan, Huachun; Zhang, Gong; Liu, Huijuan; Qu, Jiuhui

2017-01-01

Highlights: • TCAA was efficiently removed by Pd-In/Al_2O_3 based electro-reductive process. • The active species for TCAA electroreduction involved electron (e"−) and atomic H*. • The atomic H* played a major contribution to TCAA removal. - Abstract: Electrochemical reduction treatment was found to be a promising method for dechlorination of Trichloroacetic acid (TCAA), and acceleration of electron transfer or enhancement of the concentration of atomic H* significantly improve the electrochemical dechlorination process. Bimetallic Pd-based catalysts have the unique property of simultaneously catalyzing the production of atomic H* and reducing target pollutants. Herein, a bimetallic Pd–In electrocatalyst with atomic ratio of 1:1 was evenly deposited on an Al_2O_3 substrate, and the bimetallic Pd-In structure was confirmed via X-ray photoelectron spectroscopy (XPS). Electrochemical removal of trichloroacetic acid (TCAA) by the Pd-In/Al_2O_3 catalyst was performed in a three-dimensional reactor. 94% of TCAA with the initial concentration of 500 μg L"−"1 could be degraded within 30 min under a relatively low current density (0.9 mA cm"−"2). In contrast to the presence of refractory intermediates (dichloroacetic acid (DCAA)) found in the Pd/Al_2O_3 system, TCAA could be thoroughly reduced to monochloroacetic acid (MCAA) using Pd-In/Al_2O_3 catalysts. According to scavenger experiments, an electron transfer process and atomic H* formation function both existed in the TCAA reduction process, and the enhanced indirect atomic H* reduction process (confirmed by ESR signals) played a chief role in the TCAA removal. Moreover, the synergistic effects of Pd and In were proven to be able to enhance both direct electron transfer and indirect atomic H* formation, indicating a promising prospect for bimetallic electrochemical reduction treatment.

Metal Phosphate-Supported Pt Catalysts for CO Oxidation

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Xiaoshuang Qian

2014-12-01

Full Text Available Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2 have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO46(OH2, denoted as Ca-P-O here also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP atomic emission spectroscopy, X-ray diffraction (XRD, transmission electron microscopy (TEM, CO2 temperature-programmed desorption (CO2-TPD, X-ray photoelectron spectroscopy (XPS, and H2 temperature-programmed reduction (H2-TPR. This work furnishes a new catalyst system for CO oxidation and other possible reactions.

CO tolerance of PdPt/C and PdPtRu/C anodes for PEMFC

International Nuclear Information System (INIS)

Garcia, Amanda C.; Paganin, Valdecir A.; Ticianelli, Edson A.

2008-01-01

The performance of H 2 /O 2 proton exchange membrane fuel cells (PEMFCs) fed with CO-contaminated hydrogen was investigated for anodes with PdPt/C and PdPtRu/C electrocatalysts. The physicochemical properties of the catalysts were characterized by energy dispersive X-ray (EDX) analyses, X-ray diffraction (XRD) and 'in situ' X-ray absorption near edge structure (XANES). Experiments were conducted in electrochemical half and single cells by cyclic voltammetry (CV) and I-V polarization measurements, while DEMS was employed to verify the formation of CO 2 at the PEMFC anode outlet. A quite high performance was achieved for the PEMFC fed with H 2 + 100 ppm CO with the PdPt/C and PdPtRu/C anodes containing 0.4 mg metal cm -2 , with the cell presenting potential losses below 200 mV at 1 A cm -2 , with respect to the system fed with pure H 2 . For the PdPt/C catalysts no CO 2 formation was seen at the PEMFC anode outlet, indicating that the CO tolerance is improved due to the existence of more free surface sites for H 2 electrooxidation, probably due to a lower Pd-CO interaction compared to pure Pd or Pt. For PdPtRu/C the CO tolerance may also have a contribution from the bifunctional mechanism, as shown by the presence of CO 2 in the PEMFC anode outlet

Metal nanoparticles as a conductive catalyst

Science.gov (United States)

Coker, Eric N [Albuquerque, NM

2010-08-03

A metal nanocluster composite material for use as a conductive catalyst. The metal nanocluster composite material has metal nanoclusters on a carbon substrate formed within a porous zeolitic material, forming stable metal nanoclusters with a size distribution between 0.6-10 nm and, more particularly, nanoclusters with a size distribution in a range as low as 0.6-0.9 nm.

Electrochemical dopamine sensor based on P-doped graphene: Highly active metal-free catalyst and metal catalyst support.

Science.gov (United States)

Chu, Ke; Wang, Fan; Zhao, Xiao-Lin; Wang, Xin-Wei; Tian, Ye

2017-12-01

Heteroatom doping is an effective strategy to enhance the catalytic activity of graphene and its hybrid materials. Despite a growing interest of P-doped graphene (P-G) in energy storage/generation applications, P-G has rarely been investigated for electrochemical sensing. Herein, we reported the employment of P-G as both metal-free catalyst and metal catalyst support for electrochemical detection of dopamine (DA). As a metal-free catalyst, P-G exhibited prominent DA sensing performances due to the important role of P doping in improving the electrocatalytic activity of graphene toward DA oxidation. Furthermore, P-G could be an efficient supporting material for loading Au nanoparticles, and resulting Au/P-G hybrid showed a dramatically enhanced electrocatalytic activity and extraordinary sensing performances with a wide linear range of 0.1-180μM and a low detection limit of 0.002μM. All these results demonstrated that P-G might be a very promising electrode material for electrochemical sensor applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Oxygen isotope exchange on palladium catalysts

International Nuclear Information System (INIS)

Kravchuk, L.S.; Beschetvertnaya, T.I.; Novorodskij, V.G.; Novikova, M.G.; Zaretskij, M.V.; Valieva, S.V.

1983-01-01

Oxygen heteromolecular isotope exchange on unreduced palladium catalysts, distingushing by metal content is studied. Content of 18 O in gaseous phase is eoual to 46%. Calculations of heteroexchange rates are conducted with decrease of the 18 O in the gaseous phase over solid sample. Method of oxygen thermodesorption has been used to establish that palladium, deposited on γ-Al 2 O 3 during exchange process is in oxidized state; in this case strength of Pd-O bond is determined by content dispersity) of the metal. It is shown that significant increase of exchange rate on the samples with Pd >> 0.5 mass.% content can be induced as by side decomposition reaction of its oxide and corresponding dilution of gaseous mixture by ''light'' oxygen so by possibility of exchange with oxygen of PdO phase

Catalytic activity of bimetallic AuPd alloys supported MgO and MnO2 nanostructures and their role in selective aerobic oxidation of alcohols

Directory of Open Access Journals (Sweden)

Hamed Alshammari

2017-10-01

Full Text Available The use of metal oxides as supports for gold and palladium (Au-Pd nano alloys constitutes new horizons to improve catalysts materials for very important reactions. From the literatures, Pd-based bimetallic nanostructures have great properties and active catalytic performance. In this study, nanostructures of magnesium oxide (MgO and manganese dioxide (MnO₂ were synthesised and utilized as supports for Au-Pd nanoparticle catalysts. Gold and palladium were deposited on these supports using sol-immobilisation method. The MgO and MnO2 supported Au-Pd catalysts were evaluated for the oxidation of benzyl alcohol and 1-octanol, respectively. These catalysts were found to be more selective, active and reusable than the corresponding monometallic Au and Pd catalysts. The effect of base supports on the disproportionation reaction during the oxidation process was investigated. The results show that MgO stopped the disproportionation reaction for both aromatic and aliphatic alcohols while MnO₂ stopped it in the case of benzyl alcohol only. The outcomes of this work shed light on the selective aerobic oxidation of alcohols using bimetallic Au-Pd nanoalloys and pave the way to a complete investigation of more basic metal oxides for various aliphatic alcohols.

An Investigation of Palladium Oxygen Reduction Catalysts for the Direct Methanol Fuel Cell

Directory of Open Access Journals (Sweden)

G. F. Álvarez

2011-01-01

Full Text Available A comparative study of Pd and Pt was carried out in DMFC using different methanol concentrations and under different operating conditions. Cell performance was compared at methanol concentrations of 1, 3, 5, and 7 M and at temperatures of 20, 40, and 60°C. Homemade Pd nanoparticles were prepared on Vulcan XC-72R using ethylene glycol as the reducing agent at pH 11. The resulting catalyst, Pd/C, with metal nanoparticles of approximately 6 nm diameter, was tested as a cathode catalyst in DMFC. At methanol concentrations of 5 M and higher, the Pd cathode-based cell performed better than that with Pt at 60°C with air.

Physical properties of Pd and Al transition metals and Pd-Al binary metal alloy investigated by using molecular dynamics simulation

International Nuclear Information System (INIS)

Coruh, A.; Uludogan, M.; Tomak, M.; Cagin, T.

2002-01-01

In this study, physical properties, such as Pair Distribution Function g(r), Structure Factor S(k)''1'',''4, Diffusion Coefficient D''2''.''4, Intermediate Scattering function S(k,t)''3'',''4 and Dynamical Structure Factor S(k,w)''3'',''4 of some transition metals and metal alloys are investigated by using molecular dynamics simulation method. The simulation is specified for Pd, Al transition metals and Pd-Al binary metal alloys in the liquid form for different concentrations and at various temperatures by using Quantum Sutton-Chen (Q-SC) inter atomic potential. Intermediate scattering function and dynamical structure factor are calculated for various values of wave vector k. Results are in good agreement with published data''1'',''3'',''4

Magnetically separable Fe3O4@DOPA–Pd: a heterogeneous catalyst for aqueous Heck reaction

Data.gov (United States)

U.S. Environmental Protection Agency — Magnetically separable Fe3O4@DOPA–Pd catalyst has been synthesized via anchoring of palladium over dopamine-coated magnetite via co-ordinate interaction and the...

Antipollution processing of a used refining catalyst and metal recovery

Energy Technology Data Exchange (ETDEWEB)

Trinh Dinh Chan; Llido, E.

1992-04-30

The used catalyst, containing metals such as vanadium, nickel and iron, is unloaded from the plant and is first processed by stripping; it is then calcined in critical conditions, and the catalyst metals are leached with a sodium hydroxide or sodium carbonate aqueous solution. The antipollution process can be applied to oil fraction hydroconversion or hydroprocessing catalysts.

Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

Energy Technology Data Exchange (ETDEWEB)

Stanger, Keith James [Iowa State Univ., Ames, IA (United States)

2003-01-01

The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-α-acetamidocinnamate (MAC), has the illustrated structure as established by ³¹P NMR and IR studies. Spectral and catalytic investigations also suggest that the mechanism of action of the tethered complex is the same as that of the untethered complex in solution. The rhodium complexes, [Rh(COD)H]₄, [Rh(COD)₂]⁺BF₄^-, [Rh(COD)Cl]₂, and RhCl₃• 3H₂O, adsorbed on SiO₂ are optimally activated for toluene hydrogenation by pretreatment with H₂ at 200 C. The same complexes on Pd-SiO₂ are equally active without pretreatments. The active species in all cases is rhodium metal. The catalysts were characterized by XPS, TEM, DRIFTS, and mercury poisoning experiments. Rhodium on silica catalyzes the hydrogenation of fluorobenzene to produce predominantly fluorocyclohexane in heptane and 1,2-dichloroethane solvents. In heptane/methanol and heptane/water solvents, hydrodefluorination to benzene and subsequent hydrogenation to cyclohexane occurs exclusively. Benzene inhibits the hydrodefluorination of fluorobenzene. In DCE or heptane solvents, fluorocyclohexane reacts with hydrogen fluoride to form cyclohexene. Reaction conditions can be chosen to selectively yield fluorocyclohexane, cyclohexene, benzene, or cyclohexane. The oxorhenium(V) dithiolate catalyst [-S(CH₂)₃s-]Re(O)(Me)(PPh₃) was modified by linking it to a tether that could be attached to a silica support. Spectroscopic investigation and catalytic oxidation reactivity showed the heterogenized catalyst's structure and reactivity to be similar to its homogeneous analog. However, the immobilized catalyst offered additional advantages of recyclability, extended stability, and increased resistance to deactivation.

PdCo porous nanostructures decorated on polypyrrole @ MWCNTs conductive nanocomposite-Modified glassy carbon electrode as a powerful catalyst for ethanol electrooxidation

Science.gov (United States)

Fard, Leyla Abolghasemi; Ojani, Reza; Raoof, Jahan Bakhsh; Zare, Ehsan Nazarzadeh; Lakouraj, Moslem Mansour

2017-04-01

In the current study, well-defined PdCo porous nanostructure (PdCo PNS) is prepared by a simple one-pot wet-chemical method and polypyrrole@multi-walled carbon nanotubes (PPy@MWCNTs) nanocomposite is used as a catalyst support. The morphology and the structural properties of the prepared catalyst were studied by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The electrocatalytic performance of PdCo PNS/PPy@MWCNTs on glassy carbon electrode has been evaluated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) techniques. The specific activity of PdCo PNS/PPy@MWCNTs for ethanol electrooxidation (1.65 mA cm-2) is higher than those of other compared electrocatalysts. Also, PdCo PNS/PPy@MWCNTs catalyst represented higher electrocatalytic activity, better long-term stability and high level of poisoning tolerance to the carbonaceous oxidative intermediates for ethanol electrooxidation reaction in alkaline media. Furthermore, the presence of PPY@MWCNTs on the surface of GCE produce a high activity to electrocatalyst, which might be due to the easier charge transfer at polymer/carbon nanotubes interfaces, higher electrochemically accessible surface areas and electronic conductivity. The superior catalytic activity of PdCo PNS/PPy@MWCNTs suggests it to be as a promising electrocatalyst for future direct ethanol fuel cells.

Recycling of spent noble metal catalysts with emphasis on pyrometallurgical processing

Energy Technology Data Exchange (ETDEWEB)

Hagelueken, C. [Degussa Huels AG, Hanau (Germany)

1999-09-01

Precious metal catalysts for catalytic Naphta Reforming, Isomerization, Hydrogenation and other chemical and petrochemical processes are valuable assets for oil refineries and chemical companies. At the end of the service life of a reactor load of catalyst, the efficient and reliable recovery of the precious metals contained in the catalyst is of paramount importance. More than 150 years of technological advances at Degussa-Huels have resulted in refining methods for all kinds of precious metal containing materials which guarantee an optimum technical yield of the precious metals included. The refining of catalysts today is one of the important activities in the precious metals business unit. In the state-of-the-art precious metal refinery at Hanau in the centre of Germany, a wide variety of processes for the recovery of all precious metals is offered. These processes include accurate preparation, sampling and analysis as well as both wet-chemical and pyrometallurgical recovery techniques. Special emphasis in this presentation is laid on the advantages of pyrometallurgical processes for certain kinds of catalysts. To avoid any risks during transport, sampling and treatment of the spent catalyst, all parties involved in the recycling chain strictly have to follow the relevant safety regulations. Under its commitment to 'Responsible Care' standard procedures have been developed which include pre-shipment samples, safety data sheets/questionnaires and inspection of spent catalysts. These measures not only support a safe and environmentally sound catalyst recycling but also enable to determine the most suitable and economic recovery process - for the benefit of the customer. (orig.)

Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha. 1. Catalyst preparation, characterization and comparison of rate of simultaneous removal of total sulfur, nitrogen and oxygen

Energy Technology Data Exchange (ETDEWEB)

Raje, A.P.; Liaw, S.-J.; Srinivasan, R.; Davis, B.H. [University of Kentucky, Lexington, KY (United States). Center for Applied Energy Research

1997-03-13

Naphtha derived from an Illinois No. 6 coal contains appreciable quantities of sulfur-, nitrogen- and oxygen-containing compounds. The hydrotreatment of this naphtha was evaluated over unsupported transition metal sulfide catalysts (Ru, Rh, Mo, Pd, Zr, Mb). The catalysts were prepared by a room temperature precipitation reaction. Surface areas, crystalline phase and particle size distributions were determined by Brunauer-Emmet-Teller (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. A comparison of average particle sizes calculated from these three techniques has enable the understanding of the morphology of the transition metal sulfides. The catalysts exhibit a so-called volcano plot for the HDS of dibenzothiophene. Similar so-called volcano plots are also exhibited for the simultaneous hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and the hydrodeoxygenation (HDO) of the coal-derived naphtha containing a mixture of heteroatoms. The order of reactivity of the transition metal catalysts is the same for all three of the processes. Ruthenium sulfide is the most active catalyst for HDS, HDN and HDO of the coal-derived naphtha. 22 refs., 3 figs., 4 tabs.

Experimental study on the surface characteristics of Pd-based bulk metallic glass

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xiang; Sun, Bingli [School of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou 450001 (China); National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China); Zhao, Na [National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China); National Engineering Research Center for Advanced Polymer Processing Technology, Zhengzhou University, Zhengzhou 450002 (China); Li, Qian, E-mail: qianli@zzu.edu.cn [School of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou 450001 (China); National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China); National Engineering Research Center for Advanced Polymer Processing Technology, Zhengzhou University, Zhengzhou 450002 (China); Hou, Jianhua; Feng, Weina [School of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou 450001 (China); National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China)

2014-12-01

Highlights: • Wetting behavior of four polymer melts on Pd-based bulk metallic glass was investigated. • From results, in general, the contact angle of polymer on Pd-based BMG decreases with temperature increasing. • We find a critical temperature for each polymer, above this temperature, contact angle on Pd-based BMG does not decrease with temperature increasing. • Surface free energy of Pd-based BMG was estimated by Owens–Wendt method. - Abstract: The metallic glass has many unique and desirable physical and chemical characteristics for their long-range disordered atomic structure, among them the interfacial properties of the metallic glasses are crucial for their applications and manufacturing. In this work, the contact wetting angles between the polymer melts and Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} bulk metallic glass (Pd-BMG) with four kinds of roughness were analyzed. Experiments show the order of four polymers wettability on Pd-BMG was PP > HDPE > COC > PC. The surface free energy of Pd-BMG was estimated by Owens–Wendt method using the contact angles of three testing liquids. Neumann method was also used to further evidence the surface free energy of Pd-BMG comparing with PTFE, mold steels NAK80 and LKM2343ESR. The results provide theoretical and technical supports for the fabrication of metallic glass micro mold and the parameter optimization of polymer micro injection molding.

Palladium-Based Catalysts as Electrodes for Direct Methanol Fuel Cells: A Last Ten Years Review

Directory of Open Access Journals (Sweden)

Juan Carlos Calderón Gómez

2016-08-01

Full Text Available Platinum-based materials are accepted as the suitable electrocatalysts for anodes and cathodes in direct methanol fuel cells (DMFCs. Nonetheless, the increased demand and scarce world reserves of Pt, as well as some technical problems associated with its use, have motivated a wide research focused to design Pd-based catalysts, considering the similar properties between this metal and Pt. In this review, we present the most recent advancements about Pd-based catalysts, considering Pd, Pd alloys with different transition metals and non-carbon supported nanoparticles, as possible electrodes in DMFCs. In the case of the anode, different reported works have highlighted the capacity of these new materials for overcoming the CO poisoning and promote the oxidation of other intermediates generated during the methanol oxidation. Regarding the cathode, the studies have showed more positive onset potentials, as fundamental parameter for determining the mechanism of the oxygen reduction reaction (ORR and thus, making them able for achieving high efficiencies, with less production of hydrogen peroxide as collateral product. This revision suggests that it is possible to replace the conventional Pt catalysts by Pd-based materials, although several efforts must be made in order to improve their performance in DMFCs.

Effect of preparation method on the surface characteristics and activity of the Pd/OMS-2 catalysts for the oxidation of carbon monoxide, toluene, and ethyl acetate

International Nuclear Information System (INIS)

Liu, Lisha; Song, Yong; Fu, Zhidan; Ye, Qing; Cheng, Shuiyuan; Kang, Tianfang; Dai, Hongxing

2017-01-01

Highlights: • The framework-structured of cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2) has a 2 × 2 square tunnel. • Preparation route has an important impact on physicochemical property of the product. • Pd/OMS-2-DP via the deposition-precipitation route shows excellent catalytic activity. • Pd surface loading, surface atomic ratio of Mn ions, lattice oxygen mobility, oxygen vacancy, reducibility and acidity govern activity. - Abstract: The cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2)-supported Pd (0.5 wt% Pd/OMS-2-DP, 0.5 wt% Pd/OMS-2-PI, and 0.5 wt% Pd/OMS-2-EX) catalysts were prepared by the deposition-precipitation, pre-incorporation, and ion-exchanging strategies, respectively. It is shown that the preparation method exerted an important effect on the physicochemical property of the sample. Among the OMS-2-supported Pd catalysts, 0.5 wt% Pd/OMS-2-DP possessed the highest surface (Mn 2+ + Mn 3+ )/Mn 4+ atomic ratio and the highest surface Pd loading and acid sites. The 0.5 wt% Pd/OMS-2 catalysts outperformed the Pd-free counterpart, among which 0.5 wt% Pd/OMS-2-DP presented the best catalytic activity (T 50% and T 90% were 25 and 55 °C for CO oxidation, 240 and 285 °C for toluene oxidation, and 160 and 200 °C for ethyl acetate oxidation, respectively). We believe that the high Pd surface loading, high surface atomic ratio of (Mn 2+ + Mn 3+ )/Mn 4+ , and good low-temperature reducibility, good oxygen mobility, and high acidity were responsible for the excellent performance of the 0.5 wt% Pd/OMS-2-DP catalyst.

Pd nanoparticles immobilized on carbon nanotubes with a polyaniline coaxial coating for the Heck reaction: coating thickness as the key factor influencing the efficiency and stability of the catalyst

KAUST Repository

Yu, Rui

2018-02-12

Pd nanoparticles (NPs) supported on polyaniline (PANI)-coated carbon nanotubes (CNTs) were synthesized using a low-cost and simple method for application in the Heck reaction. The effects of the PANI/CNT coating weight ratio on the catalytic stability and recyclability of the composite were determined by using a combination of experimental and computational methods. The results show that through coordination of the N-species in PANI with the Pd NPs, the nitrogen-rich PANI@CNT provides a strong support for the Pd NPs. The thickness of the PANI layer is the key in determining the stability of the catalyst. PANI becomes protonated in the presence of CNTs, as electron transfer from the former to the latter creates strong interactions between the two. Thus, PANI becomes more stable in nanocomposites with a higher CNT content, e.g., PANI/CNT = 0.5 : 1. The catalyst with a PANI/CNT ratio of 0.5 : 1 exhibited the best recycling performance, and only a small loss of activity was observed after 10 cycles. However, upon increasing the PANI content (e.g., PANI/CNT = 4 : 1), the PANI units tend to form bulk structures that are less stable than those that wrap around the CNTs. Such a structure is unstable; therefore, the PANI layers can easily deform or break away from the CNT backbones. Hence, these catalysts deactivate during recycling. Thus, our study demonstrates that the assembly of noble-metal NPs on CNTs bearing a thin coaxial PANI coating is a powerful technique to prepare reusable catalysts for the Heck reaction. Coating thickness is also a key factor affecting the efficiency and stability of the catalyst.

Pd nanoparticles immobilized on carbon nanotubes with a polyaniline coaxial coating for the Heck reaction: coating thickness as the key factor influencing the efficiency and stability of the catalyst

KAUST Repository

Yu, Rui; Liu, Rui; Deng, Jie; Ran, Maofei; Wang, Ning; Chu, Wei; He, Zhiwei; Du, Zheng; Jiang, Chengfa; Sun, Wenjing

2018-01-01

Pd nanoparticles (NPs) supported on polyaniline (PANI)-coated carbon nanotubes (CNTs) were synthesized using a low-cost and simple method for application in the Heck reaction. The effects of the PANI/CNT coating weight ratio on the catalytic stability and recyclability of the composite were determined by using a combination of experimental and computational methods. The results show that through coordination of the N-species in PANI with the Pd NPs, the nitrogen-rich PANI@CNT provides a strong support for the Pd NPs. The thickness of the PANI layer is the key in determining the stability of the catalyst. PANI becomes protonated in the presence of CNTs, as electron transfer from the former to the latter creates strong interactions between the two. Thus, PANI becomes more stable in nanocomposites with a higher CNT content, e.g., PANI/CNT = 0.5 : 1. The catalyst with a PANI/CNT ratio of 0.5 : 1 exhibited the best recycling performance, and only a small loss of activity was observed after 10 cycles. However, upon increasing the PANI content (e.g., PANI/CNT = 4 : 1), the PANI units tend to form bulk structures that are less stable than those that wrap around the CNTs. Such a structure is unstable; therefore, the PANI layers can easily deform or break away from the CNT backbones. Hence, these catalysts deactivate during recycling. Thus, our study demonstrates that the assembly of noble-metal NPs on CNTs bearing a thin coaxial PANI coating is a powerful technique to prepare reusable catalysts for the Heck reaction. Coating thickness is also a key factor affecting the efficiency and stability of the catalyst.

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

Turbostratic carbon supported palladium as an efficient catalyst for reductive purification of water from trichloroethylene

Directory of Open Access Journals (Sweden)

Emil Kowalewski

2017-12-01

Full Text Available This work investigates the catalytic properties of turbostratic carbon supported Pd catalyst in hydrodechlorination of trichloroethylene (TCE HDC in aqueous phase. 1.57 wt% Pd/C was thoroughly characterized by BET, TPHD, CO chemisorption, PXRD, STEM, XPS and used as the catalyst in removal of trichloroethylene from drinking water in batch and continuous-flow reactors. The studies showed that catalytic performance of Pd/C depended on the hydrophobicity and textural properties of carbon support, which influenced noble metal dispersion and increased catalyst tolerance against deactivation by chlorination. Palladium in the form of uniformly dispersed small (~3.5 nm nanoparticles was found to be very active and stable in purification of water from TCE both in batch and continuous-flow operation.

An improved method of preparation of nanoparticular metal oxide catalysts

DEFF Research Database (Denmark)

2014-01-01

The present invention concerns an improved method of preparation of nanoparticular vanadium oxide/anatase titania catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular vanadium oxide/anatase titania catalyst precursors comprising...... combustible crystallization seeds upon which the catalyst metal oxide is coprecipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step....

Palladium nanoparticles encapsulated in core-shell silica: A structured hydrogenation catalyst with enhanced activity for reduction of oxyanion water pollutants

KAUST Repository

Wang, Yin; Liu, Jinyong; Wang, Peng; Werth, Charles; Strathmann, Timothy J.

2014-01-01

Noble metal nanoparticles have been applied to mediate catalytic removal of toxic oxyanions and halogenated hydrocarbons in contaminated water using H2 as a clean and sustainable reductant. However, activity loss by nanoparticle aggregation and difficulty of nanoparticle recovery are two major challenges to widespread technology adoption. Herein, we report the synthesis of a core-shell-structured catalyst with encapsulated Pd nanoparticles and its enhanced catalytic activity in reduction of bromate (BrO3-), a regulated carcinogenic oxyanion produced during drinking water disinfection process, using 1 atm H2 at room temperature. The catalyst material consists of a nonporous silica core decorated with preformed octahedral Pd nanoparticles that were further encapsulated within an ordered mesoporous silica shell (i.e., SiO2@Pd@mSiO2). Well-defined mesopores (2.3 nm) provide a physical barrier to prevent Pd nanoparticle (6 nm) movement, aggregation, and detachment from the support into water. Compared to freely suspended Pd nanoparticles and SiO2@Pd, encapsulation in the mesoporous silica shell significantly enhanced Pd catalytic activity (by a factor of 10) under circumneutral pH conditions that are most relevant to water purification applications. Mechanistic investigation of material surface properties combined with Langmuir-Hinshelwood modeling of kinetic data suggest that mesoporous silica shell enhances activity by promoting BrO3- adsorption near the Pd active sites. The dual function of the mesoporous shell, enhancing Pd catalyst activity and preventing aggregation of active nanoparticles, suggests a promising general strategy of using metal nanoparticle catalysts for water purification and related aqueous-phase applications.

Palladium nanoparticles encapsulated in core-shell silica: A structured hydrogenation catalyst with enhanced activity for reduction of oxyanion water pollutants

KAUST Repository

Wang, Yin

2014-10-03

Noble metal nanoparticles have been applied to mediate catalytic removal of toxic oxyanions and halogenated hydrocarbons in contaminated water using H2 as a clean and sustainable reductant. However, activity loss by nanoparticle aggregation and difficulty of nanoparticle recovery are two major challenges to widespread technology adoption. Herein, we report the synthesis of a core-shell-structured catalyst with encapsulated Pd nanoparticles and its enhanced catalytic activity in reduction of bromate (BrO3-), a regulated carcinogenic oxyanion produced during drinking water disinfection process, using 1 atm H2 at room temperature. The catalyst material consists of a nonporous silica core decorated with preformed octahedral Pd nanoparticles that were further encapsulated within an ordered mesoporous silica shell (i.e., SiO2@Pd@mSiO2). Well-defined mesopores (2.3 nm) provide a physical barrier to prevent Pd nanoparticle (6 nm) movement, aggregation, and detachment from the support into water. Compared to freely suspended Pd nanoparticles and SiO2@Pd, encapsulation in the mesoporous silica shell significantly enhanced Pd catalytic activity (by a factor of 10) under circumneutral pH conditions that are most relevant to water purification applications. Mechanistic investigation of material surface properties combined with Langmuir-Hinshelwood modeling of kinetic data suggest that mesoporous silica shell enhances activity by promoting BrO3- adsorption near the Pd active sites. The dual function of the mesoporous shell, enhancing Pd catalyst activity and preventing aggregation of active nanoparticles, suggests a promising general strategy of using metal nanoparticle catalysts for water purification and related aqueous-phase applications.

