Electrooxidative Rhodium-Catalyzed C-H/C-H Activation: Electricity as Oxidant for Cross-Dehydrogenative Alkenylation.

Science.gov (United States)

Qiu, Youai; Kong, Wei-Jun; Struwe, Julia; Sauermann, Nicolas; Rogge, Torben; Scheremetjew, Alexej; Ackermann, Lutz

2018-04-06

Rhodium(III) catalysis has enabled a plethora of oxidative C-H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we describe the first electrochemical C-H activation by rhodium catalysis that avoids hazardous chemical oxidants. Thus, environmentally-benign twofold C-H/C-H functionalizations were accomplished with weakly-coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant with H2 as the sole byproduct. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox-neutral rhodium-catalyzed C-H functionalization of arylamine N-oxides with diazo compounds: primary C(sp(3))-H/C(sp(2))-H activation and oxygen-atom transfer.

Science.gov (United States)

Zhou, Bing; Chen, Zhaoqiang; Yang, Yaxi; Ai, Wen; Tang, Huanyu; Wu, Yunxiang; Zhu, Weiliang; Li, Yuanchao

2015-10-05

An unprecedented rhodium(III)-catalyzed regioselective redox-neutral annulation reaction of 1-naphthylamine N-oxides with diazo compounds was developed to afford various biologically important 1H-benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by-products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp(3) )H bond and C(sp(2) )H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)-catalyzed coupling of readily available tertiary aniline N-oxides with α-diazomalonates was also developed under external oxidant-free conditions to access various aminomandelic acid derivatives by an O-atom-transfer reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Extended X-ray Absorption Fine Structure Study of Rhodium-Oxygen Bonds in a Highly Dispersed Rhodium/Aluminum Oxide Catalyst

NARCIS (Netherlands)

Koningsberger, D.C.; Zon, J.B.A.D. van; Blik, H.F.J. van 't; Visser, G.J.; Prins, R.; Mansour, A.N.; Sayers, D.E.; Short, D.R.

1985-01-01

Analysis of in situ EXAFS measurements on a 2.4 wt % Rh/A120, catalyst, reduced at 473 K after calcination at 623 K, shows the presence of two different rhodium-oxygen bonds (viz. 2.05 and 2.68 A). The oxygen neighbors of rhodium at a distance of 2.05 A disappear after reduction at 673 K. The

Free Rhodium (II) citrate and rhodium (II) citrate magnetic carriers as potential strategies for breast cancer therapy

Science.gov (United States)

2011-01-01

Background Rhodium (II) citrate (Rh2(H2cit)4) has significant antitumor, cytotoxic, and cytostatic activity on Ehrlich ascite tumor. Although toxic to normal cells, its lower toxicity when compared to carboxylate analogues of rhodium (II) indicates Rh2(H2cit)4 as a promising agent for chemotherapy. Nevertheless, few studies have been performed to explore this potential. Superparamagnetic particles of iron oxide (SPIOs) represent an attractive platform as carriers in drug delivery systems (DDS) because they can present greater specificity to tumor cells than normal cells. Thus, the association between Rh2(H2cit)4 and SPIOs can represent a strategy to enhance the former's therapeutic action. In this work, we report the cytotoxicity of free rhodium (II) citrate (Rh2(H2cit)4) and rhodium (II) citrate-loaded maghemite nanoparticles or magnetoliposomes, used as drug delivery systems, on both normal and carcinoma breast cell cultures. Results Treatment with free Rh2(H2cit)4 induced cytotoxicity that was dependent on dose, time, and cell line. The IC50 values showed that this effect was more intense on breast normal cells (MCF-10A) than on breast carcinoma cells (MCF-7 and 4T1). However, the treatment with 50 μM Rh2(H2cit)4-loaded maghemite nanoparticles (Magh-Rh2(H2cit)4) and Rh2(H2cit)4-loaded magnetoliposomes (Lip-Magh-Rh2(H2cit)4) induced a higher cytotoxicity on MCF-7 and 4T1 than on MCF-10A (p rhodium (II) citrate-loaded maghemite nanoparticles and magnetoliposomes induced more specific cytotoxicity on breast carcinoma cells than on breast normal cells, which is the opposite of the results observed with free Rh2(H2cit)4 treatment. Thus, magnetic nanoparticles represent an attractive platform as carriers in Rh2(H2cit)4 delivery systems, since they can act preferentially in tumor cells. Therefore, these nanopaticulate systems may be explored as a potential tool for chemotherapy drug development. PMID:21443799

Treatment of ammonia by catalytic wet oxidation process over platinum-rhodium bimetallic catalyst in a trickle-bed reactor: effect of pH.

Science.gov (United States)

Hung, Chang-Mao; Lin, Wei-Bang; Ho, Ching-Lin; Shen, Yun-Hwei; Hsia, Shao-Yi

2010-08-01

This work adopted aqueous solutions of ammonia for use in catalytic liquid-phase reduction in a trickle-bed reactor with a platinum-rhodium bimetallic catalyst, prepared by the co-precipitation of chloroplatinic acid (H2PtCl6) and rhodium nitrate [Rh(NO3)3]. The experimental results demonstrated that a minimal amount of ammonia was removed from the solution by wet oxidation in the absence of any catalyst, while approximately 97.0% of the ammonia was removed by wet oxidation over the platinum-rhodium bimetallic catalyst at 230 degrees C with an oxygen partial pressure of 2.0 MPa. The oxidation of ammonia has been studied as a function of pH, and the main reaction products were determined. A synergistic effect is manifest in the platinum-rhodium bimetallic structure, in which the material has the greatest capacity to reduce ammonia. The reaction pathway linked the oxidizing ammonia to nitric oxide, nitrogen, and water.

Chlorination of UO2, PuO2, and rare-earth oxides using ZrCl4

International Nuclear Information System (INIS)

Sakamura, Yoshiharu; Inoue, Tadashi; Iwai, Takashi; Moriyama, Hirotake

2001-01-01

A new chlorination method using ZrCl 4 , which has a high reactivity with oxygen, has been investigated for more efficient oxide treatment. After actinide oxides are chlorinated and dissolved in a molten salt bath, actinide metals can be selectively collected using the electrorefining process. This process is well suited for pyrochemical reprocessing of metallic fuels. In LiCl-KCI eutectic melts, rare-earth oxides (Y 2 O 3 , La 2 O 3 , CeO 2 , and Nd 2 O 3 ) and actinide oxides (UO 2 and PuO 2 ) were chlorinated by adding ZrCl 4 . As a result, rare-earth and actinide elements were dissolved into the salt as trivalent ions and ZrO 2 was precipitated. When an excess of ZrCI 4 was added, oxides in powder form were completely chlorinated in five hours. It was demonstrated that the ZrCI 4 chlorination method, free from corrosive gas such as chlorine, was very simple and useful. (author)

Rhodium(III)-Catalyzed [3+2]/[5+2] Annulation of 4-Aryl 1,2,3-Triazoles with Internal Alkynes through Dual C(sp2)-H Functionalization.

Science.gov (United States)

Yang, Yuan; Zhou, Ming-Bo; Ouyang, Xuan-Hui; Pi, Rui; Song, Ren-Jie; Li, Jin-Heng

2015-05-26

A rhodium(III)-catalyzed [3+2]/[5+2] annulation of 4-aryl 1-tosyl-1,2,3-triazoles with internal alkynes is presented. This transformation provides straightforward access to indeno[1,7-cd]azepine architectures through a sequence involving the formation of a rhodium(III) azavinyl carbene, dual C(sp(2))-H functionalization, and [3+2]/[5+2] annulation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal structures of bis[2-(pyridin-2-ylphenyl-κ2N,C1]rhodium(III complexes containing an acetonitrile or monodentate thyminate(1− ligand

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Mika Sakate

2016-04-01

Full Text Available The crystal structures of bis[2-(pyridin-2-ylphenyl]rhodium(III complexes with the metal in an octahedral coordination containing chloride and acetonitrile ligands, namely (OC-6-42-acetonitrilechloridobis[2-(pyridin-2-ylphenyl-κ2N,C1]rhodium(III, [RhCl(C11H8N2(CH3CN] (1, thyminate(1− and methanol, namely (OC-6-42-methanol(5-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ido-κN1bis[2-(pyridin-2-ylphenyl-κ2N,C1]rhodium(III, [Rh(C11H8N2(C5H5N2O2(CH3OH]·CH3OH·0.5H2O (2, and thyminate(1− and ethanol, namely (OC-6-42-ethanol(5-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ido-κN1bis[2-(pyridin-2-ylphenyl-κ2N,C1]rhodium(III, [Rh(C11H8N2(C5H5N2O2(C2H5OH]·C2H5OH (3, are reported. The acetonitrile complex, 1, is isostructural with the IrIII analog. In complexes 2 and 3, the monodeprotonated thyminate (Hthym− ligand coordinates to the RhIII atom through the N atom, and the resulting Rh—N(Hthym bond lengths are relatively long [2.261 (2 and 2.252 (2 Å for 2 and 3, respectively] as compared to the Rh—N bonds in the related thyminate complexes. In each of the crystals of 2 and 3, the complexes are linked via a pair of intermolecular N—H...O hydrogen bonds between neighbouring Hthym− ligands, forming an inversion dimer. A strong intramolecular O—H...O hydrogen bond between the thyminate(1− and alcohol ligands in mutually cis positions to each other is also observed.

Rhodium(I) catalysis in olefin photoreactions

International Nuclear Information System (INIS)

Salomon, R.G.; El Sanadi, N.

1975-01-01

The photorearrangement (254 nm) of 1,5-cyclooctadiene (1) in the presence of rhodium(I) chloride to give 1,4-cyclooctadiene (4) was found by deuterium labeling to involve an intramolecular [1,3] shift of hydrogen. A rate-determining cleavage of an allylic C--H bond is indicated by a deuterium isotope effect, k/sub H//k/sub D/ = 1.55 +- 0.03 for the 1 → 4 rearrangement. The acyclic 1,5-diene, 3,3-dimethyl-1,5-hexadiene (8), rearranges in the presence of rhodium(I) chloride upon uv irradiation (254 nm) to give cis-3,3-dimethyl-1,4-hexadiene (10) and the trans isomer 11 in a 1:4 ratio, respectively. This observation supports a mechanism for the photorearrangement of olefins catalyzed by rhodium(I) involving an initial photodissociation of one of two rhodium(I) coordinated carbon-carbon double bonds. This results in an increase in the coordinative unsaturation of rhodium(I) and enhances the proclivity of this d/sub s/ metal atom toward oxidative addition of an allylic C--H bond. A eta 3 -allylrhodium hydride intermediate then gives rearranged olefin by reductive elimination. Lastly, a novel photochemical, rhodium(I) catalyzed hydrogen transfer is reported which gives cyclooctene (7) from cyclooctadienes under unprecedentedly mild conditions. (auth)

Formic Acid Modified Co3O4-CeO2 Catalysts for CO Oxidation

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Ruishu Shang

2016-03-01

Full Text Available A formic acid modified catalyst, Co3O4-CeO2, was prepared via facile urea-hydrothermal method and applied in CO oxidation. The Co3O4-CeO2-0.5 catalyst, treated by formic acid at 0.5 mol/L, performed better in CO oxidation with T50 obtained at 69.5 °C and T100 obtained at 150 °C, respectively. The characterization results indicate that after treating with formic acid, there is a more porous structure within the Co3O4-CeO2 catalyst; meanwhile, despite of the slightly decreased content of Co, there are more adsorption sites exposed by acid treatment, as suggested by CO-TPD and H2-TPD, which explains the improvement of catalytic performance.

Reactivity of rhodium during co-deposition of rhodium and carbon

International Nuclear Information System (INIS)

Marot, Laurent; Steiner, Roland; De Temmerman, Gregory; Oelhafen, Peter

2009-01-01

The detailed characterizations of rhodium/carbon films prepared by co-deposition using a dual magnetron sputtering have been carried out on silicon substrates at room temperature. Effects of the carbon incorporated in the film on the chemical bonding state, optical reflectivity and crystallinity were investigated using XPS, reflectivity measurements, XRD and SEM. The incorporation of carbon changes the films' crystallinity and thus producing amorphous films. The reflectivity of the films decreases linearly as the rhodium concentration decreases. It is important to note that no chemical bonding was observed between rhodium and carbon whatever the deposition conditions, even at high deposition temperature. Concerning the reactivity of rhodium films with oxygen, after long term storage in air the rhodium surface is covered with a thin rhodium oxide (few nanometers). However, for these films no variation of the optical reflectivity was observed after long air storage.

Electrochemical behavior of rhodium(III) in 1-butyl-3-methylimidazolium chloride ionic liquid

Energy Technology Data Exchange (ETDEWEB)

Jayakumar, M.; Venkatesan, K.A. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Srinivasan, T.G. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)], E-mail: tgs@igcar.gov.in

2008-02-15

Electrochemical behavior of rhodium(III) chloride in 1-butyl-3-methylimidazolium chloride was investigated by various electrochemical transient techniques at glassy carbon working electrode at different temperatures (343-373 K). Cyclic voltammogram of rhodium(III) in bmimCl consisted of a surge in reduction current occurring at a potential of -0.48 V (vs. Pd) is due to the reduction of Rh(III) to metallic rhodium and a very small oxidation wave occurring at -0.1 V. Increase of scan rate increases the peak current and remarkably shifts the cathodic peak potential (E{sub p}{sup c1}) in negative direction indicating the irreversibility of electroreduction of rhodium(III). The diffusion coefficient of rhodium(III) in bmimCl ({approx}10{sup -9} cm{sup 2}/s) was determined and the energy of activation ({approx}25 kJ/mol) was deduced from cyclic voltammograms at various temperatures. The cathodic ({tau}{sub r}) and anodic ({tau}{sub o}) transition times were measured from chronopotential transients and the ratio {tau}{sub o}/{tau}{sub r} was found to be 1:7. Electrowinning of rhodium from bmimCl medium results in a deposition of metallic rhodium with lower (20-25%) Faradaic efficiency. A separation factor of rhodium from co-existing noble metal fission product palladium in bmimCl was determined during electrodeposition.

Nanotextured Spikes of α-Fe2O3/NiFe2O4 Composite for Efficient Photoelectrochemical Oxidation of Water.

Science.gov (United States)

Hussain, Shabeeb; Tavakoli, Mohammad Mahdi; Waleed, Aashir; Virk, Umar Siddique; Yang, Shihe; Waseem, Amir; Fan, Zhiyong; Nadeem, Muhammad Arif

2018-03-27

We demonstrate for the first time the application of p-NiFe 2 O 4 /n-Fe 2 O 3 composite thin films as anode materials for light-assisted electrolysis of water. The p-NiFe 2 O 4 /n-Fe 2 O 3 composite thin films were deposited on planar fluorinated tin oxide (FTO)-coated glass as well as on 3D array of nanospike (NSP) substrates. The effect of substrate (planar FTO and 3D-NSP) and percentage change of each component (i.e., NiFe 2 O 4 and Fe 2 O 3 ) of composite was studied on photoelectrochemical (PEC) water oxidation reaction. This work also includes the performance comparison of p-NiFe 2 O 4 /n-Fe 2 O 3 composite (planar and NSP) devices with pure hematite for PEC water oxidation. Overall, the nanostructured p-NiFe 2 O 4 /n-Fe 2 O 3 device with equal molar 1:1 ratio of NiFe 2 O 4 and Fe 2 O 3 was found to be highly efficient for PEC water oxidation as compared with pure hematite, 1:2 and 1:3 molar ratios of composite. The photocurrent density of 1:1 composite thin film on planar substrate was equal to 1.07 mA/cm 2 at 1.23 V RHE , which was 1.7 times higher current density as compared with pure hematite device (0.63 mA/cm 2 at 1.23 V RHE ). The performance of p-NiFe 2 O 4 /n-Fe 2 O 3 composites in PEC water oxidation was further enhanced by their deposition over 3D-NSP substrate. The highest photocurrent density of 2.1 mA/cm 2 at 1.23 V RHE was obtained for the 1:1 molar ratio p-NiFe 2 O 4 /n-Fe 2 O 3 composite on NSP (NF1-NSP), which was 3.3 times more photocurrent density than pure hematite. The measured applied bias photon-to-current efficiency (ABPE) value of NF1-NSP (0.206%) was found to be 1.87 times higher than that of NF1-P (0.11%) and 4.7 times higher than that of pure hematite deposited on FTO-coated glass (0.044%). The higher PEC water oxidation activity of p-NiFe 2 O 4 /n-Fe 2 O 3 composite thin film as compared with pure hematite is attributed to the Z-path scheme and better separation of electrons and holes. The increased surface area and greater light

Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

Energy Technology Data Exchange (ETDEWEB)

Xu, Songchen [Ames Laboratory; Manna, Kuntal [Ames Laboratory; Ellern, Arkady [Ames Laboratory; Sadow, Aaron D [Ames Laboratory

2014-12-08

In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(η4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(η4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(η4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(η4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(μ-Cl)(η2-C8H14)2]2 (M = Rh, Ir) provide {κ4-PhB(OxMe2)2ImMes'CH2}Rh(μ-H)(μ-Cl)Rh(η2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(η3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {κ4-PhB(OxMe2)2ImMes'CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis

trans-Carbonylchloridobis[dicyclohexyl(4-isopropylphenylphosphane]rhodium(I acetone monosolvate

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Sizwe Makhoba

2011-09-01

Full Text Available The title rhodium Vaska-type complex, trans-[RhCl{P(C6H112(C6H4-4-C3H72}2(CO], crystallizes with an accompanying acetone solvent molecule. The metal atom shows a distorted square-planar coordination environment with selected important geometrical parameters of Rh—P = 2.3237 (6 and 2.3253 (6 Å, Rh—Cl = 2.3724 (6 Å, Rh—C = 1.802 (2 Å, P—Rh—P = 173.42 (2° and Cl—Rh—C = 179.13 (7°. Effective cone angles for the two P atoms are 165 and 161°, respectively. Both isopropyl groups and the acetone molecule are disordered with occupancy values of 0.523 (5:0.477 (5, 0.554 (8:0.446 (8 and 0.735 (4:0.265 (4, respectively. The crystal packing is stabilized by weak C—H...O and C—H...Cl contacts.

The use of CeO2-Co3O4 oxides as a catalyst for the reduction of N2O emission

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Rajska Maria

2016-01-01

Full Text Available The morphological characterization of a series of cobalt-cerium oxide composites prepared by the deposition of CeO2 onto Co3O4 powder with a molar ratio of cerium oxide to Co3O4 in the range of 0 to 1 was performed. The powders were also impregnated with a solution of K2CO3 to obtain the theoretical content of potassium atoms 2at·nm−2. To investigate the effect of adding specific amount of CeO2 on the catalytic activity, the X-ray diffraction, SEM-EDX, laser particle size distribution and BET surface area measurements were used. The catalysts were tested through the low-temperature decomposition of nitrous oxide in the temperature range of 50°C to 700°C. The addition of CeO2 and K always moved the temperature of a complete N2O conversion towards lower temperatures (480°C-540°C to 340°C-420°C. The best catalytic properties were shown by the samples in which the ratio of cerium oxide to cobalt oxide ranged from 0.4 to 0.7.

Partitioning of rhodium and ruthenium between Pd–Rh–Ru and (Ru,Rh)O{sub 2} solid solutions in high-level radioactive waste glass

Energy Technology Data Exchange (ETDEWEB)

Sugawara, Toru, E-mail: toru@gipc.akita-u.ac.jp [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Ohira, Toshiaki [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Komamine, Satoshi; Ochi, Eiji [Research and Development Department, Reprocessing Business Division, Japan Nuclear Fuel Limited, 4-108, Okitsuke, Obuchi, Rokkasho-mura, Aomori 039-3212 (Japan)

2015-10-15

The partitioning of rhodium and ruthenium between Pd–Rh–Ru alloy with a face-centered cubic (FCC) structure and (Ru,Rh)O{sub 2} solid solution has been investigated between 1273 and 1573 K at atmospheric oxygen fugacity. The rhodium and ruthenium contents in FCC increase, while the RhO{sub 2} content in (Ru,Rh)O{sub 2} decreases with increasing temperature due to progressive reduction of the system. Based on the experimental results and previously reported thermodynamic data, the thermodynamic mixing properties of FCC phase and (Ru,Rh)O{sub 2} have been calibrated in an internally consistent manner. Phase equilibrium of platinum grope metals in an HLW glass was calculated by using the obtained thermodynamic parameters.

1,3-dialkyl- and 1,3-diaryl-3,4,5,6-tetrahydropyrimidin-2-ylidene rhodium(i) and palladium(II) complexes: synthesis, structure, and reactivity.

Science.gov (United States)

Mayr, Monika; Wurst, Klaus; Ongania, Karl-Hans; Buchmeiser, Michael R

2004-03-05

The synthesis of novel 1,3-diaryl- and 1,3-dialkylpyrimidin-2-ylidene-based N-heterocyclic carbenes (NHCs) and their rhodium(i) and palladium(II) complexes is described. The rhodium compounds bromo(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (7), bromo(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (8) (cod=eta(4)-1,5-cyclooctadiene, mesityl=2,4,6-trimethylphenyl), chloro(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (9), and chloro(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (10) were prepared by reaction of [[Rh(cod)Cl](2)] with lithium tert-butoxide followed by addition of 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium bromide (3), 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate (4), 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium bromide (6), and 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate, respectively. Complex 7 crystallizes in the monoclinic space group P2(1)/n, and 8 in the monoclinic space group P2(1). Complexes 9 and 10 were used for the synthesis of the corresponding dicarbonyl complexes dicarbonylchloro(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (11), and dicarbonylchloro[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (12). The wavenumbers nu(CO I)/nu(CO II) for 11 and 12 were used as a quantitative measure for the basicity of the NHC ligand. The values of 2062/1976 and 2063/1982 cm(-1), respectively, indicate that the new NHCs are among the most basic cyclic ligands reported so far. Compounds 3 and 6 were additionally converted to the corresponding cationic silver(i) bis-NHC complexes [Ag(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]AgBr(2) (13) and [Ag[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene](2)]AgBr(2) (14), which were subsequently used in transmetalation reactions for the synthesis of the corresponding palladium(II) complexes Pd(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2

Preparation, Characterization and NO-CO Redox Reaction Studies over Palladium and Rhodium Oxides Supported on Manganese Dioxide

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M.S. Fal Desai

2015-03-01

Full Text Available The catalytic activity of PdO/MnO2 and Rh2O3/MnO2 is investigated for NO-CO redox reaction. Supported catalysts are prepared by wet impregnation method. Among the tested catalysts, PdO/MnO2 shows higher activity for this reaction. Active metal dispersion on MnO2 enhances the selectivity for N2 over N2O in this reaction. The XRD substantiate the formation of MnO2 monophasic phase. SEM images show the formation of elongated particles. TEM images indicate nano-size rod-like morphologies. An increase in the catalytic activity is observed on supported Pd and Rh oxides on MnO2. Temperature programed desorption studies with NO and CO are undertaken to investigate the catalytic surface studies. © 2015 BCREC UNDIP. All rights reservedReceived: 22nd November 2014; Revised: 31st December 2014; Accepted: 2nd January 2015How to Cite: Fal Desai, M.S., Kunkalekar, R.K., Salker, A.V. (2015. Preparation, Characterization and NO-CO Redox Reaction Studies over Palladium and Rhodium Oxides Supported on Manganese Dioxide. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 98-103. (doi:10.9767/bcrec.10.1.7802.98-103Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7802.98-103 

The liquid-liquid extraction of chloro-(trichlorostannato)-rhodium(I/III) and -ruthenium (II) complexes from dilute hydrochloric acid into 4-methylpentan-2-one

International Nuclear Information System (INIS)

Wyrley-Birch, J.M.

1984-10-01

The effect of stannous chloride on the liquid-liquid extraction of rhodium and ruthenium from hydrochloric acid solutions into 4-methyl-pentan-2-one (MIBK)/hexane mixtures was studied in detail. Stannous chloride concentrations were found to considerably increase the efficiency of the extraction of rhodium and ruthenium into the organic phase. Chloro-(trichlorostannato)-rhodium (I/III) complexes were formed at room temperature. The rate of chloro-(trichlorostannato)-ruthenium (II) complex formation was extremely slow at room temperature, but increased on heating of the aqueous solutions. The amount of rhodium and ruthenium extracted into the organic phase depend on the Sn(II):M molar ratio, the HCl, H sup(+) and Cl sup(-) concentrations, as well as the equilibration time. A 119 Sn NMR study of the MIBK extracts, showed that the stoichiometry of the chloro-(trichlorostannato)-rhodium (I/III) complexes extracted into the organic phase was dependent on the Sn(II):Rh(III) molar ratio as well as the HCl, H sup(+) and Cl sup(-) concentrations in the aqueous phase. The predominant species observed in the organic phase from HCl solutions containing Sn(II):Rh(III) ratios >= 5:1, was shown to be an hydrido complex having the form [RhH(SnCl 3 ) 4 Cl] 3 sup(-) or [RhH(SnCl 3 ) 4 ]2 sup(-). An essentially quantitative separation of rhodium and ruthenium was achieved utilising the variation in the rates of rhodium-tin and ruthenium-tin complex formation

Functionalized cyclopentadienyl rhodium(III) bipyridine complexes: synthesis, characterization, and catalytic application in hydrogenation of ketones.

Science.gov (United States)

Wang, Wan-Hui; Suna, Yuki; Himeda, Yuichiro; Muckerman, James T; Fujita, Etsuko

2013-07-14

A series of highly functionalized cyclopentadienyl rhodium(III) complexes, [Cp'Rh(bpy)Br](ClO4) (Cp' = substituted cyclopentadienyl), was synthesized from various multi-substituted cyclopentadienes (Cp'H). [Rh(cod)Cl]2 and Cp'H were firstly converted to [Cp'Rh(cod)] complexes, which were then treated with Br2 to give the rhodium(III) dibromides [Cp'RhBr2]2. The novel complexes [Cp'Rh(bpy)Br](ClO4) were obtained readily by the reaction of 2,2'-bipyridine with [Cp'RhBr2]2. These rhodium complexes [Cp'Rh(bpy)Br](ClO4) were fully characterized and utilized in the hydrogenation of cyclohexanone and acetophenone with generally high yields, but they did not exhibit the same reactivity trends for the two substrate ketones. The different activity of these complexes for the different substrates may be due to the influence of the substituents on the Cp' rings.

Redox-Neutral Rhodium-Catalyzed [4+1] Annulation through Formal Dehydrogenative Vinylidene Insertion.

Science.gov (United States)

Liu, Huan; Song, Shengjin; Wang, Cheng-Qiang; Feng, Chao; Loh, Teck-Peng

2017-01-10

A synthetic protocol for the expedient construction of 5-methylene-1H-pyrrol-2(5H)-one derivatives through rhodium-catalyzed [4+1] annulation with gem-difluoroacrylate as the C 1 component was reported. By taking advantage of the twofold C-F bond cleavage occurring during the annulation, this reaction not only allows the synthesis of these heterocyclic compounds under overall oxidant-free conditions but also renders the transformation stereospecific. The very mild reaction conditions employed ensure compatibility with a wide variety of synthetically useful functional groups. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Remarkable promoting effect of rhodium on the catalytic performance of Ag/Al2O3 for the selective reduction of NO with decane

International Nuclear Information System (INIS)

Sato, Kazuhito; Yoshinari, Tomohiro; Kintaichi, Yoshiaki; Haneda, Masaaki; Hamada, Hideaki

2003-01-01

The addition of small amounts of rhodium enhanced the activity of Ag/Al 2 O 3 catalyst for the selective reduction of NO with decane at low temperatures. The Rh-promoted Ag/Al 2 O 3 showed its high performance even in the presence of low concentrations of SO 2 . Based on the catalytic activity for elementary reactions, it was suggested that the role of added rhodium is to enhance the reaction between NO x and decane-derived species, leading to NO reduction. Catalyst characterization by UV-Vis spectroscopy indicated that the major silver species on Rh-promoted Ag/Al 2 O 3 is Ag nn δ+ clusters, which would be responsible for the high activity. FT-IR measurements revealed that the formation rate of isocyanate species, which is a major reaction intermediate, is higher on Rh-promoted Ag/Al 2 O 3

Bimetallic poly- and oligo-nuclear complexes based on a rhodium(III) metalloligand

Science.gov (United States)

Vasilchenko, Danila B.; Venediktov, Anatoliy B.; Korenev, Sergey V.; Filatov, Evgeniy Yu.; Baidina, Iraida A.; Nadolinnyi, Vladimir A.

2012-10-01

Interaction of trans-[Rh(i-Nic)4Cl2]3- anions (i-Nic- - isonicotinate anion) with Cuaq2+ and Coaq2+ cations in water has afforded complex salts Co3[Rh(i-Nic)4Cl2]2·17H2O (1) and Cu3[Rh(i-Nic)4Cl2]2·14H2O (2). Oligonuclear character of 1 and 2 has been established. A coordination polymer Cu5[Rh(i-Nic)4Cl2]2(i-Nic)2(OH)2·2H2O (3) has been crystallized by hydrothermal treatment of 2 at 160 °C, and its structure was determined by X-ray structural analysis. EPR data for the complexes has been collected and interpreted. Thermal decomposition of the salts was studied by c-DTA. Bimetallic alloys rhodium-copper and rhodium-cobalt have been obtained as final products of thermal decomposition.

The crystal structure of ianthinite, [U24+(UO2)4O6(OH)4(H2O)4](H2O)5: a possible phase for Pu4+ incorporation during the oxidation of spent nuclear fuel

International Nuclear Information System (INIS)

Burns, P.C.; Hawthorne, F.C.; Miller, M.L.; Ewing, R.C.

1997-01-01

Ianthinite, [U 4+ 2 (UO 2 ) 4 O 6 (OH) 4 (H 2 O) 4 ](H 2O) 5 , is the only known uranyl oxide hydrate mineral that contains U 4+ , and it has been proposed that ianthinite may be an important Pu 4+ -bearing phase during the oxidative dissolution of spent nuclear fuel. The crystal structure of ianthinite, orthorhombic, a=0.7178(2), b=1.1473(2), c=3.039(1) nm, V=2.5027 nm 3 , Z=4, space group P2 1 cn, has been solved by direct methods and refined by least-squares methods to an R index of 9.7% and a wR index of 12.6% using 888 unique observed [ vertical stroke F vertical stroke ≥5σ vertical stroke F vertical stroke ] reflections. The structure contains both U 6+ and U 4+ . The U 6+ cations are present as roughly linear (U 6+ O 2 ) 2+ uranyl ions (Ur) that are in turn coordinated by five O 2- and OH - located at the equatorial positions of pentagonal bipyramids. The U 4+ cations are coordinated by O 2- , OH - and H 2 O in a distorted octahedral arrangement. The Urφ 5 and U 4+ φ 6 (φ: O 2- , OH - , H 2 O) polyhedra link by sharing edges to form two symmetrically distinct sheets at z∼0.0 and z∼0.25 that are parallel to (001). The sheets have the β-U 3 O 8 sheet anion-topology. There are five symmetrically distinct H 2 O groups located at z∼0.125 between the sheets of Uφ n polyhedra, and the sheets of Uφ n polyhedra are linked together only by hydrogen bonding to the intersheet H 2 O groups. The crystal-chemical requirements of U 4+ and Pu 4+ are very similar, suggesting that extensive Pu 4+ U 4+ substitution may occur within the sheets of Uφ n polyhedra in the structure of ianthinite. (orig.)