PdCu alloy nanoparticle-decorated copper nanotubes as enhanced electrocatalysts: DFT prediction validated by experiment

Science.gov (United States)

Wu, Dengfeng; Xu, Haoxiang; Cao, Dapeng; Fisher, Adrian; Gao, Yi; Cheng, Daojian

2016-12-01

In order to combine the advantages of both 0D and 1D nanostructured materials into a single catalyst, density functional theory (DFT) calculations have been used to study the PdCu alloy NP-decorated Cu nanotubes (PdCu@CuNTs). These present a significant improvement of the electrocatalytic activity of formic acid oxidation (FAO). Motivated by our theoretical work, we adopted the seed-mediated growth method to successfully synthesize the nanostructured PdCu@CuNTs. The new catalysts triple the catalytic activity for FAO, compared with commercial Pd/C. In summary, our work provides a new strategy for the DFT prediction and experimental synthesis of novel metal NP-decorated 1D nanostructures as electrocatalysts for fuel cells.

Session 6: Synergistic effects in selective hydro dechlorination on bimetallic catalysts

Energy Technology Data Exchange (ETDEWEB)

Srebowata, A.; Legawiec-Jarzyna, M.; Juszczyk, W.; Karpinski, Z. [Institute of Physical Chemistry of PAS, Warszawa (Poland)

2004-07-01

Catalytic removal of chlorine from organic compounds has recently attracted increasing interest. A special case of this important environmental issue is the hydro-dechlorination (HDC). HDC of three compounds was investigated: dichloro-difluoro-methane, carbon tetrachloride and 1,2-dichloroethane. Since the most desired products of the mentioned reactions are: CH{sub 2}F{sub 2}, chloroform and ethene (highlighted below), our attention was focused at the rates of formation of these products: CCl{sub 2}F{sub 2} {yields} CH{sub 2}F{sub 2} {yields} CH{sub 4}; CCl{sub 4} {yields} CHCl{sub 3} {yields} CH{sub 4}; ClCH{sub 2}-CH{sub 2}Cl {yields} CH{sub 2}=CH{sub 2} {yields} CH{sub 3}CH{sub 3}. In fact, Selection of the most suitable HDC catalyst depends on the C-Cl bond strength in a molecule subjected to reaction. A relatively weak C-Cl bond in CCl{sub 4} (306 kJ/mol) does not require a high dechlorination potential, which can be directly correlated with the strength of a metal-chlorine bond. Thus Pt is a better catalyst than Pd in CCl{sub 4} reaction. In addition, an improvement of Pt-based catalysts can be achieved by alloying with metals which bind chlorine even less strongly than Pt (i.e. with Au). In contrast, Pd is a better catalyst than Pt for hydro-dechlorination of a stronger C-Cl bond (about 350 kJ/mol), present in CCl{sub 2}F{sub 2} and ClCH{sub 2}-CH{sub 2}Cl. However, a good performance of Pd can still be improved by alloying it with much less active Pt (or Au), as a result of weakening of the metal-chlorine bond. This effect leads to a higher selectivity toward partial dehalogenation, i.e. to formation of a desired CH{sub 2}F{sub 2} (at the expense of CH{sub 4}). In a similar way, combination of Pd with Co and Cu is rationalized. For HDC of ClCH{sub 2}-CH{sub 2}Cl, addition of a metal characterized by a poor hydrogenation strength (like Cu or Ag) to Pd (or Pt) reduces undesired formation of ethane, giving higher yields of ethene. (authors)

Surfactant-controlled synthesis of Pd/Ce{sub 0.6}Zr{sub 0.4}O{sub 2} catalyst for NO reduction by CO with excess oxygen

Energy Technology Data Exchange (ETDEWEB)

Chen, L.F. [Laboratorio de Catalisis y Materiales, SEPI-ESIQIE, Instituto Politecnico Nacional, Av. Politecnico S/N, Col. Zacatenco, 07738 Mexico D.F. (Mexico); Departamento de Ingenieria Quimica, Universidad Autonoma Metropolitana-A, Av. San Pablo 180, Col. Reynosa-Tamaulipas, 02200 Mexico D.F. (Mexico); Gonzalez, G. [Laboratorio de Catalisis y Materiales, SEPI-ESIQIE, Instituto Politecnico Nacional, Av. Politecnico S/N, Col. Zacatenco, 07738 Mexico D.F. (Mexico); Wang, J.A. [Laboratorio de Catalisis y Materiales, SEPI-ESIQIE, Instituto Politecnico Nacional, Av. Politecnico S/N, Col. Zacatenco, 07738 Mexico D.F. (Mexico)]. E-mail: jwang@ipn.mx; Norena, L.E. [Departamento de Ingenieria Quimica, Universidad Autonoma Metropolitana-A, Av. San Pablo 180, Col. Reynosa-Tamaulipas, 02200 Mexico D.F. (Mexico); Toledo, A. [Grupo de Molecular Ingenieria, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico); Castillo, S. [Grupo de Molecular Ingenieria, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico); Moran-Pineda, M. [Grupo de Molecular Ingenieria, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico)

2005-04-30

For the first time, this work reports a surfactant-controlled synthetic method to obtain a nanophase of mesoporous ceria-zirconia solid solution containing cationic defects in the crystalline structure. The incorporation of a cationic surfactant (myristyltrimethylammonium bromide) into the ceria-zirconia solid network not only controlled the pore diameter distribution but also induced creation of the lattice defect. Ceria-zirconia solid solution showed crystal microstrain and structural distortion that varied with the calcination temperature. Compared to pure ceria, the addition of zirconium to the ceria promoted the bulk oxygen reducibility and enhanced the thermal stability of the solid. Hydrogen could be stored into or released from the PdO/Ce{sub 0.6}Zr{sub 0.4}O{sub 2} catalyst during the TPR procedure, which is associated to the formation/decomposition of a PdH{sub x} phase, due to the hydrogen dissociation catalyzed by metallic Pd. At cool start of reaction, NO reduction by CO with excess oxygen over the Pd/Ce{sub 0.6}Zr{sub 0.4}O{sub 2} catalyst showed selectivity around 100% to N{sub 2}. A competition between NO reduction by CO and CO oxidation by O{sub 2} was observed: at reaction temperatures below 200 deg. C, NO inhibited CO oxidation activity; however, at reaction temperatures above 200 deg. C, high activity of CO oxidation resulted in an inhibition effect on NO reduction.

Physical properties of the GaPd2 intermetallic catalyst in bulk and nanoparticle morphology

DEFF Research Database (Denmark)

Wencka, M.; Schwerin, J.; Klanjšek, M.

2015-01-01

Intermetallic compound GaPd2 is a highly selective catalyst material for the semi-hydrogenation of acetylene. We have determined anisotropic electronic, thermal and magnetic properties of a GaPd2 monocrystal along three orthogonal orthorhombic directions of the structure. By using 69Ga and 71Ga NMR...... properties of the GaPd2 phase on going from the bulk material to the nanoparticles morphology, we have synthesized GaPd2/SiO2 supported nanoparticles and determined their electronic DOS at εF from the 71Ga NMR spin-lattice relaxation rate. The electronic DOS of the GaPd2 was also studied theoretically from...... spectroscopy, we have determined the electric-field-gradient tensor at the Ga site in the unit cell and the Knight shift, which yields the electronic density of states (DOS) at the Fermi energy εF. The DOS at εF was determined independently also from the specific heat. To see the change of electronic...

Interfacial charge distributions in carbon-supported palladium catalysts

DEFF Research Database (Denmark)

Rao, Radhika G.; Blume, Raoul; Hansen, Thomas Willum

2017-01-01

Controlling the charge transfer between a semiconducting catalyst carrier and the supported transition metal active phase represents an elite strategy for fine turning the electronic structure of the catalytic centers, hence their activity and selectivity. These phenomena have been theoretically...... and experimentally elucidated for oxide supports but remain poorly understood for carbons due to their complex nanoscale structure. Here, we combine advanced spectroscopy and microscopy on model Pd/C samples to decouple the electronic and surface chemistry effects on catalytic performance. Our investigations reveal...... treatments can be used to tune the interfacial charge distribution, hereby providing a strategy to rationally design carbon-supported catalysts.Control over charge transfer in carbon-supported metal nanoparticles is essential for designing new catalysts. Here, the authors show that thermal treatments...

Enhanced hydrogen reaction kinetics of nanostructured Mg-based composites with nanoparticle metal catalysts dispersed on supports

International Nuclear Information System (INIS)

Yoo, Yeong; Tuck, Mark; Kondakindi, Rajender; Seo, Chan-Yeol; Dehouche, Zahir; Belkacemi, Khaled

2007-01-01

Hydrogen reaction kinetics of nanocrystalline MgH 2 co-catalyzed with Ba 3 (Ca 1+x Nb 2-x )O 9-δ (BCN) proton conductive ceramics and nanoparticle bimetallic catalyst of Ni/Pd dispersed on single wall carbon nanotubes (SWNTs) support has been investigated. The nanoparticle bimetallic catalysts of Ni/Pd supported by SWNTs were synthesized based on a novel polyol method using NiCl 2 .6H 2 O, PdCl 2 , NaOH and ethylene glycol (EG). The nanostructured Mg composites co-catalyzed with BCN and bimetallic supported catalysts exhibited stable hydrogen desorption capacity of 6.3-6.7 wt.% H 2 and the significant enhancement of hydrogen desorption kinetics at 230-300 deg. C in comparison to either non-catalyzed MgH 2 or the nanocomposite of MgH 2 catalyzed with BCN

Effect of preparation method on the surface characteristics and activity of the Pd/OMS-2 catalysts for the oxidation of carbon monoxide, toluene, and ethyl acetate

Energy Technology Data Exchange (ETDEWEB)

Liu, Lisha; Song, Yong; Fu, Zhidan [Key Laboratory of Beijing on Regional Air Pollution Control, Department of Environmental Science, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Ye, Qing, E-mail: yeqing@bjut.edu.cn [Key Laboratory of Beijing on Regional Air Pollution Control, Department of Environmental Science, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Cheng, Shuiyuan; Kang, Tianfang [Key Laboratory of Beijing on Regional Air Pollution Control, Department of Environmental Science, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Dai, Hongxing, E-mail: hxdai@bjut.edu.cn [Beijing Key Laboratory for Green Catalysis and Separation, Key Laboratory of Beijing on Regional Air Pollution Control, Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China)

2017-02-28

Highlights: • The framework-structured of cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2) has a 2 × 2 square tunnel. • Preparation route has an important impact on physicochemical property of the product. • Pd/OMS-2-DP via the deposition-precipitation route shows excellent catalytic activity. • Pd surface loading, surface atomic ratio of Mn ions, lattice oxygen mobility, oxygen vacancy, reducibility and acidity govern activity. - Abstract: The cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2)-supported Pd (0.5 wt% Pd/OMS-2-DP, 0.5 wt% Pd/OMS-2-PI, and 0.5 wt% Pd/OMS-2-EX) catalysts were prepared by the deposition-precipitation, pre-incorporation, and ion-exchanging strategies, respectively. It is shown that the preparation method exerted an important effect on the physicochemical property of the sample. Among the OMS-2-supported Pd catalysts, 0.5 wt% Pd/OMS-2-DP possessed the highest surface (Mn{sup 2+} + Mn{sup 3+})/Mn{sup 4+} atomic ratio and the highest surface Pd loading and acid sites. The 0.5 wt% Pd/OMS-2 catalysts outperformed the Pd-free counterpart, among which 0.5 wt% Pd/OMS-2-DP presented the best catalytic activity (T{sub 50%} and T{sub 90%} were 25 and 55 °C for CO oxidation, 240 and 285 °C for toluene oxidation, and 160 and 200 °C for ethyl acetate oxidation, respectively). We believe that the high Pd surface loading, high surface atomic ratio of (Mn{sup 2+} + Mn{sup 3+})/Mn{sup 4+}, and good low-temperature reducibility, good oxygen mobility, and high acidity were responsible for the excellent performance of the 0.5 wt% Pd/OMS-2-DP catalyst.

Molecular metal catalysts on supports: organometallic chemistry meets surface science.

Science.gov (United States)

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal

Performance of carbon nanofiber supported Pd-Ni catalysts for electro-oxidation of ethanol in alkaline medium

Science.gov (United States)

Maiyalagan, T.; Scott, Keith

Carbon nanofibers (CNF) supported Pd-Ni nanoparticles have been prepared by chemical reduction with NaBH 4 as a reducing agent. The Pd-Ni/CNF catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical voltammetry analysis. TEM showed that the Pd-Ni particles were quite uniformly distributed on the surface of the carbon nanofiber with an average particle size of 4.0 nm. The electro-catalytic activity of the Pd-Ni/CNF for oxidation of ethanol was examined by cyclic voltammetry (CV). The onset potential was 200 mV lower and the peak current density four times higher for ethanol oxidation for Pd-Ni/CNF compared to that for Pd/C. The effect of an increase in temperature from 20 to 60 °C had a great effect on increasing the ethanol oxidation activity.

Metal leaching from refinery waste hydroprocessing catalyst.