The far infrared radiation characteristics for Li2O.Al2O3.4SiO2(LAS) glass-ceramics and transition-metal oxide

International Nuclear Information System (INIS)

Huh, Nam Jung; Yang, Joong Sik

1991-01-01

The far infrared radiation characteristic for Li 2 O.Al 2 O 3 .4SiO 2 (LAS) glass, the LAS glass-ceramic and sintered transition metal oxides such as CuO, Fe 2 O 3 and Co 3 O 4 , were investigated. LAS glass and LAS glass-ceramic was higher than that of the LAS glass. Heat-treated CuO and Co 3 o 4 had radiation characteristic of high efficiency infrared radiant, and heat-treated Fe 2 O 3 had radiation characteristic that infrared emissivity decreased in higher was length above 15μm. (Author)

Dihydropyranone Formation by Ipso C–H Activation in a Glucal 3-Carbamate-Derived Rhodium Acyl Nitrenoid

Science.gov (United States)

Hurlocker, Brisa; Abascal, Nadia C.; Repka, Lindsay M.; Santizo-Deleon, Elsy; Smenton, Abigail L.; Baranov, Victoria; Gupta, Ritu; Bernard, Sarah E.; Chowdhury, Shenjuti; Rojas, Christian M.

2011-01-01

By using (N-tosyloxy)-3-O-carbamoyl-D-glucal 10, which removes the need for a hypervalent iodine(III) oxidant, we provide evidence for rhodium nitrenoid-mediated ipso C–H activation as the origin of a C3-oxidized dihydropyranone product 3. This system may be especially susceptible to such a pathway due to the ease of forming a cation upon hydride transfer to the rhodium-complexed acyl nitrene. PMID:21381715

Altering properties of cerium oxide thin films by Rh doping

International Nuclear Information System (INIS)

Ševčíková, Klára; Nehasil, Václav; Vorokhta, Mykhailo; Haviar, Stanislav; Matolín, Vladimír

2015-01-01

Highlights: • Thin films of ceria doped by rhodium deposited by RF magnetron sputtering. • Concentration of rhodium has great impact on properties of Rh–CeO x thin films. • Intensive oxygen migration in films with low concentration of rhodium. • Oxygen migration suppressed in films with high amount of Rh dopants. - Abstract: Ceria containing highly dispersed ions of rhodium is a promising material for catalytic applications. The Rh–CeO x thin films with different concentrations of rhodium were deposited by RF magnetron sputtering and were studied by soft and hard X-ray photoelectron spectroscopies, Temperature programmed reaction and X-ray powder diffraction techniques. The sputtered films consist of rhodium–cerium mixed oxide where cerium exhibits a mixed valency of Ce 4+ and Ce 3+ and rhodium occurs in two oxidation states, Rh 3+ and Rh n+ . We show that the concentration of rhodium has a great influence on the chemical composition, structure and reducibility of the Rh–CeO x thin films. The films with low concentrations of rhodium are polycrystalline, while the films with higher amount of Rh dopants are amorphous. The morphology of the films strongly influences the mobility of oxygen in the material. Therefore, varying the concentration of rhodium in Rh–CeO x thin films leads to preparing materials with different properties

SO4= uptake and catalase role in preconditioning after H2O2-induced oxidative stress in human erythrocytes.

Science.gov (United States)

Morabito, Rossana; Remigante, Alessia; Di Pietro, Maria Letizia; Giannetto, Antonino; La Spada, Giuseppina; Marino, Angela

2017-02-01

Preconditioning (PC) is an adaptive response to a mild and transient oxidative stress, shown for the first time in myocardial cells and not described in erythrocytes so far. The possible adaptation of human erythrocytes to hydrogen peroxide (H 2 O 2 )-induced oxidative stress has been here verified by monitoring one of band 3 protein functions, i.e., Cl - /HCO 3 - exchange, through rate constant for SO 4 = uptake measurement. With this aim, erythrocytes were exposed to a mild and transient oxidative stress (30 min to either 10 or 100 μM H 2 O 2 ), followed by a stronger oxidant condition (300- or, alternatively, 600-μM H 2 O 2 treatment). SO 4 = uptake was measured by a turbidimetric method, and the possible role of catalase (CAT, significantly contributing to the anti-oxidant system in erythrocytes) in PC response has been verified by measuring the rate of H 2 O 2 degradation. The preventive exposure of erythrocytes to 10 μM H 2 O 2 , and then to 300 μM H 2 O 2 , significantly ameliorated the rate constant for SO 4 = uptake with respect to 300 μM H 2 O 2 alone, showing thus an adaptive response to oxidative stress. Our results show that (i) SO 4 = uptake measurement is a suitable model to monitor the effects of a mild and transient oxidative stress in human erythrocytes, (ii) band 3 protein anion exchange capability is retained after 10 μM H 2 O 2 treatment, (iii) PC response induced by the 10 μM H 2 O 2 pretreatment is clearly detected, and (iv) PC response, elicited by low-concentrated H 2 O 2 , is mediated by CAT enzyme and does not involve band 3 protein tyrosine phosphorylation pathways. Erythrocyte adaptation to a short-term oxidative stress may serve as a basis for future studies about the impact of more prolonged oxidative events, often associated to aging, drug consumption, chronic alcoholism, hyperglycemia, or neurodegenerative diseases.

Oxide (CeO{sub 2}, NiO, Co{sub 3}O{sub 4} and Mn{sub 3}O{sub 4})-promoted Pd/C electrocatalysts for alcohol electrooxidation in alkaline media

Energy Technology Data Exchange (ETDEWEB)

Xu, Changwei; Tian, Zhiqun; Jiang, San Ping [School of Mechanical and Aerospace Engineering, Nanyang Technological University (Singapore); Shen, Peikang [School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China)

2008-01-01

This study investigated Pt/C, Pd/C and oxide (CeO{sub 2}, NiO, Co{sub 3}O{sub 4} and Mn{sub 3}O{sub 4})-promoted Pd/C for electrooxidation reactions of methanol, ethanol, ethylene glycol and glycerol in alkaline media. The results show that Pd/C electrocatalysts alone have low activity and very poor stability for the alcohol electrooxidation. However, addition of oxides like CeO{sub 2}, NiO, Co{sub 3}O{sub 4} and Mn{sub 3}O{sub 4} significantly promotes catalytic activity and stability of the Pd/C electrocatalysts for the alcohol electrooxidation. The Pd-Co{sub 3}O{sub 4} (2:1, w:w)/C shows the highest activity for the electrooxidation of methanol, EG and glycerol while the most active catalyst for the ethanol electrooxidation is Pd-NiO (6:1, w:w)/C. On the other hand, Pd-Mn{sub 3}O{sub 4}/C shows significantly better performance stability than other oxide-promoted Pd/C for the alcohol electrooxidation. The poor stability of the Pd-Co{sub 3}O{sub 4}/C electrocatalysts is most likely related to the limited solubility of cobalt oxides in alkaline solutions. (author)

DFT studies of elemental mercury oxidation mechanism by gaseous advanced oxidation method: Co-interaction with H2O2 on Fe3O4 (111) surface

Science.gov (United States)

Zhou, Changsong; Song, Zijian; Zhang, Zhiyue; Yang, Hongmin; Wang, Ben; Yu, Jie; Sun, Lushi

2017-12-01

Density functional theory calculations have been carried out for H2O2 and Hg0 co-interaction on Fe3O4 (111) surface. On the Fetet1-terminated Fe3O4 (111) surface, the most favored configurations are H2O2 decomposition and produce two OH groups, which have strong interaction with Hg atom to form an OHsbnd Hgsbnd OH intermediate. The adsorbed OHsbnd Hgsbnd OH is stable and hardly detaches from the catalyst surface due to the highly endothermic process. A large amount of electron transfer has been found from Hg to the produced OH groups and has little irreversible effect on the Fe3O4 (111) surface. On the Feoct2-terminated Fe3O4 (111) surface, the Feoct2 site is more active than Fetet1 site. H2O2 decomposition and Hg0 oxidation processes are more likely to occur due to that the Feoct2 site both contains Fe2+ and Fe3+ cations. The calculations reveal that Hg0 oxidation by the OH radical produced from H2O2 is energetically favored. Additionally, Hg0 and H2O2 co-interaction mechanism on the Fe3O4 (111) interface has been investigated on the basis of partial local density of state calculation.

Highly efficient alkane oxidation catalyzed by [Mn(V)(N)(CN)4](2-). Evidence for [Mn(VII)(N)(O)(CN)4](2-) as an active intermediate.

Science.gov (United States)

Ma, Li; Pan, Yi; Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Chen, Gui; Lau, Kai-Chung; Lau, Tai-Chu

2014-05-28

The oxidation of various alkanes catalyzed by [Mn(V)(N)(CN)4](2-) using various terminal oxidants at room temperature has been investigated. Excellent yields of alcohols and ketones (>95%) are obtained using H2O2 as oxidant and CF3CH2OH as solvent. Good yields (>80%) are also obtained using (NH4)2[Ce(NO3)6] in CF3CH2OH/H2O. Kinetic isotope effects (KIEs) are determined by using an equimolar mixture of cyclohexane (c-C6H12) and cyclohexane-d12 (c-C6D12) as substrate. The KIEs are 3.1 ± 0.3 and 3.6 ± 0.2 for oxidation by H2O2 and Ce(IV), respectively. On the other hand, the rate constants for the formation of products using c-C6H12 or c-C6D12 as single substrate are the same. These results are consistent with initial rate-limiting formation of an active intermediate between [Mn(N)(CN)4](2-) and H2O2 or Ce(IV), followed by H-atom abstraction from cyclohexane by the active intermediate. When PhCH2C(CH3)2OOH (MPPH) is used as oxidant for the oxidation of c-C6H12, the major products are c-C6H11OH, c-C6H10O, and PhCH2C(CH3)2OH (MPPOH), suggesting heterolytic cleavage of MPPH to generate a Mn═O intermediate. In the reaction of H2O2 with [Mn(N)(CN)4](2-) in CF3CH2OH, a peak at m/z 628.1 was observed in the electrospray ionization mass spectrometry, which is assigned to the solvated manganese nitrido oxo species, (PPh4)[Mn(N)(O)(CN)4](-)·CF3CH2OH. On the basis of the experimental results the proposed mechanism for catalytic alkane oxidation by [Mn(V)(N)(CN)4](2-)/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4](2-) to generate a manganese(VII) nitrido oxo active species, [Mn(VII)(N)(O)(CN)4](2-), which then oxidizes alkanes (R'H) via a H-atom abstraction/O-rebound mechanism. The proposed mechanism is also supported by density functional theory calculations.

Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2.

Science.gov (United States)

Kowal, A; Li, M; Shao, M; Sasaki, K; Vukmirovic, M B; Zhang, J; Marinkovic, N S; Liu, P; Frenkel, A I; Adzic, R R

2009-04-01

Ethanol, with its high energy density, likely production from renewable sources and ease of storage and transportation, is almost the ideal combustible for fuel cells wherein its chemical energy can be converted directly into electrical energy. However, commercialization of direct ethanol fuel cells has been impeded by ethanol's slow, inefficient oxidation even at the best electrocatalysts. We synthesized a ternary PtRhSnO(2)/C electrocatalyst by depositing platinum and rhodium atoms on carbon-supported tin dioxide nanoparticles that is capable of oxidizing ethanol with high efficiency and holds great promise for resolving the impediments to developing practical direct ethanol fuel cells. This electrocatalyst effectively splits the C-C bond in ethanol at room temperature in acid solutions, facilitating its oxidation at low potentials to CO(2), which has not been achieved with existing catalysts. Our experiments and density functional theory calculations indicate that the electrocatalyst's activity is due to the specific property of each of its constituents, induced by their interactions. These findings help explain the high activity of Pt-Ru for methanol oxidation and the lack of it for ethanol oxidation, and point to the way to accomplishing the C-C bond splitting in other catalytic processes.

Obtention of superconductivity by room temperature electrochemical oxidation of La2CuO4

International Nuclear Information System (INIS)

Casan-Pastor, N.; Fuertes, A.; Gomez-Romero, P.

1993-01-01

The undoped oxide La2CuO4 has required traditionally synthesis under high pressure of oxygen (and high temperatures) to incorporate excess oxygen into its structure and become a superconductor. The electrochemical oxidation of this same oxide at room temperature and pressure constitutes a striking example of the use of an alternative driving force for the oxidation of oxides to become superconductors. Electrochemical treatment of oxides has been frequently applied to their reduction with cationic intercalation. Oxidations of these solid with the concomitant intercalation of anions into their lattice shows also great promises. The paper reports recent results in the electrochemical oxidation of La2CuO4 and other cuprates, showing also the important role of post-oxidation thermal treatments on the properties of the resulting solids

Investigation into cathode polarization during deposition of rhodium-nickel and rhodium-indium alloys

International Nuclear Information System (INIS)

Evdokimova, N.V.; Byacheslavov, P.M.; Lokshtanova, O.G.

1979-01-01

The results of kinetic regularities experimental investigations during electrodeposition of rhodium-nickel and rhonium-indium alloys are presented. Methods of general and partial polarization curves have been used to show the nature of polarization during the rhonium-nickel and rhodium-indium alloys deposition. It is shown that indium into the rhodium-indium alloy and nickel into the rhodium-nickel alloy deposit with great depolarization ( PHIsub(In)sup(0)=-0.33B, PHIsub(Ni)sup(0)=-0.23B). Indium and nickel in pure form do not deposit from the electrolytes of the given composition (H 2 SO 4 - 50 g/l, HNH 2 SO 3 -10 g/l). The recalculation of partial polarization curve of indium precipitation into the rhodium-indium alloy in the mixed kinetics coordinates gives a straight line with 40 mV inclination angle. This corresponds to the delayed stage of the second electron addition with the imposition of diffusion limitations

Topotactic dehydration of the lamellar oxide HK2Ti5NbO14 x H2O: the oxide K4Ti10Nb2O27

International Nuclear Information System (INIS)

Grandin, A.; Borel, M.M.; Hervieu, M.; Raveau, B.

1987-01-01

The lamellar oxide HK 2 Ti 5 NbO 14 x H 2 O can be topotactically dehydrated to K 4 Ti 10 Nb 2 O 27 . Electron diffraction and X-ray diffraction studies of this phase lead to a monoclinic cell with the parameters a = 17.005, b = 3.78, c = 9.01 A and β 92.14 0 . Diffusion streaks on the electron diffraction patterns indicate disorder whereas the existence of two sets of lattices on the same crystal give evidence of the topotactic character of the reaction. A structural model is proposed for K 4 Ti 10 Nb 2 O 27 , which corresponds to the intergrowth of K 3 TiNbO 14 layers with the K 2 Ti 6 O 13 tunnel structure. The possibility of formation of various intergrowths such as (KTi 5 NbO 13 )/sub n/ (HK 2 Ti 5 NbO 14 )/sub n/' is suggested

RuO4-mediated oxidation of secondary amines 2. imines as main reaction intermediates

Directory of Open Access Journals (Sweden)

Florea Cristina A.

2017-01-01

Full Text Available Oxidation by RuO4 (generated in situ from RuO2 and NaIO4 of secondary amines such as Bn–NH–CH2R (1; R=H, Me gave complex reaction mixtures, but mainly amides. In the presence of cyanide, the leading products were α-aminonitriles. Comparison of the oxidation products of 1 with those from the corresponding imines PhCH=N–CH2R and Bn–N=CH–R showed that formation of the indicated imines is the first main step in the oxidation of 1. A detailed mechanism is proposed.

Theoretical study of the adsorption of rhodium on a TiO2 (1 1 0)-1 × 1 surface

Czech Academy of Sciences Publication Activity Database

Mutombo, Pingo; Balázs, N.; Majzik, Zsolt; Berkó, A.; Cháb, Vladimír

2012-01-01

Roč. 258, č. 10 (2012), s. 4478-4482 ISSN 0169-4332 R&D Projects: GA MŠk MEB040921 Grant - others:Czech-Hungarian Intergovernmental Science&Technology Program(HU) CZ-06/2008 TET Institutional research plan: CEZ:AV0Z10100521 Keywords : density functional theory * rhodium * oxide surface * scanning tunneling spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.112, year: 2012 http://www.sciencedirect.com/science/article/pii/S0169433212000232

Low temperature phase transition of the stoichiometric Ln2NiO4 oxides

International Nuclear Information System (INIS)

Fernandez, F.; Saez-Puche, R.; Botto, I.L.; Baran, E.J.

1991-01-01

In this paper we will present a comparative study of the structural phase transition in Ln 2 NiO 4 oxides, by means of neutron diffraction and infrared(IR) spectroscopy. In the Ln 2 NiO 4 oxides (Ln=La, Pr and Nd), there is a low temperature structural phase transition from the orthorhombic symmetry to a tetragonal phase, of first order character. The IR spectra show, at low temperature, a splitting of the bands related with the stretching Ni-O, strongly correlated with the phase transformation. From the neutron data, the phase transition can be visualized as a sudden tilt of the nickel octahedra

Oxidative Olefination of Anilides with Unactivated Alkenes Catalyzed by an (Electron-Deficient η(5) -Cyclopentadienyl)Rhodium(III) Complex Under Ambient Conditions.

Science.gov (United States)

Takahama, Yuji; Shibata, Yu; Tanaka, Ken

2015-06-15

The oxidative olefination of sp(2) C-H bonds of anilides with both activated and unactivated alkenes using an (electron-deficient η(5) -cyclopentadienyl)rhodium(III) complex is reported. In contrast to reactions using this electron-deficient rhodium(III) catalyst, [Cp*RhCl2 ]2 showed no activity against olefination with unactivated alkenes. In addition, the deuterium kinetic isotope effect (DKIE) study revealed that the C-H bond cleavage step is thought to be the turnover-limiting step. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

{2-[Bis(2,4-di-tert-butylphenoxyphosphanyloxy-κP]-3,5-di-tert-butylphenyl-κC1}[(1,2,5,6-η-cycloocta-1,5-diene]rhodium(I toluene monosolvate

Directory of Open Access Journals (Sweden)

Detlef Selent

2012-02-01

Full Text Available The reaction of (η3-allyl[(1,2,5,6-η-cycloocta-1,5-diene]rhodium(I with tris(2,4-di-tert-butylphenylphosphite in toluene produces the title compound, [Rh(C42H62O3P(C8H12]·C7H8, by spontaneous metallation at one of the nonsubstituted phenyl ortho-C atoms of the phosphite molecule. The coordination geometry at the RhI ion is distorted square-planar. The toluene solvent molecule is disordered over two different orientations, with site-occupation factors of 0.810 (2 and 0.190 (2.

Industrial tests of rhodium self-powered detectors: the Golfech 2 experimentation

International Nuclear Information System (INIS)

Mourlevat, J.L.; Janvier, D.; Warren, H.D.

2000-01-01

In co-operation with Electricite de France (EDF), FRAMATOME has been testing two in-core strings which are equipped with rhodium self-powered detectors (SPDs) in the Golfech Unit 2 reactor (1300 MW, 4L plant) since August 1997. The rhodium SPDs and the strings which support them were designed and built by the US FRAMATOME subsidiary FRAMATOME-COGEMA-FUEL (FCF). The rhodium signals and some other plant parameters are acquired through the use of a specific device designed by the CEA (Commissariat a l'Energie Atomique) and are processed off-line by FRAMATOME. This demonstration test is planned to last until mid-2000. The following presentation is focused on the results obtained during the first demonstration cycle (from 08/97 to 12/98). The tests that have been conducted consist of checking the rhodium depletion and of comparing the rhodium signals to the movable probes. In order to compensate for the delay in the rhodium signals, a deconvolution algorithm has also been tested. Up to now, the results are very satisfactory and a future large scale industrial application is being discussed with the EDF. The main objective of the next experimentation phase is to test - under industrial conditions - a prototype of an on-line monitoring unit known as the Partial In-Core Monitoring System (PIMS). This system will include 16 rhodium in-core strings and will use an on-line 3-D core model. (authors)

Reaction mechanisms at 4H-SiC/SiO2 interface during wet SiC oxidation

Science.gov (United States)

Akiyama, Toru; Hori, Shinsuke; Nakamura, Kohji; Ito, Tomonori; Kageshima, Hiroyuki; Uematsu, Masashi; Shiraishi, Kenji

2018-04-01

The reaction processes at the interface between SiC with 4H structure (4H-SiC) and SiO2 during wet oxidation are investigated by electronic structure calculations within the density functional theory. Our calculations for 4H-SiC/SiO2 interfaces with various orientations demonstrate characteristic features of the reaction depending on the crystal orientation of SiC: On the Si-face, the H2O molecule is stable in SiO2 and hardly reacts with the SiC substrate, while the O atom of H2O can form Si-O bonds at the C-face interface. Two OH groups are found to be at least necessary for forming new Si-O bonds at the Si-face interface, indicating that the oxidation rate on the Si-face is very low compared with that on the C-face. On the other hand, both the H2O molecule and the OH group are incorporated into the C-face interface, and the energy barrier for OH is similar to that for H2O. By comparing the calculated energy barriers for these reactants with the activation energies of oxide growth rate, we suggest the orientation-dependent rate-limiting processes during wet SiC oxidation.

Block copolymer lithography of rhodium nanoparticles for high temperature electrocatalysis.

Science.gov (United States)

Boyd, David A; Hao, Yong; Li, Changyi; Goodwin, David G; Haile, Sossina M

2013-06-25

We present a method for forming ordered rhodium nanostructures on a solid support. The approach makes use of a block copolymer to create and assemble rhodium chloride nanoparticles from solution onto a surface; subsequent plasma and thermal processing are employed to remove the polymer and fully convert the nanostructures to metallic rhodium. Films cast from a solution of the triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) dissolved in toluene with rhodium(III) chloride hydrate were capable of producing a monolayer of rhodium nanoparticles of uniform size and interparticle spacing. The nanostructures were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The electrocatalytic performance of the nanoparticles was investigated with AC impedance spectroscopy. We observed that the addition of the particles to a model solid oxide fuel cell anode provided up to a 14-fold improvement in the anode activity as evidenced by a decrease in the AC impedance resistance. Examination of the anode after electrochemical measurement revealed that the basic morphology and distribution of the particles were preserved.

Dual functional rhodium oxide nanocorals enabled sensor for both non-enzymatic glucose and solid-state pH sensing.

Science.gov (United States)

Dong, Qiuchen; Huang, Yikun; Song, Donghui; Wu, Huixiang; Cao, Fei; Lei, Yu

2018-07-30

Both pH-sensitive and glucose-responsive rhodium oxide nanocorals (Rh 2 O 3 NCs) were synthesized through electrospinning followed by high-temperature calcination. The as-prepared Rh 2 O 3 NCs were systematically characterized using various advanced techniques including scanning electron microscopy, X-ray powder diffraction and Raman spectroscopy, and then employed as a dual functional nanomaterial to fabricate a dual sensor for both non-enzymatic glucose sensing and solid-state pH monitoring. The sensing performance of the Rh 2 O 3 NCs based dual sensor toward pH and glucose was evaluated using open circuit potential, cyclic voltammetry and amperometric techniques, respectively. The results show that the as-prepared Rh 2 O 3 NCs not only maintain accurate and reversible pH sensitivity of Rh 2 O 3 , but also demonstrate a good electrocatalytic activity toward glucose oxidation in alkaline medium with a sensitivity of 11.46 μA mM -1 cm -2 , a limit of detection of 3.1 μM (S/N = 3), and a reasonable selectivity against various interferents in non-enzymatic glucose detection. Its accuracy in determining glucose in human serum samples was further demonstrated. These features indicate that the as-prepared Rh 2 O 3 NCs hold great promise as a dual-functional sensing material in the development of a high-performance sensor forManjakkal both solid-state pH and non-enzymatic glucose sensing. Copyright © 2018 Elsevier B.V. All rights reserved.

Antitumor effect and toxicity of free rhodium (II) citrate and rhodium (II) citrate-loaded maghemite nanoparticles in mice bearing breast cancer.

Science.gov (United States)

Carneiro, Marcella Lemos Brettas; Peixoto, Raphael C A; Joanitti, Graziela A; Oliveira, Ricardo G S; Telles, Luis A M; Miranda-Vilela, Ana L; Bocca, Anamélia L; Vianna, Leonora M S; da Silva, Izabel C R; de Souza, Aparecido R; Lacava, Zulmira G M; Báo, Sônia N

2013-02-16

Magnetic fluids containing superparamagnetic iron oxide nanoparticles represent an attractive platform as nanocarriers in chemotherapy. Recently, we developed a formulation of maghemite nanoparticles coated with rhodium (II) citrate, which resulted in in vitro cytotoxicity enhanced up to 4.6 times when compared to free rhodium (II) citrate formulation on breast carcinoma cells. In this work, we evaluate the antitumor activity and toxicity induced by these formulations in Balb/c mice bearing orthotopic 4T1 breast carcinoma. Mice were evaluated with regard to the treatments' toxicity through analyses of hemogram, serum levels of alanine aminotransferase, iron, and creatinine; DNA fragmentation and cell cycle of bone marrow cells; and liver, kidney and lung histology. In addition, the antitumor activity of rhodium (II) citrate and maghemite nanoparticles coated with rhodium (II) citrate was verified by tumor volume reduction, histology and immunohistochemistry. Regarding the treatments' toxicity, no experimental groups had alterations in levels of serum ALT or creatinine, and this suggestion was corroborated by the histopathologic examination of liver and kidney of mice. Moreover, DNA fragmentation frequency of bone marrow cells was lower than 15% in all experimental groups. On the other hand, the complexes rhodium (II) citrate-functionalized maghemite and free rhodium (II) citrate led to a marked growth inhibition of tumor and decrease in CD31 and Ki-67 staining. In summary, we demonstrated that both rhodium (II) citrate and maghemite nanoparticles coated with rhodium (II) citrate formulations exhibited antitumor effects against 4T1 metastatic breast cancer cell line following intratumoral administration. This antitumor effect was followed by inhibition of both cell proliferation and microvascularization and by tumor tissue injury characterized as necrosis and fibrosis. Remarkably, this is the first published report demonstrating the therapeutic efficacy of maghemite

A study of the accelerated zircaloy-4 oxidation reaction with H2O/H2 mixture gas

International Nuclear Information System (INIS)

Kim, Y. S.; Cho, I. J.

2001-01-01

A study of the Zircaloy-4 reaction with H 2 O/H 2 mixture gas is carried out by using TGA (Thermo Gravimetric Apparatus) to estimate the hydrogen embrittlement which can possibly cause catastrophic nuclear fuel rod failure. Reaction rates are measured as a function of H 2 /H 2 O. In the experiments reaction temperature is set at 500 .deg. C and total pressure of the mixture gas is maintained at 1 atm. Experimental results reveal that hydriding and oxidation reaction are competing. In early stage, hydriding kinetics is faster than oxidation, however, oxidant in H 2 O forms oxide on the surface as steam environment is maintained, thus, this growing oxide begins to protect the zirconium base metal against hydrogen permeation. In this second stage, the total kinetic rate follows enhanced oxidation kinetics. In the final stage, it is observed that the oxide is broken down and massive hydriding takes place through the mechanical defects in the oxide, whose kinetics is similar to pure hydriding kinetics. These results are confirmed by SEM and EDX analysis along with hydrogen concentration measurements

Room temperature chemically oxidized La2CuO4+y: Phase separation induced by thermal treatment

DEFF Research Database (Denmark)

Rial,C.; Moran, E.; Alario-Franco, M.A.

1997-01-01

The structure of roam temperature chemically oxidized La2CuO4+y [y = 0.103(4)] has been refined from powder neutron diffraction data using the space group Bmab. The modifications induced in the CuO2 and the LaO planes by the insertion of oxygen are consistent with the high T-c measured for this m......The structure of roam temperature chemically oxidized La2CuO4+y [y = 0.103(4)] has been refined from powder neutron diffraction data using the space group Bmab. The modifications induced in the CuO2 and the LaO planes by the insertion of oxygen are consistent with the high T-c measured...... a short treatment at 433 K, La2CuO4.103(4) undergoes a phase separation into two phases: phase 1, with estimated y(1) = 0.086(4) and T-cl = 30 K, and phase 2, with estimated y(2) = 0.12(1) and T-c2 = 17 K. By increasing the annealing times, phase 2 transforms to phase I and finally disappears. Therefore...

Ion flotation of rhodium(III) and palladium(II) with anionic surfactants.

Science.gov (United States)

He, X C

1991-03-01

The ion flotation of rhodium(III) and palladium(II) with some anionic surfactants has been investigated. Two flotation procedures are proposed for the separation of some platinum metals, based on differences in the kinetic properties of the chloro-complexes of rhodium(III), palladium(II) and platinum(IV). The first involves the selective flotation of Rh(H(2)O)(3+)(6) from PdCl(2-)(4) and PtCl(2-)(6) in dilute hydrochloric acid with sodium dodecylbenzenesulfonate (SDBS). After precipitation of the hydroxide and redissolution in dilute acid, the Rh(III) is converted into Rh(H(2)O)(3+)(6), Pd(II) and Pt(IV) remaining as PdCl(2-)(4) and PtCl(2-)(6) respectively, and separation is achieved by floating the Rh(H(2)O)(3+)(6) with SDBS. The second is for separation of Pd(II). Prior to flotation, the solution of PdCl(2-)(4) and PtCl(2-)(6) is heated with ammonium acetate to convert PdCl(2-)(4) into Pd(NH(3))(2+)(4). The chloro-complex of Pt(IV) is unaffected. The complex cation, Pd(NH(3))(2+)(4), is then selectively floated with SDBS. The procedures are fast, simple and do not require expensive reagents and apparatus.

Simultaneous determination of palladium, platinum and rhodium by on-line column enrichment and HPLC with 2,4-dihydroxybenzylidenethiorhodanine as pre-column derivatization reagent

Directory of Open Access Journals (Sweden)

Dong Xuechang

2006-01-01

Full Text Available A new method for the simultaneous determination of palladium, platinum and rhodium ions as metal-DHBTR chelates was developed. The palladium, platinum and rhodium ions were pre-column derivatized with 2,4-dihydroxybenzylidenethiorhodanine (DHBTR to form colored chelates. The Pd-DHBTR, Pt-DHBTR and Rh-DHBTR chelates can be absorbed onto the front of the enrichment column when they were injected into the injector and sent to the enrichment column with a 0.05 mol L-1 sodium acetate-acetic acid buffer solution (pH 3.5 as mobile phase. After the enrichment had finished, by switching the six ports switching valve, the retained chelates were back-flushed by mobile phase and traveling towards the analytical column. These chelates separation on the analytical column was satisfactory with 62% (v/v acetonitrile (containing 0.05 mol L-1 of pH 3.5 sodium acetate-acetic acid buffer salt and 0.1% (m/v of tritonX-100 as mobile phase. The Limits of detection of palladium, platinum and rhodium are 3.6 ng L-1, 3.2 ng L-1 and 4.5 ng L-1, respectively. This method was applied to the determination of palladium, platinum and rhodium in water, urine and soil samples with good results.

The decomposition of mixed oxide Ag2Cu2O3: Structural features and the catalytic properties in CO and C2H4 oxidation

Science.gov (United States)

Svintsitskiy, Dmitry A.; Kardash, Tatyana Yu.; Slavinskaya, Elena M.; Stonkus, Olga A.; Koscheev, Sergei V.; Boronin, Andrei I.

2018-01-01

The mixed silver-copper oxide Ag2Cu2O3 with a paramelaconite crystal structure is a promising material for catalytic applications. The as-prepared sample of Ag2Cu2O3 consisted of brick-like particles extended along the [001] direction. A combination of physicochemical techniques such as TEM, XPS and XRD was applied to investigate the structural features of this mixed silver-copper oxide. The thermal stability of Ag2Cu2O3 was investigated using in situ XRD under different reaction conditions, including a catalytic CO + O2 mixture. The first step of Ag2Cu2O3 decomposition was accompanied by the appearance of ensembles consisting of silver nanoparticles with sizes of 5-15 nm. Silver nanoparticles were strongly oriented to each other and to the surface of the initial Ag2Cu2O3 bricks. Based on the XRD data, it was shown that the release of silver occurred along the a and b axes of the paramelaconite structure. Partial decomposition of Ag2Cu2O3 accompanied by the formation of silver nanoparticles was observed during prolonged air storage under ambient conditions. The high reactivity is discussed as a reason for spontaneous decomposition during Ag2Cu2O3 storage. The full decomposition of the mixed oxide into metallic silver and copper (II) oxide took place at temperatures higher than 300 °C regardless of the nature of the reaction medium (helium, air, CO + O2). Catalytic properties of partially and fully decomposed samples of mixed silver-copper oxide were measured in low-temperature CO oxidation and C2H4 epoxidation reactions.

Thermodynamic modeling of La2O3-SrO-Mn2O3-Cr2O3 for solid oxide fuel cell applications

DEFF Research Database (Denmark)

Povoden-Karadeniz, E.; Chen, Ming; Ivas, Toni

2012-01-01

The thermodynamic La–Sr–Mn–Cr–O oxide database is obtained as an extension of thermodynamic descriptions of oxide subsystems using the calculation of phase diagrams approach. Concepts of the thermodynamic modeling of solid oxide phases are discussed. Gibbs energy functions of SrCrO4, Sr2.67Cr2O8......, Sr2CrO4, and SrCr2O4 are presented, and thermodynamic model parameters of La–Sr–Mn–Chromite perovskite are given. Experimental solid solubilities and nonstoichiometries in La1xSrxCrO3d and LaMn1xCrxO3d are reproduced by the model. The presented oxide database can be used for applied computational...... thermodynamics of traditional lanthanum manganite cathode with Cr-impurities. It represents the fundament for extensions to higher orders, aiming on thermodynamic calculations in noble symmetric solid oxide fuel cells...

Thermodynamics of CoAl2O4-CoGa2O4 solid solutions

International Nuclear Information System (INIS)

Lilova, Kristina I.; Navrotsky, Alexandra; Melot, Brent C.; Seshadri, Ram

2010-01-01

CoAl 2 O 4 , CoGa 2 O 4 , and their solid solution Co(Ga z Al 1-z ) 2 O 4 have been studied using high temperature oxide melt solution calorimetry in molten 2PbO.B 2 O 3 at 973 K. There is an approximately linear correlation between lattice parameters, enthalpy of formation from oxides, and the Ga content. The experimental enthalpy of mixing is zero within experimental error. The cation distribution parameters are calculated using the O'Neill and Navrotsky thermodynamic model. The enthalpies of mixing calculated from these parameters are small and consistent with the calorimetric data. The entropies of mixing are calculated from site occupancies and compared to those for a random mixture of Ga and Al ions on octahedral site with all Co tetrahedral and for a completely random mixture of all cations on both sites. Despite a zero heat of mixing, the solid solution is not ideal in that activities do not obey Raoult's Law because of the more complex entropy of mixing. - Graphical abstract: Measured enthalpies of mixing of CoAl 2 O 4 -CoGa 2 O 4 solid solutions are close to zero but entropies of mixing reflect the complex cation distribution, so the system is not an ideal solution.

About the extraction recovery of fission rhodium from radioactive wastes

International Nuclear Information System (INIS)

Khaperskaya, A.V.; Renard, E.V.; Koltunov, V.S.

2000-01-01

The report will cover a radically new approach to the problem of rhodium recovery from HLLW after the transformation of kinetically inert poly-aqua cation of trivalent rhodium (which is not recoverable by the majority known extractants) to Rh (IV) form by chemical methods. Presented are the research results of Rh (IV) extraction from nitric acid solutions by several extractants that are of considerable current use in noble metals and radiochemical industries (tri-n-butyl phosphate, di-octyl-sulphide, tri-n-octylamine, quaternary ammonium bases). High level of rhodium extraction has been found for the above extractants: for several systems, for example, tri-n-octylamine - diethyl-benzene, rhodium distribution coefficient achieves high values (10-plus), as well as the sufficient extraction kinetics. Rhodium extraction increases with a decrease of the acidity, a rise in phase mixing time and in the following series: tri-n-butyl phosphate → di-octyl-sulphide → quaternary ammonium bases → tri-n-octylamine. Rh (IV) can be easily reduced to non-extractable Rh (III) by such reductants as Fe (II), HCOOH, C 6 H 8 O 6 , NH 2 OH, N 2 H 4 et al, that may be applied for the re-extraction process. (authors)

High-Performance Asymmetric Supercapacitors of MnCo2O4 Nanofibers and N-Doped Reduced Graphene Oxide Aerogel.

Science.gov (United States)

Pettong, Tanut; Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Sukha, Phansiri; Sirisinudomkit, Pichamon; Seubsai, Anusorn; Chareonpanich, Metta; Kongkachuichay, Paisan; Limtrakul, Jumras; Sawangphruk, Montree

2016-12-14

The working potential of symmetric supercapacitors is not so wide because one type of material used for the supercapacitor electrodes prefers either positive or negative charge to both charges. To address this problem, a novel asymmetrical supercapacitor (ASC) of battery-type MnCo 2 O 4 nanofibers (NFs)//N-doped reduced graphene oxide aerogel (N-rGO AE ) was fabricated in this work. The MnCo 2 O 4 NFs at the positive electrode store the negative charges, i.e., solvated OH - , while the N-rGO AE at the negative electrode stores the positive charges, i.e., solvated K + . An as-fabricated aqueous-based MnCo 2 O 4 //N-rGO AE ASC device can provide a wide operating potential of 1.8 V and high energy density and power density at 54 W h kg -1 and 9851 W kg -1 , respectively, with 85.2% capacity retention over 3000 cycles. To understand the charge storage reaction mechanism of the MnCo 2 O 4 , the synchrotron-based X-ray absorption spectroscopy (XAS) technique was also used to determine the oxidation states of Co and Mn at the MnCo 2 O 4 electrode after being electrochemically tested. The oxidation number of Co is oxidized from +2.76 to +2.85 after charging and reduced back to +2.75 after discharging. On the other hand, the oxidation state of Mn is reduced from +3.62 to +3.44 after charging and oxidized to +3.58 after discharging. Understanding in the oxidation states of Co and Mn at the MnCo 2 O 4 electrode here leads to the awareness of the uncertain charge storage mechanism of the spinel-type oxide materials. High-performance ASC here in this work may be practically used in high-power applications.

Controlled Oxygen Chemisorption on an Alumina Supported Rhodium Catalyst. The Formation of a New Metal-Metal Oxide Interface Determined with EXAFS.

NARCIS (Netherlands)

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

1989-01-01

An alumina-supported rhodium catalyst has been studied with EXAFS. After reduction and evacuation, oxygen was admitted at 100 and 300 K. EXAFS spectra of the catalyst after oxygen admission at 100 K indicated the beginning of oxidation. At 300 K only a small part of the rhodium particles remained

Pentamethylcyclopentadienyl-rhodium and iridium complexes containing (N^N and N^O) bound chloroquine analogue ligands: synthesis, characterization and antimalarial properties.

Science.gov (United States)

Ekengard, Erik; Kumar, Kamlesh; Fogeron, Thibault; de Kock, Carmen; Smith, Peter J; Haukka, Matti; Monari, Magda; Nordlander, Ebbe

2016-03-07

The synthesis and characterization of twenty new pentamethylcyclopentadienyl-rhodium and iridium complexes containing N^N and N^O-chelating chloroquine analogue ligands are described. The in vitro antimalarial activity of the new ligands as well as the complexes was evaluated against the chloroquine sensitive (CQS) NF54 and the chloroquine resistant (CQR) Dd2 strains of Plasmodium falciparum. The antimalarial activity was found to be good to moderate; although all complexes are less active than artesunate, some of the ligands and complexes showed better activity than chloroquine (CQ). In particular, rhodium complexes were found to be considerably more active than iridium complexes against the CQS NF54 strain. Salicylaldimine Schiff base ligands having electron-withdrawing groups (F, Cl, Br, I and NO2) in para position of the salicyl moiety and their rhodium complexes showed good antiplasmodial activity against both the CQS-NF54 and the CQR-Dd2 strains. The crystal structures of (η(5)-pentamethylcyclopentadienyl){N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)} chlororhodium(III) chloride and (η(5)-pentamethylcyclopentadienyl){(4-chloro-2-(((2-((7-chloroquinolin-4-yl)amino)ethyl)imino)methyl)phenolate)}chlororhodium(III) chloride are reported. The crystallization of the amino-pyridyl complex (η(5)-pentamethylcyclopentadienyl){(N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)}chloroiridium(III) chloride in acetone resulted in the formation of the imino-pyridyl derivative (η(5)-pentamethylcyclopentadienyl){(N1-(7-chloroquinolin-4-yl)-N2-(pyridin-2-ylmethylene)ethane-1,2-diamine)}chloroiridium(III) chloride, the crystal structure of which is also reported.

Mechanistic studies of mercury adsorption and oxidation by oxygen over spinel-type MnFe{sub 2}O{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Yang, Yingju [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Liu, Jing, E-mail: liujing27@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Shenzhen Institute of Huazhong University of Science and Technology, Shenzhen 518000 (China); Zhang, Bingkai; Liu, Feng [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

2017-01-05

Highlights: • Hg adsorption and oxidation mechanisms on MnFe{sub 2}O{sub 4} were studied using DFT method. • Hg{sup 0} adsorption on Mn-terminated MnFe{sub 2}O{sub 4} (100) surface is a chemisorption process. • HgO shows high chemical reactivity for its adsorption on MnFe{sub 2}O{sub 4} surface. • The reaction between adsorbed Hg and surface oxygen is the rate-determining step. - Abstract: MnFe{sub 2}O{sub 4} has been regarded as a very promising sorbent for mercury emission control in coal-fired power plants because of its high adsorption capacity, magnetic, recyclable and regenerable properties. First-principle calculations based on density functional theory (DFT) were used to elucidate the mercury adsorption and oxidation mechanisms on MnFe{sub 2}O{sub 4} surface. DFT calculations show that Mn-terminated MnFe{sub 2}O{sub 4} (1 0 0) surface is much more stable than Fe-terminated surface. Hg{sup 0} is physically adsorbed on Fe-terminated MnFe{sub 2}O{sub 4} (1 0 0) surface. Hg{sup 0} adsorption on Mn-terminated MnFe{sub 2}O{sub 4} (1 0 0) surface is a chemisorption process. The partial density of states (PDOS) analysis indicates that Hg atom interacts strongly with surface Mn atoms through the orbital hybridization. HgO is adsorbed on the MnFe{sub 2}O{sub 4} surface in a chemical adsorption manner. The small HOMO–LUMO energy gap implies that HgO molecular shows high chemical reactivity for HgO adsorption on MnFe{sub 2}O{sub 4} surface. The energy barriers of Hg{sup 0} oxidation by oxygen on Fe- and Mn-terminated MnFe{sub 2}O{sub 4} surfaces are 206.37 and 76.07 kJ/mol, respectively. Mn-terminated surface is much more favorable for Hg{sup 0} oxidation than Fe-terminated surface. In the whole Hg{sup 0} oxidation process, the reaction between adsorbed mercury and surface oxygen is the rate-determining step.

Three new d10 transition metal selenites containing PO4 tetrahedron: Cd7(HPO4)2(PO4)2(SeO3)2, Cd6(PO4)1.34(SeO3)4.66 and Zn3(HPO4)(SeO3)2(H2O)

Science.gov (United States)

Ma, Yun-Xiang; Gong, Ya-Ping; Hu, Chun-li; Mao, Jiang-Gao; Kong, Fang

2018-06-01

Three new d10 transition metal selenites containing PO4 tetrahedron, namely, Cd7(HPO4)2(PO4)2(SeO3)2 (1), Cd6(PO4)1.34(SeO3)4.66 (2) and Zn3(HPO4)(SeO3)2(H2O) (3), have been synthesized by hydrothermal reaction. They feature three different structural types. Compound 1 exhibits a novel 3D network composed of 3D cadmium selenite open framework with phosphate groups filled in the 1D helical tunnels. The structure of compound 2 displays a new 3D framework consisted of 2D cadmium oxide layers bridged by SeO3 and PO4 groups. Compound 3 is isostructural with the reported solids of Co3(SeO3)3-x(PO3OH)x(H2O) when x is equal to 1.0. Its structure could be viewed as a 3D zinc oxide open skeleton with SeO3 and HPO4 polyhedra attached on the wall of the tunnels. They represent the only examples in metal selenite phosphates in addition to the above cobalt compounds. Optical diffuse reflectance spectra revealed that these solids are insulators, which are consistent with the results of band structure computations based on DFT algorithm.

Effect of Co3O4 and Co3O4/CeO2 infiltration on the catalytic and electro-catalytic activity of LSM15/CGO10 porous cells stacks for oxidation of propene

DEFF Research Database (Denmark)

Ippolito, Davide; Kammer Hansen, Kent

2015-01-01

The objective of this work was to study the effect of Co3O4 and Co3O4/CeO2 infiltration on the propene oxidation catalytic activity of a La0.85Sr0.15MnO3/Ce0.9Gd0.1O1.95 electrochemical porous cell stack (11 layers, 5 single cells in series). The effect of the infiltration of Co3O4 and Co3O4/CeO2...... on the electrochemical properties of the porous cell stack was also investigated by electrochemical impedance spectroscopy (EIS). Co3O4 and Co3O4/CeO2 exhibited high catalytic activity for propene oxidation. The increase of propene oxidation rate with +4 V (0.8 V/cell) polarization reached 10% for the Co3O4 infiltrated...... reactor and 48% of efficiency at 300 °C. The Co3O4/CeO2 co-infiltration decreased the reactor polarization resistance, while Co3O4 infiltration had negligible effect on reactor electrochemical performance. The beneficial effect of CeO2 on the electrode activity was attributed to the increased...

One-step synthesis of sea urchin-like alpha-MnO2 using KIO4 as the oxidant and its oxidation of arsenite

NARCIS (Netherlands)

Wang, M.X.; Tan, W.F.; Feng, X.H.; Koopal, L.K.; Liu, M.M.; Liu, F.

2012-01-01

Among several types of manganese oxides alpha-MnO2 is the most active due to its good catalytic, adsorption and ion exchange properties. Sea urchin-like alpha-MnO2 particles were synthesized by a one-step chemistry route at room temperature using MnSO4 in combination with KIO4 as oxidant. The

XPS and EELS characterization of Mn{sub 2}SiO{sub 4}, MnSiO{sub 3} and MnAl{sub 2}O{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Grosvenor, A.P., E-mail: andrew.grosvenor@usask.ca [Department of Chemistry, University of Saskatchewan, Saskatoon, SK S7N 5C9 (Canada); Bellhouse, E.M., E-mail: erika.bellhouse@arcelormittal.com [Global R & D—Hamilton, ArcelorMittal Dofasco, 1330 Burlington St. E, Hamilton, ON L8N 3J5 (Canada); Korinek, A., E-mail: korinek@mcmaster.ca [Canadian Centre for Electron Microscopy, Brockhouse Institute for Materials Research, McMaster University, 1280 Main St. W., Hamilton, ON L8S 4M1 (Canada); Bugnet, M., E-mail: bugnetm@mcmaster.ca [Canadian Centre for Electron Microscopy, Brockhouse Institute for Materials Research, McMaster University, 1280 Main St. W., Hamilton, ON L8S 4M1 (Canada); McDermid, J.R., E-mail: mcdermid@mcmaster.ca [Steel Research Centre, McMaster University, 1280 Main St. W., Hamilton, ON L8S 4M1 (Canada)

2016-08-30

Graphical abstract: XPS and EELS spectra were acquired from Mn2Al2O4, MnSiO3 and Mn2SiO4 standards and unique features identified that will allow unambiguous identification of these compounds when studying the selective oxidation of advanced steels. - Highlights: • Mn2Al2O4, MnSiO3 and Mn2SiO4 standards were synthesized and characterized using both XPS and EELS. • Unique features in both the XPS high resolution and EELS spectra were identified for all compounds. • The spectra can be used to identify these compounds when studying the selective oxidation of steels. - Abstract: X-ray Photoelectron Spectroscopy (XPS) and Electron Energy Loss Spectroscopy (EELS) are strong candidate techniques for characterizing steel surfaces and substrate-coating interfaces when investigating the selective oxidation and reactive wetting of advanced high strength steels (AHSS) during the continuous galvanizing process. However, unambiguous identification of ternary oxides such as Mn{sub 2}SiO{sub 4}, MnSiO{sub 3}, and MnAl{sub 2}O{sub 4} by XPS or EELS, which can play a significant role in substrate reactive wetting, is difficult due to the lack of fully characterized standards in the literature. To resolve this issue, samples of Mn{sub 2}SiO{sub 4}, MnSiO{sub 3} and MnAl{sub 2}O{sub 4} were synthesized and characterized by XPS and EELS. The unique features of the XPS and EELS spectra for the Mn{sub 2}SiO{sub 4}, MnSiO{sub 3} and MnAl{sub 2}O{sub 4} standards were successfully derived, thereby allowing investigators to fully differentiate and identify these oxides at the surface and subsurface of Mn, Si and Al alloyed AHSS using these techniques.

Synthesis and physico-chemical characterization of CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} mixed oxides

Energy Technology Data Exchange (ETDEWEB)

Hernandez E, J. M.; Silva R, R.; Garcia A, R. [Instituto Tecnologico de Ciudad Madero, Div. de Estudios de Posgrado e Investigacion, Juventino Rosas y Jesus Urueta s/n, Col. Los Mangos, 89440 Ciudad Madero, Tamaulipas (Mexico); Garcia S, L. A. [IPN, Centro Interdisciplinario de Investigaciones y de Estudios sobre Medio Ambiente y Desarrollo, 30 de Junio No. 1520, Barrio La Laguna Ticoman, 07340 Mexico D. F. (Mexico); Handy, B. E.; Cardenas G, G. [Universidad Autonoma de San Luis Potosi, CIEP, Facultad de Ciencias Quimicas, Av. Dr. Manuel Nava No. 6, Zona Universitaria, 78210 SLP, San Luis Potosi (Mexico); Cueto H, A. [Universidad Autonoma Metropolitana, Unidad Azcapotzalco, Av. San Pablo No. 180, Col. Reynosa Tamaulipas, 02200 Mexico D. F. (Mexico)

2012-07-01

Environmentally friendly solid-acid catalysts CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} were prepared by the sol gel method varying CeO{sub 2} content (10, 20 and 30 wt %) and using sulfation in situ, maintaining the sulfate ions amount present in the materials at 20 wt %. ZrO{sub 2} and ZrO{sub 2}-SO{sub 4}{sup 2-} were also prepared for comparison proposes using the same synthesis method. The materials were characterized by X-ray diffraction, nitrogen physisorption, potentiometric titration with n-butylamine, decomposition of 2-propanol and n-pentane isomerization. The specific surface area of ZrO{sub 2}-SO{sub 4}{sup 2-} was high (160 m{sup 2}/g) compared with the unmodified ZrO{sub 2} (80 m{sup 2}/g), however this area decreased with increasing the CeO{sub 2} content (37-100 m{sup 2}/g). There was no significant effect of CeO{sub 2} on the tetragonal structure of ZrO{sub 2}-SO{sub 4}{sup 2-}. The variation of acid sites amount runs parallel to the change of specific surface area. The acid sites amount decreased with increasing cerium oxide content. The decomposition of 2-propanol results fundamentally in the formation of dehydration products such as propylene and diisopropyl ether, both involving acid sites. In addition, a good performance during the n-pentane isomerization was observed for these materials. The selectivity towards isopentane reaches 84% when the Pt/CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} catalyst with the highest CeO{sub 2} content was used. (Author)

Graphene oxide (rGO)-metal oxide (TiO2/Fe3O4) based nanocomposites for the removal of methylene blue

Science.gov (United States)

Banerjee, Soma; Benjwal, Poonam; Singh, Milan; Kar, Kamal K.

2018-05-01

Herein, ternary nanocomposites based on titanium dioxide, ferric oxide and reduced graphene oxide (GO) have been developed for photocatalytic degradation of methylene blue. The nanocomposites are prepared by simple sol-gel and wet assembly methods with varying weight ratio of each components to obtain efficient photocatalytic degradation. Due to the synergistic effect among the three components, a swift removal of methylene blue becomes possible under visible and UV light. The rGO-Fe3O4-TiO2 nanocomposite having composition 1:1:2 has achieved maximum degradation of methylene blue from the aqueous solution. About 99% of the dye has been removed within 6 min under UV irradiation, while in presence of visible light, 94% has been degraded from the wastewater. The enhancement of photocatalytic activity in this ternary system is attributed to the efficient separation of charge carriers from TiO2 to rGO under the exposure of light and the initiation of photo-Fenton reaction due to the incorporated Fe3O4 nanoparticles in presence of H2O2, which provides highly reactive hydroxyl ions that mineralize the pollutants. All these results indicate that these ternary nanocomposites possess great potential for both UV and visible light driven methylene blue destruction from the wastewater.

Sign system choice influence on the substance formation forecast in A2MoO4-B2(MoO4)3 and A2MoO4-CMoO4 systems

International Nuclear Information System (INIS)

Manzanov, Yu.E.; Lutsik, V.I.; Mokhosoev, M.V.

1987-01-01

Three sign spaces were used for forecasting compound formation in A 2 MoO 4 -B 2 (MoO 4 ) 3 (5:1 ratio, where A-Li, Na, K, Rb, Cs; B-Al, In, Ga, Sc, Cr, Fe, Bi, La, Nd, Sm-Lu, Y) and A 2 MoO 4 -CMoO 4 (1:2 ratio, where A-Li, Na, K, RB, Cs, Tl; C-Mg, Ca, Sr, Ba, Cu, Zn, Cd, Pd, Mn, Co, Ni) systems: 1-electron distribution on energy shells of cations and their valency; 2-the type of incomplete electron shell, charge of cations, three first ionization potentials, standard heat capacity, ionic radius of cations; 3-standard formation enthalpy and standard entropy, oxide melting points and ionic radius of cations. It is shown that sign space, related with thermodynamic properties of oxides contains data, necessary for forecasting interaction in molybdate systems. This enables to improve reliability of forecasting

Chemical consequences of the neutron irradiation of ionic antimony oxides and Fe Sb2O4

Energy Technology Data Exchange (ETDEWEB)

Facetti, J F [Asuncion Nacional Univ. (Paraguay). Inst. de Ciencias

1970-01-01

The chemical consequences fo the neutron irradiation of ionic antimony oxides and Fe Sb2O4 are studied. The nature of the Sb-O2 bond effects the yield of SbV the higher the yield the more covalent the bond. In addition, the Fe Sb2O4 obeys the Maddock's rule.

Steam reforming of ethanol over Co3O4–Fe2O3 mixed oxides

KAUST Repository

Abdelkader, A.

2013-05-03

Co3O4, Fe2O3 and a mixture of the two oxides Co-Fe (molar ratio of Co3O4/Fe 2O3 = 0.67 and atomic ratio of Co/Fe = 1) were prepared by the calcination of cobalt oxalate and/or iron oxalate salts at 500 C for 2 h in static air using water as a solvent/dispersing agent. The catalysts were studied in the steam reforming of ethanol to investigate the effect of the partial substitution of Co3O4 with Fe2O 3 on the catalytic behaviour. The reforming activity over Fe 2O3, while initially high, underwent fast deactivation. In comparison, over the Co-Fe catalyst both the H2 yield and stability were higher than that found over the pure Co3O4 or Fe 2O3 catalysts. DRIFTS-MS studies under the reaction feed highlighted that the Co-Fe catalyst had increased amounts of adsorbed OH/water; similar to Fe2O3. Increasing the amount of reactive species (water/OH species) adsorbed on the Co-Fe catalyst surface is proposed to facilitate the steam reforming reaction rather than decomposition reactions reducing by-product formation and providing a higher H2 yield. © Copyright © 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Mixed oxides forming in CdO-OsO2 and PbO-OsO2 systems

International Nuclear Information System (INIS)

Shaplygin, I.S.; Lazarev, V.B.

1978-01-01

The formation of mixed oxides in systems CdO-OsO 2 and PbO-OsO 2 was studied by derivatography, X-ray phase analysis, and IR spectroscopy. It was established that in the system CdO-OsO 2 cubic phases of Cdsub(2)Ossub(2)Osub(6.7) and Cdsub(2)Ossub(2)Osub(7.2) with a pyrochlor-type structure, as well as new compounds with the structure of rhombic perovskite CdOsO 3 and Cd(Cdsub(0.5)Ossub(0.5))Osub(3) containing osmium in the formal degree of oxidation +4 and +6, respectively, are formed. The thermal stability of the compounds obtained was studied and their electrical properties determined

Fabrication of graphene oxide decorated with Fe3O4@SiO2 for immobilization of cellulase

Science.gov (United States)

Li, Yue; Wang, Xiang-Yu; Jiang, Xiao-Ping; Ye, Jing-Jing; Zhang, Ye-Wang; Zhang, Xiao-Yun

2015-01-01

Fe3O4@SiO2-graphene oxide (GO) composites were successfully fabricated by chemical binding of functional Fe3O4@SiO2 and GO and applied to immobilization of cellulase via covalent attachment. The prepared composites were further characterized by transmission electron microscopy and Fourier transform infrared spectroscopy. Fe3O4 nanoparticles (NPs) were monodisperse spheres with a mean diameter of 17 ± 0.2 nm. The thickness of SiO2 layer was calculated as being 6.5 ± 0.2 nm. The size of Fe3O4@SiO2 NPs was 24 ± 0.3 nm, similar to that of Fe3O4@SiO2-NH2. Fe3O4@SiO2-GO composites were synthesized by linking of Fe3O4@SiO2-NH2 NPs to GO with the catalysis of EDC and NHS. The prepared composites were used for immobilization of cellulase. A high immobilization yield and efficiency of above 90 % were obtained after the optimization. The half-life of immobilized cellulase (722 min) was 3.34-fold higher than that of free enzyme (216 min) at 50 °C. Compared with the free cellulase, the optimal temperature of the immobilized enzyme was not changed; but the optimal pH was shifted from 5.0 to 4.0, and the thermal stability was enhanced. The immobilized cellulase could be easily separated and reused under magnetic field. These results strongly indicate that the cellulase immobilized onto the Fe3O4@SiO2-GO composite has potential applications in the production of bioethanol.

Fe2O3/Reduced Graphene Oxide/Fe3O4 Composite in Situ Grown on Fe Foil for High-Performance Supercapacitors.

Science.gov (United States)

Zhao, Chongjun; Shao, Xiaoxiao; Zhang, Yuxiao; Qian, Xiuzhen

2016-11-09

A Fe 2 O 3 /reduced graphene oxide (RGO)/Fe 3 O 4 nanocomposite in situ grown on Fe foil was synthesized via a simple one-step hydrothermal growth process, where the iron foil served as support, reductant of graphene oxide, Fe source of Fe 3 O 4 , and also the current collector of the electrode. When it directly acted as the electrode of a supercapacitor, as-synthesized Fe 2 O 3 /RGO/Fe 3 O 4 @Fe exhibited excellent electrochemical performance with a high capability of 337.5 mF/cm 2 at 20 mA/cm 2 and a superior cyclability with 2.3% capacity loss from the 600th to the 2000th cycle.

Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe2O4 complex oxide catalyst

International Nuclear Information System (INIS)

Pardeshi, Satish K.; Pawar, Ravindra Y.

2010-01-01

The CaFe 2 O 4 spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 o C which was lower than that of ferrite prepared by other methods. CaFe 2 O 4 catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H 2 O 2 (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 ± 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 ± 2 mol% and minor product phenyl acetaldehyde up to 9 ± 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H 2 O 2 molar ratio and solvents on the conversion and product distribution were studied.

A rhodium(III) complex inhibits LPS-induced nitric oxide production and angiogenic activity in cellulo.

Science.gov (United States)

Liu, Li-Juan; Lin, Sheng; Chan, Daniel Shiu-Hin; Vong, Chi Teng; Hoi, Pui Man; Wong, Chun-Yuen; Ma, Dik-Lung; Leung, Chung-Hang

2014-11-01

Metal-containing complexes have arisen as viable alternatives to organic molecules as therapeutic agents. Metal complexes possess a number of advantages compared to conventional carbon-based compounds, such as distinct geometries, interesting electronic properties, variable oxidation states and the ability to arrange different ligands around the metal centre in a precise fashion. Meanwhile, nitric oxide (NO) plays key roles in the regulation of angiogenesis, vascular permeability and inflammation. We herein report a novel cyclometalated rhodium(III) complex as an inhibitor of lipopolysaccharides (LPS)-induced NO production in RAW264.7 macrophages. Experiments suggested that the inhibition of NO production in cells by complex 1 was mediated through the down-regulation of nuclear factor-κB (NF-κB) activity. Furthermore, complex 1 inhibited angiogenesis in human umbilical vein endothelial cells (HUVECs) as revealed by an endothelial tube formation assay. This study demonstrates that kinetically inert rhodium(III) complexes may be potentially developed as effective anti-angiogenic agents. Copyright © 2014 Elsevier Inc. All rights reserved.

Rhodium-catalyzed regioselective olefination directed by a carboxylic group.

Science.gov (United States)

Mochida, Satoshi; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

2011-05-06

The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids such as methacrylic acid also undergo the olefination at the β-position. Under the rhodium catalysis, the cine-olefination of heteroarene carboxylic acids such as thiophene-2-carboxylic acid proceeds smoothly accompanied by decarboxylation to selectively produce the corresponding vinylheteroarene derivatives. © 2011 American Chemical Society

Fusibility diagram and phase composition of special section ZrO2-MgCr2O4 in oxidative and inert atmospheres

International Nuclear Information System (INIS)

Sennikov, S.G.; Revzin, G.E.; Chistyakova, M.V.

1982-01-01

Using the differential-thermal and microroentgenospectral analyses fusibility diagram is built and phase transformations in subsolidus region of partial cross-section ZrO 2 -MgCr 2 O 4 in the air and in argon atmosphere are studied. It is established that the system studied is attributed to simple eutectics, with the eutectics composition 43 mol.%ZrO 2 and temperature 2005+-15 deg C. Mutual solubility of components is of a limited character. Using the methods of roentgenography and by thermodynamical calculations it has been shown that above 1300 K in oxidative atmosphere enrichment of samples with magnesium oxide and their composition sift to the field of elementary triangle take place

Metal-Organic Framework-Derived Reduced Graphene Oxide-Supported ZnO/ZnCo2O4/C Hollow Nanocages as Cathode Catalysts for Aluminum-O2 Batteries.