Science.gov (United States)

Marafi, Meena; Rana, Mohan S

2018-05-18

The present study aims to develop an eco-friendly methodology for the recovery of nickel (Ni), molybdenum (Mo), and vanadium (V) from the refinery waste spent hydroprocessing catalyst. The proposed process has two stages: the first stage is to separate alumina, while the second stage involves the separation of metal compounds. The effectiveness of leaching agents, such as NH 4 OH, (NH 4 ) 2 CO 3 , and (NH 4 ) 2 S 2 O 8 , for the extraction of Mo, V, Ni, and Al from the refinery spent catalyst has been reported as a function of reagent concentration (0.5 to 2.0 molar), leaching time (1 to 6 h), and temperature (35 to 60°C). The optimal leaching conditions were achieved to obtain the maximum recovery of Mo, Ni, and V metals. The effect of the mixture of multi-ammonium salts on the metal extraction was also studied, which showed an adverse effect for Ni and V, while marginal improvement was observed for Mo leaching. The ammonium salts can form soluble metal complexes, in which stability or solubility depends on the nature of ammonium salt and the reaction conditions. The extracted metals and support can be reused to synthesize a fresh hydroprocessing catalyst. The process will reduce the refinery waste and recover the expensive metals. Therefore, the process is not only important from an environmental point of view but also vital from an economic perspective.

Ultra-low Pt decorated PdFe Alloy Nanoparticles for Formic Acid Electro-oxidation

International Nuclear Information System (INIS)

Zhou, Yawei; Du, Chunyu; Han, Guokang; Gao, Yunzhi; Yin, Geping

2016-01-01

Highlights: • A cost-efficient way is used to prepare transition-noble metal alloy nanoparticles. • The Pd 50 Fe 50 /C catalyst shows excellent activity for formic acid oxidation (FAO). • Much activity enhancement of FAO is acquired by ultra-low Pt decorated Pd 50 Fe 50 . • A synergistic mechanism between Pt clusters and PdFe is proposed during the FAO. - Abstract: Palladium (Pd), has demonstrated promising electro-catalytic activity for formic acid oxidation, but suffers from extremely low abundance. Recently alloying with a transition metal has been considered as an effective approach to reducing the loading of Pd and enhancing the activity of Pd-based catalysts simultaneously. Herein, carbon supported PdFe nanoparticles (NPs) are synthesized at room temperature by using sodium borohydride as reducing agent and potassium ferrocyanide as Fe precursor. The Pd 50 Fe 50 alloy sample annealed at 900 °C for 1 h shows the best catalytic activity among Pd x Fe 1-x (x = 0.2, 0.4, 0.5, 0.6, and 0.8) towards formic acid oxidation. To further improve both catalytic activity and stability, the ultra-low Pt (0.09 wt %) decorated Pd 50 Fe 50 NPs (PtPd/PdFe) are prepared via the galvanic replacement reaction. Compared with Pd 50 Fe 50 /C, the PtPd/PdFe/C Exhibits 1.52 times higher catalytic activity and lower onset potential (−0.12 V). The significant enhancements of formic acid oxidation can be attributed to the accelerated dehydrogenation reaction of formic acid by Pt atomic clusters. Moreover, the PtPd/PdFe/C also demonstrates better tolerance to poisons during formic acid oxidation.

O{sub 2} adsorption and dissociation on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Li, Sha; Yang, Yongpeng; Huang, Shiping, E-mail: huangsp@mail.buct.edu.cn

2017-07-15

Highlights: • O{sub 2} adsorption and dissociation on Pd{sub 13-n}Ni{sub n}@Pt{sub 42} NPs are performed by DFT. • Adsorption energies of O{sub 2} and O are strongly affected by the coordination number. • Adsorption energy and d-band center displays the opposite change tendency. • Ni{sub 13}@Pt{sub 42} is the most active catalyst among Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) NPs. - Abstract: Density functional theory calculations are performed to investigate O{sub 2} adsorption and dissociation on the icosahedral Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles. The parallel adsorption of O{sub 2} on Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) is stronger than the vertical adsorption. The adsorption of O{sub 2} on the bridge site (B1) is favorable in the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) nanoparticles, while the adsorption of O atom on the hollow site (H1) is preferred. The adsorption energies of O{sub 2} and O are strongly affected by the coordination number. Low coordination site shows strong adsorption of O{sub 2} and O on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) nanoparticles. The adsorption energies of O{sub 2} and O atoms are found to be correlated well with the d-band center of surface Pt. For the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and13) nanoparticles catalysts, the ORR activity follows the order of Ni{sub 13}@Pt{sub 42} > Pd{sub 13}@Pt{sub 42} > Pd{sub 12}Ni{sub 1}@Pt{sub 42} > Pd{sub 1}Ni{sub 12}@Pt{sub 42}, illustrating that the Ni{sub 13}@Pt{sub 42} is the strongest ORR activity among the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and13) nanoparticles catalysts. Our results have important significance to understand the mechanism of O{sub 2} dissociation on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles.

Nanostructured carbon-supported Pd electrocatalysts for ethanol oxidation: synthesis and characterization

Science.gov (United States)

Gacutan, E. M.; Climaco, M. I.; Telan, G. J.; Malijan, F.; Hsu, H. Y.; Garcia, J.; Fulo, H.; Tongol, B. J.

2012-12-01

The need to lower the construction cost of fuel cells calls for the development of non-Pt based electrocatalysts. Among others, Pd has emerged as a promising alternative to Pt for fuel cell catalysis. This research aims to investigate the synthesis and characterization of nanostructured Pd-based catalysts dispersed on carbon support as anode materials in direct ethanol fuel cells. For the preparation of the first Pd-based electrocatalyst, palladium nanoparticles (NPs) were synthesized via oleylamine (OAm)-mediated synthesis and precursor method with a mean particle size of 3.63 ± 0.59 nm as revealed by transmission electron microscopy (TEM). Carbon black was used as a supporting matrix for the OAm-capped Pd NPs. Thermal annealing and acetic acid washing were used to remove the OAm capping agent. To evaluate the electrocatalytic activity of the prepared electrocatalyst towards ethanol oxidation, cyclic voltammetry (CV) studies were performed using 1.0 M ethanol in basic medium. The CV data revealed the highest peak current density of 11.05 mA cm-2 for the acetic acid-washed Pd/C electrocatalyst. Meanwhile, the fabrication of the second Pd-based electrocatalyst was done by functionalization of the carbon black support using 3:1 (v/v) H2SO4:HNO3. The metal oxide, NiO, was deposited using precipitation method while polyol method was used for the deposition of Pd NPs. X-ray diffraction (XRD) analysis revealed that the estimated particle size of the synthesized catalysts was at around 9.0-15.0 nm. CV results demonstrated a 36.7% increase in the catalytic activity of Pd-NiO/C (functionalized) catalyst towards ethanol oxidation compared to the non-functionalized catalyst.

A Pd/C-CeO2 Anode Catalyst for High-Performance Platinum-Free Anion Exchange Membrane Fuel Cells.

Science.gov (United States)

Miller, Hamish A; Lavacchi, Alessandro; Vizza, Francesco; Marelli, Marcello; Di Benedetto, Francesco; D'Acapito, Francesco; Paska, Yair; Page, Miles; Dekel, Dario R

2016-05-10

One of the biggest obstacles to the dissemination of fuel cells is their cost, a large part of which is due to platinum (Pt) electrocatalysts. Complete removal of Pt is a difficult if not impossible task for proton exchange membrane fuel cells (PEM-FCs). The anion exchange membrane fuel cell (AEM-FC) has long been proposed as a solution as non-Pt metals may be employed. Despite this, few examples of Pt-free AEM-FCs have been demonstrated with modest power output. The main obstacle preventing the realization of a high power density Pt-free AEM-FC is sluggish hydrogen oxidation (HOR) kinetics of the anode catalyst. Here we describe a Pt-free AEM-FC that employs a mixed carbon-CeO2 supported palladium (Pd) anode catalyst that exhibits enhanced kinetics for the HOR. AEM-FC tests run on dry H2 and pure air show peak power densities of more than 500 mW cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamics of Pore Filling Metal Clusters in Metal Organic Frameworks: Pd in UiO-66

DEFF Research Database (Denmark)

Vilhelmsen, Lasse; Sholl, David S.

2012-01-01

Metal organic frameworks (MOFs) have experimentally been demonstrated to be capable of supporting isolated transition-metal clusters, but the stability of these clusters with respect to aggregation is unclear. In this letter we use a genetic algorithm together with density functional theory...... calculations to predict the structure of Pd clusters in UiO-66. The cluster sizes examined are far larger than those in any previous modeling studies of metal clusters in MOFs and allow us to test the hypothesis that the physically separated cavities in UiO-66 could stabilize isolated Pd clusters. Our...... calculations show that Pd clusters in UiO-66 are, at best, metastable and will aggregate into connected pore filling structures at equilibrium....

Properties and application of noble metal catalysts for heterogeneous catalytic hydrogenations

Energy Technology Data Exchange (ETDEWEB)

Horn, G; Frohning, C D; Cornils, B [Ruhrchemie A.G., Oberhausen (Germany, F.R.)

1976-07-01

The special properties of the six platinum group elements - ruthenium, rhodium, palladium, osmium, iridium, platinum - make them useful as active metals for catalytic reactions. Especially valuable is their property of favouring a single reaction even when the possibility of a number of parallel reactions exists under certain reaction conditions. This selectivity of the noble metal catalyst may be directed or enhanced through appropriate choise of the metal, the reaction conditions, the duration of the reaction, the amount of hydrogen etc. Even the physical state of the catalyst - supported or unsupported - is of influence when using noble metal catalysts as described in this report.

Selective metal pattern formation and its EMI shielding efficiency

International Nuclear Information System (INIS)

Lee, Ho-Chul; Kim, Jin-Young; Noh, Chang-Ho; Song, Ki Yong; Cho, Sung-Heon

2006-01-01

A novel method for selective metal pattern formation by using an enhanced life-time of photoexcited electron-hole pairs in bilayer thin film of amorphous titanium dioxide and hole-scavenger-containing poly(vinyl alcohol) was proposed. By UV-irradiation through photomask on the bilayer film, the photodefined image of photoelectrons could be easily and simply produced, consequently resulting in selective palladium (Pd) catalyst deposition by reduction. The successive electrolessplating on Pd catalysts and electroplating on electrolessplated pattern were possible. Furthermore, the electromagnetic interference shielding efficiencies of the metal mesh patterns with various characteristic length scales of line width and thickness were investigated

PdCo porous nanostructures decorated on polypyrrole @ MWCNTs conductive nanocomposite—Modified glassy carbon electrode as a powerful catalyst for ethanol electrooxidation

Energy Technology Data Exchange (ETDEWEB)

Fard, Leyla Abolghasemi [Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, 3rd Kilometer of Air Force Road, 47416-95447, Babolsar (Iran, Islamic Republic of); Ojani, Reza, E-mail: fer-o@umz.ac.ir [Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, 3rd Kilometer of Air Force Road, 47416-95447, Babolsar (Iran, Islamic Republic of); Raoof, Jahan Bakhsh [Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, 3rd Kilometer of Air Force Road, 47416-95447, Babolsar (Iran, Islamic Republic of); Zare, Ehsan Nazarzadeh; Lakouraj, Moslem Mansour [Polymer Research Laboratory Department of Organic-Polymer Chemistry, Faculty of Chemistry, University of Mazandaran, 3rd Kilometer of Air Force Road, 47416-95447, Babolsar (Iran, Islamic Republic of)

2017-04-15

Highlights: • The PdCo PNS/PPy@MWCNT electrocatalyst was easily prepared. • The electrocatalyst exhibits high electrocatalytic activity and stability toward the EOR. • The specific activity of PdCo PNS/PPy@MWCNTs for ethanol electrooxidation (1.65 mA cm{sup −2}) is higher than those of other compared electrocatalysts. • The high electrocatalytic performance is attributed to concerted effects of Porous nature, Co and PPy@MWCNT. • The PdCo PNS/PPy@MWCNT electrocatalyst has never been reported. - Abstract: In the current study, well-defined PdCo porous nanostructure (PdCo PNS) is prepared by a simple one-pot wet-chemical method and polypyrrole@multi-walled carbon nanotubes (PPy@MWCNTs) nanocomposite is used as a catalyst support. The morphology and the structural properties of the prepared catalyst were studied by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The electrocatalytic performance of PdCo PNS/PPy@MWCNTs on glassy carbon electrode has been evaluated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) techniques. The specific activity of PdCo PNS/PPy@MWCNTs for ethanol electrooxidation (1.65 mA cm{sup −2}) is higher than those of other compared electrocatalysts. Also, PdCo PNS/PPy@MWCNTs catalyst represented higher electrocatalytic activity, better long-term stability and high level of poisoning tolerance to the carbonaceous oxidative intermediates for ethanol electrooxidation reaction in alkaline media. Furthermore, the presence of PPY@MWCNTs on the surface of GCE produce a high activity to electrocatalyst, which might be due to the easier charge transfer at polymer/carbon nanotubes interfaces, higher electrochemically accessible surface areas and electronic conductivity. The superior catalytic activity of PdCo PNS/PPy@MWCNTs suggests it to be as a promising electrocatalyst for future direct ethanol fuel cells.

Preparation and Characterization of Pd Modified TiO2 Nanofiber Catalyst for Carbon–Carbon Coupling Heck Reaction

Directory of Open Access Journals (Sweden)

Leah O. Nyangasi

2017-01-01

Full Text Available TiO2 fibers were prepared through electrospinning of poly methyl methacrylate (PMMA and titanium isopropoxide (TIP solution followed by calcination of fibers in air at 500°C. Cetyltrimethylammonium bromide (CTAB protected palladium nanoparticles (Pd NPs prepared through reduction method were successfully adsorbed on the TiO2 nanofibers (NF. Combined studies of X-ray diffraction (XRD, scanning electron microscope (SEM, and transmission electron microscope (TEM indicated that the synthesized Pd/TiO2 had anatase. BET indicated that the synthesized TiO2 and Pd/TiO2 had a surface area of 53.4 and 43.4 m2/g, respectively. The activity and selectivity of 1 mol% Pd/TiO2 in the Heck reaction have been investigated towards the Mizoroki-Heck carbon–carbon cross-coupling of bromobenzene (ArBr and styrene. Temperature, time, solvent, and base were optimized and catalyst was recycled thrice. 1H NMR and 13C NMR indicated that stilbene, a known compound from literature, was obtained in various Heck reactions at temperatures between 100°C and 140°C but the recyclability was limited due to some palladium leaching and catalyst poisoning which probably arose from some residual carbon from the polymer. The catalyst was found to be highly active under air atmosphere with reaction temperatures up to 140°C. Optimized reaction condition resulted in 89.7% conversions with a TON of 1993.4 and TOF value of 332.2 hr−1.