Science.gov (United States)

Liu, Yisi; Jiang, Hao; Hao, Jiayu; Liu, Yulong; Shen, Haibo; Li, Wenzhang; Li, Jie

2017-09-20

Aluminum-air battery is a promising candidate for large-scale energy applications because of its low cost and high energy density. Remarkably, tremendous efforts have been concentrated on developing efficient and stable cathode electrocatalysts toward the oxygen reduction reaction. In this work, a hydrothermal-calcination approach was utilized to prepare novel reduced graphene oxide (rGO)-supported hollow ZnO/ZnCo 2 O 4 nanoparticle-embedded carbon nanocages (ZnO/ZnCo 2 O 4 /C@rGO) using a zeolitic imidazolate framework (ZIF-67)/graphene oxide/zinc nitrate composite as the precursor. The ZnO/ZnCo 2 O 4 /C@rGO hybrid exhibits remarkable electrocatalytic performance for oxygen reduction reaction under alkaline conditions and superior stability and methanol tolerance to those of the commercial Pt/C catalyst. Furthermore, novel and simple Al-air coin cells were first fabricated using the hybrid materials as cathode catalysts under ambient air conditions to further investigate their catalytic performance. The coin cell with the ZnO/ZnCo 2 O 4 /C@rGO cathode catalyst displays a higher open circuit voltage and discharge voltage and more sluggish potential drop than those of the cell with the ZnO/ZnCo 2 O 4 /C cathode catalyst, which confirms that rGO can enhance the electrocatalytic activity and stability of the catalyst system. The excellent electrocatalytic performance of the ZnO/ZnCo 2 O 4 /C@rGO hybrid is attributed to the prominent conductivity and high specific surface area resulting from rGO, the more accessible catalytic active sites induced by the unique porous hollow nanocage structure, and synergic covalent coupling between rGO sheets and ZnO/ZnCo 2 O 4 /C nanocages.

Fabrication of graphene oxide decorated with Fe3O4@SiO2 for immobilization of cellulase

International Nuclear Information System (INIS)

Li, Yue; Wang, Xiang-Yu; Jiang, Xiao-Ping; Ye, Jing-Jing; Zhang, Ye-Wang; Zhang, Xiao-Yun

2015-01-01

Fe 3 O 4 @SiO 2 –graphene oxide (GO) composites were successfully fabricated by chemical binding of functional Fe 3 O 4 @SiO 2 and GO and applied to immobilization of cellulase via covalent attachment. The prepared composites were further characterized by transmission electron microscopy and Fourier transform infrared spectroscopy. Fe 3 O 4 nanoparticles (NPs) were monodisperse spheres with a mean diameter of 17 ± 0.2 nm. The thickness of SiO 2 layer was calculated as being 6.5 ± 0.2 nm. The size of Fe 3 O 4 @SiO 2 NPs was 24 ± 0.3 nm, similar to that of Fe 3 O 4 @SiO 2 –NH 2 . Fe 3 O 4 @SiO 2 –GO composites were synthesized by linking of Fe 3 O 4 @SiO 2 –NH 2 NPs to GO with the catalysis of EDC and NHS. The prepared composites were used for immobilization of cellulase. A high immobilization yield and efficiency of above 90 % were obtained after the optimization. The half-life of immobilized cellulase (722 min) was 3.34-fold higher than that of free enzyme (216 min) at 50 °C. Compared with the free cellulase, the optimal temperature of the immobilized enzyme was not changed; but the optimal pH was shifted from 5.0 to 4.0, and the thermal stability was enhanced. The immobilized cellulase could be easily separated and reused under magnetic field. These results strongly indicate that the cellulase immobilized onto the Fe 3 O 4 @SiO 2 –GO composite has potential applications in the production of bioethanol

Dispersive oxidation of rhodium clusters in Na-Y by the combined action of zeolite protons and carbon monoxide

International Nuclear Information System (INIS)

Wong, T.T.T.; Sachtler, W.M.H.; Stakheev, A.Yu.

1992-01-01

This paper uses x-ray photoelectron spectroscopy, fourier transform infrared spectroscopy and temperature programmed mass-spectrometric analysis to study the interaction of Na-Y supported rhodium with hydrogen, carbon monoxide, and zeolite protons. This report attempts to clarify the mechanism of dispersive oxidation of reduced Rh particles in the presence of CO, leading to the formation of Rh + (CO) 2 cations

Oxidation of Refractory Benzothiazoles with PMS/CuFe2O4: Kinetics and Transformation Intermediates

KAUST Repository

Zhang, Tao; Chen, Yin; Leiknes, TorOve

2016-01-01

Benzothiazole (BTH) and its derivatives, 2-(methylthio)bezothiazole (MTBT), 2-benzothiazolsulfonate (BTSA) and 2-hydroxybenzothiazole (OHBT), are refractory pollutants ubiquitously existing in urban runoff at relatively high concentrations. Here, we report their oxidation by CuFe2O4-activated peroxomonosulfate (PMS/CuFe2O4), focusing on kinetics and transformation intermediates. These benzothiazoles can be efficiently degraded by this oxidation process which is confirmed to generate mainly sulfate radicals (with negligible hydroxyl-radical formation) under slightly acidic to neutral pH conditions. The molar exposure ratio of sulfate radical to residual PMS (i.e. Rct) of this process is a constant which is related to reaction condition and can be easily determined. Reaction rate constants of these benzothiazoles towards sulfate radical are (3.3 ± 0.3) × 109, (1.4 ± 0.3) × 109, (1.5 ± 0.1) × 109 and (4.7 ± 0.5) × 109 M-1s-1, respectively (pH 7 and 20 oC). Based on Rct and these rate constants, their degradation in the presence of organic matter can be well predicted. A number of transformation products were detected and tentatively identified using triple-quadruple/linear ion trap MS/MS and high-resolution MS. It appears that sulfate radicals attack BTH, MTBT and BTSA on their benzo ring via electron transfer, generating multiple hydroxylated intermediates which are reactive towards common oxidants. For OHBT oxidation, it prefers to break down the thiazole ring. Due to competitions of the transformation intermediates, a minimum PMS/pollutant molar ratio of 10-20 is required for effective degradation. The flexible PMS/CuFe2O4 could be a useful process to remove the benzothiazoles from low DOC waters like urban runoff or polluted groundwater.

Oxidation of Refractory Benzothiazoles with PMS/CuFe2O4: Kinetics and Transformation Intermediates

KAUST Repository

Zhang, Tao

2016-05-04

Benzothiazole (BTH) and its derivatives, 2-(methylthio)bezothiazole (MTBT), 2-benzothiazolsulfonate (BTSA) and 2-hydroxybenzothiazole (OHBT), are refractory pollutants ubiquitously existing in urban runoff at relatively high concentrations. Here, we report their oxidation by CuFe2O4-activated peroxomonosulfate (PMS/CuFe2O4), focusing on kinetics and transformation intermediates. These benzothiazoles can be efficiently degraded by this oxidation process which is confirmed to generate mainly sulfate radicals (with negligible hydroxyl-radical formation) under slightly acidic to neutral pH conditions. The molar exposure ratio of sulfate radical to residual PMS (i.e. Rct) of this process is a constant which is related to reaction condition and can be easily determined. Reaction rate constants of these benzothiazoles towards sulfate radical are (3.3 ± 0.3) × 109, (1.4 ± 0.3) × 109, (1.5 ± 0.1) × 109 and (4.7 ± 0.5) × 109 M-1s-1, respectively (pH 7 and 20 oC). Based on Rct and these rate constants, their degradation in the presence of organic matter can be well predicted. A number of transformation products were detected and tentatively identified using triple-quadruple/linear ion trap MS/MS and high-resolution MS. It appears that sulfate radicals attack BTH, MTBT and BTSA on their benzo ring via electron transfer, generating multiple hydroxylated intermediates which are reactive towards common oxidants. For OHBT oxidation, it prefers to break down the thiazole ring. Due to competitions of the transformation intermediates, a minimum PMS/pollutant molar ratio of 10-20 is required for effective degradation. The flexible PMS/CuFe2O4 could be a useful process to remove the benzothiazoles from low DOC waters like urban runoff or polluted groundwater.

Electromagnetic characteristics of manganese oxide-coated Fe3O4 nanoparticles at 2-18 GHz

Science.gov (United States)

Yang, R. B.; Liang, W. F.; Lin, C. K.

2011-04-01

The dielectric and magnetic properties of manganese oxide-coated Fe3O4 nanoparticles (NPs) were measured by the transmission/reflection method in 2-18 GHz. MnOx-coated Fe3O4 NPs were prepared by sol-gel method followed by heat-treating at 300, 400, and 500 °C, respectively. The heat-treated powders were then used as magnetic fillers and added to an epoxy resin to prepare MnOx-coated Fe3O4 composites for the complex permittivity (ɛ'-jɛ″) and permeability (μ'-jμ″) measurements. After the sol-gel process, the coating of manganese oxide (mixture of major Mn2O3 and minor Mn3O4) reduced the value of ɛ'. The lower the heat-treating temperature, the larger the decrease in ɛ'. The relative decrease in ɛ', compared with uncoated Fe3O4 nanoparticles, is 28.7, 23.5, and 20.0% for coated MnOx heat-treated at 300, 400, and 500 °C, respectively, while the relative decrease in ɛ″ is 74.1, 68.8, and 65.2%, respectively. In the present study, MnOx-coated Fe3O4 exhibited a significant decrease in dielectric loss tangent of ˜100% compared to that of uncoated NPs and can be of practical use for microwave components.

Graphene oxide coated with porous iron oxide ribbons for 2, 4-Dichlorophenoxyacetic acid (2,4-D) removal.

Science.gov (United States)

Nethaji, S; Sivasamy, A

2017-04-01

Graphene oxide (GO) was prepared from commercially available graphite powder. Porous iron oxide ribbons were grown on the surface of GO by solvothermal process. The prepared GO-Fe 3 O 4 nanocomposites are characterized by FT-IR, XRD, VSM, SEM, TEM, Raman spectroscopy, surface functionality and zero point charge studies. The morphology of the iron oxide ribbons grown on GO is demonstrated with TEM at various magnifications. The presence of magnetite nanoparticles is evident from XRD peaks and the magnetization value is found to be 37.28emu/g. The ratio of intensity of D-peak to G-peak from Raman spectrum is 0.995. The synthesized Graphene oxide-Fe 3 O 4 nanocomposites (GO-Fe 3 O 4 ) were explored for its surface adsorptive properties by using a model organic compound, 2,4-Dichlorophenoxy acetic acid (2,4-D) from aqueous solution. Batch adsorption studies were performed and the equilibrium data are modelled with Langmuir, Freundlich and Temkin isotherms. The maximum monolayer capacity from Langmuir isotherm is 67.26mg/g. Kinetic studies were also carried out and the studied adsorption process followed pseudo second-order rate equation. Mechanism of the adsorption process is studied by fitting the data with intraparticle diffusion model and Boyd plot. The studied adsorption process is both by film diffusion and intraparticle diffusion. Copyright © 2017 Elsevier Inc. All rights reserved.

The reaction mechanism of the partial oxidation of methane to synthesis gas: a transient kinetic study over rhodium and a comparison with platinum

NARCIS (Netherlands)

Mallens, E.P.J.; Hoebink, J.H.B.J.; Marin, G.B.M.M.

1997-01-01

The partial oxidation of methane to synthesis gas over rhodium sponge has been investigated by admitting pulses of pure methane and pure oxygen as well as mixtures of methane and oxygen to rhodium sponge at temperatures from 873 to 1023 K. Moreover, pulses of oxygen followed by methane and vice

Theoretical study of the adsorption of rhodium on a TiO2(1 1 0)-1 × 1 surface

International Nuclear Information System (INIS)

Mutombo, P.; Balázs, N.; Majzik, Z.; Berkó, A.; Cháb, V.

2012-01-01

Density functional theory (DFT) calculations were used to study the adsorption of rhodium on a TiO 2 (1 1 0)-1 × 1 surface as a function of coverage. It was found that Rh atom prefers the hollow site between a bridging oxygen atom, a threefold oxygen atom and a fivefold coordinated Ti atom, regardless of the coverage used. DFT calculations also suggest that Rh-Rh interaction is attractive along the [0 0 1] direction, implying that the Rh 1D nanostructure should grow preferentially along this direction. Simulated Rh dimer clusters resemble strongly Pd dimers resolved in STM experiments suggesting that both metals occupy the same adsorption site at the TiO 2 (1 1 0) surface.

Effects of CO, O2, NO, H2O, and irradiation temperature on the radiation-induced oxidation of SO2

International Nuclear Information System (INIS)

Tokunaga, Okihiro; Nishimura, Koichi; Suzuki, Nobutake; Washino, Masamitsu

1977-01-01

When a SO 2 -H 2 O-O 2 -N 2 gaseous mixture was irradiated by electron beams of 1.5 MeV, SO 2 was easily oxidized to H 2 SO 4 . Effects of CO, O 2 , NO, H 2 O, and irradiation temperature on the radiation-induced oxidation of SO 2 were studied by measuring the SO 2 concentration gas chromatographically. The G(-SO 2 ) increased greatly at the addition of a small amount of O 2 , and then decreased gradually with an increase in the O 2 concentration, i.e., the G(-SO 2 ) values were 0.9, 8.0, and 5.3 for the 0, 0.1, and 20% O 2 concentrations at 100 0 C, respectively (Fig.4). The G(-SO 2 ) was independent of the H 2 O concentration in the range of 0.84 to 8.4% (Fig.5). The G(-SO 2 ) decreased with a rise in the irradiation temperature (Fig.6) and an apparent activation energy of the oxidation reaction of SO 2 obtained was -4.2 kcal.mol -1 . The effects of CO, NO, and O 2 on the G(-SO 2 ) showed that SO 2 was mainly oxidized by OH and O and that the contribution of OH to the oxidation of SO 2 increased with an increase in the O 2 concentration (Table 1). The rate constants for the reactions of SO 2 with OH and O, obtained from competitive reactions of SO 2 with CO and O 2 , were 5.4 x 10 11 cm 3 .mol -1 .sec -1 and 5.0 x 10 11 cm 3 .mol -1 .sec -1 , respectively. (auth.)

REGIOSELECTIVE OXIDATIONS OF EQUILENIN DERIVATIVES CATALYZED BY A RHODIUM (III) PORPHYRIN COMPLEX-CONTRAST WITH THE MANGANESE (III) PORPHYRIN. (R826653)

Science.gov (United States)

AbstractEquilenin acetate and dihydroequilenin acetate were oxidized with iodosobenzene and a rhodium(III) porphyrin catalyst. The selectivity of the reactions differs from that with the corresponding Mn(III) catalyst, or from that of free radical chain oxidation.

Thermogravimetric, Calorimetric, and Structural Studies of the Co3 O4 /CoO Oxidation/Reduction Reaction

Science.gov (United States)

Unruh, Karl; Cichocki, Ronald; Kelly, Brian; Poirier, Gerald

2015-03-01

To better assess the potential of cobalt oxide for thermal energy storage (TES), the Co3O4/CoO oxidation/reduction reaction has been studied by thermogravimetric (TGA), calorimetric (DSC), and x-ray diffraction (XRD) measurements in N2 and atmospheric air environments. TGA measurements showed an abrupt mass loss of about 6.6% in both N2 and air, consistent with the stoichiometric reduction of Co3O4 to CoO and structural measurements. The onset temperature of the reduction of Co3O4 in air was only weakly dependent on the sample heating rate and occurred at about 910 °C. The onset temperature for the oxidation of CoO varied between about 850 and 875 °C for cooling rates between 1 and 20 °C/min, but complete re-conversion to Co3O4 could only be achieved at the slowest cooling rates. Due to the dependence of the rate constant on the oxygen partial pressure, the oxidation of Co3O4 in a N2 environment occurred at temperatures between about 775 and 825 °C for heating rates between 1 and 20 °C/min and no subsequent re-oxidation of the reduced Co3O4 was observed on cooling to room temperature. In conjunction with a measured transition heat of about 600 J/g of Co3O4, these measurements indicate that cobalt oxide is a viable TES material.

The extraction of rhodium from aqueous nitric acid by dinonylnaphthalene sulphonic acid

International Nuclear Information System (INIS)

Patel, N.M.; Miles, J.H.; Thornback, J.R.

1987-01-01

The extraction of rhodium from aqueous nitric acid using dinonylnaphthalene sulphonic acid has been investigated. The extraction occurs readily from 0.1 M to 1.0 M nitric acid and, since the rhodium is extracted as {Rh(H 2 O) 6 } 3+ into the inverted micelles of the organic solution, equilibration times are less than 5 minutes. Extraction is enhanced by addition of nitrite ion to form {Rh(H 2 O) 5 NO 2 } 2+ as the extracted species. (author)

Treatment of landfill leachate biochemical effluent using the nano-Fe3O4/Na2S2O8 system: Oxidation performance, wastewater spectral analysis, and activator characterization.

Science.gov (United States)

Liu, Zhanmeng; Li, Xian; Rao, Zhiwei; Hu, Fengping

2018-02-15

Nano-Fe 3 O 4 was used as heterogeneous catalyst to activate Na 2 S 2 O 8 for the generation of the sulfate radicals (SO 4 - ) to oxidize the residual pollutants in landfill leachate biochemical effluent. The oxidation performance, wastewater spectral analysis and activator characterization were discussed. Oxidation experimental result shows that nano-Fe 3 O 4 has obvious catalytic effect on Na 2 S 2 O 8 and can significantly enhance the oxidation efficiencies of Na 2 S 2 O 8 on landfill leachate biochemical effluent, with COD and color removals above 63% and 95%, respectively. Based on the analyses of three-dimensional excitation emission matrix fluorescence spectrum (3DEEM), ultraviolet-visible spectra (UV-vis), and Fourier Transform infrared spectroscopy (FTIR) of wastewater samples before and after treatment, it can be concluded that the pollution level of dissolved organic matter (DOM) declined and that the humic acid (HA) fractions were efficiently degraded into small molecules of fulvic acid (FA) fractions with less weight and stable structure. Compared to the raw wastewater sample, the aromaticity and substituent groups of the DOM were lessened in the treated wastewater sample. Moreover, the main structure of the organics and functional groups were changed by the Fe 3 O 4 /Na 2 S 2 O 8 system, with substantial decrease of conjugated double bonds. The micro morphology of nano-Fe 3 O 4 was characterized before and after reaction by the methods of scanning electron microscope spectra (SEM), X-ray diffraction pattern (XRD), and X-ray photoelectron spectroscopy (XPS). The XRD pattern analysis showed that nano-Fe 3 O 4 was oxidized into r-Fe 2 O 3 and that the particle size of it also became smaller after reaction. XPS was employed to analyze the content and iron valence on the nano-Fe 3 O 4 surface, and it can be found that the ratio of Fe 3+ /Fe 2+ decreased from 1.8 before reaction to 0.8 after reaction. From the SEM analysis after the treatment, it was

Effect of ZrO{sub 2} particle on the performance of micro-arc oxidation coatings on Ti6Al4V

Energy Technology Data Exchange (ETDEWEB)

Li, Hong; Sun, Yezi; Zhang, Jin, E-mail: zhangjin@ustb.edu.cn

2015-07-01

Highlights: • An anti-oxidation TiO{sub 2}/ZrO{sub 2} composite coating on Ti6Al4V alloy was prepared using micro-arc oxidation technology by adding ZrO{sub 2} particles in single phosphoric acid solution. • The composite coating displays excellent anti-oxidation characteristic at 700 °C in the air. • The concentration of ZrO{sub 2} particles not only influences the roughness and thickness of the coating, but the morphologies, phase composition, oxidation resistance and wear resistance. - Abstract: This paper investigates the effect of ZrO{sub 2} particle on the oxidation resistance and wear properties of coatings on a Ti6Al4V alloy generated using the micro-arc oxidation (MAO) technique. Different concentrations micron ZrO{sub 2} particles were added in phosphate electrolyte and dispersed by magnetic stirring apparatus. The composition of coating was characterized using X-ray diffraction and energy dispersive spectrum, and the morphology was examined using SEM. The high temperature oxidation resistance of the coating sample at 700 °C was investigated. Sliding wear behaviour was tested by a wear tester. The results showed that the coating consisted of ZrTiO{sub 4}, ZrO{sub 2}, TiO{sub 2}. With ZrO{sub 2} particle addition, the ceramic coating's forming time reduced by the current dynamic curve. It was shown that the addition of ZrO{sub 2} particles (3 g/L, 6 g/L) expressed an excellent oxidation resistance at 700 °C and wear resistance.

High-pressure synthesis and single-crystal structure elucidation of the indium oxide-borate In{sub 4}O{sub 2}B{sub 2}O{sub 7}

Energy Technology Data Exchange (ETDEWEB)

Ortner, Teresa S.; Vitzthum, Daniela; Heymann, Gunter; Huppertz, Hubert [Department of General, Inorganic and Theoretical Chemistry, Centre of Chemistry and Biomedicine (CCB), Leopold-Franzens-University Innsbruck (Austria)

2017-12-29

The indium oxide-borate In{sub 4}O{sub 2}B{sub 2}O{sub 7} was synthesized under high-pressure/high-temperature conditions at 12.5 GPa/1420 K using a Walker-type multianvil apparatus. Single-crystal X-ray structure elucidation showed edge-sharing OIn{sub 4} tetrahedra and B{sub 2}O{sub 7} units building up the oxide-borate. It crystallizes with Z = 8 in the monoclinic space group P2{sub 1}/n (no. 14) with a = 1016.54(3), b = 964.55(3), c = 1382.66(4) pm, and β = 109.7(1) . The compound was also characterized by powder X-ray diffraction and vibrational spectroscopy. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Efficiency Enhancement in Bulk Heterojunction Polymer Photovoltaic Cells Using ZrTiO4/Bi2O3 Metal-Oxide Nanocomposites

DEFF Research Database (Denmark)

Abdul Jabbar, Mohammed Hussain; Neppolian, B.; Shim, Hee-Sang

2010-01-01

We report the effect of metal-oxide nanocomposites on the performance of bulk heterojunction polymer solar cells. A photoactive layer composed of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) was blended with a newly developed ZrTiO4/Bi2O3 (BITZ) metal-oxide...

Thermophysical properties of Na2Th (MoO4)3 (s) and Na4Th (MoO4)4 (s)

International Nuclear Information System (INIS)

Dash, Smruti; Rakshit, S.K.; Singh, Ziley; Keskar, Meera; Dahale, N.D.

2009-01-01

The heat capacity of Na 2 Th (MoO 4 ) 3 (s) and Na 4 Th (MoO 4 ) 4 (s) have been measured by differential scanning calorimeter in the temperature range 318 to 845 K. The corresponding values are: C p,m (Na 2 Th (MoO 4 ) 3 ,s,T) (JK-1 mol-1) 368.710+ 1.0 10-1 (T/K) - 4950267 (K/T)2 (318 ≤ T (K) ≤ 845). C p,m (Na 4 Th (MoO 4 ) 4 ,s,T) (JK-1 mol-1) = 638.761+ 5.12 10-3 (T/K) - 12691691 (K/T)-2 (318 ≤ T (K) ≤ 845). Experimental heat capacity values for Na 2 Th (MoO 4 ) 3 (s) match reasonably well with that of additive oxide values. But C p,m (T) values of Na 4 Th (MoO 4 ) 4 (s) deviates substantially from the additive oxide values above 700 K. The uncertainty of the measurements reported in this study is calculated to be within 1 to 3 % . (author)

Light-induced reduction of rhodium(III) and palladium(II) on titanium dioxide dispersions and the selective photochemical separation and recovery of gold(III), platinum(IV), and rhodium(III) in chloride media

Energy Technology Data Exchange (ETDEWEB)

Borgarello, E.; Serpone, N.; Emo, G.; Harris, R.; Pelizzetti, E.; Minero, C.

1986-12-03

Irradiation of aqueous TiO/sub 2/ dispersions containing palladium(II) or rhodium(III) chloride salts with AM1 simulated sunlight leads to the photoreduction of these metals, which are deposited on the semiconductor particle surface. Oxygen is detrimental to the photoreduction of rhodium(III) but not the photoreduction of palladium(II). However, in both cases the reduction process is most efficient if the solution contains CH/sub 3/OH, which acts to scavenge valence band holes of the illuminated TiO/sub 2/ semiconductor. The selective photoreduction and recovery of precious metals from a dilute solution (as might be found in industrial wastes) have been investigated for a mixture of gold(III), platinum(IV), and rhodium(III) chloride salts as a function of various parameters (pH, presence or absence of O/sub 2/, presence or absence of a hole scavenger, and the concentration of the semiconductor). At pH 0, gold is easily separated from platinum and rhodium. The rate of photoreduction of gold(III) on TiO/sub 2/ is nearly independent of the concentration of the semiconductor, under the experimental conditions employed; the limiting rate is 2.7 x 10/sup -7/ M s/sup -1/. The potential utility of this selective photochemical technique is discussed.

Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes.

Science.gov (United States)

Li, Changkun; Kähny, Matthias; Breit, Bernhard

2014-12-08

A rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes to give branched N-allyl 2-pyridones is reported. Preliminary mechanistic studies support the hypothesis that the reaction was initiated from the more acidic 2-hydroxypyridine form, and the initial kinetic O-allylation product was finally converted into the thermodynamically more stable N-allyl 2-pyridones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-pot fabrication of NiFe2O4 nanoparticles on α-Ni(OH)2 nanosheet for enhanced water oxidation

Science.gov (United States)

Chen, Hong; Yan, Junqing; Wu, Huan; Zhang, Yunxia; Liu, Shengzhong (Frank)

2016-08-01

Water splitting has been intensively investigated as a promising solution to resolve the future environmental and energy crises. The oxygen evolution reaction (OER) of the photo- and electric field-induced water splitting limits the development of other reactions, including hydrogen evolution reaction (HER). Fe, Ni and NiFe (hydro) oxide-based catalysts are generally acknowledged among the best candidates of OER catalysts for water splitting. Herein, we developed a one-pot simple hydrothermal process to assemble NiFe2O4 nanoparticles onto the α-Ni(OH)2 nanosheets. The first formed NiFe2O4 under high temperature and pressure environment induces and assists the α-Ni(OH)2 formation without any further additives, because the distance between the neighboring Ni atoms in the cubic NiFe2O4 is similar to that in the α-Ni(OH)2 {003} facets. We have synthesized a series of NiFe2O4/α-Ni(OH)2 compounds and find that the overpotential decreases with the increase of Ni(OH)2 content while the OER kinetics stays unchanged, suggesting that Ni(OH)2 plays a major role in overpotential while NiFe2O4 mainly affects the OER kinetics. The obtained NiFe2O4/α-Ni(OH)2 compounds is also found to be a promising co-catalyst for the photocatalytic water oxidation. In fact, it is even more active than the noble PtOx with acceptable stability for the oxygen generation.

Using H2O2 as oxidant in leaching of uranium ores. The new research on the reaction of H2O2 with Fe2+

International Nuclear Information System (INIS)

Gao Xizhen

1997-05-01

The new research on the reaction of H 2 O 2 with Fe 2+ has been studied. Through determining the electric potential, pH and O 2 release during the mutual titration between H 2 O 2 solution and FeSO 4 solution, deduced the chemical equations of H 2 O 2 (without free hydroxyl) oxidizing FeSO 4 and Fe 2 (SO 4 ) 3 oxidizing H 2 O 2 . The research results show that acid is a catalytic agent for decomposing H 2 O 2 to be O 2 and H 2 O besides iron ions. The maximum oxidizing potential is up to about 640 mV. While using H 2 O 2 as an oxidant in uranium heap leaching and in-situ leaching, controlling electric potential can be regarded as a method for adjusting the feeding speed of H 2 O 2 to keep the electric potential below 500 mV, thus the H 2 O 2 decomposition can be reduced. (13 refs., 3 tabs., 1 fig.)

Hydrothermal synthesis and crystal structure of a new molybdenum oxide compound with manganese-o-phen subunit: [Mn(o-phen)(H2O)MoO4]·H2O (o-phen=o-phenanthroline)

International Nuclear Information System (INIS)

Zhang Quanzheng; Lu Canzhong; Yang Wenbin; Chen Shumei; Yu Yaqin; He Xiang; Yan Ying; Liu Jiuhui; Xu Xinjiang; Xia Changkun; Wu Xiaoyuan; Chen Lijuan

2004-01-01

A new one-dimensional molybdenum oxide compound with manganese-o-phen subunit: [Mn(o-phen)(H 2 O)MoO 4 ]·H 2 O (1) (o-phen=o-phenanthroline) was synthesized by the hydrothermal reaction of Na 2 MoO 4 ·2H 2 O, MnSO 4 ·H 2 O, oxalic acid, o-phenanthroline (o-phen) and water. Its structure was determined by elemental analyses, ESR spectrum, TG analysis, IR spectrum and single-crystal X-ray diffraction. Compound 1 crystallizes in triclinic system, space group P-1 with a=7.0401(2) A, b=10.4498(2) A, c=10.5720(2) A, α=73.26(7) deg., β=83.34(8) deg., γ=77.33(9) deg., V=725.5089(0) A 3 , Z=2, and R 1 =0.0322 for 2337 observed reflections. Compound 1 exhibits one-dimensional chain structure. The chains are linked up via hydrogen bonding to 2D layers, which are further assembled through π-π stacking interactions to a 3D supermolecular structure

Combined CO/CH4 oxidation tests over Pd/Co3O4 monolithic catalyst. Effects of high reaction temperature and SO2 exposure on the deactivation process

International Nuclear Information System (INIS)

Liotta, L.F.; Venezia, A.M.; Di Carlo, G.; Pantaleo, G.; Deganello, G.; Merlone Borla, E.; Pidria, M.

2007-01-01

CO and CH 4 combined oxidation tests were performed over a Pd (70 g/ft 3 )/Co 3 O 4 monolithic catalyst in conditions of GHSV = 100,000 h -1 and feed composition close to that of emission from bi-fuel vehicles. The effect of SO 2 (5 ppm) on CO and CH 4 oxidation activity under lean condition (λ 2) was investigated. The presence of sulphur strongly deactivated the catalyst towards methane oxidation, while the poisoning effect was less drastic in the oxidation of CO. Saturation of the Pd/Co 3 O 4 catalytic sites via chemisorbed SO 3 and/or sulphates occurred upon exposure to SO 2 . A treatment of regeneration to remove sulphate species was attempted by performing a heating/cooling cycle up to 900 C in oxidizing atmosphere. Decomposition of PdO and Co 3 O 4 phases at high temperature, above 750 C, was observed. Moreover, sintering of Pd 0 and PdO particles along with of CoO crystallites takes place. (author)

Cu2O-based solar cells using oxide semiconductors

Science.gov (United States)

Minami, Tadatsugu; Nishi, Yuki; Miyata, Toshihiro

2016-01-01

We describe significant improvements of the photovoltaic properties that were achieved in Al-doped ZnO (AZO)/n-type oxide semiconductor/p-type Cu2O heterojunction solar cells fabricated using p-type Cu2O sheets prepared by thermally oxidizing Cu sheets. The multicomponent oxide thin film used as the n-type semiconductor layer was prepared with various chemical compositions on non-intentionally heated Cu2O sheets under various deposition conditions using a pulsed laser deposition method. In Cu2O-based heterojunction solar cells fabricated using various ternary compounds as the n-type oxide thin-film layer, the best photovoltaic performance was obtained with an n-ZnGa2O4 thin-film layer. In most of the Cu2O-based heterojunction solar cells using multicomponent oxides composed of combinations of various binary compounds, the obtained photovoltaic properties changed gradually as the chemical composition was varied. However, with the ZnO-MgO and Ga2O3-Al2O3 systems, higher conversion efficiencies (η) as well as a high open circuit voltage (Voc) were obtained by using a relatively small amount of MgO or Al2O3, e.g., (ZnO)0.91-(MgO)0.09 and (Ga2O3)0.975-(Al2O3)0.025, respectively. When Cu2O-based heterojunction solar cells were fabricated using Al2O3-Ga2O3-MgO-ZnO (AGMZO) multicomponent oxide thin films deposited with metal atomic ratios of 10, 60, 10 and 20 at.% for the Al, Ga, Mg and Zn, respectively, a high Voc of 0.98 V and an η of 4.82% were obtained. In addition, an enhanced η and an improved fill factor could be achieved in AZO/n-type multicomponent oxide/p-type Cu2O heterojunction solar cells fabricated using Na-doped Cu2O (Cu2O:Na) sheets that featured a resistivity controlled by optimizing the post-annealing temperature and duration. Consequently, an η of 6.25% and a Voc of 0.84 V were obtained in a MgF2/AZO/n-(Ga2O3-Al2O3)/p-Cu2O:Na heterojunction solar cell fabricated using a Cu2O:Na sheet with a resistivity of approximately 10 Ω·cm and a (Ga0.975Al0.025)2

Cu2O-based solar cells using oxide semiconductors

International Nuclear Information System (INIS)

Minami, Tadatsugu; Nishi, Yuki; Miyata, Toshihiro

2016-01-01

We describe significant improvements of the photovoltaic properties that were achieved in Al-doped ZnO (AZO)/n-type oxide semiconductor/p-type Cu 2 O heterojunction solar cells fabricated using p-type Cu 2 O sheets prepared by thermally oxidizing Cu sheets. The multicomponent oxide thin film used as the n-type semiconductor layer was prepared with various chemical compositions on non-intentionally heated Cu 2 O sheets under various deposition conditions using a pulsed laser deposition method. In Cu 2 O-based heterojunction solar cells fabricated using various ternary compounds as the n-type oxide thin-film layer, the best photovoltaic performance was obtained with an n-ZnGa 2 O 4 thin-film layer. In most of the Cu 2 O-based heterojunction solar cells using multicomponent oxides composed of combinations of various binary compounds, the obtained photovoltaic properties changed gradually as the chemical composition was varied. However, with the ZnO-MgO and Ga 2 O 3 -Al 2 O 3 systems, higher conversion efficiencies (η) as well as a high open circuit voltage (V oc ) were obtained by using a relatively small amount of MgO or Al 2 O 3 , e.g., (ZnO) 0.91 –(MgO) 0.09 and (Ga 2 O 3 ) 0.975 –(Al 2 O 3 ) 0.025 , respectively. When Cu 2 O-based heterojunction solar cells were fabricated using Al 2 O 3 –Ga 2 O 3 –MgO–ZnO (AGMZO) multicomponent oxide thin films deposited with metal atomic ratios of 10, 60, 10 and 20 at.% for the Al, Ga, Mg and Zn, respectively, a high V oc of 0.98 V and an η of 4.82% were obtained. In addition, an enhanced η and an improved fill factor could be achieved in AZO/n-type multicomponent oxide/p-type Cu 2 O heterojunction solar cells fabricated using Na-doped Cu 2 O (Cu 2 O:Na) sheets that featured a resistivity controlled by optimizing the post-annealing temperature and duration. Consequently, an η of 6.25% and a V oc of 0.84 V were obtained in a MgF 2 /AZO/n-(Ga 2 O 3 –Al 2 O 3 )/p-Cu 2 O:Na heterojunction solar cell fabricated using

Dinuclear ditertiary phosphite derivatives of rhodium

International Nuclear Information System (INIS)

Meintjies, E.

1981-08-01

The overall objective of the research described in this thesis was the design, synthesis, characterization and chemistry of dinuclear complexes of rhodium in which the metal atoms are held in close proximity to each other. Complexes of this nature are of considerable interest owing, in part, to their potential as models for multicentred metal catalysts, as well as to the highly novel and unusual chemistry already discovered for a number of them. A survey of dinuclear complexes of rhodium containing carbonyl and group V donor ligands has been presented as a background introduction to the research reported in this thesis. The coordination behaviour of the diphosphazane ligands, (RO) 2 PN(R')P(OR) 2 (R=Ph or Me, R' = Et; R = Et or Pr/i, R' = Me), and the ditertiary phosphite ligand, (EtO) 2 POP(OEt) 2 , towards certain rhodium precursors has been investigated. A number of highly unusual neutral dinuclear complexes of rhodium, in which these ligands bridge-bond the two rhodium atoms, have been synthesized. Two types of monocarbonyl decarbonylation products are observed for compounds of the type, [Rh 2 Cl 2 (CO) 2 (μ-diphosphazane) 2 ]. 1 H and 31 P[ 1 H] n.m.r. spectral studies have been carried out with the object of establishing the nature of the bridging halogen ligands in the tricarbonyl species. Asymetric zerovalent dinuclear species of the type, [Rh 2 (CO) 3 -[μ-(RO) 2 PN(R')P(OR) 2 ] 2 ] (R = Ph or Me, R' = Et; R = Pr/i, R' = Me), are obtained. A single crystal X-ray analysis has been carried out. Homoleptic cationic species are obtained by reaction of the alkoxydiphosphazane ligands with [Rh(C 8 H 12 )(solvent)(n)] + under the appropriate reaction conditions. The solution and solid-state infrared spectra and the 31 P[ 1 H] n.m.r. spectra of all new compounds synthesized in this study are discussed in terms of possible structures for these compounds. Where appropriate, the n.m.r. spectral data are also discussed in terms of fluxional behaviour

Impact of the Valence Charge of Transition Metals on the Cobalt- and Rhodium-Catalyzed Synthesis of Indenamines, Indenols, and Isoquinolinium Salts: A Catalytic Cycle Involving MIII/MV [M = Co, Rh] for [4+2] Annulation.

Science.gov (United States)

Chiou, Mong-Feng; Jayakumar, Jayachandran; Cheng, Chien-Hong; Chuang, Shih-Ching

2018-06-13

Reaction mechanisms for the synthesis of indenamines, indenols, and isoquinolinium salts through cobalt- and rhodium-catalysis were investigated using density functional theory calculations. We found that the valence charge of transition metals dramatically influences the reaction pathways. Catalytic reactions involving lower-oxidation-state transition metals (M I /M III , M = Co and Rh) generally favor a [3+2] cyclization pathway, whereas those involving higher oxidation states (M III /M V ) proceed through a [4+2] cyclization pathway. A catalytic cycle with novel M III /M V as a crucial species was successfully revealed for isoquinolinium salts synthesis, which highly valent M V was not only encountered in the [RhCp*]-catalysis but also in the [CoCp*]-catalysis.

Photocatalytic oxidation of aromatic amines using MnO2@g-C3N4

Data.gov (United States)

U.S. Environmental Protection Agency — An efficient and direct oxidation of aromatic amines to aromatic azo-compounds has been achieved using a MnO2@g-C3N4 catalyst under visible light as a source of...

Effect of Water Content on Properties of Homogeneous [bmim]Fe(IIICl4–H2O Mixtures and Their Application in Oxidative Absorption of H2S

Directory of Open Access Journals (Sweden)

Jianhong Wang

2018-01-01

Full Text Available The potential of 1-butyl-3-methylimidazolium tetrachloroferrate ([bmim]Fe(IIICl4 for replacing an iron(III chelate catalytic solution in the catalytic oxidation of H2S is attributed to its no side reaction and no degradation of the chelating agent. The catalytic oxidation product of water in non-aqueous [bmim]Fe(IIICl4 possibly has an influence on the oxidative absorption of H2S. Water and hydrophobic [bmim]Fe(IIICl4 mixtures at water volume percents from 40% to 70% formed separate phases after srirring, without affecting the oxidative absorption of hydrogen sulfide. Then, studies on the properties of homogeneous [bmim]Fe(IIICl4–H2O mixtures at water volume percents in the range of 5.88–30% and above 80% reveal that these mixtures are both Brønsted and Lewis acids at vol % (H2O ≤ 30%, and only Lewis acids at vol % (H2O ≥ 80%. Raman spectra showed that [bmim]Fe(IIICl4 was the dominating species at vol % (H2O ≤ 30%, in contrast, [bmim]Fe(IIICl4 decomposed into FeCl3·2H2O and [bmim]Cl at vol % (H2O ≥ 80%. Further research on oxidative absorption of H2S by homogeneous [bmim]Fe(IIICl4–H2O mixtures demonstrated that [bmim]Fe(IIICl4 was reduced by H2S to [bmim]Fe(IICl4H and FeCl3·2H2O was reduced to FeCl2, at the same time, H2S was oxidized to S8. In addition, the decrease in acidity caused by increasing the water content increased the weight percent of absorbed H2S, and decreased volatile HCl emissions. However, it is difficult to prevent the suspended S8 generated at vol % (H2O ≥ 80% from the formation of sulfur blockage. Therefore, oxidative absorption of H2S by [bmim]Fe(IIICl4–H2O mixtures is feasible at vol % (H2O < 80% without sulfur blockage.

Nano-sized Mn3O4 and β-MnOOH from the decomposition of β-cyclodextrin-Mn: 2. The water-oxidizing activities.

Science.gov (United States)

Najafpour, Mohammad Mahdi; Mostafalu, Ramin; Hołyńska, Małgorzata; Ebrahimi, Foad; Kaboudin, Babak

2015-11-01

Nano-sized Mn oxides contain Mn3O4, β-MnOOH and Mn2O3 have been prepared by a previously reported method using thermal decomposition of β-cyclodextrin-Mn complexes. In the next step, the water-oxidizing activities of these Mn oxides using cerium(IV) ammonium nitrate as a chemical oxidant are studied. The turnover frequencies for β-MnO(OH) and Mn3O4 are 0.24 and 0.01-0.17 (mmol O2/mol Mns), respectively. Subsequently, water-oxidizing activities of these compounds are compared to the other previously reported Mn oxides. Important factors affecting water oxidation by these Mn oxides are also discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

First-principles study on the effect of SiO{sub 2} layers during oxidation of 4H-SiC

Energy Technology Data Exchange (ETDEWEB)

Ono, Tomoya, E-mail: ono@ccs.tsukuba.ac.jp [Center for Computational Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8577 (Japan); JST-PRESTO, Kawaguchi, Saitama 332-0012 (Japan); Saito, Shoichiro [Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan)

2015-02-23

The effect of SiO{sub 2} layers during the thermal oxidation of a 4H-SiC(0001) substrate is examined by performing the first-principles total-energy calculations. Although it is expected that a CO molecule is the most preferable product during the oxidation, CO{sub 2} molecules are mainly emitted from the SiC surface at the initial stage of the oxidation. As the oxidation proceeds, CO{sub 2} emission becomes less favorable and CO molecules are emitted from the interface. We conclude that the interface stress due to the lattice constant mismatch between 4H-SiC(0001) and SiO{sub 2} is responsible for the removal of C during the oxidation, resulting in the characteristic electronic property of the interface fabricated by the thermal oxidation.

Conclusive evidence on the mechanism of the rhodium-mediated decyanative borylation.

Science.gov (United States)

Esteruelas, Miguel A; Oliván, Montserrat; Vélez, Andrea

2015-09-30

The stoichiometric reactions proposed in the mechanism of the rhodium-mediated decyanative borylation have been performed and all relevant intermediates isolated and characterized including their X-ray structures. Complex RhCl{xant(P(i)Pr2)2} (1, xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) reacts with bis(pinacolato)diboron (B2pin2), in benzene, to give the rhodium(III) derivative RhHCl(Bpin){xant(P(i)Pr2)2} (4) and PhBpin. The reaction involves the oxidative addition of B2pin2 to 1 to give RhCl(Bpin)2{xant(P(i)Pr2)2}, which eliminates ClBpin generating Rh(Bpin){xant(P(i)Pr2)2} (2). The reaction of the latter with the solvent yields PhBpin and the monohydride RhH{xant(P(i)Pr2)2} (6), which adds the eliminated ClBpin. Complex 4 and its catecholboryl counterpart RhHCl(Bcat){xant(P(i)Pr2)2} (7) have also been obtained by oxidative addition of HBR2 to 1. Complex 2 is the promoter of the decyanative borylation. Thus, benzonitrile and 4-(trifluoromethyl)benzonitrile insert into the Rh-B bond of 2 to form Rh{C(R-C6H4)═NBpin}{xant(P(i)Pr2)2} (R = H (8), p-CF3 (9)), which evolve into the aryl derivatives RhPh{xant(P(i)Pr2)2} (3) and Rh(p-CF3-C6H4){xant(P(i)Pr2)2} (10), as a result of the extrusion of CNBpin. The reactions of 3 and 10 with B2pin2 yield the arylBpin products and regenerate 2.

Reactivity Control of Rhodium Cluster Ions by Alloying with Tantalum Atoms.

Science.gov (United States)

Mafuné, Fumitaka; Tawaraya, Yuki; Kudoh, Satoshi

2016-02-18

Gas phase, bielement rhodium and tantalum clusters, RhnTam(+) (n + m = 6), were prepared by the double laser ablation of Rh and Ta rods in He carrier gas. The clusters were introduced into a reaction gas cell filled with nitric oxide (NO) diluted with He and were subjected to collisions with NO and He at room temperature. The product species were observed by mass spectrometry, demonstrating that the NO molecules were sequentially adsorbed on the RhnTam(+) clusters to form RhnTam(+)NxOx (x = 1, 2, 3, ...) species. In addition, oxide clusters, RhnTam(+)O2, were also observed, suggesting that the NO molecules were dissociatively adsorbed on the cluster, the N atoms migrated on the surface to form N2, and the N2 molecules were released from RhnTam(+)N2O2. The reactivity, leading to oxide formation, was composition dependent: oxide clusters were dominantly formed for the bielement clusters containing both Rh and Ta atoms, whereas such clusters were hardly formed for the single-element Rhn(+) and Tam(+) clusters. DFT calculations indicated that the Ta atoms induce dissociation of NO on the clusters by lowering the dissociation energy, whereas the Rh atoms enable release of N2 by lowering the binding energy of the N atoms on the clusters.

Defect kinetics in spinels: Long-time simulations of MgAl2O4, MgGa2O4, and MgIn2O4

International Nuclear Information System (INIS)

Uberuaga, B. P.; Voter, A. F.; Sickafus, K. E.; Bacorisen, D.; Smith, Roger; Ball, J. A.; Grimes, R. W.

2007-01-01

Building upon work in which we examined defect production and stability in spinels, we now turn to defect kinetics. Using temperature accelerated dynamics (TAD), we characterize the kinetics of defects in three spinel oxides: magnesium aluminate MgAl 2 O 4 , magnesium gallate MgGa 2 O 4 , and magnesium indate MgIn 2 O 4 . These materials have varying tendencies to disorder on the cation sublattices. In order to understand chemical composition effects, we first examine defect kinetics in perfectly ordered, or normal, spinels, focusing on point defects on each sublattice. We then examine the role that cation disorder has on defect mobility. Using TAD, we find that disorder creates local environments which strongly trap point defects, effectively reducing their mobility. We explore the consequences of this trapping via kinetic Monte Carlo (KMC) simulations on the oxygen vacancy (V O ) in MgGa 2 O 4 , finding that V O mobility is directly related to the degree of inversion in the system

Effect of phase interaction on catalytic CO oxidation over the SnO_2/Al_2O_3 model catalyst

International Nuclear Information System (INIS)

Chai, Shujing; Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang; Xian, Hui; Mi, Wenbo; Li, Xingang

2017-01-01

Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO_2 and Al_2O_3. • Interaction between SnO_2 and Al_2O_3 phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn"4"+ cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO_2/Al_2O_3 model catalysts. Our results show that interaction between the Al_2O_3 and SnO_2 phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO_2/Al_2O_3 catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO_2, which probably results from the change of electron concentration on the interface of the SnO_2 and Al_2O_3 phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn"4"+ cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO_2-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

Chemical and Electrochemical Asymmetric Dihydroxylation of Olefins in I(2)-K(2)CO(3)-K(2)OsO(2)(OH)(4) and I(2)-K(3)PO(4)/K(2)HPO(4)-K(2)OsO(2)(OH)(4) Systems with Sharpless' Ligand.

Science.gov (United States)

Torii, Sigeru; Liu, Ping; Bhuvaneswari, Narayanaswamy; Amatore, Christian; Jutand, Anny

1996-05-03

Iodine-assisted chemical and electrochemical asymmetric dihydroxylation of various olefins in I(2)-K(2)CO(3)-K(2)OsO(2)(OH)(4) and I(2)-K(3)PO(4)/K(2)HPO(4)-K(2)OsO(2)(OH)(4) systems with Sharpless' ligand provided the optically active glycols in excellent isolated yields and high enantiomeric excesses. Iodine (I(2)) was used stoichiometrically for the chemical dihydroxylation, and good results were obtained with nonconjugated olefins in contrast to the case of potassium ferricyanide as a co-oxidant. The potentiality of I(2) as a co-oxidant under stoichiometric conditions has been proven to be effective as an oxidizing mediator in electrolysis systems. Iodine-assisted asymmetric electro-dihydroxylation of olefins in either a t-BuOH/H(2)O(1/1)-K(2)CO(3)/(DHQD)(2)PHAL-(Pt) or t-BuOH/H(2)O(1/1)-K(3)PO(4)/K(2)HPO(4)/(DHQD)(2)PHAL-(Pt) system in the presence of potassium osmate in an undivided cell was investigated in detail. Irrespective of the substitution pattern, all the olefins afforded the diols in high yields and excellent enantiomeric excesses. A plausible mechanism is discussed on the basis of cyclic voltammograms as well as experimental observations.

Carnosol promotes endothelial differentiation under H2O2-induced oxidative stress

Directory of Open Access Journals (Sweden)

Ou Shulin

2017-01-01

Full Text Available Oxidative stress causes deregulation of endothelial cell differentiation. Carnosol is a potent antioxidant and antiinflammatory compound. In the present study, we examined whether the antioxidant effect of carnosol might protect bone marrow stem cells against H2O2-induced oxidative stress and promote endothelial differentiation. We examined cell viability by the MTT assay; oxidative stress and apoptosis were analyzed through changes in ROS levels, apoptotic ratio and caspase-3 activity; changes in protein expression of OCT-4, Flk-1, CD31 and Nrf-2 were assessed by Western blot analysis. H2O2 treatment increased oxidative stress and reduced cell viability, while the stem cell marker OCT-4 and endothelial markers Flk-1, CD31 were significantly downregulated as a result of the treatment with H2O2. Treatment with carnosol improved the antioxidant status, increased OCT-4 expression and promoted endothelial differentiation. This study provides evidence that carnosol could increase the antioxidant defense mechanism and promote endothelial differentiation.

Isotope signatures of N2O emitted from vegetable soil: Ammonia oxidation drives N2O production in NH4(+)-fertilized soil of North China.

Science.gov (United States)

Zhang, Wei; Li, Yuzhong; Xu, Chunying; Li, Qiaozhen; Lin, Wei

2016-07-08

Nitrous oxide (N2O) is a potent greenhouse gas. In North China, vegetable fields are amended with high levels of N fertilizer and irrigation water, which causes massive N2O flux. The aim of this study was to determine the contribution of microbial processes to N2O production and characterize isotopic signature effects on N2O source partitioning. We conducted a microcosm study that combined naturally abundant isotopologues and gas inhibitor techniques to analyze N2O flux and its isotopomer signatures [δ(15)N(bulk), δ(18)O, and SP (intramolecular (15)N site preference)] that emitted from vegetable soil after the addition of NH4(+) fertilizers. The results show that ammonia oxidation is the predominant process under high water content (70% water-filled pore space), and nitrifier denitrification contribution increases with increasing N content. δ(15)N(bulk) and δ(18)O of N2O may not provide information about microbial processes due to great shifts in precursor signatures and atom exchange, especially for soil treated with NH4(+) fertilizer. SP and associated two end-member mixing model are useful to distinguish N2O source and contribution. Further work is needed to explore isotopomer signature stability to improve N2O microbial process identification.

Mesoporous NiCo2O4 nanoneedles grown on 3D graphene-nickel foam for supercapacitor and methanol electro-oxidation

International Nuclear Information System (INIS)

Yu, Mei; Chen, Jianpeng; Liu, Jianhua; Li, Songmei; Ma, Yuxiao; Zhang, Jingdan; An, Junwei

2015-01-01

Mesoporous NiCo 2 O 4 nanoneedles were directly grown on three dimensional (3D) graphene-nickel foam which was prepared by chemical vapor deposition, labeled as NCO/GNF. The structure and morphology of NCO/GNF were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, element mapping and Raman spectroscopy. The NCO/GNF was employed as electrodes for supercapacitor and methanol electro-oxidation. When used for supercapacitor, the NiCo 2 O 4 nanoneedles exhibit hi exhibit high specific capacitance (1588 F g −1 at 1 A g −1 ), high power density and energy density (33.88 Wh kg −1 at 5 kW kg −1 ) as well as long cycling stability. In methanol electro-oxidation, the NiCo 2 O 4 nanoneedles deliver high electro-oxidation activity (93.3 A g −1 at 0.65 V) and electro-oxidation stability. The good electrochemical performance of NiCo 2 O 4 nanoneedles is attributed to the 3D structure with large specific area, high conductivity and fast ions/electrons transport

Synthesis of 2-Butanol by Selective Hydrogenolysis of 1,4-Anhydroerythritol over Molybdenum Oxide-Modified Rhodium-Supported Silica.

Science.gov (United States)

Arai, Takahiro; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

2016-07-07

Rh-MoOx /SiO2 (Mo/Rh=0.13) is an effective catalyst for the hydrogenolysis of 1,4-anhydroerythritol (1,4-AHERY) and provides 2-BuOH in high yield of 51 %. This is the first report of the production of 2-BuOH from 1,4-AHERY by hydrogenolysis. 1,4-AHERY was more suitable as a starting material than erythritol because the 2-BuOH yield from erythritol was low (34 %). Based on the kinetics and comparison of reactivities of the related compounds using Rh-MoOx /SiO2 and Rh/SiO2 catalysts, the modification of Rh/SiO2 with MoOx leads to the high activity and high selectivity to 2-BuOH because of the generation of reactive hydride species and the strong adsorption of 1,4-AHERY on MoOx species. The reaction proceeds by main two routes, (I) the combination of single C-O hydrogenolysis with the desorption of intermediates, a usual route in hydrogenolysis, and (II) multiple C-O hydrogenolysis without the desorption of intermediates from the active site, and the reaction mechanism for Route (II) is proposed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

REMOVAL OF ORGANIC DYES FROM CONTAMINATED WATER USING COFE2O4 /REDUCED GRAPHENE OXIDE NANOCOMPOSITE

Directory of Open Access Journals (Sweden)

F. Sakhaei

2016-12-01

Full Text Available Up to now, lots of materials such as active carbon, iron, manganese, zirconium, and metal oxides have been widely used for removal of dyes from contaminated water. Among these, ferrite nanoparticle is an interesting magnetic material due to its moderate saturation magnetization, excellent chemical stability and mechanical hardness. Graphene, a new class of 2D carbonaceous material with atom thick layer features, has attracted much attention recently due to its high specific surface area. Reduced graphene oxide (rGO has also been of great interest because of its unique properties, which are similar to those of graphene, such as specific surface area, making it an ideal candidate for dye removal. Thus far, few works have been carried out on the preparation of CoFe2O4-rGO composite and its applications in removal of contaminants from water. In this paper, CoFe2O4 reduced graphene oxide nanocomposite was fabricated using hydrothermal process. During the hydrothermal process, the reduction of graphene oxide and growth of CoFe2O4 simultaneously occurred on the carbon basal planes under the conditions generated in the hydrothermal system. The samples were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, and Fourier transform infrared spectroscopy contaminant and UV-Vis spectroscopy as the analytical method. The experimental results suggest that this material has great potential for treating Congo red contaminated water.

First-principles study of hydrogen diffusion in transition metal Rhodium

International Nuclear Information System (INIS)

Bao, Wulijibilige; Cui, Xin; Wang, Zhi-Ping

2015-01-01

In this study, the diffuse pattern and path of hydrogen in transition metal rhodium are investigated by the first-principles calculations. Density functional theory is used to calculate the system energies of hydrogen atom occupying different positions in rhodium crystal lattice. The results indicate that the most stable position of hydrogen atom in rhodium crystal lattice locates at the octahedral interstice, and the tetrahedral interstice is the second stable site. The activation barrier energy for the diffusion of atomic hydrogen in transition metal rhodium is quantified by determining the most favorable path, i.e., the minimum-energy pathway for diffusion, that is the indirect octahedral-tetrahedral-octahedral (O-T-O) pathway, and the activation energy is 0.8345eV

Rhodium(I)-catalyzed cyclization of allenynes with a carbonyl group through unusual insertion of a C-O bond into a rhodacycle intermediate.

Science.gov (United States)

Oonishi, Yoshihiro; Yokoe, Takayuki; Hosotani, Akihito; Sato, Yoshihiro

2014-01-20

Rhodium(I)-catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp(2) )-rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8-oxabicyclo[3.2.1]octane skeleton, while β-hydride elimination from the same intermediate gives products that contain fused five- and seven-membered rings in high yields. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Estudo da oxidação parcial do etanol em catalisadores de Rh por DRIFTS

Directory of Open Access Journals (Sweden)

Raquel Lima Oliveira

2013-01-01

Full Text Available The partial oxidation of ethanol on γ-Al2O3, CeO2, ZrO2 and Ce xZr1-xO2 supported rhodium catalysts was investigated by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS. The catalysts were characterized by temperature-programmed reduction (TPR and cyclohexane dehydrogenation. DRIFTS studies on the partial oxidation of ethanol showed that ethanol is adsorbed dissociatively, through O-H bond breaking, with the formation of ethoxy species, followed by successive dehydrogenation to acetaldehyde and acetyl species. Further oxidation to acetate and carbonate species lead to the formation of CO, CH4 and H2 by decomposition. The presence of CeO2 in the catalysts favored the oxidation steps due to its oxygen storage capacity.

Partial catalytic oxidation of CH{sub 4} to synthesis gas for power generation - Final report

Energy Technology Data Exchange (ETDEWEB)

Mantzaras, I.; Schneider, A.

2006-03-15

The partial oxidation of methane to synthesis gas over rhodium catalysts has been investigated experimentally and numerically in the pressure range of 4 to 10 bar. The methane/oxidizer feed has been diluted with large amounts of H{sub 2}O and CO{sub 2} (up to 70% vol.) in order to simulate new power generation cycles with large exhaust gas recycle. Experiments were carried out in an optically accessible channel-flow reactor that facilitated laser-based in situ measurements, and also in a subscale gas-turbine catalytic reactor. Full-elliptic steady and transient two-dimensional numerical codes were used, which included elementary hetero-/homogeneous chemical reaction schemes. The following are the key conclusions: a) Heterogeneous (catalytic) and homogeneous (gas-phase) schemes have been validated for the partial catalytic oxidation of methane with large exhaust gas recycle. b) The impact of added H{sub 2}O and CO{sub 2} has been elucidated. The added H{sub 2}O increased the methane conversion and hydrogen selectivity, while it decreased the CO selectivity. The chemical impact of CO{sub 2} (dry reforming) was minimal. c) The numerical model reproduced the measured catalytic ignition times. It was further shown that the chemical impact of H{sub 2}O and CO{sub 2} on the catalytic ignition delay times was minimal. d) The noble metal dispersion increased with different support materials, in the order Rh/{alpha}-Al{sub 2}O{sub 3}, Rh/ZrO{sub 2}, and Rh/Ce-ZrO{sub 2}. An evident relationship was established between the noble metal dispersion and the catalytic behavior. (authors)

Oxide, interface, and border traps in thermal, N2O, and N2O-nitrided oxides

International Nuclear Information System (INIS)

Fleetwood, D.M.; Saks, N.S.

1996-01-01

We have combined thermally stimulated-current (TSC) and capacitance endash voltage (C endash V) measurements to estimate oxide, interface, and effective border trap densities in 6 endash 23 nm thermal, N 2 O, and N 2 O-nitrided oxides exposed to ionizing radiation or high-field electron injection. Defect densities depend strongly on oxide processing, but radiation exposure and moderate high-field stress lead to similar trapped hole peak thermal energy distributions (between ∼1.7 and ∼2.0 eV) for all processes. This suggests that similar defects dominate the oxide charge trapping properties in these devices. Radiation-induced hole and interface trap generation efficiencies (0.1%endash 1%) in the best N 2 O and N 2 O-nitrided oxides are comparable to the best radiation hardened oxides in the literature. After ∼10 Mrad(SiO 2 ) x-ray irradiation or ∼10 mC/cm 2 constant current Fowler endash Nordheim injection, effective border trap densities as high as ∼5x10 11 cm -2 are inferred from C endash V hysteresis. These measurements suggest irradiation and high-field stress cause similar border trap energy distributions. In each case, even higher densities of compensating trapped electrons in the oxides (up to 2x10 12 cm -2 ) are inferred from combined TSC and C endash V measurements. These trapped electrons prevent conventional C endash V methods from providing accurate estimates of the total oxide trap charge density in many irradiation or high-field stress studies. Fewer compensating electrons per trapped hole (∼26%±5%) are found for irradiation of N 2 O and N 2 O-nitrided oxides than for thermal oxides (∼46%±7%). (Abstract Truncated)

Synthesis and characterization of the Rhodium (II) citrate complex

International Nuclear Information System (INIS)

Najjar, R.; Santos, F.S. dos; Seidel, W.

1987-01-01

The preparation and characterization of the rhodium (II) citrate is described. Rhodium citrate was prepared by reacting citric acid trihydrated (3,4 g, 16 mmols) with anhydrous rhodium acetate (0,44 g, 1 mmol). Th electronic instruments, thermogravimetric curve and spectrum of rhodium (II) citrate are analysed. (M.J.C.) [pt

Experimental thermochemistry of neptunium oxides: Np2O5 and NpO2

Science.gov (United States)

Zhang, Lei; Dzik, Ewa A.; Sigmon, Ginger E.; Szymanowski, Jennifer E. S.; Navrotsky, Alexandra; Burns, Peter C.

2018-04-01

Neptunium (Np) compounds are important in the nuclear fuel cycle because of the buildup and long half-life (2.14 Ma) of Np-237 in nuclear waste, especially during long-term disposal in a geological repository. Neptunium in environmental conditions exists mainly in two oxidation states (+5 and + 4) and can substitute for uranium and/or rare earths in solid phases. Yet thermochemical data for solid neptunium compounds are scarce, despite being critical for evaluating the environmental transport of this radioactive and toxic element. Although high temperature oxide melt solution calorimetry has proven very useful in obtaining thermodynamic data for the formation of uranium and thorium oxide materials, it has not yet been applied to transuranium compounds. Continuing a program at Notre Dame to study the thermodynamics of transuranium compounds, we report the first determination of the enthalpies of drop solution of well-characterized neptunium oxides (Np2O5 and NpO2) using oxide melt solution calorimetry in molten sodium molybdate solvent at 973 K. The enthalpy of the decomposition reaction, Np2O5(cr) = 2NpO2(cr) + 1/2O2(g) at 298 K, is determined to be 7.70 ± 5.86 kJ/mol, and this direct measurement is consistent with existing thermodynamic data. The calorimetric methodology is straightforward and produces reliable data using milligram quantities of radioactive materials, and can be applied to many other transuranium compounds.