Performance of carbon nanofiber supported Pd-Ni catalysts for electro-oxidation of ethanol in alkaline medium

Energy Technology Data Exchange (ETDEWEB)

Maiyalagan, T.; Scott, Keith [School of Chemical Engineering and Advanced Materials, University of Newcastle upon Tyne, Newcastle upon Tyne NE1 7RU (United Kingdom)

2010-08-15

Carbon nanofibers (CNF) supported Pd-Ni nanoparticles have been prepared by chemical reduction with NaBH{sub 4} as a reducing agent. The Pd-Ni/CNF catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical voltammetry analysis. TEM showed that the Pd-Ni particles were quite uniformly distributed on the surface of the carbon nanofiber with an average particle size of 4.0 nm. The electro-catalytic activity of the Pd-Ni/CNF for oxidation of ethanol was examined by cyclic voltammetry (CV). The onset potential was 200 mV lower and the peak current density four times higher for ethanol oxidation for Pd-Ni/CNF compared to that for Pd/C. The effect of an increase in temperature from 20 to 60 C had a great effect on increasing the ethanol oxidation activity. (author)

Pd-RuSe/C as ORR specific catalyst in alkaline solution containing methanol

Energy Technology Data Exchange (ETDEWEB)

Maheswari, S.; Sridhar, P.; Pitchumani, S. [CSIR-Central Electrochemical Research Institute-Madras Unit, CSIR Complex, Chennai 600 113 (India)

2012-12-15

Carbon supported RuSe (RuSe/C) catalyst in varying atomic ratios of Ru to Se, namely, 1:1, 2:1, and 3:1 were prepared and their performances were compared with carbon supported Ru (Ru/C). Based on the performance, Palladium was incorporated into as prepared RuSe(2:1)/C and heat treated HTRuSe(2:1)/C. Ru/C, RuSe/C, and Pd-RuSe/C were characterized by X-ray diffraction (XRD) and transmission electron microscopy techniques. The XRD analyses of Ru/C, RuSe/C and Pd-HTRuSe/C show the formation of the hcp structure of Ru particles and the mean particle size was obtained from Ru(101) peak. The electrochemical characterizations of Ru/C, RuSe/C, Pd-HTRuSe(2:1)/C and Pd-RuSe(2:1)/C were conducted by cyclic voltammetry. Linear Sweep Voltammetric studies showed that incorporation of Pd in HTRu-Se(2:1)/C resulted in better catalytic activity toward oxygen reduction with resistance to methanol oxidation. The quantity of hydrogen peroxide produced was obtained from rotating ring disk electrode studies. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Perovskite Catalysts—A Special Issue on Versatile Oxide Catalysts

Directory of Open Access Journals (Sweden)

Yu-Chuan Lin

2014-08-01

Full Text Available Perovskite-type catalysts have been prominent oxide catalysts for many years due to attributes such as flexibility in choosing cations, significant thermal stability, and the unique nature of lattice oxygen. Nearly 90% metallic elements of the Periodic Table can be stabilized in perovskite’s crystalline framework [1]. Moreover, by following the Goldschmidt rule [2], the A- and/or B-site elements can be partially substituted, making perovskites extremely flexible in catalyst design. One successful example is the commercialization of noble metal-incorporated perovskites (e.g., LaFe0.57Co0.38Pd0.05O3 for automotive emission control used by Daihatsu Motor Co. Ltd. [3]. Thus, growing interest in, and application of perovskites in the fields of material sciences, heterogeneous catalysis, and energy storage have prompted this Special Issue on perovskite catalysts. [...

Enzyme-Free Electrochemical Glucose Sensors Prepared by Dealloying Pd-Ni-P Metallic Glasses

Directory of Open Access Journals (Sweden)

Yuqiao Zeng

2014-01-01

Full Text Available We report the formation of enzyme-free electrochemical glucose sensors by electrochemical dealloying palladium-containing Pd-Ni-P metallic glasses. When metallic glasses with different Pd contents are used as the dealloying precursor alloys, palladium-based nanoporous metals with different ligament and pore sizes can be obtained. The chemical compositions of the nanoporous metals also vary according to the different precursor compositions. All the as-obtained nanoporous metals exhibit electrochemical catalytic activity towards the oxidation of d-glucose, indicating that the nanoporous metals prepared by dealloying the Pd-Ni-P metallic glasses are promising materials for enzyme-free electrochemical glucose sensor.

Studies of Heterogenous Palladium and Related Catalysts for Aerobic Oxidation of Primary Alcohols

Science.gov (United States)

Ahmed, Maaz S.

alcohol solvent and the surface of the catalyst: (listed in order of strength) lone pair-surface (heterocyclic primary alcohols) > pi-surface (aryl primary alcohols) > van der Waals-surface (alkyl primary alcohols). These interactions were previously underappreciated in condensed phase heterogeneously catalyzed aerobic oxidations. Bi and Te serve as synergistic promoters that enhance both the rate and yield of the reactions relative to reactions employing Pd alone or Pd in combination with Bi or with Te as the sole promoter. We report X-ray absorption spectroscopic studies of the heterogenous catalyst. These methods show that the promoters undergo oxidation in preference to Pd, maintaining the Pd surface in the active metallic state and preventing inhibition by surface Pd-oxide formation. The data also suggest formation of a Pd-Te alloy phase that modifies the electronic properties of the Pd catalyst. Collectively, these results provide valuable insights into the synergistic benefits of multiple promoters in heterogeneous catalytic oxidation reactions.

Ultrasmall PdmMn1-mOx binary alloyed nanoparticles on graphene catalysts for ethanol oxidation in alkaline media

Science.gov (United States)

Ahmed, Mohammad Shamsuddin; Park, Dongchul; Jeon, Seungwon

2016-03-01

A rare combination of graphene (G)-supported palladium and manganese in mixed-oxides binary alloyed catalysts (BACs) have been synthesized with the addition of Pd and Mn metals in various ratios (G/PdmMn1-mOx) through a facile wet-chemical method and employed as an efficient anode catalyst for ethanol oxidation reaction (EOR) in alkaline fuel cells. The as prepared G/PdmMn1-mOx BACs have been characterized by several instrumental techniques; the transmission electron microscopy images show that the ultrafine alloyed nanoparticles (NPs) are excellently monodispersed onto the G. The Pd and Mn in G/PdmMn1-mOx BACs have been alloyed homogeneously, and Mn presents in mixed-oxidized form that resulted by X-ray diffraction. The electrochemical performances, kinetics and stability of these catalysts toward EOR have been evaluated using cyclic voltammetry in 1 M KOH electrolyte. Among all G/PdmMn1-mOx BACs, the G/Pd0.5Mn0.5Ox catalyst has shown much superior mass activity and incredible stability than that of pure Pd catalysts (G/Pd1Mn0Ox, Pd/C and Pt/C). The well dispersion, ultrafine size of NPs and higher degree of alloying are the key factor for enhanced and stable EOR electrocatalysis on G/Pd0.5Mn0.5Ox.

Carbon supported Pd-Co-Mo alloy as an alternative to Pt for oxygen reduction in direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Rao, Ch. Venkateswara [National Centre for Catalysis Research, Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, TN (India); Viswanathan, B., E-mail: bvnathan@acer.iitm.ernet.i [National Centre for Catalysis Research, Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, TN (India)

2010-03-01

Carbon black (CDX975) supported Pd and Pd-Co-Mo alloy nanoparticles are prepared by the reduction of metal precursors with hydrazine in reverse microemulsion of water/Triton-X-100/propanol-2/cyclohexane. The as-synthesized Pd-Co-Mo/CDX975 is heat treated at 973, 1073 and 1173 K to promote alloy formation. The prepared materials are characterized by powder XRD and EDX. Face-centred cubic structure of Pd is evident from XRD. The chemical composition of the respective elements in the catalysts is evaluated from the EDX analysis and observed that it is in good agreement with initial metal precursor concentrations. Oxygen reduction measurements performed by linear sweep voltammetry indicate the good catalytic activity of Pd-Co-Mo alloys compared to Pd. This is due to the suppression of (hydr)oxy species on Pd surface by the presence of alloying elements, Co and Mo. Among the investigated catalysts, heat-treated Pd-Co-Mo/CDX975 at 973 K exhibited good ORR activity compared to the catalysts heat treated at 1073 and 1173 K. This is due to the small crystallite size and high surface area. Rotating disk electrode (RDE) measurements indicated the comparable ORR activity of heat-treated Pd-Co-Mo/CDX975 at 973 K with that of commercial Pt/C. Kinetic analysis reveals that the ORR on Pd-Co-Mo/CDX975 follows the four-electron pathway leading to water. Moreover, Pd-Co-Mo/CDX975 exhibited substantially higher ethanol tolerance during the ORR than Pt/C. Good dispersion of metallic nanoparticles on the carbon support is observed from HRTEM images. Single-cell direct ethanol fuel cell tests indicated the comparable performance of Pd-Co-Mo/CDX975 with that of commercial Pt/C. Stability under DEFC operating conditions for 50 h indicated the good stability of Pd-Co-Mo/CDX975 compared with that of Pt/C.

Allotropic Carbon Nanoforms as Advanced Metal-Free Catalysts or as Supports

Directory of Open Access Journals (Sweden)

Hermenegildo Garcia

2014-01-01

Full Text Available This perspective paper summarizes the use of three nanostructured carbon allotropes as metal-free catalysts (“carbocatalysts” or as supports of metal nanoparticles. After an introductory section commenting the interest of developing metal-free catalysts and main features of carbon nanoforms, the main body of this paper is focused on exemplifying the opportunities that carbon nanotubes, graphene, and diamond nanoparticles offer to develop advanced catalysts having active sites based on carbon in the absence of transition metals or as large area supports with special morphology and unique properties. The final section provides my personal view on future developments in this field.

Selective hydrogenation of halogenated arenes using porous manganese oxide (OMS-2) and platinum supported OMS-2 catalysts.

Science.gov (United States)

McManus, Iain J; Daly, Helen; Manyar, Haresh G; Taylor, S F Rebecca; Thompson, Jillian M; Hardacre, Christopher

2016-07-04

Porous manganese oxide (OMS-2) and platinum supported on OMS-2 catalysts have been shown to facilitate the hydrogenation of the nitro group in chloronitrobenzene to give chloroaniline with no dehalogenation. Complete conversion was obtained within 2 h at 25 °C and, although the rate of reaction increased with increasing temperature up to 100 °C, the selectivity to chloroaniline remained at 99.0%. Use of Pd/OMS-2 or Pt/Al2O3 resulted in significant dechlorination even at 25 °C and 2 bar hydrogen pressure giving a selectivity to chloroaniline of 34.5% and 77.8%, respectively, at complete conversion. This demonstrates the potential of using platinum group metal free catalysts for the selective hydrogenation of halogenated aromatics. Two pathways were observed for the analogous nitrobenzene hydrogenation depending on the catalyst used. The hydrogenation of nitrobenzene was found to follow a direct pathway to aniline and nitrosobenzene over Pd/OMS-2 in contrast to the OMS and Pt/OMS-2 catalysts which resulted in formation of nitrosobenzene, azoxybenzene and azobenzene/hydrazobenzene intermediates before complete conversion to aniline. These results indicate that for Pt/OMS-2 the hydrogenation proceeds predominantly over the support with the metal acting to dissociate hydrogen. In the case of Pd/OMS-2 both the hydrogenation and hydrogen adsorption occur on the metal sites.

Shape-controlled synthesis of Pd polyhedron supported on polyethyleneimine-reduced graphene oxide for enhancing the efficiency of hydrogen evolution reaction

Science.gov (United States)

Li, Jing; Zhou, Panpan; Li, Feng; Ma, Jianxin; Liu, Yang; Zhang, Xueyao; Huo, Hongfei; Jin, Jun; Ma, Jiantai

2016-01-01

The catalytic activity of noble-metal nanoparticles (NPs) often has closely connection with their sizes and geometric shape. In the work, polyhedral NPs of palladium (Pd) with controlled sizes, shapes, and different proportions of {100} to {111} facets on the surface were prepared by a seed-mediated approach. Electrochemical experiment demonstrates that the catalytic performance of the Pd nanocubes (NCs) enclosed by {100} facets is more active than Pd octahedrons enclosed by {111} facets for the hydrogen evolution reaction (HER), which is consistent with density functional theory (DFT) calculation results. Meanwhile, with the assistance of a polyethyleneimine-reduced graphene oxide (PEI-rGO) support, the examined Pd cube/PEI-rGO50:1 (10 wt. %) electrocatalyst presents outstanding HER activity comparable with that of commercial Pt/C catalyst. This correlation between the HER catalytic activity and surface structure will contribute to the reasonable design of Pd catalysts for HER with high efficiency and low metal loading.

Flower-Like ZnO-Assisted One-Pot Encapsulation of Noble Metal Nanoparticles Supported Catalysts with ZIFs

Science.gov (United States)

Lin, Lu; Liu, Haiou; Zhang, Xiongfu

2018-03-01

Rational design of efficient approaches to fabricate MOFs-coated core-shell composites is promising but challenging. We report here the encapsulation of Pd nanoparticles (Pd NPs) supported flower-like ZnO (F-ZnO) microspheres with ZIF-8 shell through a facile strategy, in which the formation and immobilization of Pd NPs on F-ZnO supports and the subsequent growth of ZIF-8 shells over them are effectively integrated into one-pot synthetic route. Importantly, the utilization of ZnO both as support of Pd NPs and Zn2+ source of ZIF-8 is favorable for the implement of one-pot synthesis, due to its functions in anchoring Pd NPs and inducing ZIF-8 formation. Further insights into the morphological influence of zinc oxide particles on the resulting materials indicate that the flower-like microspheres with 2D nanosheets as subunits also benefit the coating of Pd NPs supported cores with ZIF-8, resulting in a well-defined core-shell catalyst. The achieved catalyst deliveries remarkable performance in terms of selectivity, anti-poisoning and recyclability in the liquid hydrogenations of alkenes.

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

A heterogeneous Pd-Bi/C catalyst in the synthesis of L-lyxose and L-ribose from naturally occurring D-sugars.

Science.gov (United States)

Fan, Ao; Jaenicke, Stephan; Chuah, Gaik-Khuan

2011-10-26

A critical step in the synthesis of the rare sugars, L-lyxose and L-ribose, from the corresponding D-sugars is the oxidation to the lactone. Instead of conventional oxidizing agents like bromine or pyridinium dichromate, it was found that a heterogeneous catalyst, Pd-Bi/C, could be used for the direct oxidation with molecular oxygen. The composition of the catalyst was optimized and the best results were obtained with 5 : 1 atomic ratio of Pd : Bi. The overall yields of the five-step procedure to L-ribose and L-lyxose were 47% and 50%, respectively. The synthetic procedure is advantageous from the viewpoint of overall yield, reduced number of steps, and mild reaction conditions. Furthermore, the heterogeneous oxidation catalyst can be easily separated from the reaction mixture and reused with no loss of activity.