Excess Substrate is a Spectator Ligand in a Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates with Tolanes

Science.gov (United States)

Oinen, Mark Emil; Yu, Robert T.; Rovis, Tomislav

2009-01-01

Excess substrate has been identified as an unintended spectator ligand affecting enantioselectivity in the [2+2+2] cycloaddition of alkenyl isocyanates with tolanes. Replacement of excess substrate with an exogenous additive affords products with consistent and higher ee’s. The increase in enantioselectivity is the result of a change in composition of a proposed rhodium(III) intermediate on the catalytic cycle. The net result is a rational probe of a short-lived rhodium(III) intermediate, and gives insight that may have applications in many rhodium catalyzed reactions. PMID:19803471

Epitaxial YBa2Cu3O7-δ/Sr2RuO4 heterostructures

International Nuclear Information System (INIS)

Schlom, D.G.; Merritt, B.A.; Madhavan, S.

1997-01-01

The anisotropic oxide superconductors YBa 2 Cu 3 O 7-δ and Sr 2 RuO 4 have been epitaxially combined in various ways (c-axis on c-axis, c-axis on a-axis, and a-axis on a-axis) though the use of appropriate substrates. Phase-pure a-axis oriented or c-axis oriented epitaxial Sr 2 RuO 4 films were grown by pulsed laser deposition. YBa 2 Cu 3 O 7-δ films were then grown on both orientations of Sr 2 RuO 4 films and the resulting epitaxy was characterized

Study of electrocatalytic properties of iridium carbonyl cluster and rhodium carbonyl cluster compounds for the oxygen reduction and hydrogen oxidation reactions in 0.5 MH{sub 2}SO{sub 4} in presence and absence of methanol and carbon monoxide, respectively

Energy Technology Data Exchange (ETDEWEB)

Uribe-Godinez, J.; Borja-Arco, E.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)

2006-07-01

The suitability of carbonyl cluster compounds as a substitute to platinum (Pt) in fuel cell catalysts was investigated. Iridium (Ir{sub 4}(CO){sub 12} and rhodium (Rh{sub 6}(CO){sub 116}) cluster compounds were investigated as potential new electrocatalysts for oxygen reduction reaction (ORR) in the presence and absence of methanol at different concentrations, as well as for the hydrogen oxidation reaction (HOR) with pure hydrogen and a hydrogen/carbon monoxide mixture. The materials were studied using room temperature rotating disk electrode (RDE) measurements and cyclic and linear sweep voltammetry techniques (LSV). Tafel slope and exchange current density were calculated using the LSV polarization curves. Cyclic voltamperometry results suggested that the electrocatalysts were tolerant to methanol. However, electrochemical behaviour of the materials altered in the presence of CO, and peaks corresponding to CO oxidation were observed in both cases. The rhodium carbonyl showed a higher current density for the ORR than the iridium carbonyl. The current potential curves in the presence of methanol were similar to those obtained without methanol. Results confirmed the tolerance properties of the materials to perform the ORR. Decreased current density values were observed during HOR, and were attributed to changes in the hydrogen solubility and diffusion coefficient due to the presence of CO. The Tafel slopes indicated that the mechanics of the HOR were Heyrovsky-Volmer. Results showed that the materials are capable of performing both ORR and HOR in an acid medium. It was noted that the iridium carbonyl cluster followed a 4-electron transfer mechanism towards the formation of water. It was concluded that the compounds are suitable for use as both cathodes and anodes in proton exchange membrane fuel cells (PEMFCs) and as cathodes in direct methanol fuel cells (DMFCs). 3 refs., 2 tabs., 3 figs.

Theoretical study of the adsorption of rhodium on a TiO{sub 2}(1 1 0)-1 Multiplication-Sign 1 surface

Energy Technology Data Exchange (ETDEWEB)

Mutombo, P., E-mail: mutombo@fzu.cz [Institute of Physics of Academy of Sciences of the Czech Republic, Cukrovarnicka 10, 16253 Praha 6 (Czech Republic); Balazs, N. [Reaction Kinetics Laboratory, Institute of Nanochemistry and Catalysis, CRC of the Hungarian Academy of Sciences, University of Szeged, P.O. Box 168, H-6701 Szeged (Hungary); Majzik, Z. [Institute of Physics of Academy of Sciences of the Czech Republic, Cukrovarnicka 10, 16253 Praha 6 (Czech Republic); Reaction Kinetics Laboratory, Institute of Nanochemistry and Catalysis, CRC of the Hungarian Academy of Sciences, University of Szeged, P.O. Box 168, H-6701 Szeged (Hungary); Berko, A. [Reaction Kinetics Laboratory, Institute of Nanochemistry and Catalysis, CRC of the Hungarian Academy of Sciences, University of Szeged, P.O. Box 168, H-6701 Szeged (Hungary); Chab, V. [Institute of Physics of Academy of Sciences of the Czech Republic, Cukrovarnicka 10, 16253 Praha 6 (Czech Republic)

2012-03-01

Density functional theory (DFT) calculations were used to study the adsorption of rhodium on a TiO{sub 2}(1 1 0)-1 Multiplication-Sign 1 surface as a function of coverage. It was found that Rh atom prefers the hollow site between a bridging oxygen atom, a threefold oxygen atom and a fivefold coordinated Ti atom, regardless of the coverage used. DFT calculations also suggest that Rh-Rh interaction is attractive along the [0 0 1] direction, implying that the Rh 1D nanostructure should grow preferentially along this direction. Simulated Rh dimer clusters resemble strongly Pd dimers resolved in STM experiments suggesting that both metals occupy the same adsorption site at the TiO{sub 2}(1 1 0) surface.

Electrochemical oxidation of 2,4,5-trichlorophenoxyacetic acid by metal-oxide-coated Ti electrodes.

Science.gov (United States)

Maharana, Dusmant; Xu, Zesheng; Niu, Junfeng; Rao, Neti Nageswara

2015-10-01

Electrochemical oxidation of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) over metal-oxide-coated Ti anodes, i.e., Ti/SnO2-Sb/Ce-PbO2, Ti/SnO2-Sb and Ti/RuO2, was examined. The degradation efficiency of over 90% was attained at 20 min at different initial concentrations (0.5-20 mg L(-1)) and initial pH values (3.1-11.2). The degradation efficiencies of 2,4,5-T on Ti/SnO2-Sb/Ce-PbO2, Ti/SnO2-Sb and Ti/RuO2 anodes were higher than 99.9%, 97.2% and 91.5% at 30 min, respectively, and the respective total organic carbon removal ratios were 65.7%, 54.6% and 37.2%. The electrochemical degradation of 2,4,5-T in aqueous solution followed pseudo-first-order kinetics. The compounds, i.e., 2,5-dichlorohydroquinone and 2,5-dihydroxy-p-benzoquinone, have been identified as the main aromatic intermediates by liquid chromatography-mass spectrometry. The results showed that the energy efficiencies of 2,4,5-T (20 mg L(-1)) degradation with Ti/SnO2-Sb/Ce-PbO2 anode at the optimal current densities from 2 to 16 mA cm(-2) ranged from 8.21 to 18.73 kWh m(-3). Copyright © 2015 Elsevier Ltd. All rights reserved.

A new way for preparing superconducting materials: the electrochemical oxidation of La2CuO4

International Nuclear Information System (INIS)

Wattiaux, A.; Park, J.C.; Grenier, J.C.; Pouchard, M.

1990-01-01

The electrochemical oxidation in alkaline medium is described as a new way for preparing superconducting oxides at room temperature. The application of this method to La 2 CuO 4 gave rise to a metallic material with a superconducting behaviour below 39 K and whose physical and chemical features appear as quite promising [fr

Synthesis and electromagnetic absorption properties of Ag-coated reduced graphene oxide with MnFe_2O_4 particles

International Nuclear Information System (INIS)

Wang, Yan; Wu, Xinming; Zhang, Wenzhi; Huang, Shuo

2016-01-01

A ternary composite of Ag/MnFe_2O_4/reduced graphene oxide (RGO) was synthesized by a facile hydrothermal method. The morphology, microstructure, magnetic and electromagnetic properties of as-prepared Ag/MnFe_2O_4/RGO composite were characterized by means of XRD, TEM, XPS, VSM and vector network analyzer. The maximum reflection loss (R_L) of Ag/ MnFe_2O_4/RGO composite shows maximum absorption of −38 dB at 6 GHz with the thickness of 3.5 mm, and the absorption bandwidth with the R_L below −10 dB is up to 3.5 GHz (from 3.7 to 7.2 GHz). The result demonstrates that the introduction of Ag significantly leads to the multiple absorbing mechanisms. It is believed that such composite could serve as a powerful candidate for microwave absorber. - Highlights: • A ternary composite of Ag/MnFe_2O_4/reduced graphene oxide (RGO) was synthesized by a facile method. • The morphology, microstructure, magnetic and electromagnetic properties were characterized. • The maximum reflection loss of Ag/MnFe_2O_4/RGO is −38 dB at 6 GHz with a thickness of 3.5 mm. • The composite shows a wide absorption band.

Rhodium(I)-Complexes Catalyzed 1,4-Conjugate Addition of Arylzinc Chlorides to N-Boc-4-pyridone.

Science.gov (United States)

Guo, Fenghai; McGilvary, Matthew A; Jeffries, Malcolm C; Graves, Briana N; Graham, Shekinah A; Wu, Yuelin

2017-05-01

Rhodium(I)-complexes catalyzed the 1,4-conjugate addition of arylzinc chlorides to N -Boc-4-pyridone in the presence of chlorotrimethylsilane (TMSCl). A combination of [RhCl(C₂H₄)₂]₂ and BINAP was determined to be the most effective catalyst to promote the 1,4-conjugate addition reactions of arylzinc chlorides to N -Boc-4-pyridone. A broad scope of arylzinc reagents with both electron-withdrawing and electron-donating substituents on the aromatic ring successfully underwent 1,4-conjugate addition to N -Boc-4-pyridone to afford versatile 1,4-adducts 2-substituted-2,3-dihydropyridones in good to excellent yields (up to 91%) and excellent ee (up to 96%) when ( S )-BINAP was used as chiral ligand.

Physicochemical study of properties of complex oxides of the system Li2O-MoO3-SnO2

International Nuclear Information System (INIS)

Safonov, V.V.; Chaban, N.G.; Kuz'mina, N.P.; Vashman, A.A.; Petrov, K.I.

1990-01-01

By the method of differential thermal analysis using X-ray phase analysis in the Li 2 O-MoO 3 -SnO 2 system (Li 2 Sn(MoO 4 ) 3 -Sn(MoO 4 ) 2 cross section) formation of a new complex of the composition Li 2 Sn 3 (MoO 4 ) 7 incongruently melting at 480 deg C is ascertained. IR, Raman and NMR spectra of Li 4 SnMo 2 O 10 , Li 2 Sn(MoO 4 ) 3 and Li 2 Sn 3 (MoO 4 ) 7 complex oxides are presented. According to 7 Li NMR spectra of Li 4 SnMo 2 O 10 , Li 2 Sn(MoO 4 ) 3 and Li 2 Sn 3 (MoO 4 ) 7 complex are presented. According to 7 Li NMR spectra the value of the lithium diffusion increases in the series Li 4 SnMo 2 O 10 →Li 2 Sn(MoO 4 ) 3 →Li 2 Sn 3 (MoO 4 ) 7

Dehydrogenation of Surface-Oxidized Mixtures of 2LiBH4 + Al/Additives (TiF3 or CeO2

Directory of Open Access Journals (Sweden)

Juan Luis Carrillo-Bucio

2017-11-01

Full Text Available Research for suitable hydrogen storage materials is an important ongoing subject. LiBH4–Al mixtures could be attractive; however, several issues must be solved. Here, the dehydrogenation reactions of surface-oxidized 2LiBH4 + Al mixtures plus an additive (TiF3 or CeO2 at two different pressures are presented. The mixtures were produced by mechanical milling and handled under welding-grade argon. The dehydrogenation reactions were studied by means of temperature programmed desorption (TPD at 400 °C and at 3 or 5 bar initial hydrogen pressure. The milled and dehydrogenated materials were characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD, and Fourier transformed infrared spectroscopy (FT-IR The additives and the surface oxidation, promoted by the impurities in the welding-grade argon, induced a reduction in the dehydrogenation temperature and an increase in the reaction kinetics, as compared to pure (reported LiBH4. The dehydrogenation reactions were observed to take place in two main steps, with onsets at 100 °C and 200–300 °C. The maximum released hydrogen was 9.3 wt % in the 2LiBH4 + Al/TiF3 material, and 7.9 wt % in the 2LiBH4 + Al/CeO2 material. Formation of CeB6 after dehydrogenation of 2LiBH4 + Al/CeO2 was confirmed.

Magnetic ordering and electrical resistivity in Co0.2Zn0.8Fe2O4 spinel oxide

International Nuclear Information System (INIS)

Bhowmik, R.N.; Ranganathan, R.; Ghosh, B.; Kumar, S.; Chattopadhyay, S.

2008-01-01

We report the magnetic, Moessbauer spectroscopy and resistivity measurements in order to understand the electronic behaviour of bulk Co 0.2 Zn 0.8 Fe 2 O 4 spinel oxide. The effect of magnetic order on electrical behaviour is observed from the resistivity measurements in the absence and presence of magnetic field. The analysis of Moessbauer spectra suggests the absence of Fe 2+ ions in the system, which implies that complete hopping of charge carriers between localized Fe 3+ /Co 2+ and Fe 2+ /Co 3+ pair of ions in B sublattice is not the favourable mechanism in Co 0.2 Zn 0.8 Fe 2 O 4 . We suggest that electrical behaviour of the present sample may be consistent with a model of fractional charge transfer via Fe B 3+ -O 2- -Co B 2+ superexchange path

Energetic driving force of H spillover between rhodium and titania surfaces : a DFT view

NARCIS (Netherlands)

Conradie, J.; Gracia, J.; Niemantsverdriet, J.W.

2012-01-01

Hydrogen spillover from a rhodium particle, over the most stable (111) surface, to a TiO2 rutile support occurs at low hydrogen coverage because the adsorption energy of H atoms at low hydrogen coverage on rutile is larger than that on rhodium. H diffuses over the support with an activation barrier

Structural features of layered iron pnictide oxides (Fe{sub 2}As{sub 2})(Sr{sub 4}M{sub 2}O{sub 6})

Energy Technology Data Exchange (ETDEWEB)

Ogino, H., E-mail: tuogino@mail.ecc.u-tokyo.ac.j [Department of Applied Chemistry, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); JST-TRIP, Sanban-cho, Chiyoda-ku, Tokyo 102-0075 (Japan); Sato, S.; Matsumura, Y.; Kawaguchi, N.; Ushiyama, K. [Department of Applied Chemistry, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); JST-TRIP, Sanban-cho, Chiyoda-ku, Tokyo 102-0075 (Japan); Katsura, Y. [Magnetic Materials Laboratory, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198 (Japan); Horii, S. [JST-TRIP, Sanban-cho, Chiyoda-ku, Tokyo 102-0075 (Japan); Kochi University of Technology, Kami, Kochi 782-8502 (Japan); Kishio, K.; Shimoyama, J. [Department of Applied Chemistry, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); JST-TRIP, Sanban-cho, Chiyoda-ku, Tokyo 102-0075 (Japan)

2010-12-15

Structural features of newly found perovskite-based iron pnictide oxide system have been studied. Compared to REFePnO system, perovskite-based system tend to have smaller Pn-Fe-Pn angle and higher pnictogen height owing to low electronegativity of alkaline earth metal and small repulsive force between pnictogen and oxigen atoms. As-Fe-As angles of (Fe{sub 2}As{sub 2})(Sr{sub 4}Cr{sub 2}O{sub 6}), (Fe{sub 2}As{sub 2})(Sr{sub 4}V{sub 2}O{sub 6}) and (Fe{sub 2}Pn{sub 2})(Sr{sub 4}MgTiO{sub 6}) are close to ideal tetrahedron and those pnictogen heights of about 1.40 A are close to NdFeAsO with optimized carrier concentration. These structural features of this system may lead to realization of high-T{sub c} superconductivity in this system.

Mathematical modeling of the radiation-chemical oxidation of U(IV) in HClO4

International Nuclear Information System (INIS)

Vladimirova, M.V.

1995-01-01

Mathematical modeling of U(IV) oxidation in 0.5-12 M HClO 4 upon α, γ-radiolysis, based on the proposed scheme of radiation-chemical reactions, has been performed. The rate constants of the U(VI) + HO 2 , U(IV) + HO 2 , U(IV) + ClO 2 , and U(IV) + ClO 2 - reactions have been determined by the comparison of the calculated and experimental kinetic and dose curves and radiation-chemical yields of U(IV) oxidation or U(VI) formation. General equations for uranium (IV) oxidation constants at various HClO 4 concentrations, based on the analysis of the rates of particular radiation-chemical reactions composing oxidation process, have been obtained

HRTEM Study of Oxide Nanoparticles in 16Cr-4Al-2W-0.3Ti-0.3Y2O3 ODS Steel

Energy Technology Data Exchange (ETDEWEB)

Hsiung, L; Fluss, M; Wall, M; Kimura, A

2009-11-18

Crystal and interfacial structures of oxide nanoparticles in 16Cr-4Al-2W-0.3Ti-0.3Y{sub 2}O{sub 3} ODS ferritic steel have been examined using high-resolution transmission electron microscopy (HRTEM) techniques. Oxide nanoparticles with a complex-oxide core and an amorphous shell were frequently observed. The crystal structure of complex-oxide core is identified to be mainly monoclinic Y{sub 4}Al{sub 2}O{sub 9} (YAM) oxide compound. Orientation relationships between the oxide and matrix are found to be dependent on the particle size. Large particles (> 20 nm) tend to be incoherent and have a spherical shape, whereas small particles (< 10 nm) tend to be coherent or semi-coherent and have a faceted interface. The observations of partially amorphous nanoparticles lead us to propose three-stage mechanisms to rationalize the formation of oxide nanoparticles containing core/shell structures in as-fabricated ODS steels.

Rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes with substituted allenes: stereoselective construction of tri- and tetrasubstituted exocyclic olefins.

Science.gov (United States)

Evans, P Andrew; Negru, Daniela E; Shang, Deju

2015-04-13

The development of the stereoselective rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes (ACPs) with substituted allenes is described. This work demonstrates that activated and unactivated allenes preferentially undergo carbometalation at the distal terminus to generate tri- and tetrasubstituted exocyclic olefins with a neutral rhodium catalyst. In addition, this method provides a strategy for the total synthesis of the guaiane family of sesquiterpenes, which are not directly accessible using alkynes as exogenous π-components. Finally, the preparation of the bicyclo[5.4.0]undecane ring system using a homologated ACP tether serves to further illustrate the versatility of this approach. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

LaCrO3/CuFe2O4 Composite-Coated Crofer 22 APU Stainless Steel Interconnect of Solid Oxide Fuel Cells

Science.gov (United States)

Hosseini, Seyedeh Narjes; Enayati, Mohammad Hossein; Karimzadeh, Fathallah; Dayaghi, Amir Masoud

2017-07-01

Rapidly rising contact resistance and cathode Cr poisoning are the major problems associated with unavoidable chromia scale growth on ferritic stainless steel (FSS) interconnects of solid oxide fuel cells. This work investigates the performance of the novel screen-printed composite coatings consisting of dispersed conductive LaCrO3 particles in a CuFe2O4 spinel matrix for Crofer 22 APU FSS, with emphasis on the oxidation behavior and electrical conductivity of these coatings. The results show that the presence of protective spinel coating, accompanied by the effective role of LaCrO3 particle incorporation, prevents the Cr2O3 subscale growth as well as chromium migration into the coating surface at the end of 400 hours of oxidation at 1073 K (800 °C) in air. In addition, the composite coatings decreased the area specific resistance (ASR) from 51.7 and 13.8 mΩ cm2 for uncoated and spinel-coated samples, respectively, to a maximum of 7.7 mΩ cm2 for composite-coated samples after 400 hours of oxidation.

Enzyme mimics of spinel-type CoxNi1−xFe2O4 magnetic nanomaterial for eletroctrocatalytic oxidation of hydrogen peroxide

International Nuclear Information System (INIS)

Luo, Liqiang; Zhang, Yuting; Li, Fang; Si, Xiaojing; Ding, Yaping; Deng, Dongmei; Wang, Tianlin

2013-01-01

Graphical abstract: -- Highlights: •Spinel-type Co x Ni 1−x Fe 2 O 4 (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) were synthesized. •Co x Ni 1−x Fe 2 O 4 were first employed as novel enzyme mimic sensing materials of H 2 O 2 . •Co 0.5 Ni 0.5 Fe 2 O 4 /CPE showed excellent electrocatalytic activity to H 2 O 2 . •Co 0.5 Ni 0.5 Fe 2 O 4 /CPE was successfully applied to determine H 2 O 2 in toothpastes. -- Abstract: A series of spinel-type Co x Ni 1−x Fe 2 O 4 (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) magnetic nanomaterials were solvothermally synthesized as enzyme mimics for the eletroctrocatalytic oxidation of H 2 O 2 . X-ray diffraction and scanning electron microscope were employed to characterize the composition, structure and morphology of the material. The electrochemical properties of spinel-type Co x Ni 1−x Fe 2 O 4 with different (Co/Ni) molar ratio toward H 2 O 2 oxidation were investigated, and the results demonstrated that Co 0.5 Ni 0.5 Fe 2 O 4 modified carbon paste electrode (Co 0.5 Ni 0.5 Fe 2 O 4 /CPE) possessed the best electrocatalytic activity for H 2 O 2 oxidation. Under optimum conditions, the calibration curve for H 2 O 2 determination on Co 0.5 Ni 0.5 Fe 2 O 4 /CPE was linear in a wide range of 1.0 × 10 −8 –1.0 × 10 −3 M with low detection limit of 3.0 × 10 −9 M (S/N = 3). The proposed Co 0.5 Ni 0.5 Fe 2 O 4 /CPE was also applied to the determination of H 2 O 2 in commercial toothpastes with satisfactory results, indicating that Co x Ni 1−x Fe 2 O 4 is a promising hydrogen peroxidase mimics for the detection of H 2 O 2

Low-Temperature Transformations of Protonic Forms of Layered Complex Oxides HLnTiO4 and H2Ln2Ti3O10 (Ln = La, Nd)

International Nuclear Information System (INIS)

Abdulaeva, L.D.; Silyukov, O.I.; Zvereva, I.A.; Petrov, Yu.V.

2013-01-01

In the present work protonic forms of layered Ruddlesden-Popper oxides HLnTiO 4 and H 2 Ln 2 Ti 3 O 10 (Ln = La, Nd) were used as the starting point for soft chemistry synthesis of two series of perovskite-like compounds by acid leaching and exfoliation, promoted by vanadyl sulfate. The last route leads to the nano structured VO 2+ containing samples. Characterization by SEM, powder XRD, and TGA has been performed for the determination of the structure and composition of synthesized oxides

Line profile analyses of rhodium metal obtained by decomposition of rhodium carbonyl

International Nuclear Information System (INIS)

Chandra, D.; Mandalia, H.; Garner, M.L.; Blakely, M.K.; Lau, K.H.

1995-01-01

Metal carbonyls are important for chemical vapor deposition (CVD) of metals and alloys and formation of high surface area metallic particles which have potential applications as catalysts. Rhodium carbonyl [Rh 6 (CO) 16 ] produces high surface area metallic particles whose structure has been reported as monoclinic (I2/a) with lattice dimensions, a=17.00(±0.03)Angstrom, b=9.78(±0.02)Angstrom, c=17.53(±0.03)Angstrom and Β=121 degrees 45' ± 30' at room temperature. Generally, metal carbonyl crystals dissociate under vacuum as carbonyl gas and decompose to metallic crystals and carbon monoxide at higher temperatures. However, the behavior of rhodium carbonyl crystals is different; they decompose directly to metallic rhodium without the formation of rhodium carbonyl gas in vacuum. Several residual fine grains of rhodium metal are found after the decomposition in vacuum at relatively low temperatures. The metallic samples of rhodium were obtained from vapor pressure experiments using torsion Knudsen-effusion apparatus. X-ray diffraction analyses performed on these gains showed severely broadened Bragg reflections indicative of small particle size and/or lattice microgram. In this study, a comparison of lattice strains and domain sizes obtained by integral breadth and Fourier methods has been made. In addition a comparison of the lattice strains and domain sizes has been made between the Cauchy, Gaussian, Cauchy-Gaussian and Aqua integral breadth methods

Sonolytic Oxidation of Tc(IVO2nH2O Nanoparticles to Tc(VIIO4 in Aqueous Solution

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M. Zakir

2010-04-01

Full Text Available Sonolysis of a hydrosol of TcO2nH2O was investigated in the Ar- or He- atmosphere. Colloidal TcO2nH2O nanoparticles were irradiated with a 200 kHz and 1.25 W/cm2 ultrasound. It was found that the TcO2nH2O colloids dispersed in an aqueous solution (under Ar or He atmosphere was completely dissolved by ultrasonic irradiation (200 kHz, 200 W. The original brownish black color of the suspension slowly disappeared leaving behind a colorless solution. This change suggests that oxidation of Tc(IV to Tc(VII takes place. The oxidation was almost complete during 30 minutes sonication time under argon atmosphere for initial concentration of 6.0E-5 M. Addition of t-butyl alcohol, an effective radical scavenger which readily reacts with OH radicals, supressed the dissolution of TcO2nH2O colloids. This reaction indicates that TcO2nH2O molecules are oxidized by OH radicals produced in cavitation bubbles.

Synthesis of MoS2-reduced graphene oxide/Fe3O4 nanocomposite for enhanced electromagnetic interference shielding effectiveness

Science.gov (United States)

Prasad, Jagdees; Singh, Ashwani Kumar; Shah, Jyoti; Kotnala, R. K.; Singh, Kedar

2018-05-01

This article presents a facile two step hydrothermal process for the synthesis of MoS2-reduced graphene oxide/Fe3O4 (MoS2-rGO/Fe3O4) nanocomposite and its application as an excellent electromagnetic interference shielding material. Characterization tools like; scanning electron microscope, transmission electron microscope, x-ray diffraction, and Raman spectroscopy were used to confirm the formation of nanocomposite and found that spherical Fe3O4 nanoparticles are well dispersed over MoS2-rGO composite with average particle size ∼25–30 nm was confirmed by TEM. Structural characterization done by XRD was found inconsistent with the known lattice parameter of MoS2 nanosheet, reduced graphene oxide and Fe3O4 nanoparticles. Electromagnetic shielding effectiveness of MoS2-rGO/Fe3O4 nanocomposite was evaluated and found to be an excellent EMI shielding material in X-band range (8.0–12.0 GHz). MoS2-rGO composite shows poor shielding capacity (SET ∼ 3.81 dB) in entire range as compared to MoS2-rGO/Fe3O4 nanocomposite (SET ∼ 8.27 dB). It is due to interfacial polarization in the presence of EM field. The result indicates that MoS2-rGO/Fe3O4 nanocomposite provide a new stage for the next generation in high-performance EM wave absorption and EMI shielding effectiveness.

Synthesis of KMnO4-treated magnetic graphene oxide nanocomposite (Fe3O4@GO/MnO x ) and its application for removing of Cu2+ ions from aqueous solution

Science.gov (United States)

Zhang, Huining; Chang, Qing; Jiang, Yu; Li, Huili; Yang, Yahong

2018-04-01

A magnetic KMnO4-treated graphene-oxide-based nanocomposite, Fe3O4@GO/MnO x , was synthesized through a facile hydrothermal technique. The properties of the Fe3O4@GO/MnO x nanocomposite were characterized by SEM, XRD and FTIR. Batch experiments showed that the maximum adsorption capacity calculated by the Langmuir model for Cu2+ was 62.65 mg g-1 at T = 303.15 K. Kinetics and XPS analysis also revealed that the mechanism of Cu2+ removal was mainly a chemical adsorption process involving both the MnO x particles and oxygen functional groups. The prepared Fe3O4@GO/MnO x was found to be an ideal adsorbent for the removal of Cu2+ ions due to the MnO x particle coating, and was easily separated using a magnetic field after utilization. Reusability studies imply that Fe3O4@GO/MnO x is a suitable material for heavy metal ion removal from aqueous solutions in real applications.

The role of reduced graphene oxide on the electrochemical activity of MFe2O4 (M = Fe, Co, Ni and Zn) nanohybrids

Science.gov (United States)

Suresh, Shravan; Prakash, Anand; Bahadur, D.

2018-02-01

In this work, a comparative study of electrochemical performance of reduced graphene oxide-ferrites (RGO-MFe2O4, M = Fe, Co, Ni, and Zn) nanohybrids synthesized by hydrothermal method was done. The structural morphology and investigation of other physical properties of nanohybrids confirm the cubic spinel phase of the MFe2O4, reduction of graphene oxide and the distribution of ferrite nanoparticles (NPs) on RGO nanosheets. The role of RGO on the electrochemical behavior of nanohybrids was understood by quantifying the charge storage capacitance and charging-discharging behavior in a 0.1 M Na2SO4 electrolyte. The specific capacitance values of pristine Fe3O4, CoFe2O4, NiFe2O4, and ZnFe2O4 are 128, 117, 15.2 and 9.1 F g-1 respectively whereas specific capacitance of RGO-Fe3O4, RGO-CoFe2O4, RGO-NiFe2O4 and RGO-ZnFe2O4 are 233, 200, 25 and 66.8 F g-1 respectively. Our investigation suggests that apart from specific surface area of nanohybrids other factors such as structural morphology determine interaction between nanohybrids and electrolyte ions which play critical role in elevating the performance of electrodes.

Raman and Fluorescence Spectroscopy of CeO2, Er2O3, Nd2O3, Tm2O3, Yb2O3, La2O3, and Tb4O7

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Jianlan Cui

2015-01-01

Full Text Available To better understand and ascertain the mechanisms of flotation reagent interaction with rare earth (RE minerals, it is necessary to determine the physical and chemical properties of the constituent components. Seven rare earth oxides (CeO2, Er2O3, Nd2O3, Tm2O3, Yb2O3, La2O3, and Tb4O7 that cover the rare earth elements (REEs from light to heavy REEs have been investigated using Raman spectroscopy. Multiple laser sources (wavelengths of 325 nm, 442 nm, 514 nm, and 632.8 nm for the Raman shift ranges from 100 cm−1 to 5000 cm−1 of these excitations were used for each individual rare earth oxide. Raman shifts and fluorescence emission have been identified. Theoretical energy levels for Er, Nd, and Yb were used for the interpretation of fluorescence emission. The experimental results showed good agreement with the theoretical calculation for Er2O3 and Nd2O3. Additional fluorescence emission was observed with Yb2O3 that did not fit the reported energy level diagram. Tb4O7 was observed undergoing laser induced changes during examination.

The effect on phase separation of the oxidation state of molybdenum in a Na2O-B2O3-SiO2 glass

International Nuclear Information System (INIS)

Kawamoto, Y.; Clemens, K.; Tomozawa, M.; Warden, J.T.

1981-01-01

The effect of oxidation state on phase separation was studied for 13Na 2 O, 49B 2 O 3 , 38SiO 2 (mol%) glasses containing 1 mol% Mo oxide. The glasses were melted under various conditions to vary the oxidation states of Mo ions. The oxidation states of Mo ions were determined by chemical analysis and ESR. The crystallisation tendency, the immiscibility temperature, and the phase separation morphology of the glasses were examined by DTA, x-ray diffraction, opalescence method, and replica electron microscopy. Glasses containing Mo 4+ ions have a great tendency to precipitate MoO 2 crystals. The immiscibility temperature of glass goes through a minimum when the oxidation states of Mo ions are changed. It was suggested that there is an optimum oxidation state to prevent crystallisation and to suppress the phase separation tendency of this system. (author)

DPP4 deficiency exerts protective effect against H2O2 induced oxidative stress in isolated cardiomyocytes.

Directory of Open Access Journals (Sweden)

Hui-Chun Ku

Full Text Available Apart from the antihyperglycemic effects, DPP4 inhibitors and GLP-1 molecules are involved in the preservation of cardiac functions. We have demonstrated that DPP4-deficient rats possess resistance to endotoxemia and ischemia/reperfusion stress. However, whether the decrease of DPP4 activity simply augmented the GLP-1 signaling or that such decrease resulted in a change of cellular function remain unclear. Accordingly, we investigated the responses of H(2O(2-induced oxidative stress in adult wild-type and DPP4-deficient rats isolated cardiomyocytes. The coadministration of GLP-1 or DPP4 inhibitor was also performed to define the mechanisms. Cell viability, ROS concentration, catalase activity, glucose uptake, prosurvival, proapoptotic signaling, and contractile function were examined after cells exposed to H(2O(2. DPP4-deficient cardiomyocytes were found to be resistant to H(2O(2-induced cell death via activating AKT signaling, enhancing glucose uptake, preserving catalase activity, diminishing ROS level and proapoptotic signaling. GLP-1 concentration-dependently improved cell viability in wild-type cardiomyocyte against ROS stress, and the ceiling response concentration (200 nM was chosen for studies. GLP-1 was shown to decrease H(2O(2-induced cell death by its receptor-dependent AKT pathway in wild-type cardiomyocytes, but failed to cause further activation of AKT in DPP4-deficient cardiomyocytes. Acute treatment of DPP4 inhibitor only augmented the protective effect of low dose GLP-1, but failed to alter fuel utilization or ameliorate cell viability in wild-type cardiomyocytes after H(2O(2 exposure. The improvement of cell viability after H(2O(2 exposure was correlated with the alleviation of cellular contractile dysfunction in both DPP4-deficient and GLP-1 treated wild-type cardiomyocytes. These findings demonstrated that GLP-1 receptor-dependent pathway is important and exert protective effect in wild-type cardiomyocyte. Long term loss of

A DRIFTS study of the partial oxidation of ethanol on Rh catalysts; Estudo da oxidacao parcial do etanol em catalisadores de Rh por DRIFTS

Energy Technology Data Exchange (ETDEWEB)

Oliveira, Raquel Lima; Passos, Fabio Barboza, E-mail: fbpassos@vm.uff.br [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Departamento de Engenharia Quimica e de Petroleo

2013-09-01

The partial oxidation of ethanol on {gamma}-Al{sub 2}O{sub 3}, CeO{sub 2}, ZrO{sub 2} and Ce{sub x}Zr{sub 1-x}O{sub 2} supported rhodium catalysts was investigated by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The catalysts were characterized by temperature-programmed reduction (TPR) and cyclohexane dehydrogenation. DRIFTS studies on the partial oxidation of ethanol showed that ethanol is adsorbed dissociatively, through O-H bond breaking, with the formation of ethoxy species, followed by successive dehydrogenation to acetaldehyde and acetyl species. Further oxidation to acetate and carbonate species lead to the formation of CO, CH{sub 4} and H{sub 2} by decomposition. The presence of CeO{sub 2} in the catalysts favored the oxidation steps due to its oxygen storage capacity. (author)

Rhodium-rich silicides RERh{sub 6}Si{sub 4} (RE=La, Nd, Tb, Dy, Er, Yb)

Energy Technology Data Exchange (ETDEWEB)

Vosswinkel, Daniel; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

2017-07-01

Polycrystalline RERh{sub 6}Si{sub 4} (RE=La, Nd, Tb, Dy, Er, Yb) samples can be synthesized by arc-melting of the elements. Single crystals of LaRh{sub 6}Si{sub 4}, NdRh{sub 6}Si{sub 4} and YbRh{sub 6}Si{sub 4} were synthesized from the elements in bismuth fluxes (non-reactive flux medium). The structures were refined on the basis of single-crystal X-ray diffractometer data: LiCo{sub 6}P{sub 4} type, P anti 6m2, a=700.56(3), c=380.55(1) pm, wR2=0.0257, 317 F{sup 2} values, 19 variables for LaRh{sub 6}Si{sub 4}, a=698.4(5), c=377.7(2) pm, wR2=0.0578, 219 F{sup 2} values, 19 variables for NdRh{sub 6}Si{sub 4} and a=696.00(3), c=371.97(1) pm, wR2=0.0440, 309 F{sup 2} values, 19 variables for YbRh{sub 6}Si{sub 4}. The rhodium and silicon atoms build up three-dimensional, covalently bonded [Rh{sub 6}Si{sub 4}]{sup δ-} polyanionic networks with Rh-Si distances ranging from 239 to 249 pm. The rare earth atoms fill larger cavities within channels of these networks and they are coordinated by six silicon and twelve rhodium atoms in the form of hexa-capped hexagonal prisms.

Properties of Mn0.4Zn0.6Fe2O4 and Mn0.6Zn0.4Fe2O4 as Nanocatalyst for Ammonia Production

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Puspitasari Poppy

2017-01-01

Full Text Available Ammonia synthesis requires high pressure and high temperature process. Unfortunately, the capital intensive cost resulting low yield of ammonia by using recent catalyst which is iron oxide. Therefore, manganese zinc ferrite as a soft ferrite material will be introduced as a new nanocatalyst to enhance the ammonia yield. As a new nanocatalyst for ammonia production, study of comparasion two different concentration of MnZn Ferrite is very important. This paper will compare the yield of ammonia by using two different nanocatalyst which are Mn0.4Zn0.6Fe2O4 and Mn0.6Zn0.4Fe2O4. Both were synthesized by sol-gel method and has been characterize by using FESEM (morphology, XRD (phase identification, EDX (elemental analysis and TPR (oxide reduction. The ammonia was produce with and without magnetic field applied. The result shows that the ammonia yield is higher for Mn0.4Zn0.6Fe2O4 nanocatalyst than Mn0.6Zn0.4Fe2O4 by using magnetic field applied. 67.2% of yield has been achieved by using new nanocatalyst Mn0.6Zn0.4Fe2O4 and magnetic field applied at ambient environment.

Ag3PO4-TiO2-Graphene Oxide Ternary Composites with Efficient Photodegradation, Hydrogen Evolution, and Antibacterial Properties

Directory of Open Access Journals (Sweden)

Fu-Jye Sheu

2018-02-01

Full Text Available Ag3PO4-TiO2-graphene oxide ternary composite photocatalysts were fabricated by the photocatalytic reduction and ion exchange methods. The properties and photocatalytic activity of the composites were examined, and the photodegradation mechanism was investigated. More TiO2 nanoparticles in the composites were found to improve light absorption, but caused a larger impedance and inferior charge transport. Excess TiO2 nanoparticles distributed over the surfaces of Ag3PO4 and graphene oxide decreased the specific surface area and thus lowered light absorbance. An appropriate TiO2 content enhanced photocatalytic performance. When the molar ratio of Ag3PO4 to TiO2 was 0.6, the highest efficiency in photodegradation, hydrogen production (with a quantum efficiency of 8.1% and a hydrogen evolution rate of 218.7 μmole·g−1·h−1 and bacterial inactivation was achieved. Trapping experiments demonstrated that superoxide radicals and holes are the major active species involved in the photodegradation process.

Fabrication of graphene oxide decorated with Fe{sub 3}O{sub 4}@SiO{sub 2} for immobilization of cellulase

Energy Technology Data Exchange (ETDEWEB)

Li, Yue; Wang, Xiang-Yu; Jiang, Xiao-Ping; Ye, Jing-Jing; Zhang, Ye-Wang, E-mail: zhangyewang@ujs.edu.cn [Jiangsu University, School of Pharmacy (China); Zhang, Xiao-Yun, E-mail: zhangxiaoyungu@126.com [Jiangsu University, School of Food and Biological Engineering (China)

2015-01-15

Fe{sub 3}O{sub 4}@SiO{sub 2}–graphene oxide (GO) composites were successfully fabricated by chemical binding of functional Fe{sub 3}O{sub 4}@SiO{sub 2} and GO and applied to immobilization of cellulase via covalent attachment. The prepared composites were further characterized by transmission electron microscopy and Fourier transform infrared spectroscopy. Fe{sub 3}O{sub 4} nanoparticles (NPs) were monodisperse spheres with a mean diameter of 17 ± 0.2 nm. The thickness of SiO{sub 2} layer was calculated as being 6.5 ± 0.2 nm. The size of Fe{sub 3}O{sub 4}@SiO{sub 2} NPs was 24 ± 0.3 nm, similar to that of Fe{sub 3}O{sub 4}@SiO{sub 2}–NH{sub 2}. Fe{sub 3}O{sub 4}@SiO{sub 2}–GO composites were synthesized by linking of Fe{sub 3}O{sub 4}@SiO{sub 2}–NH{sub 2} NPs to GO with the catalysis of EDC and NHS. The prepared composites were used for immobilization of cellulase. A high immobilization yield and efficiency of above 90 % were obtained after the optimization. The half-life of immobilized cellulase (722 min) was 3.34-fold higher than that of free enzyme (216 min) at 50 °C. Compared with the free cellulase, the optimal temperature of the immobilized enzyme was not changed; but the optimal pH was shifted from 5.0 to 4.0, and the thermal stability was enhanced. The immobilized cellulase could be easily separated and reused under magnetic field. These results strongly indicate that the cellulase immobilized onto the Fe{sub 3}O{sub 4}@SiO{sub 2}–GO composite has potential applications in the production of bioethanol.

Highly efficient extraction and oxidative desulfurization system using Na7H2LaW10O36⋅32 H2O in [bmim]BF4 at room temperature.

Science.gov (United States)

Xu, Junhua; Zhao, Shen; Chen, Wei; Wang, Miao; Song, Yu-Fei

2012-04-10

Highly efficient, deep desulfurization of model oil containing dibenzothiophene (DBT), benzothiophene (BT), or 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been achieved under mild conditions by using an extraction and catalytic oxidative desulfurization system (ECODS) in which a lanthanide-containing polyoxometalate Na(7)H(2)LnW(10)O(36)⋅32 H(2)O (LnW(10); Ln = Eu, La) acts as catalyst, [bmim]BF(4) (bmim = 1-butyl-3-methylimidazolium) as extractant, and H(2)O(2) as oxidant. Sulfur removal follows the order DBT>4,6-DMDBT>BT at 30 °C. DBT can be completely oxidized to the corresponding sulfone in 25 min under mild conditions, and the LaW(10)/[bmim]BF(4) system could be recycled for ten times with only slight decrease in activity. Thus, LaW(10) in [bmim]BF(4) is one of the most efficient systems for desulfurization using ionic liquids as extractant reported so far. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal structures of fac-tri?chlorido?tris?(tri?methyl?phosphane-?P)rhodium(III) monohydrate and fac-tri?chlorido?tris?(tri?methyl?phosphane-?P)rhodium(III) methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs

OpenAIRE

Merola, Joseph S.; Franks, Marion A.

2015-01-01

The crystal structures of two solvates of fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P)3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P)3]·0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013 ▶). Polyhedron, 54, 67-73]. Comparison is made bet...

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

Science.gov (United States)

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

2014-09-01

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

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

International Nuclear Information System (INIS)

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

2015-01-01

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

(+-Chlorido[(1,2,3,4-η;κP2′-2′-diphenylphosphanyl-2-diphenylphosphoryl-1,1′-binaphthyl]rhodium(I methanol monosolvate

Directory of Open Access Journals (Sweden)

Hans-Joachim Drexler

2012-03-01

Full Text Available In the title complex, [RhCl(C44H32OP2]·CH3OH, the RhI ion is coordinated by a naphthyl group of a partially oxidized 2,2′-bis(diphenylphosphanyl-1,1′-binaphthyl (BINAP ligand in a η4 mode, one P atom of the diphenylphosphanyl group and one Cl atom. The P=O group does not interact with the RhI ion but accepts an O—H...O hydrogen bond from the methanol solvent molecule.

Reduced graphene oxide wrapped Fe3O4-Co3O4 yolk-shell nanostructures for advanced catalytic oxidation based on sulfate radicals

Science.gov (United States)

Zhang, Lishu; Yang, Xijia; Han, Erfen; Zhao, Lijun; Lian, Jianshe

2017-02-01

In this work, we designed and synthesized a high performance catalyst of reduced graphene oxide (RGO) wrapped Fe3O4-Co3O4 (RGO/Fe3O4-Co3O4) yolk-shell nanostructures for advanced catalytic oxidation based on sulfate radicals. The synergistic catalytic action of the RGO/Fe3O4-Co3O4 yolk-shell nanostructures activate the peroxymonosulfate (PMS) to produce sulfate radicals (SO4rad -) for organic dyes degradation, and the Orange II can be almost completely degradated in 5 min. Meanwhile the RGO wrapping prevents the loss of cobalt in the catalytic process, and the RGO/Fe3O4-Co3O4 can be recycled after catalyzed reaction due to the presence of magnetic iron core. What's more, it can maintain almost the same high catalytic activity even after 10 cycles through repeated NaBH4 reduction treatment. Hence, RGO/Fe3O4-Co3O4 yolk-shell nanostructures possess a great opportunity to become a promising candidate for waste water treatment in industry.

Effects of extra oxygen on the structure and superconductivity of La2-xCaxCuO4+y prepared by chemical oxidation

DEFF Research Database (Denmark)

Rial, C.; Moran, E.; Alario Franco, M.A.

1998-01-01

are strongly conditioned by the smaller size of Ca2+ with respect to La3+. Indeed, this peculiarity clearly differentiates the oxidized La2-xCaxCuO4+y series from the Sr2+ and the Ba2+ substituted systems, where the size of the dopant is larger than that of La3+. In the present work the analogies...... and the differences concerning the insertion of oxygen and the modifications induced in La2-xMxCuO4+y (M = Ca, Sr, Ba) are presented and discussed. (C) 1998 Elsevier Science B.V....... improve considerably upon oxidation. The oxidized Ca-doped materials with x less than or equal to 0.08 show an almost constant T-c of similar to 38 K, close to that corresponding to the optimum hole-doping in La2-xMxCuO4; however, the oxidized samples with higher Ca contents present slightly lower T...

Ag2CuMnO4: A new silver copper oxide with delafossite structure

International Nuclear Information System (INIS)

Munoz-Rojas, David; Subias, Gloria; Oro-Sole, Judith; Fraxedas, Jordi; Martinez, Benjamin; Casas-Cabanas, Montse; Canales-Vazquez, Jesus; Gonzalez-Calbet, Jose; Garcia-Gonzalez, Ester; Walton, Richard I.; Casan-Pastor, Nieves

2006-01-01

The use of hydrothermal methods has allowed the synthesis of a new silver copper mixed oxide, Ag 2 CuMnO 4 , the first example of a quaternary oxide containing both elements. It crystallizes with the delafossite 3R structure, thus being the first delafossite to contain both Ag and Cu. Synthesis conditions affect the final particle size (30-500nm). Powder X-ray diffraction Rietveld refinement indicates a trigonal structure (R3-bar m) and cell parameters a=2.99991A and c=18.428A, where Cu and Mn are disordered within the octahedral B positions in the plane and linearly coordinated Ag occupies de A position between layers. X-ray absorption near edge spectroscopy (XANES) for copper and manganese, and XPS for silver evidence +2, +4, and +1 oxidation states. The microstructure consists of layered particles that may form large twins showing 5nm nanodomains. Finally, magnetic measurements reveal the existence of ferromagnetic coupling yielding in-plane moments that align antiferromagnetically at lower temperatures. The singularity of the new phase resides on the fact that is an example of a bidimensional arrangement of silver and copper in an oxide that also shows clear bidimensionality in its physical properties. That is of special relevance to the field of high T c superconducting oxides, while the ferromagnetic coupling in a bidimensional system deserves itself special attention

Catalytic Oxidation of Benzophenone Hydrazone with Alumina-supported KMnO4 under Oxygen Atmosphere

International Nuclear Information System (INIS)

Lee, Kang Hyeok; Ko, Kwang Youn

2006-01-01

KMnO 4 /alumina reagent, which is cheap and environmentally safe, can serve as a catalytic oxidant under O 2 atmosphere for the oxidation of benzophenone hydrazone. To the best of our knowledge, the present works are the first example where KMnO 4 /alumina reagent acts as a catalytic oxidant under O 2 atmosphere. Diphenyldiazomethane (Ph 2 CN 2 ) is widely used for the protection of carboxylic acids by conversion to their diphenylmethyl (dpm) esters since dpm group can be easily deprotected by mild acidic condition or hydrogenolysis, especially in the field of b-lactams and peptides. Diphenyldiazomethane has been prepared by the oxidation of benzophenone hydrazone with reagents such as active manganese dioxide, mercuric oxide, peracetic acid, iodosobenzene diacetate or OXONE. However, some methods suffer from a disadvantage such as toxic nature of reagent, strong oxidative conditions or incompatibility with certain functional groups. For example, OXONE may not be employed for the in situ protection of carboxylic acid containing sulfide group due to the possibility of the concomitant oxidation of sulfide group

Characterization of surface-modified LiMn2O4 cathode materials with indium tin oxide (ITO) coatings and their electrochemical performance

International Nuclear Information System (INIS)

Kim, Chang-Sam; Kwon, Soon-Ho; Yoon, Jong-Won

2014-01-01

Graphical abstract: -- Highlights: • Indium tin oxide (ITO) is used to modify the surface of LiMn 2 O 4 by a sol–gel method. • The surface-modified layer was observed at a scale of several nanometers on LiMn 2 O 4 . • The ITO-coated LiMn 2 O 4 shows better capacity retention at 30 and 55 °C than pristine LiMn 2 O 4 . -- Abstract: Indium tin oxide (ITO) is used to modify the surface of LiMn 2 O 4 by a sol–gel method in an attempt to improve its electrochemical performance at elevated temperatures. The surface-modified LiMn 2 O 4 is characterized via XRD, FE-SEM, TEM, Auger electron spectroscopy (AES) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The surface layer modified by substitution with indium was observed at a scale of several nanometers near the surface on LiMn 2 O 4 . The concentration of ITO for electrochemical performance was varied from 0.3 wt% to 0.8 wt%. The 0.5 wt% ITO coated LiMn 2 O 4 showed the best electrochemical performance. This enhancement in electrochemical performance is mainly attributed to the effect of the surface layer modified through ITO, which could suppress Mn dissolution and reduce the charge transfer resistance at the solid electrolyte interface

Desulfurization from thiophene by SO(4)(2-)/ZrO(2) catalytic oxidation at room temperature and atmospheric pressure.

Science.gov (United States)

Wang, Bo; Zhu, Jianpeng; Ma, Hongzhu

2009-05-15

Thiophene, due to its poison, together with its combustion products which causes air pollution and highly toxic characteristic itself, attracted more and more attention to remove from gasoline and some high concentration systems. As the purpose of achieving the novel method of de-thiophene assisted by SO(4)(2-)/ZrO(2) (SZ), three reactions about thiophene in different atmosphere at room temperature and atmospheric pressure were investigated. SO(4)(2-)/ZrO(2) catalyst were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The products were detected by gas chromatography-mass spectrometry (GC-MS). XP spectra show that ozone-catalyst system (SZO) have two forms of sulfur element (S(6+) and S(2-)) on the catalyst surface, which distinguished from that of air-catalyst system (SZA) and blank-catalyst system (SZB) (S(6+)). And the results of GC-MS exhibited that some new compounds has been produced under this extremely mild condition. Especially, many kinds of sulfur compounds containing oxygen, that is easier to be extracted by oxidative desulfurization (ODS), have been detected in the SZA-1.5h and SZB-3h system. In addition, some long chain hydrocarbons have also been detected. While in SZO-0.5h system, only long chain hydrocarbons were found. The results show that total efficiency of desulfurization from thiophene with ozone near to 100% can be obtained with the SO(4)(2-)/ZrO(2) catalytic oxidation reaction.

Al2O3-Cact-(CuO, Cr2O3, Co3O4 Adsorbents-Catalysts: Preparation and Characterization

Directory of Open Access Journals (Sweden)

Gitana DABRILAITĖ-KUDŽMIENĖ

2013-03-01

Full Text Available Al2O3-Cact-(CuO, Cr2O3 Co3O4 adsorbents-catalysts were prepared using Al2O3-Cact (alumina gel–activated carbon adsorbent and different amount of CuO, Cr2O3 and Co3O4. The active components were incorporated into wet alumina gel–carbon mixture using different conditions (by sol-gel method and mixing a milled metal oxides. Equilibrium adsorptive capacity measurements of alcohol vapours were carried out in order to determine the influence of preparation conditions on the stability of prepared adsorbents–catalysts. Specific surface area of the prepared adsorbents-catalysts were measured by BET method. It was established that for adsorbent-catalyst produced by sol-gel method SBET = 244.7 m2/g. Surface area SBET = 29.32 m2/g was obtained for adsorbent-catalyst with metal oxides. On the basis of these results it was assumed that active carbon was lost in this adsorbent-catalyst during the preparation process. Sol-gel derived adsorbent–catalyst was tested for the oxidation of methanol vapours. Catalytic oxidation was carried out in fixed-bed reactor. Experimental data indicate that adsorptive capacity of the adsorbent–catalyst is (3.232 – 3.259 mg/m3 CH3OH at relative air humidity is 40 % – 50 %. During a fast heating of CH3OH – saturated adsorbent-catalyst a part of adsorbate is converted to CO2 and H2O. Methanol conversion increases with increasing of adsorbent-catalyst heating rate.DOI: http://dx.doi.org/10.5755/j01.ms.19.1.3832

Complexing in (NH4)2SeO4-UO2SeO4 H2O system

International Nuclear Information System (INIS)

Serezhkina, L.B.

1994-01-01

Isotherm of solubility in the (NH 4 ) 2 SeO 4 -UO 2 SeO 4 -H 2 O system has been constructed at 25 deg C. (NH 4 ) 2 (UO 2 ) 2 (SeO 4 ) 3 x6H 2 O formation is established for the first time and certain its physicochemical properties are determined. Regularities of complexing in the R 2 Se) 4 -UO 2 SeO 4 -H 2 O systems, where R-univalent cation are under discussion. 6 refs.; 3 tabs

Suggestion for search of ethylene oxide (c-C2H4O) in a cosmic object

Science.gov (United States)

Sharma, M. K.; Sharma, M.; Chandra, S.

2018-05-01

Ethylene oxide (c-C2H4O) and its isomer acetaldehyde (CH3CHO) are important organic molecules because of their potential role in the formation of amino acids. The c-C2H4O molecule is a b-type asymmetric top molecule and owing to half-spin of each of the four hydrogen atoms, it has two distinct ortho (nuclear spin one) and para (nuclear spin zero and two) species. It has been detected in the Sgr B2N. Using the rotational and centrifugal distortion constants along with the electric dipole moment, we have calculated energies of 100 rotational levels of each of the ortho and para species of c-C2H4O molecule and the Einstein A-coefficients for radiative transitions between the levels. The values of Einstein A-coefficients along with the scaled values for the collisional rate coefficients are used for solving a set of statistical equilibrium equations coupled with the equations of radiative transfer. Brightness-temperatures of five rotational transitions of each of the ortho and para species of c-C2H4O molecule are investigated. Out of these ten transitions, three transitions are found to show the anomalous absorption and rest seven are found to show the emission feature. We have also investigated seven transitions observed unblended in the Sgr B2(N). We have found that the transitions 3_{3 0} - 3_{2 1} (23.134 GHz), 2_{2 0} - 2_{1 1} (15.603 GHz), 3_{3 1} - 3_{2 2} (39.680 GHz) and 1_{1 1} - 0_{0 0} (39.582 GHz) may play important role for the identification of ethylene oxide in a cosmic object.

High pressure oxidation of C2H4/NO mixtures

DEFF Research Database (Denmark)

Giménez-López, J.; Alzueta, M.U.; Rasmussen, C.T.

2011-01-01

An experimental and kinetic modeling study of the interaction between C2H4 and NO has been performed under flow reactor conditions in the intermediate temperature range (600–900K), high pressure (60bar), and for stoichiometries ranging from reducing to oxidizing conditions. The main reaction...... pathways of the C2H4/O2/NOx conversion, the capacity of C2H4 to remove NO, and the influence of the presence of NOx on the C2H4 oxidation are analyzed. Compared to the C2H4/O2 system, the presence of NOx shifts the onset of reaction 75–150K to lower temperatures. The mechanism of sensitization involves...... the reaction HOCH2CH2OO+NO→CH2OH+CH2O+NO2, which pushes a complex system of partial equilibria towards products. This is a confirmation of the findings of Doughty et al. [3] for a similar system at atmospheric pressure. Under reducing conditions and temperatures above 700K, a significant fraction of the NOx...

Reduced graphene oxide wrapped Cu2O supported on C3N4: An efficient visible light responsive semiconductor photocatalyst

Science.gov (United States)

Ganesh Babu, S.; Vinoth, R.; Surya Narayana, P.; Bahnemann, Detlef; Neppolian, B.

2015-10-01

Herein, Cu2O spheres were prepared and encapsulated with reduced graphene oxide (rGO). The Cu2O-rGO-C3N4 composite covered the whole solar spectrum with significant absorption intensity. rGO wrapped Cu2O loading caused a red shift in the absorption with respect to considering the absorption of bare C3N4. The photoluminescence study confirms that rGO exploited as an electron transport layer at the interface of Cu2O and C3N4 heterojunction. Utmost, ˜2 fold synergistic effect was achieved with Cu2O-rGO-C3N4 for the photocatalytic reduction of 4-nitrophenol to 4-aminophenol in comparison with Cu2O-rGO and C3N4. The Cu2O-rGO-C3N4 photocatalyst was reused for four times without loss in its activity.

Fenton-like oxidation of 4-chlorophenol using H2O2 in situ generated by Zn-Fe-CNTs composite.

Science.gov (United States)

Liu, Yong; Fan, Qing; Liu, Yanlan; Wang, Jianlong

2018-05-15

In this paper, a zinc-iron-carbon nanotubes (Zn-Fe-CNTs) composite was prepared, characterized and used to develop a Fenton-like system of Zn-Fe-CNTs/O 2 for the degradation of 4-chlorophenol (4-CP), in which H 2 O 2 was generated in situ from zinc-carbon galvanic cells and oxygen in aqueous solution was activated by iron attached on the surface of CNTs to produce ·OH radicals for the oxidation of 4-CP. The experimental results showed that the particles of Zn and Fe in Zn-Fe-CNTs composite were adhered to the surface of CNTs, which accelerated the electron transfer process. The BET area of Zn-Fe-CNTs composite was 32.9 m 2 /g. The contents of Zn and Fe (% w) in the composite were 44.7% and 4.2%, respectively. The removal efficiency of 4-CP and TOC in Zn-Fe-CNTs/O 2 system was 90.8% and 52.9%, respectively, with the initial pH of 2.0, O 2 flow rate of 800 mL/min, Zn-Fe-CNTs dosage of 1.0 g/L, 4-CP concentration of 50 mg/L and reaction time of 20 min. Based on the analysis of the degradation intermediate products with LC-MS and IC, a possible degradation pathway of 4-CP in Zn-Fe-CNTs/O 2 system was proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sr{sub 2}CoMoO{sub 6} anode for solid oxide fuel cell running on H{sub 2} and CH{sub 4} fuels

Energy Technology Data Exchange (ETDEWEB)

Zhang, Ping [Engineering Research Center of Nano-GEO Materials of Education Ministry, China University of Geosciences, Wuhan 430074 (China); Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); Huang, Yun-Hui [Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); State Key Laboratory of Materials Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan 430074 (China); Cheng, Jin-Guang; Goodenough, John B. [Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); Mao, Zong-Qiang [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China)

2011-02-15

The double perovskite Sr{sub 2}CoMoO{sub 6-{delta}} was investigated as a candidate anode for a solid oxide fuel cell (SOFC). Thermogravimetric analysis (TGA) and powder X-ray diffraction (XRD) showed that the cation array is retained to 800 C in H{sub 2} atmosphere with the introduction of a limited concentration of oxide-ion vacancies. Stoichiometric Sr{sub 2}CoMoO{sub 6} has an antiferromagnetic Neel temperature T{sub N} {approx} 37 K, but after reduction in H{sub 2} at 800 C for 10 h, long-range magnetic order appears to set in above 300 K. In H{sub 2}, the electronic conductivity increases sharply with temperature in the interval 400 C < T < 500 C due to the onset of a loss of oxygen to make Sr{sub 2}CoMoO{sub 6-{delta}} a good mixed oxide-ion/electronic conductor (MIEC). With a 300-{mu}m-thick La{sub 0.8}Sr{sub 0.12}Ga{sub 0.83}Mg{sub 0.17}O{sub 2.815} (LSGM) as oxide-ion electrolyte and SrCo{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} as the cathode, the Sr{sub 2}CoMoO{sub 6-{delta}} anode gave a maximum power density of 1017 mW cm{sup -2} in H{sub 2} and 634 mW cm{sup -2} in wet CH{sub 4}. A degradation of power in CH{sub 4} was observed, which could be attributed to coke build up observed by energy dispersive spectroscopy (EDS). (author)

Photoelectrochemical enhancement of ZnO/BiVO4/ZnFe2O4/rare earth oxide hetero-nanostructures

Science.gov (United States)

She, Xuefeng; Zhang, Zhuo; Baek, Minki; Yong, Kijung

2018-01-01

Over the decades, researchers have made great efforts to turn the world into a cleaner place through efficient recycling of industrial waste and developing of green energy. Here we demonstrate a prototype heterostructure photoelectrochemical (PEC) cell fabricated using recycled industrial waste. ZnFe2O4 (ZFO) nanorod (NR) clusters were synthesized on the BiVO4@ZnO hetero-nanostructures using recycled rare earth oxide (REO) slags as Fe source. The NR-based PEC cell exhibited a significantly enhanced photon to hydrogen conversion efficiency over the entire UV and visible spectrum. Further study demonstrates that the photo-carrier separation and migration processes can be facilitated by the cascade band alignment of the heterostructure and the clustered nanostructure network. In addition, the life-time of the photo-carriers can be enhanced by the REO passivation layer, leading to a further increased PEC performance. Our results present a novel approach for high efficiency PEC cells, and offer great promises to the efficient recycling of industrial waste for clean renewable energy applications.