Polymer Catalysts Imprinted with Metal Ions as Biomimics of Metalloenzymes

Directory of Open Access Journals (Sweden)

Joanna Czulak

2013-01-01

Full Text Available This work presents the preparation and properties of molecularly imprinted polymers (MIPs with catalytic centers that mimic the active sites of metalloenzymes. The MIP synthesis was based on suspension polymerization of functional monomers (4-vinylpyridine and acrylonitrile with trimethylolpropane trimethacrylate as a crosslinker in the presence of transition metal ions and 4-methoxybenzyl alcohol as a template. Four metal ions have been chosen for imprinting from among the microelements that are the most essential in the native enzymes: Cu2+, Co2+, Mn2+, and Zn2+. To prepare catalysts, the required loading of metal ions was obtained during sorption process. The catalysts imprinted with Cu2+, Co2+, and Zn2+ were successfully used for hydroquinone oxidation in the presence of hydrogen peroxide. The Mn2+-imprinted catalyst showed no activity due to the insufficient metal loading. Cu2+ MIP showed the highest efficiency. In case of Cu- and Co-MIP catalysts, their activity was additionally increased by the use of surface imprinting technique.

Pd supported on carbon containing nickel, nitrogen and sulfur for ethanol electrooxidation.

Science.gov (United States)

Yang, Zi-Rui; Wang, Shang-Qing; Wang, Jing; Zhou, Ai-Ju; Xu, Chang-Wei

2017-11-13

Carbon material containing nickel, nitrogen and sulfur (Ni-NSC) has been synthesized using metal-organic frameworks (MOFs) as precursor by annealing treatment with a size from 200 to 300 nm. Pd nanoparticles supported on the Ni-NSC (Pd/Ni-NSC) are used as electrocatalysts for ethanol oxidation in alkaline media. Due to the synergistic effect between Pd and Ni, S, N, free OH radicals can form on the surface of Ni, N and S atoms at lower potentials, which react with CH 3 CO intermediate species on the Pd surface to produce CH 3 COO - and release the active sites. On the other hand, the stronger binding force between Pd and co-doped N and S is responsible for enhancing dispersion and preventing agglomeration of the Pd nanoparticles. The Pd(20 wt%)/Ni-NSC shows better electrochemical performance of ethanol oxidation than the traditional commercial Pd(20 wt%)/C catalyst. Onset potential on the Pd(20 wt%)/Ni-NSC electrode is 36 mV more negative compared with that on the commercial Pd(20 wt%)/C electrode. The Pd(20 wt%)/Ni-NSC in this paper demonstrates to have excellent electrocatalytic properties and is considered as a promising catalyst in alkaline direct ethanol fuel cells.

Synthesis and characterization of bulky mesoporous silica Pd-MCM-41

International Nuclear Information System (INIS)

Nagata, Hidezumi; Nakahira, Atsushi; Hirao, Norie; Baba, Yuji; Onoki, Takamasa; Yamasaki, Yuki

2008-01-01

Bulky palladium catalyst supported on mesoporous silica MCM-41 (Pd-MCM-41) was successfully synthesized by hydrothermal hot-pressing method. In this study, the structure of the palladium species in Pd-MCM-41 bulk before and after heat-treatment process was revealed by X-ray diffraction (XRD), X-ray absorption near edge structure (XANES) and transmission electron microscopy (TEM). Also, the microstructure and mesoporous property of Pd-MCM-41 bulk was discussed. As a result, it was revealed that these dense Pd-MCM-41 bulks possessed a high surface area of over 1000 m 2 /g and the structure of palladium of Pd-MCM-41 bulk is almost equal to palladium (0) metal. (author)

Low temperature incineration of mixed wastes using bulk metal oxide catalysts

International Nuclear Information System (INIS)

Gordon, M.J.; Gaur, S.; Kelkar, S.; Baldwin, R.M.

1996-01-01

Volume reduction of low-level mixed wastes from former nuclear weapons facilities is a significant environmental problem. Processing of these materials presents unique scientific and engineering problems due to the presence of minute quantities of radionuclides which must be contained and concentrated for later safe disposal. Low-temperature catalytic incineration is one option that has been utilized at the Rocky Flats facility for this purpose. This paper presents results of research regarding evaluation of bulk metal oxides as catalysts for low-temperature incineration of carbonaceous residues which are typical by-products of fluidized bed combustion of mixed wastes under oxygen-lean conditions. A series of 14 metal oxides were screened in a thermogravimetric analyzer, using on-line mass spectrometry for speciation of reaction product gases. Catalyst evaluation criteria focused on the thermal-redox activity of the metals using both carbon black and PVC char as surrogate waste materials. Results indicated that metal oxides which were P-type semiconductor materials were suitable as catalysts for this application. Oxides of cobalt, molybdenum, vanadium, and manganese were found to be particularly stable and active catalysts under conditions specific to this process (T<650C, low oxygen partial pressures). Bench-scale evaluation of these metal oxides with respect to stability to chlorine (HCl) attack was carried out at 550C using a TG/MS system. Cobalt oxide was found to be resistant to metal loss in a HCl/He gaseous environment while metal loss from Mo, Mn, and V-based catalysts was moderate to severe. XRD and SEM/EDX analysis of spent Co catalysts indicated the formation of non-stoichiometric cobalt chlorides. Regeneration of chlorinated cobalt was found to successfully restore the low-temperature combustion activity to that of the fresh metal oxide

Electrochemical CO2 and CO reduction on metal-functionalized porphyrin-like graphene

DEFF Research Database (Denmark)

Tripkovic, Vladimir; Vanin, Marco; Karamad, Mohammedreza

2013-01-01

Porphyrin-like metal-functionalized graphene structures have been investigated as possible catalysts for CO2 and CO reduction to methane or methanol. The late transition metals (Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os) and some p (B, Al, Ga) and s (Mg) metals comprised the center of the po......Porphyrin-like metal-functionalized graphene structures have been investigated as possible catalysts for CO2 and CO reduction to methane or methanol. The late transition metals (Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os) and some p (B, Al, Ga) and s (Mg) metals comprised the center...... instead of CO2. Volcano plots were constructed on the basis of scaling relations of reaction intermediates, and from these plots the reaction steps with the highest overpotentials were deduced. The Rh-porphyrin-like functionalized graphene was identified as the most active catalyst for producing methanol...... from CO, featuring an overpotential of 0.22 V. Additionally, we have also examined the hydrogen evolution and oxidation reaction, and in their case, too, Rh-porphyrin turned out to be the best catalyst with an overpotential of 0.15 V. © 2013 American Chemical Society....

Solid, double-metal cyanide catalysts for synthesis of ...

Indian Academy of Sciences (India)

Sci. Vol. 126, No. 2, March 2014, pp. 499–509. c Indian Academy of Sciences. Solid, double-metal cyanide catalysts for ... drimers, HPs have a highly branched structural design ... geneous catalysts and corrosion of the reactor lin- ... Carbon dioxide is a greenhouse gas. .... polymer product was reprecipitated from the liquid.

Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

Energy Technology Data Exchange (ETDEWEB)

Arslan, Ilke [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Gates, Bruce C. [Univ. of California, Davis, CA (United States); Katz, Alexander [Univ. of California, Berkeley, CA (United States)

2015-09-30

To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-the art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify

Study and development of membrane electrode assemblies for Proton Exchange Membrane Fuel Cell (PEMFC) with palladium based catalysts

International Nuclear Information System (INIS)

Bonifacio, Rafael Nogueira

2013-01-01

PEMFC systems are capable of generating electricity with high efficiency and low or no emissions, but durability and cost issues prevent its large commercialization. In this work MEA with palladium based catalysts were developed, Pd/C, Pt/C and alloys PdPt/C catalysts with different ratios between metals and carbon were synthesized and characterized. A study of the ratio between catalyst and Nafion Ionomer for formation of high performance triple-phase reaction was carried out, a mathematical model to implement this adjustment to catalysts with different relations between metal and support taking into account the volumetric aspects of the catalyst layer was developed and then a study of the catalyst layer thickness was performed. X-ray diffraction, Transmission and Scanning Electron Microscopy, X-ray Energy Dispersive, Gas Pycnometry, Mercury Intrusion Porosimetry, Gas adsorption according to the BET and BJH equations, and Thermo Gravimetric Analysis techniques were used for characterization and particle size, specific surface areas and lattice parameters determinations were also carried out. All catalysts were used on MEAs preparation and evaluated in 5 cm 2 single cell from 25 to 100 °C at 1 atm and the best composition was also evaluated at 3 atm. In the study of metals for reactions, to reduce the platinum applied to the electrodes without performance losses, Pd/C and PdPt/C 1:1 were selected for anodes and cathodes, respectively. The developed MEA structure used 0,25 mgPt.cm -2 , showing power densities up to 550 mW.cm -2 and power of 2.2 kW net per gram of platinum. The estimated costs showed that there was a reduction of up to 64.5 %, compared to the MEA structures previously known. Depending on the temperature and operating pressure, values from US$ 1,475.30 to prepare MEAs for each installed kilowatt were obtained. Taking into account recent studies, it was concluded that the cost of the developed MEA is compatible with PEMFC stationary application

First-row transition metal hydrogenation and hydrosilylation catalysts

Science.gov (United States)

Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja; Levin, Hagit Ben-Daat; Porter, Tyler M.; Ghosh, Chandrani

2017-07-18

Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

Nanostructure analysis of friction welded Pd-Ni-P/Pd-Cu-Ni-P metallic glass interface

International Nuclear Information System (INIS)

Ohkubo, T.; Shoji, S.; Kawamura, Y.; Hono, K.

2005-01-01

Friction welded Pd 40 Ni 40 P 20 /Pd 40 Cu 30 Ni 10 P 20 metallic glass interface has been characterized by energy filtering transmission electron microscopy. The interface is fully amorphous with a gradual compositional change of Cu and Ni in the range of 30 nm. By annealing above T g , the interdiffusion of Cu and Ni progressed in the supercooled liquid region, and the crystallization occurred from the Pd 40 Ni 40 P 20 glass

Facile synthesis of PdAgTe nanowires with superior electrocatalytic activity

Science.gov (United States)

Hong, Wei; Wang, Jin; Wang, Erkang

2014-12-01

In this work, ultrathin Te nanowires (NWs) with high-aspect-ratio are prepared by a simple hydrothermal method. By using Te NWs as the sacrificial template, we demonstrate a facile and efficient method for the synthesis of PdAgTe NWs with high-quality through the partly galvanic replacement between Te NWs and the corresponding noble metal salts precursors in an aqueous solution. The compositions of PdAgTe NWs can be tuned by simply altering the concentration of the precursors. After cyclic voltammetry treatment, multi-component PdAgTe NW with a highly active and stable surface can be obtained. The structure and composition of the as-prepared nanomaterials are analyzed by transmission electron microscope, X-ray diffraction, energy dispersive X-ray spectroscopy, inductively coupled plasma-mass spectroscopy and X-ray photoelectron spectroscopy. Electrochemical catalytic measurement results prove that the as synthesized PdAgTe NWs present superior catalytic activity toward ethanol electrooxidation in alkaline solution than the commercial Pd/C catalyst, which making them can be used as effective catalysts for the direct ethanol fuel cells.

New catalysts for coal processing: Metal carbides and nitrides

Energy Technology Data Exchange (ETDEWEB)

S. Ted Oyama; David F. Cox

1999-12-03

The subject of this research project was to investigate the catalytic properties of a new class of materials, transition metal carbides and nitrides, for treatment of coal liquid and petroleum feedstocks. The main objectives were: (1) preparation of catalysts in unsupported and supported form; (2) characterization of the materials; (3) evaluation of their catalytic properties in HDS and HDN; (4) measurement of the surface properties; and (5) observation of adsorbed species. All of the objectives were substantially carried out and the results will be described in detail below. The catalysts were transition metal carbides and nitrides spanning Groups 4--6 in the Periodic Table. They were chosen for study because initial work had shown they were promising materials for hydrotreating. The basic strategy was first to prepare the materials in unsupported form to identify the most promising catalyst, and then to synthesize a supported form of the material. Already work had been carried out on the synthesis of the Group VI compounds Mo{sub 2}C, Mo{sub 2}N, and WC, and new methods were developed for the Group V compounds VC and NbC. All the catalysts were then evaluated in a hydrotreating test at realistic conditions. It was found that the most active catalyst was Mo{sub 2}C, and further investigations of the material were carried out in supported form. A new technique was employed for the study of the bulk and surface properties of the catalysts, near edge x-ray absorption spectroscopy (NEXAFS), that fingerprinted the electronic structure of the materials. Finally, two new research direction were explored. Bimetallic alloys formed between two transition metals were prepared, resulting in catalysts having even higher activity than Mo{sub 2}C. The performance of the catalysts in hydrodechloration was also investigated.

Interaction between Nafion ionomer and noble metal catalyst for PEMFCs

DEFF Research Database (Denmark)

Andersen, Shuang Ma

The implement of polymer impregnation in electrode structure (catalyst layer) decreasing the noble metal catalyst loading by a factor of ten , , is one of the essential mile stones in the evolution of Proton Exchange Membrane Fuel Cells’ development among the application of catalyst support and e...

Hierarchical Pd-Sn alloy nanosheet dendrites: an economical and highly active catalyst for ethanol electrooxidation.

Science.gov (United States)

Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren

2013-01-01

Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures.

Measurement of benzenethiol adsorption to nanostructured Pt, Pd, and PtPd films using Raman spectroelectrochemistry.

Science.gov (United States)

Pomfret, Michael B; Pietron, Jeremy J; Owrutsky, Jeffrey C

2010-05-04

Raman spectroscopy and electrochemical methods were used to study the behavior of the model adsorbate benzenethiol (BT) on nanostructured Pt, Pd, and PtPd electrodes as a function of applied potential. Benzenethiol adsorbs out of ethanolic solutions as the corresponding thiolate, and voltammetric stripping data reveal that BT is oxidatively removed from all of the nanostructured metals upon repeated oxidative and reductive cycling. Oxidative stripping potentials for BT increase in the order Pt oxidizing potentials via cleavage of the Pt-S bond. In contrast, on nanoscale Pd and PtPd, BT is irreversibly lost due to cleavage of BT C-S bonds at oxidizing potentials, which leaves adsorbed sulfur oxides on Pd and PtPd films and effects the desulfurization of BT. While Pd and PtPd films are less sulfur-resistant than Pt films, palladium oxides, which form at higher potentials than Pt oxides, oxidatively desulfurize BT. In situ spectroelectrochemical Raman spectroscopy provides real-time, chemically specific information that complements the cyclic voltammetric data. The combination of these techniques affords a powerful and convenient method for guiding the development of sulfur-tolerant PEMFC catalysts.

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.

COATING OF POLYMERIC SUBSTRATE CATALYSTS ON METALLIC SURFACES

Directory of Open Access Journals (Sweden)

H. HOSSEINI

2010-12-01

Full Text Available This article presents results of a study on coating of a polymeric substrate ca-talyst on metallic surface. Stability of coating on metallic surfaces is a proper specification. Sol-gel technology was used to synthesize adhesion promoters of polysilane compounds that act as a mediator. The intermediate layer was coated by synthesized sulfonated polystyrene-divinylbenzene as a catalyst for production of MTBE in catalytic distillation process. Swelling of catalyst and its separation from the metal surface was improved by i increasing the quantity of divinylbenzene in the resin’s production process and ii applying adhesion pro¬moters based on the sol-gel process. The rate of ethyl silicate hydrolysis was intensified by increasing the concentration of utilized acid while the conden¬sation polymerization was enhanced in the presence of OH–. Sol was formed at pH 2, while the pH should be 8 for the formation of gel. By setting the ratio of the initial concentrations of water to ethyl silicate to 8, the gel formation time was minimized.

Application of Metal Catalysts for High Selectivity of Glycerol Conversion to Alcohols

Science.gov (United States)

2010-11-01

The objective of this project is to determine the applicability of metal-based catalysts and optimize the process conditions for thermochemically producing primary alcohols. Metal catalysts were evaluated for their selectivities for producing alcohol...

Intermetallic nickel silicide nanocatalyst-A non-noble metal-based general hydrogenation catalyst.

Science.gov (United States)

Ryabchuk, Pavel; Agostini, Giovanni; Pohl, Marga-Martina; Lund, Henrik; Agapova, Anastasiya; Junge, Henrik; Junge, Kathrin; Beller, Matthias

2018-06-01

Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO 2 as the silicon atom source. The process involves thermal reduction of Si-O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon-carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H 2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal-based catalysts.

Hydrodechlorination of Tetrachloromethane over Palladium Catalysts Supported on Mixed MgF2-MgO Carriers

Directory of Open Access Journals (Sweden)

Magdalena Bonarowska

2016-11-01

Full Text Available Pd/MgO, Pd/MgF2 and Pd/MgO-MgF2 catalysts were investigated in the reaction of CCl4 hydrodechlorination. All the catalysts deactivated in time on stream, but the degree of deactivation varied from catalyst to catalyst. The MgF2-supported palladium with relatively large metal particles appeared the best catalyst, characterized by good activity and selectivity to C2-C5 hydrocarbons. Investigation of post-reaction catalyst samples allowed to find several details associated with the working state of hydrodechlorination catalysts. The role of support acidity was quite complex. On the one hand, a definite, although not very high Lewis acidity of MgF2 is beneficial for shaping high activity of palladium catalysts. The MgO-MgF2 support characterized by stronger Lewis acidity than MgF2 contributes to very good catalytic activity for a relatively long reaction period (~5 h but subsequent neutralization of stronger acid centers (by coking eliminates them from the catalyst. On the other hand, the role of acidity evolution, which takes place when basic supports (like MgO are chlorided during HdCl reactions, is difficult to assess because different events associated with distribution of chlorided support species, leading to partial or even full blocking of the surface of palladium, which plays the role of active component in HdCl reactions.

Palladium catalyst system comprising zwitterion and/or acid-functionalized ionic liquid

DEFF Research Database (Denmark)

2011-01-01

The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3......COCHCOCH3), Pd (CF3COO)2, Pd(PPh3)4 or Pd2(dibenzylideneacetone)3. Such catalyst systems can be used for e.g. alkoxycarbonylation reactions, carboxylation reactions, and/or in a co-polymerization reaction, e.g. in the production of methyl propionate and/or propanoic acid, optionally in processes forming...... methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications....

Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Dumesic, James A. [Univ. of Wisconsin, Madison, WI (United States)

2016-01-04

The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron

Nanostructured carbon-supported Pd electrocatalysts for ethanol oxidation: synthesis and characterization

International Nuclear Information System (INIS)

Gacutan, E M; Tongol, B J; Climaco, M I; Telan, G J; Malijan, F; Hsu, H Y; Garcia, J; Fulo, H

2012-01-01

The need to lower the construction cost of fuel cells calls for the development of non-Pt based electrocatalysts. Among others, Pd has emerged as a promising alternative to Pt for fuel cell catalysis. This research aims to investigate the synthesis and characterization of nanostructured Pd-based catalysts dispersed on carbon support as anode materials in direct ethanol fuel cells. For the preparation of the first Pd-based electrocatalyst, palladium nanoparticles (NPs) were synthesized via oleylamine (OAm)-mediated synthesis and precursor method with a mean particle size of 3.63 ± 0.59 nm as revealed by transmission electron microscopy (TEM). Carbon black was used as a supporting matrix for the OAm-capped Pd NPs. Thermal annealing and acetic acid washing were used to remove the OAm capping agent. To evaluate the electrocatalytic activity of the prepared electrocatalyst towards ethanol oxidation, cyclic voltammetry (CV) studies were performed using 1.0 M ethanol in basic medium. The CV data revealed the highest peak current density of 11.05 mA cm −2 for the acetic acid-washed Pd/C electrocatalyst. Meanwhile, the fabrication of the second Pd-based electrocatalyst was done by functionalization of the carbon black support using 3:1 (v/v) H 2 SO 4 :HNO 3 . The metal oxide, NiO, was deposited using precipitation method while polyol method was used for the deposition of Pd NPs. X-ray diffraction (XRD) analysis revealed that the estimated particle size of the synthesized catalysts was at around 9.0–15.0 nm. CV results demonstrated a 36.7% increase in the catalytic activity of Pd–NiO/C (functionalized) catalyst towards ethanol oxidation compared to the non-functionalized catalyst. (paper)

Development of Coke-tolerant Transition Metal Catalysts for Dry Reforming of Methane

KAUST Repository

Al-Sabban, Bedour E.

2016-11-07

Dry reforming of methane (DRM) is an attractive and promising process for the conversion of methane and carbon dioxide which are the most abundant carbon sources into valuable syngas. The produced syngas, which is a mixture of hydrogen and carbon monoxide, can be used as intermediates in the manufacture of numerous chemicals. To achieve high conversion, DRM reaction is operated at high temperatures (700-900 °C) that can cause major drawbacks of catalyst deactivation by carbon deposition, metal sintering or metal oxidation. Therefore, the primary goal is to develop a metal based catalyst for DRM that can completely suppress carbon formation by designing the catalyst composition. The strategy of this work was to synthesize Ni-based catalysts all of which prepared by homogeneous deposition precipitation method (HDP) to produce nanoparticles with narrow size distribution. In addition, control the reactivity of the metal by finely tuning the bimetallic composition and the reaction conditions in terms of reaction temperature and pressure. The highly endothermic dry reforming of methane proceeds via CH4 decomposition to leave surface carbon species, followed by removal of C with CO2-derived species to give CO. Tuning the reactivity of the active metal towards these reactions during DRM allows in principle the catalyst surface to remain active and clean without carbon deposition for a long-term. The initial attempt was to improve the resistance of Ni catalyst towards carbon deposition, therefore, a series of 5 wt.% bimetallic Ni9Pt1 were supported on various metal oxides (Al2O3, CeO2, and ZrO2). The addition of small amount of noble metal improved the stability of the catalyst compared to their monometallic Ni and Pt catalysts, but still high amount of carbon (> 0.1 wt.%) was formed after 24 h of the reaction. The obtained results showed that the catalytic performance, particle size and amount of deposited carbon depends on the nature of support. Among the tested

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

Energy Technology Data Exchange (ETDEWEB)

Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin (UC)

2016-08-30

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells.

Science.gov (United States)

Kim, Jiyoung; Jang, Jin-Sung; Peck, Dong-Hyun; Lee, Byungrok; Yoon, Seong-Ho; Jung, Doo-Hwan

2016-08-15

Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF) was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC). The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR) activities and the electrochemical double layer compared with common carbon black (CB). To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF-supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA) of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected.

Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells

Directory of Open Access Journals (Sweden)

Jiyoung Kim

2016-08-01

Full Text Available Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC. The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR activities and the electrochemical double layer compared with common carbon black (CB. To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF–supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected.

Hydrodeoxygenation of mono- and dimeric lignin model compounds on noble metal catalysts

NARCIS (Netherlands)

Guvenatam, Burcu; Kursun, Osman; Heeres, Hero; Pidko, Evgeny A.; Hensen, Emiel J. M.

2014-01-01

The influence of reaction conditions (temperature, acidity) on the catalytic performance of supported Pt, Pd and Ru catalysts for the aqueous phase hydrodeoxygenation (HDO) of lignin model compounds was systematically investigated. Phenol conversion proceeds via hydrogenation of the aromatic ring

Pd-Pt Catalysts on Mesoporous SiO2-Al2O3 with Superior Activity for HDS of 4,6-Dimethyldibenzothiophene: Effect of Metal Loading and Support Composition

Czech Academy of Sciences Publication Activity Database

Vít, Zdeněk; Gulková, Daniela; Kaluža, Luděk; Kupčík, Jaroslav

2015-01-01

Roč. 179, DEC 2015 (2015), s. 44-53 ISSN 0926-3373 R&D Projects: GA ČR GAP106/11/0902 Institutional support: RVO:67985858 ; RVO:61388980 Keywords : Pd-Pt catalyst * mesoporous silica-alumina * 4,6-DMDBT Subject RIV: CF - Physical ; Theoretical Chemistry ; CA - Inorganic Chemistry (UACH-T) Impact factor: 8.328, year: 2015

Colloidal Au and Au-alloy catalysts for direct borohydride fuel cells: Electrocatalysis and fuel cell performance

Science.gov (United States)

Atwan, Mohammed H.; Macdonald, Charles L. B.; Northwood, Derek O.; Gyenge, Elod L.

Supported colloidal Au and Au-alloys (Au-Pt and Au-Pd, 1:1 atomic ratio) on Vulcan XC-72 (with 20 wt% metal load) were prepared by the Bönneman method. The electrocatalytic activity of the colloidal metals with respect to borohydride electro-oxidation for fuel cell applications was investigated by voltammetry on static and rotating electrodes, chronoamperometry, chronopotentiometry and fuel cell experiments. The fundamental electrochemical techniques showed that alloying Au, a metal that leads to the maximum eight-electron oxidation of BH 4 -, with Pd or Pt, well-known catalysts of dehydrogenation reactions, improved the electrode kinetics of BH 4 - oxidation. Fuel cell experiments corroborated the kinetic studies. Using 5 mg cm -2 colloidal metal load on the anode, it was found that Au-Pt was the most active catalyst giving a cell voltage of 0.47 V at 100 mA cm -2 and 333 K, while under identical conditions the cell voltage using colloidal Au was 0.17 V.

Colloidal Au and Au-alloy catalysts for direct borohydride fuel cells: Electrocatalysis and fuel cell performance

Energy Technology Data Exchange (ETDEWEB)

Atwan, Mohammed H.; Northwood, Derek O. [Department of Mechanical, Auto and Materials Engineering, University of Windsor, Windsor (Canada N9B 3P4); Macdonald, Charles L.B. [Department of Chemistry and Biochemistry, University of Windsor, Windsor (Canada N9B 3P4); Gyenge, Elod L. [Department of Chemical and Biological Engineering, The University of British Columbia, Vancouver, BC (Canada V6T 1Z4)

2006-07-14

Supported colloidal Au and Au-alloys (Au-Pt and Au-Pd, 1:1 atomic ratio) on Vulcan XC-72 (with 20wt% metal load) were prepared by the Bonneman method. The electrocatalytic activity of the colloidal metals with respect to borohydride electro-oxidation for fuel cell applications was investigated by voltammetry on static and rotating electrodes, chronoamperometry, chronopotentiometry and fuel cell experiments. The fundamental electrochemical techniques showed that alloying Au, a metal that leads to the maximum eight-electron oxidation of BH{sub 4}{sup -}, with Pd or Pt, well-known catalysts of dehydrogenation reactions, improved the electrode kinetics of BH{sub 4}{sup -} oxidation. Fuel cell experiments corroborated the kinetic studies. Using 5mgcm{sup -2} colloidal metal load on the anode, it was found that Au-Pt was the most active catalyst giving a cell voltage of 0.47V at 100mAcm{sup -2} and 333K, while under identical conditions the cell voltage using colloidal Au was 0.17V. (author)

Selective Hydrogenation of Acrolein Over Pd Model Catalysts: Temperature and Particle-Size Effects.

Science.gov (United States)

O'Brien, Casey P; Dostert, Karl-Heinz; Schauermann, Swetlana; Freund, Hans-Joachim

2016-10-24

The selectivity in the hydrogenation of acrolein over Fe 3 O 4 -supported Pd nanoparticles has been investigated as a function of nanoparticle size in the 220-270 K temperature range. While Pd(111) shows nearly 100 % selectivity towards the desired hydrogenation of the C=O bond to produce propenol, Pd nanoparticles were found to be much less selective towards this product. In situ detection of surface species by using IR-reflection absorption spectroscopy shows that the selectivity towards propenol critically depends on the formation of an oxopropyl spectator species. While an overlayer of oxopropyl species is effectively formed on Pd(111) turning the surface highly selective for propenol formation, this process is strongly hindered on Pd nanoparticles by acrolein decomposition resulting in CO formation. We show that the extent of acrolein decomposition can be tuned by varying the particle size and the reaction temperature. As a result, significant production of propenol is observed over 12 nm Pd nanoparticles at 250 K, while smaller (4 and 7 nm) nanoparticles did not produce propenol at any of the temperatures investigated. The possible origin of particle-size dependence of propenol formation is discussed. This work demonstrates that the selectivity in the hydrogenation of acrolein is controlled by the relative rates of acrolein partial hydrogenation to oxopropyl surface species and of acrolein decomposition, which has significant implications for rational catalyst design. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poly (pyrrole-co-aniline) hollow nanosphere supported Pd nanoflowers as high-performance catalyst for methanol electrooxidation in alkaline media

International Nuclear Information System (INIS)

Fard, Leyla Abolghasemi; Ojani, Reza; Raoof, Jahan Bakhsh; Zare, Ehsan Nazarzadeh; Lakouraj, Moslem Mansour

2017-01-01

In this work, first poly (pyrrole-co-aniline) (PPCA) hollow nanosphere (HN) as a catalyst support material is fabricated through in-situ emulsion polymerization. Then we reported a one-step and template-free approach to fabricate Pd NFs on a PPCA HN coated glassy carbon electrode by a facile electrochemical approach. Several techniques such as FTIR (Fourier transform infrared spectroscopy), SEM (scanning electron microscopy) and EDS (energy dispersive spectroscopy) were utilized for the characterization of the synthesized materials. The catalytic performance of Pd NFs/PPCA HN catalyst is evaluated by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy toward methanol oxidation as a model reaction in alkaline media. The comparison of specific activities for Pd NFs/PPCA HN (1.79 mA cm"−"2), Pd NFs/PPy (1.28 mA cm"−"2), Pd NFs/PANI (0.93 mA cm"−"2) and Pd NFs (0.78 mA cm"−"2) shows that the PPCA supported Pd NFs with high surface area exhibits the excellent electrocatalytic activity than other electrodes for the electro-oxidation reaction in alkaline media. This might be due to the easier charge transfer at conductive copolymer interfaces, higher electrochemically accessible surface areas and electronic conductivity. This strategy provides a promising platform for direct methanol fuel cells. - Highlights: • Pd nanoflowers supported on poly (pyrrole-co-aniline) hollow nanosphere is prepared by a facile electrochemical approach. • The as-prepared nanocatalyst displays the enhanced electrocatalytic activity and stability for methanol oxidation. • The high performance is attributed to facile electron transfer on poly (pyrrole-co-aniline) hollow nanosphere substrate.

Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd-Mo catalyst.

Science.gov (United States)

Duan, Haohong; Dong, Juncai; Gu, Xianrui; Peng, Yung-Kang; Chen, Wenxing; Issariyakul, Titipong; Myers, William K; Li, Meng-Jung; Yi, Ni; Kilpatrick, Alexander F R; Wang, Yu; Zheng, Xusheng; Ji, Shufang; Wang, Qian; Feng, Junting; Chen, Dongliang; Li, Yadong; Buffet, Jean-Charles; Liu, Haichao; Tsang, Shik Chi Edman; O'Hare, Dermot

2017-09-19

Bio-oil, produced by the destructive distillation of cheap and renewable lignocellulosic biomass, contains high energy density oligomers in the water-insoluble fraction that can be utilized for diesel and valuable fine chemicals productions. Here, we show an efficient hydrodeoxygenation catalyst that combines highly dispersed palladium and ultrafine molybdenum phosphate nanoparticles on silica. Using phenol as a model substrate this catalyst is 100% effective and 97.5% selective for hydrodeoxygenation to cyclohexane under mild conditions in a batch reaction; this catalyst also demonstrates regeneration ability in long-term continuous flow tests. Detailed investigations into the nature of the catalyst show that it combines hydrogenation activity of Pd and high density of both Brønsted and Lewis acid sites; we believe these are key features for efficient catalytic hydrodeoxygenation behavior. Using a wood and bark-derived feedstock, this catalyst performs hydrodeoxygenation of lignin, cellulose, and hemicellulose-derived oligomers into liquid alkanes with high efficiency and yield.Bio-oil is a potential major source of renewable fuels and chemicals. Here, the authors report a palladium-molybdenum mixed catalyst for the selective hydrodeoxygenation of water-insoluble bio-oil to mixtures of alkanes with high carbon yield.

Chemoselective Oxidation of Bio-Glycerol with Nano-Sized Metal Catalysts

DEFF Research Database (Denmark)

Li, Hu; Kotni, Ramakrishna; Zhang, Qiuyun

2015-01-01

to selectively oxidize glycerol and yield products with good selectivity is the use of nano-sized metal particles as heterogeneous catalysts. In this short review, recent developments in chemoselective oxidation of glycerol to specific products over nano-sized metal catalysts are described. Attention is drawn...... to various reaction parameters such as the type of the support, the size of the metal particles, and the acid/base properties of the reaction medium which were illustrated to largely influence the activity of the nanocatalyst and selectivity to the target product. - See more at: http...

Structure and Mobility of Metal Clusters in MOFs: Au, Pd, and AuPd Clusters in MOF-74

DEFF Research Database (Denmark)

Vilhelmsen, Lasse; Walton, Krista S.; Sholl, David S.

2012-01-01

is just as important for nanocluster adsorption as open Zn or Mg metal sites. Using the large number of clusters generated by the GA, we developed a systematic method for predicting the mobility of adsorbed clusters. Through the investigation of diffusion paths a relationship between the cluster......Understanding the adsorption and mobility of metal–organic framework (MOF)-supported metal nanoclusters is critical to the development of these catalytic materials. We present the first theoretical investigation of Au-, Pd-, and AuPd-supported clusters in a MOF, namely MOF-74. We combine density...... functional theory (DFT) calculations with a genetic algorithm (GA) to reliably predict the structure of the adsorbed clusters. This approach allows comparison of hundreds of adsorbed configurations for each cluster. From the investigation of Au8, Pd8, and Au4Pd4 we find that the organic part of the MOF...

A general approach to mesoporous metal oxide microspheres loaded with noble metal nanoparticles

KAUST Repository

Jin, Zhao; Xiao, Manda; Bao, Zhihong; Wang, Peng; Wang, Jianfang

2012-01-01

Catalytic microspheres: A general approach is demonstrated for the facile preparation of mesoporous metal oxide microspheres loaded with noble metal nanoparticles (see TEM image in the picture). Among 18 oxide/noble metal catalysts, TiO 2/0.1 mol Pd microspheres showed the highest turnover frequency in NaBH 4 reduction of 4-nitrophenol (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A general approach to mesoporous metal oxide microspheres loaded with noble metal nanoparticles

KAUST Repository

Jin, Zhao

2012-04-26

Catalytic microspheres: A general approach is demonstrated for the facile preparation of mesoporous metal oxide microspheres loaded with noble metal nanoparticles (see TEM image in the picture). Among 18 oxide/noble metal catalysts, TiO 2/0.1 mol Pd microspheres showed the highest turnover frequency in NaBH 4 reduction of 4-nitrophenol (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microenvironment effects in electrocatalysis: ionic-liquid-like coating on carbon nanotubes enhances the Pd-electrocatalytic alcohol oxidation.

Science.gov (United States)

Li, Shuwen; Dong, Zhengping; Yang, Honglei; Guo, Shujing; Gou, Galian; Ren, Ren; Zhu, Zhejun; Jin, Jun; Ma, Jiantai

2013-02-11

A new catalyst consisting of ionic liquid (IL)-functionalized carbon nanotubes (CNTs) obtained through 1,3-dipolar cycloaddition support-enhanced electrocatalytic Pd nanoparticles (Pd@IL(Cl(-))-CNTs) was successfully fabricated and applied in direct ethanol alkaline fuel cells. The morphology, structure, component and stability of Pd@IL(Cl(-))-CNTs were systematic characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Raman spectra, thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The new catalyst exhibited higher electrocatalytic activity, better tolerance and electrochemical stability than the Pd nanoparticles (NPs) immobilized on CNTs (Pd@CNTs), which was ascribed to the effects of the IL, larger electrochemically active surface area (ECSA), and greater processing performance. Cyclic voltammograms (CVs) at various scan rates illustrated that the oxidation behaviors of ethanol at all electrodes were controlled by diffusion processes. The investigation of the different counteranions demonstrated that the performance of the IL-CNTs hybrid material was profoundly influenced by the subtly varied structures of the IL moiety. All the results indicated that the Pd@IL(Cl(-))-CNTs catalyst is an efficient anode catalyst, which has potential applications in direct ethanol fuel cells and the strategy of IL functionalization of CNTs could be available to prepare other carbonaceous carrier supports to enhance the dispersivity, stability, and catalytic performance of metal NPs as well. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles

Institute of Scientific and Technical Information of China (English)

Dunfeng Gao; Fan Yang; Shu Miao; Jianguo Wang; Guoxiong Wang; Xinhe Bao; Hu Zhou; Fan Cai; Dongniu Wang; Yongfeng Hu; Bei Jiang; Wen-Bin Cai; Xiaoqi Chen; Rui Si

2017-01-01

Active-phase engineering is regularly utilized to tune the selectivity of metal nanoparticles (NPs) in heterogeneous catalysis.However,the lack of understanding of the active phase in electrocatalysis has hampered the development of efficient catalysts for CO2 electroreduction.Herein,we report the systematic engineering of active phases of Pd NPs,which are exploited to select reaction pathways for CO2 electroreduction.In situ X-ray absorption spectroscopy,in situ attenuated total reflection-infrared spectroscopy,and density functional theory calculations suggest that the formation of a hydrogen-adsorbed Pd surface on a mixture of the α-and β-phases of a palladium-hydride core (α+β PdHx@PdHx) above-0.2 V (vs.a reversible hydrogen electrode) facilitates formate production via the HCOO* intermediate,whereas the formation of a metallic Pd surface on the β-phase Pd hydride core (β PdHx@Pd) below-0.5 V promotes CO production via the COOH* intermediate.The main product,which is either formate or CO,can be selectively produced with high Faradaic efficiencies (＞90％) and mass activities in the potential window of 0.05 to-0.9 V with scalable application demonstration.

Preparation of supported Au–Pd and Cu–Pd by the combined strong ...

Indian Academy of Sciences (India)

BOONTIDA PONGTHAWORNSAKUN

2017-10-25

Oct 25, 2017 ... Bimetallic catalyst; Au–Pd/TiO2; Cu–Pd/TiO2; strong electrostatic adsorption; electroless deposition .... The liquid samples .... composition and gas mixture product at the outlet of reactor ... the TiO2 support (no change in the deposition curve of. TiO2). ..... TrimmDL1980In Design of Industrial Catalysts (Ams-.

Determination of platinum group metal catalyst residues in active pharmaceutical ingredients by means of total reflection X-ray spectrometry

International Nuclear Information System (INIS)

Marguí, Eva; Queralt, Ignasi; Hidalgo, Manuela

2013-01-01

The control of metal catalyst residues (i.e., platinum group metals (PGMs)) in different stages of the manufacturing processes of the active pharmaceutical ingredients (APIs) and, especially, in the final product is crucial. For API specimens, there are strict guidelines to limit the levels of metal residues based on their individual levels of safety concern. For PGMs the concentration limit has been established at 10 mg/kg in the API. Therefore great effort is currently being devoted to the development of new and simple procedures to control metals in pharmaceuticals. In the present work, an analytical methodology based on benchtop total reflection X-ray fluorescence spectrometry (TXRF) has been developed for the rapid and simple determination of some PGM catalyst impurities (Rh, Pd, Ir and Pt) in different types of API samples. An evaluation of different sample treatments (dissolution and digestion of the solid pharmaceutical samples) has been carried out and the developed methodologies have been validated according to the analytical parameters to be considered and acceptance criteria for PGM determination according to the United States Pharmacopeia (USP). Limits of quantification obtained for PGM metals were in the range of 2–4 mg/kg which are satisfactory according to current legislation. From the obtained results it is shown that the developed TXRF method can be implemented in the pharmaceutical industries to increase productivity of the laboratory; offering an interesting and complementary analytical tool to other atomic spectroscopic methods. - Highlights: • A TXRF method for PGM catalyst residue determination in API samples is presented. • Analysis can be performed using 10 μL of the internal standardized dissolved API. • The method is rapid, simple and suitable according to the USP requirements

Superior mercury-free catalysts for acetylene hydrochlorination to VCM. Achieving high productivities and long catalyst life-time

Energy Technology Data Exchange (ETDEWEB)

Liebens, A.T.; Piccinini, M. [Solvay S.A., Bruxelles (Belgium)

2013-11-01

New mercury-free catalytic systems based on the use of ionic liquids (IL) and noble metals (e.g. Pd, Au) have been evaluated for the hydrochlorination reaction of acetylene to produce Vinyl Chloride Monomer (VCM). Two different approaches have been investigated: gas-liquid homogeneous catalytic systems in the presence of molten IL/Metal and heterogeneous gas-solid ones using solid materials. For the latter case, very positive results have been obtained using SILP-type catalysts (SILP: Supported Ionic Liquid Phase) where IL/Metal were deposited onto a solid mesoporous support. Remarkably, both systems display very high Space Time Yield (STY) and breakthrough life-time stability. No deactivation is observed even after 500 h on stream indicating the strong advantages of these new materials compared to most investigated Au/C supported systems. The development of heterogeneous catalysts was preferred as the scale-up of gas-liquid technology implies important CAPEX investments to convert current plants from gas-solid to gas-liquid equipment. (orig.)

Synthesis of Pd and Rh metal nanoparticles in the interlayer space of organically modified montmorillonite

International Nuclear Information System (INIS)

Patel, Hasmukh A.; Bajaj, Hari C.; Jasra, Raksh Vir

2008-01-01

This study reports the synthesis of palladium and rhodium metal nanoparticles supported on montmorillonite (MMT) and partially organically modified MMT (POMM) using tetraamine palladium and hexaamine rhodium complex as precursor for palladium and rhodium respectively. The synthesized nanoparticles were characterized by powder X-ray diffraction PXRD and TEM. The PXRD study shows characteristic crystallographic planes for Pd and Rh metal and confirm the formation of metal nanoparticles in MMT and POMM. The TEM images reveal the effect of organic modification of MMT on decreasing particle size of Pd and Rh metal. The Pd and Rh metal nanoparticles are agglomerated in pristine MMT while nanoparticles are well dispersed in POMM. ICP-AES analysis was carried out to estimate quantitative amount of Pd and Rh metal in MMT and POMM

Influence of metal coating methods on the activity of bimetal-containing zeolite catalysts of Co, Pd-ZSM-5 in carbon monoxide oxidation

Science.gov (United States)

Oleksenko, L. P.; Lutsenko, L. V.; Yatsimirskii, V. K.

2011-07-01

It has been established that catalytic activity in the CO oxidation of bimetal-containing zeolite Co,Pd-systems based on ZSM-5 and obtained via ion exchange and impregnation at different orders of the introduction of metal cations is higher than that of monometal-containing systems Co-ZSM-5 and Pd—ZSM-5. Through TPD of NH3, it was determined that coordination-unsaturated bicationic associates are formed in Co,Pd/ZSM-5 zeolites obtained by ion exchange. It was found that the activity of bimetal-containing systems depends on the relation of the active components.

Palladium catalyst system comprising zwitterion and/or acid-​functionalized ionic liquid