Facile Synthesis of Co3O4/Mildly Oxidized Multiwalled Carbon Nanotubes/Reduced Mildly Oxidized Graphene Oxide Ternary Composite as the Material for Supercapacitors

International Nuclear Information System (INIS)

Lv, Meiyu; Liu, Kaiyu; Li, Yan; Wei, Lai; Zhong, Jianjian; Su, Geng

2014-01-01

A three-dimensional (3D) Co 3 O 4 /mildly oxidized multiwalled carbon nanotubes (moCNTs)/reduced mildly oxidized graphene oxide (rmGO) ternary composite was prepared via a simple and green hydrolysis-hydrothermal approach by mixing Co(Ac) 2 ·4H 2 O with moCNTs and mGO suspension in mixed ethanol/H 2 O. As characterized by scanning electron microscopy and transmission electron microscopy, Co 3 O 4 nanoparticles with size of 20-100 nm and moCNTs are effectively anchored in mGO. Cyclic voltammetry and galvanostatic charge-discharge measurements were adopted to investigate the electrochemical properties of Co 3 O 4 /moCNTs/rmGO ternary composite in 6 M KOH solution. In a potential window of 0-0.6 V vs. Hg/HgO, the composite delivers an initial specific capacitance of 492 F g -1 at 0.5 A g -1 and the capacitance remains 592 F g -1 after 2000 cycles, while the pure Co 3 O 4 shows obviously capacitance fading, indicating that rmGO and moCNTs greatly enhance the electrochemical performance of Co 3 O 4

Effects of TiO2 and Co3O4 Nanoparticles on Circulating Angiogenic Cells

Science.gov (United States)

Spigoni, Valentina; Cito, Monia; Alinovi, Rossella; Pinelli, Silvana; Passeri, Giovanni; Zavaroni, Ivana; Goldoni, Matteo; Campanini, Marco; Aliatis, Irene; Mutti, Antonio

2015-01-01

Background and Aim Sparse evidence suggests a possible link between exposure to airborne nanoparticles (NPs) and cardiovascular (CV) risk, perhaps through mechanisms involving oxidative stress and inflammation. We assessed the effects of TiO2 and Co3O4 NPs in human circulating angiogenic cells (CACs), which take part in vascular endothelium repair/replacement. Methods CACs were isolated from healthy donors’ buffy coats after culturing lymphomonocytes on fibronectin-coated dishes in endothelial medium for 7 days. CACs were pre-incubated with increasing concentration of TiO2 and Co3O4 (from 1 to 100 μg/ml) to test the effects of NP – characterized by Transmission Electron Microscopy – on CAC viability, apoptosis (caspase 3/7 activation), function (fibronectin adhesion assay), oxidative stress and inflammatory cytokine gene expression. Results Neither oxidative stress nor cell death were associated with exposure to TiO2 NP (except at the highest concentration tested), which, however, induced a higher pro-inflammatory effect compared to Co3O4 NPs (p<0.01). Exposure to Co3O4 NPs significantly reduced cell viability (p<0.01) and increased caspase activity (p<0.01), lipid peroxidation end-products (p<0.05) and pro-inflammatory cytokine gene expression (p<0.05 or lower). Notably, CAC functional activity was impaired after exposure to both TiO2 (p<0.05 or lower) and Co3O4 (p<0.01) NPs. Conclusions In vitro exposure to TiO2 and Co3O4 NPs exerts detrimental effects on CAC viability and function, possibly mediated by accelerated apoptosis, increased oxidant stress (Co3O4 NPs only) and enhancement of inflammatory pathways (both TiO2 and Co3O4 NPs). Such adverse effects may be relevant for a potential role of exposure to TiO2 and Co3O4 NPs in enhancing CV risk in humans. PMID:25803285

Fabrication of novel ternary Au/CeO2@g-C3N4 nanocomposite: kinetics and mechanism investigation of 4-nitrophenol reduction, and benzyl alcohol oxidation

Science.gov (United States)

Kohantorabi, Mona; Gholami, Mohammad Reza

2018-06-01

Au nanoparticles supported on cerium oxide/graphitic carbon nitride (CeO2@g-C3N4) was synthesized and used as heterogeneous catalyst in redox reaction. The catalyst was characterized by different techniques such as FT-IR, XRD, FE-SEM, EDS, TEM, BET, TGA, and ICP. The as-prepared ternary nanocomposite was used as an effective catalyst for the reduction of toxic 4-nitrophenol to useful 4-aminophenol by NaBH4. The rate constant value of reduction reaction reached up to 0.106 s-1 by Au/CeO2@g-C3N4, which was 3.8, and 8.8 times higher than that of Au@CeO2 (0.028 s-1), and Au@g-C3N4 (0.012 s-1) nanocomposites, respectively. The superior catalytic performance of as-prepared catalyst in 4-NP reduction can be attributed to synergistic effect between Au nanoparticles and CeO2@g-C3N4 support, and efficient electron transfer. The reduction reaction was carried out at different temperatures, and the energy of activation ({Ea}), and thermodynamic parameters including, activation of entropy (Δ S^ ≠), enthalpy (Δ H^ ≠), and Gibbs free energy (Δ G^ ≠) were determined. Additionally, the mechanism of reaction was studied in details, and equilibrium constants of 4-NP ( K 4-NP), and {BH}4^{ - } ({K_{{BH}4^{{ - }} }}) were calculated using Langmuir-Hinshelwood model. Furthermore, this nanocomposite exhibited excellent catalytic activity in oxidation of benzyl alcohol by molecular oxygen as a green oxidant. This study revealed that the ternary Au/CeO2@g-C3N4 nanocomposite is an attractive candidate for catalytic applications.

Graphene oxide-MnO2 nanocomposite for supercapacitor application

Science.gov (United States)

Muhammed Shafi, P.; Vishal, Jose K.; Chandra Bose, A.

2016-09-01

Increased depletion of fossil fuels along with global warming and climate change made the society to think about alternate green and sustainable energy sources and better energy storage devices. Extensive research has been performed on the development of solar cells, fuel cells, Lithium- ion battery and supercapacitors to combat the green house effect and its consequences, and to meet the increased energy crisis. Supercapacitors, also known as electrochemical capacitors are gained a great attention because of their pulse power supply, long cycle life (>100,000), simple principle and high dynamic of charge propagation. Its greater power density than lithium- ion battery and much larger energy density than conventional capacitors brought super capacitors to a promising energy storage device to meet the increased energy demands. Here we demonstrate supercapacitor electrode materials with graphene oxide (electric double layer capacitor) and α-MnO2 nanomaterial (pseudo-capacitor), as well as composite of these materials, which means that the bulk of the material undergoes a fast redox reaction to provide the capacitive response and they exhibit superior specific energies in addition to the carbon-based supercapacitors (double-layer capacitors). A simple soft chemical route is utilized to synthesize graphene oxide, α-MnO2 and graphene oxide-MnO2 composite. The phase and the structure of the synthesized materials are studied using X-ray diffractometry (XRD). The functional group and the presence of impurities are understood from Fourier transform infrared (FTIR) spectra. The capacitive properties of the graphene oxide, graphene oxide - MnO2 nanocomposite and α-MnO2 are tested with the help of cyclic voltammetry (CV) and galvanostatic charge - discharge techniques using 1 M Na2SO4 in aqueous solution as electrolyte. It was found that graphene oxide - MnO2 nanocomposite shows better electrochemical behaviour compared to individual graphene oxide and α-MnO2 nanomaterial.

Effect of phase interaction on catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalyst

Energy Technology Data Exchange (ETDEWEB)

Chai, Shujing [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); The Institute of Seawater Desalination and Miltipurpose Utilization, State Oceanic Administration, Tianjin 300192 (China); Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); Xian, Hui [Tianjin Polytechnic University, School of Computer Science & Software Engineering, Tianjin 300387 (China); Mi, Wenbo [Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparation Technology, Faculty of Science, Tianjin University, Tianjin 300354 (China); Li, Xingang, E-mail: xingang_li@tju.edu.cn [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China)

2017-04-30

Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO{sub 2} and Al{sub 2}O{sub 3}. • Interaction between SnO{sub 2} and Al{sub 2}O{sub 3} phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn{sup 4+} cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalysts. Our results show that interaction between the Al{sub 2}O{sub 3} and SnO{sub 2} phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO{sub 2}/Al{sub 2}O{sub 3} catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO{sub 2}, which probably results from the change of electron concentration on the interface of the SnO{sub 2} and Al{sub 2}O{sub 3} phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn{sup 4+} cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO{sub 2}-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

Total catalytic wet oxidation of phenol and its chlorinated derivates with MnO2/CeO2 catalyst in a slurry

Directory of Open Access Journals (Sweden)

A. J. Luna

2009-09-01

Full Text Available In the present work, a synthetic effluent of phenol was treated by means of a total oxidation process-Catalyzed Wet Oxidation (CWO. A mixed oxide of Mn-Ce (7:3, the catalyst, was synthesized by co-precipitation from an aqueous solution of MnCl2 and CeCl3 in a basic medium. The mixed oxide, MnO2/CeO2, was characterized and used in the oxidation of phenol in a slurry reactor in the temperature range of 80-130ºC and pressure of 2.04-4.76 MPa. A phenol solution containing 2.4-dichlorophenol and 2.4-dichlorophenoxyacetic acid was also degraded with good results. A lumped kinetic model, with two parallel reaction steps, fits precisely with the integrated equation and the experimental data. The kinetic parameters obtained are in agreement with the Arrhenius equation. The activation energies were determined to be 38.4 for the total oxidation and 53.4 kJ/mol for the organic acids formed.

The influence of pH on the in vitro permeation of rhodium through human skin.

Science.gov (United States)

Jansen Van Rensburg, Sané; Franken, Anja; Du Plessis, Jeanetta; Du Plessis, Johannes Lodewykus

2017-06-01

Workers in precious metals refineries are at risk of exposure to salt compounds of the platinum group metals through inhalation, as well as through the skin. Rhodium salt permeation through the skin has previously been proven using rhodium trichloride (RhCl 3 ) dissolved in synthetic sweat at a pH of 6.5. However, the skin surface pH of refinery workers may be lower than 6.5. The aim of this study was to investigate the influence of pH 6.5 and 4.5 on the in vitro permeation of rhodium through intact Caucasian skin using Franz diffusion cells. A concentration of 0.3 mg mL -1 rhodium was used and analyses were performed using inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry. Results indicated a cumulative increase in permeation over 24 h. Rhodium permeation after 12 h was significantly greater at pH 4.5 (1.56 ± 0.24 ng cm -2 ) than at 6.5 (0.85 ± 0.13 ng cm -2 ; p = 0.02). At both pH levels, there was a highly significant difference ( p rhodium remaining in the skin (1428.68 ± 224.67 ng cm -2 at pH 4.5 and 1029.90 ± 115.96 ng cm -2 at pH 6.5) and the mass that diffused through (0.88 ± 0.17 ng cm -2 at pH 4.5 and 0.62 ± 0.10 ng cm -2 at pH 6.5). From these findings, it is evident that an acidic working environment or low skin surface pH may enhance permeation of rhodium salts, contributing to sensitization and adverse health effects.

Pulsed laser deposited MnCo{sub 2}O{sub 4} protective layer on SS430 for solid oxide fuel cell application

Energy Technology Data Exchange (ETDEWEB)

Gaur, Anshu, E-mail: gauranshu20@gmail.com, E-mail: ahamed.vza@gmail.com; Mohiddon, Md. Ahamad, E-mail: gauranshu20@gmail.com, E-mail: ahamed.vza@gmail.com [National Institute of Technology Andhra Pradesh, Tadepalliguem 534101 (India); Prasad, Muvva D. [UGC Networking Centre, School of Chemistry, University of Hyderabad, Hyderabad 500046, India. Phone:+91-40-23134382, Fax:+91-40-23010227 (India)

2016-05-23

The growth and oxidation study of pulsed laser deposited MnCo{sub 2}O{sub 4} protective layer on SS430 substrate for solid oxide fuel cell application is demonstrated. MnCo{sub 2}O{sub 4} has been achieved in three different ways including, deposition at higher substrate temperature (700°C), and deposition at room temperature on pre-oxidized and untreated SS430 substrate followed by annealing at 700°C for 2 hrs. X-ray diffraction and Raman spectroscopy has been applied to demonstrate the kind of phases developed in each case. These three samples were subjected to heat treatment at 750°C for 5 hr. The extent of undesired Fe{sub 2}O{sub 3} phase formation in the post deposition heat treated samples is discussed based on Raman spectroscopic results.

Methane Steam Reforming Kinetics for a Rhodium-Based Catalyst

DEFF Research Database (Denmark)

Jakobsen, Jon Geest; Jakobsen, M.; Chorkendorff, Ib

2010-01-01

Methane steam reforming is the key reaction to produce synthesis gas and hydrogen at the industrial scale. Here the kinetics of methane steam reforming over a rhodium-based catalyst is investigated in the temperature range 500-800 A degrees C and as a function of CH4, H2O and H-2 partial pressures....... The methane steam reforming reaction cannot be modeled without taking CO and H coverages into account. This is especially important at low temperatures and higher partial pressures of CO and H-2. For methane CO2 reforming experiments, it is also necessary to consider the repulsive interaction of CO...

Spectrophotometric determination of ruthenium (III) and rhodium (III) with 9,10-phenanthrenequinone monoxime after extraction into molten naphthalene

International Nuclear Information System (INIS)

Wasey, A.; Bansal, R.K.; Puri, B.K.; Satake, Masatada.

1983-01-01

9,10-Phenanthrenequinone monoxime has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction into molten naphthalene. The extracted mixture of the metal complex and naphthalene was dissolved in chloroform and ruthenium and rhodium were determined spectrophotometrically. Beer's law holds in the concentration range of 0.2-4.1 μg/cm 3 for ruthenium and 0.3-5.3 μg/cm 3 for rhodium in 10 cm 3 of the final solution. The molar absorptivities and Sandell sensitivities are calculated to be 9.70 x 10 3 l mol -1 cm -1 and 0.01 μg/cmsup(2 ) (660 nm) for ruthenium and 1.13 x 10 4 l mol -1 cm -1 and 0.009 μg/cm 2 (410 nm) for rhodium respectively. Aliquots containing 2.0 μg of ruthenium and 4.1 μg of rhodium give mean absorbances of 0.192 and 0.451 with standard deviations of 0.0017 and 0.0039, respectively. Interference of various ions has been studied and the method has been applied to the determination of ruthenium and rhodium in various synthetic mixtures. This procedure is also applied to the simultaneous determination of ruthenium and rhodium present together in a solution. (author)

Preparation and characterization of self-assembled layer by layer NiCo2O4–reduced graphene oxide nanocomposite with improved electrocatalytic properties

International Nuclear Information System (INIS)

Srivastava, Manish; Elias Uddin, Md.; Singh, Jay; Kim, Nam Hoon; Lee, Joong Hee

2014-01-01

Graphical abstract: NiCo 2 O 4 were grown on RGO by in situ synthesis process. FE-SEM investigation revealed self assembled layer by layer growth of NiCo 2 O 4 –RGO nanocomposite. NiCo 2 O 4 –RGO nanocomposite exhibited synergetic effect of NiCo 2 O 4 nanoparticles and RGO on its electrochemical performance. -- Highlights: • NiCo 2 O 4 were grown on RGO by in-situ synthesis process. • FE-SEM image revealed self-assembled layer by layer growth of NiCo 2 O 4 -RGO nanocomposite. • NiCo 2 O 4 -RGO nanocomposite exhibited synergetic effects on its electrochemical performance. -- Abstract: NiCo 2 O 4 nanoparticles dispersed on reduced graphene oxide (RGO) are prepared by simultaneously reducing graphene oxide (GO), nickel and cobalt nitrate via a hydrothermal method assisted by post annealing at low temperature. The method involves formation of hydroxides on GO using ammonia under hydrothermal conditions. Subsequent thermal treatment at 300 °C led to the conversion of hydroxides into single-phase NiCo 2 O 4 atop the RGO. The synthesized products are characterized through several techniques including X-ray diffraction (XRD), ultraviolet–visible spectroscopy (UV–Vis), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy (RS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The FE-SEM investigations reveal the growth of a layer by layer assembly of NiCo 2 O 4 –RGO (2:1) nanocomposite, where the NiCo 2 O 4 nanoparticles are tightly packed between the layers of RGO. Further, the catalytic properties of the NiCo 2 O 4 –RGO nanocomposite are investigated for the oxygen evolution reaction (OER) through cyclic voltammetry (CV) measurements. It is observed that the special structural features of the NiCo 2 O 4 –RGO (2:1) nanocomposite, including layer by layer assembly, integrity and excellent dispersion of the NiCo 2 O 4 nanoparticles atop the RGO, produced

Properties of thermally oxidized and nitrided Zr-oxynitride thin film on 4H–SiC in diluted N2O ambient

International Nuclear Information System (INIS)

Wong, Yew Hoong; Cheong, Kuan Yew

2012-01-01

A systematic investigation on the structural, chemical, and electrical properties of thermally oxidized and nitrided sputtered Zr thin film in various N 2 O ambient (10–100%) at 500 °C for 15 min to form Zr-oxynitride on 4H–SiC substrate has been carried out. The chemical composition, depth profile analysis, and energy band alignment have been evaluated by X-ray photoelectron spectrometer. Zr-oxynitride layer and its interfacial layer comprised of compounds related to Zr–O, Zr–N, Zr–O–N, Si–N, and/or C–N were identified. A model related to the oxidation and nitridation mechanism has been suggested. Supportive results related to the model were obtained by energy filtered transmission electron microscopy, X-ray diffraction, and Raman analyses. A proposed crystal structure was employed to elucidate the surface roughness and topographies of the samples, which were characterized by atomic force microscopy. The electrical results revealed that 10% N 2 O sample has possessed the highest breakdown field and reliability. This was owing to the confinement of nitrogen-related compounds of Zr–O–N and/or Zr–N at or near interfacial layer region, smaller grain with finer structure on the surface, the lowest interface trap density, total interface trap density, and effective oxide charge, and highest barrier height between conduction band edge of oxide and semiconductor. -- Highlights: ► Zr-oxynitride as the gate oxide deposited on 4H–SiC substrate. ► Simultaneous oxidation and nitridation of sputtered Zr thin film on 4H–SiC using various concentrations of N 2 O gas. ► Presence of interfacial layer comprised of mixed compounds related to Zr–O, Zr–N, Zr–O–N, Si–N, and/or C–N. ► The highest electrical breakdown and highest reliability at diluted N 2 O of 10%.

Study of the mechanisms controlling the oxide growth under irradiation: characterization of irradiated zircaloy-4 and Zr-1 Nb-O oxide scales

International Nuclear Information System (INIS)

Bossis, Ph.; Thomazet, J.; Lefebvre, F.

2002-01-01

In PWRs, the Zr-1Nb-O alloy shows a marked enhancement in corrosion resistance in comparison with Zircaloy-4. The aim of this work is to analyze the reasons for these different behaviors and to determine the respective nature of the oxide growth controlling mechanisms under irradiation. Samples taken from Zircaloy-4 irradiated 1, 2, and 4 cycles and Zr-1Nb-O irradiated 1 and 3 cycles have been systematically characterized by optical microscopy, SEM coupled with image analysis, hydride distribution, and XRD. Specific TEM characterizations have been performed on the Zr-1Nb-O samples. A XPS analysis of a nonirradiated sample is also reported. It has been shown that under irradiation the slow oxidation kinetics of the Zr-1Nb-O alloy is associated with very regular metal-oxide interface and oxide layer. On the contrary, the accelerated oxidation kinetics of Zircaloy-4 is associated with highly perturbed metal-oxide interface and oxide layer. On both irradiated alloys, cracks are observed to initiate preferentially above the delayed parts of the oxidation front. Hydrogen intake during water oxidation in PWR environment is found to be much lower on the Zr-1Nb-O alloy than on Zircaloy-4. More β-ZrO 2 is found on the oxide layer formed on Zircaloy-4 than on Zr-1NbO after oxidation in PWR. Classical irradiation-induced microstructural evolution is observed in the Zr-1Nb-O metallic alloy after 3 cycles, i.e., a fine β-Nb precipitation. β-Nb precipitates are observed to undergo a delayed oxidation associated with a crystalline to amorphous transformation. After water oxidation in autoclave, a pronounced Nb segregation is detected on the oxide surface of a Zr-1Nb-O sample. These results suggest that the oxidation kinetics of Zircaloy-4 is controlled essentially by oxygen diffusion through the inner barrier layer, which is significantly accelerated under irradiation. The oxidation kinetics of Zr-1Nb-O is controlled by both oxygen diffusion through the inner barrier and by

Rhodium segregation in dilute silver-rhodium alloys

International Nuclear Information System (INIS)

Krolas, K.; Sternik, M.

1995-01-01

Segregation of Rh in Ag-based alloys has been studied using the perturbed angular correlation of γ-rays emitted in the nuclear decay of radioactive 111 In. The formation of impurity complexes, consisting of an 111 In probe atom and one or more Rh atoms, was observed as a function of annealing time and temperature. Rhodium atom aggregation starts at about 600 K. From the fraction of 111 In bound to isolated Rh atoms the solute rhodium atom concentration was determined. It increases with the nominal alloy concentration up to about 0.04 at.% and then it is essentially constant for the nominal Rh concentration varying between 0.1 and 0.5 at.%. The solute rhodium atom concentration is 3 times larger at the melting point than at 750 K

Moessbauer characterization of calcium-ferrite oxides prepared by calcining Fe2O3 and CaO

International Nuclear Information System (INIS)

Hirabayashi, Daisuke; Sakai, Yoichi; Yoshikawa, Takeshi; Mochizuki, Kazuhiro; Kojima, Yoshihiro; Suzuki, Kenzi; Ohshita, Kazumasa; Watanabe, Yasuo

2006-01-01

Calcium ferrite oxides were prepared by calcining a mixture powder of iron- and calcium oxide. The 57 Fe-Moessbauer spectra of the calcium ferrites oxides were measured, revealing that the products should be Ca 2 Fe 2 O 5 and CaFe 2 O 4 , the ratio of which was dependent of the Fe/Ca atomic ratio of the mixture powder.

A calorimetric and thermodynamic investigation of A2[(UO2)2(MoO4)O2] compounds with A = K and Rb and calculated phase relations in the system (K2MoO4 + UO3 + H2O)

International Nuclear Information System (INIS)

Lelet, Maxim I.; Suleimanov, Evgeny V.; Golubev, Aleksey V.; Geiger, Charles A.; Bosbach, Dirk; Alekseev, Evgeny V.

2015-01-01

Highlights: • We determined the low temperature heat capacity of A 2 [(UO 2 ) 2 (MoO 4 )O 2 ] compounds with A = K and Rb. • We determined enthalpy of formation of K 2 [(UO 2 ) 2 (MoO 4 )O 2 ] by HF solution calorimetry. • We calculated Δ f G° (T = 298 K) of all phases from studied series. • Using obtained data we performed a thermodynamic modelling in the system (K 2 MoO 4 + UO 3 + H 2 O). - Abstract: A calorimetric and thermodynamic investigation of two alkali-metal uranyl molybdates with general composition A 2 [(UO 2 ) 2 (MoO 4 )O 2 ], where A = K and Rb, was performed. Both phases were synthesized by solid-state sintering of a mixture of potassium or rubidium nitrate, molybdenum (VI) oxide and gamma-uranium (VI) oxide at high temperatures. The synthetic products were characterised by X-ray powder diffraction and X-ray fluorescence methods. The enthalpy of formation of K 2 [(UO 2 ) 2 (MoO 4 )O 2 ] was determined using HF-solution calorimetry giving Δ f H° (T = 298 K, K 2 [(UO 2 ) 2 (MoO 4 )O 2 ], cr) = −(4018 ± 8) kJ · mol −1 . The low-temperature heat capacity, C p °, was measured using adiabatic calorimetry from T = (7 to 335) K for K 2 [(UO 2 ) 2 (MoO 4 )O 2 ] and from T = (7 to 326) K for Rb 2 [(UO 2 ) 2 (MoO 4 )O 2 ]. Using these C p ° values, the third law entropy at T = 298.15 K, S°, is calculated as (374 ± 1) J · K −1 · mol −1 for K 2 [(UO 2 ) 2 (MoO 4 )O 2 ] and (390 ± 1) J · K −1 · mol −1 for Rb 2 [(UO 2 ) 2 (MoO 4 )O 2 ]. These new experimental results, together with literature data, are used to calculate the Gibbs energy of formation, Δ f G°, for both phases giving: Δ f G° (T = 298 K, K 2 [(UO 2 ) 2 (MoO 4 )O 2 ], cr) = (−3747 ± 8) kJ · mol −1 and Δ f G° (T = 298 K, Rb 2 [(UO 2 ) 2 (MoO 4 )], cr) = −3736 ± 5 kJ · mol −1 . Smoothed C p °(T) values between 0 K and 320 K are presented, along with values for S° and the functions [H°(T) − H°(0)] and [G°(T) − H°(0)], for both phases. The

Low gravity containerless processing of immiscible gold rhodium alloys

Science.gov (United States)

Andrews, J. Barry

1986-01-01

Under normal one-g conditions immiscible alloys segregate extensively during solidification due to sedementation of the more dense of the immiscible liquid phases. However, under low-g conditions it should be possible to form a dispersion of the two immiscible liquids and maintain this dispersed structure during solidification. Immiscible (hypermonotectic) gold-rhodium alloys were processed in the Marshall Space Flight Center 105 meter drop tube in order to investigate the influence of low gravity, containerless solidification on their microstructure. Hypermonotectic alloys composed of 65 atomic % rhodium exhibited a tendency for the gold rich liquid to wet the outer surface of the containerless processed samples. This tendency led to extensive segregation in several cases. However, well dispersed microstructures consisting of 2 to 3 micron diameter rhodium-rich spheres in a gold-rich matrix were produced in 23.4 atomic % rhodium alloys. This is one of the best dispersions obtained in research on immiscible alloy-systems to data.

Catalytic Oxidation of Benzophenone Hydrazone with Alumina-supported KMnO{sub 4} under Oxygen Atmosphere

Energy Technology Data Exchange (ETDEWEB)

Lee, Kang Hyeok; Ko, Kwang Youn [Ajou University, Suwon (Korea, Republic of)

2006-02-15

KMnO{sub 4}/alumina reagent, which is cheap and environmentally safe, can serve as a catalytic oxidant under O{sub 2} atmosphere for the oxidation of benzophenone hydrazone. To the best of our knowledge, the present works are the first example where KMnO{sub 4}/alumina reagent acts as a catalytic oxidant under O{sub 2} atmosphere. Diphenyldiazomethane (Ph{sub 2}CN{sub 2}) is widely used for the protection of carboxylic acids by conversion to their diphenylmethyl (dpm) esters since dpm group can be easily deprotected by mild acidic condition or hydrogenolysis, especially in the field of b-lactams and peptides. Diphenyldiazomethane has been prepared by the oxidation of benzophenone hydrazone with reagents such as active manganese dioxide, mercuric oxide, peracetic acid, iodosobenzene diacetate or OXONE. However, some methods suffer from a disadvantage such as toxic nature of reagent, strong oxidative conditions or incompatibility with certain functional groups. For example, OXONE may not be employed for the in situ protection of carboxylic acid containing sulfide group due to the possibility of the concomitant oxidation of sulfide group.

Mechanism of intermolecular hydroacylation of vinylsilanes catalyzed by a rhodium(I) olefin complex: a DFT study.

Science.gov (United States)

Meng, Qingxi; Shen, Wei; Li, Ming

2012-03-01

Density functional theory (DFT) was used to investigate the Rh(I)-catalyzed intermolecular hydroacylation of vinylsilane with benzaldehyde. All intermediates and transition states were optimized completely at the B3LYP/6-31G(d,p) level (LANL2DZ(f) for Rh). Calculations indicated that Rh(I)-catalyzed intermolecular hydroacylation is exergonic, and the total free energy released is -110 kJ mol(-1). Rh(I)-catalyzed intermolecular hydroacylation mainly involves the active catalyst CA2, rhodium-alkene-benzaldehyde complex M1, rhodium-alkene-hydrogen-acyl complex M2, rhodium-alkyl-acyl complex M3, rhodium-alkyl-carbonyl-phenyl complex M4, rhodium-acyl-phenyl complex M5, and rhodium-ketone complex M6. The reaction pathway CA2 + R2 → M1b → T1b → M2b → T2b1 → M3b1 → T4b → M4b → T5b → M5b → T6b → M6b → P2 is the most favorable among all reaction channels of Rh(I)-catalyzed intermolecular hydroacylation. The reductive elimination reaction is the rate-determining step for this pathway, and the dominant product predicted theoretically is the linear ketone, which is consistent with Brookhart's experiments. Solvation has a significant effect, and it greatly decreases the free energies of all species. The use of the ligand Cp' (Cp' = C(5)Me(4)CF(3)) decreased the free energies in general, and in this case the rate-determining step was again the reductive elimination reaction.

Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

Science.gov (United States)

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-07-12

A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

Enantioselective rhodium/ruthenium photoredox catalysis en route to chiral 1,2-aminoalcohols.

Science.gov (United States)

Ma, Jiajia; Harms, Klaus; Meggers, Eric

2016-08-09

A rhodium-based chiral Lewis acid catalyst combined with [Ru(bpy)3](PF6)2 as a photoredox sensitizer allows for the visible-light-activated redox coupling of α-silylamines with 2-acyl imidazoles to afford, after desilylation, 1,2-amino-alcohols in yields of 69-88% and with high enantioselectivity (54-99% ee). The reaction is proposed to proceed via an electron exchange between the α-silylamine (electron donor) and the rhodium-chelated 2-acyl imidazole (electron acceptor), followed by a stereocontrolled radical-radical reaction. Substrate scope and control experiments reveal that the trimethylsilyl group plays a crucial role in this reductive umpolung of the carbonyl group.

Highly active sulfided CoMo catalysts supported on (ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} ternary oxides

Energy Technology Data Exchange (ETDEWEB)

Escobar, José, E-mail: jeaguila@imp.mx [Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, Col. San Bartolo Atepehuacan, Gustavo A. Madero, México, D.F. 07730 (Mexico); De Los Reyes, José A., E-mail: jarh@xanum.uam.mx [Area de Ing. Química, UAM – Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, México, D.F. 09340 (Mexico); Ulín, Carlos A. [Area de Ing. Química, UAM – Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, México, D.F. 09340 (Mexico); Barrera, María C., E-mail: mcbdgavilan@gmail.com [Facultad de Ciencias Químicas, Universidad Veracruzana, Av. Universidad km. 7.5, Col. Santa Isabel, Coatzacoalcos, Veracruz, México, D.F. 96538 (Mexico)

2013-12-16

(ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} ternary oxide at 20 mol% Al{sub 2}O{sub 3} (80% ZrO{sub 2}–TiO{sub 2}, in turn at 40–60 mol ratio) prepared by controlled co-precipitation (by urea thermal decomposition) of zirconium (ZrOCl{sub 2}·8H{sub 2}O) and titanium (TiCl{sub 4}) chlorides over a ground alumina substrate constitutes a promising material to be used as carrier of sulfided hydrodesulfurization (HDS) catalysts. After calcining (at 500 °C), the ternary oxide presented textural properties (S{sub g} = 387 m{sup 2} g{sup −1}, V{sub p} = 0.74 ml g{sup −1}, mean pore diameter = 7.6 nm) suitable to its utilization as carrier of catalysts applied in the oil-derived middle distillates HDS. As determined by temperature programmed-reduction and Raman and UV–vis spectroscopies ZrO{sub 2}–TiO{sub 2} deposition over alumina substrate resulted in decreased proportion of Mo{sup 6+} species in tetrahedral coordination on the oxidic impregnated material. As those species constitute hardly reducible precursors, their diminished concentration could be reflected in enhanced amount of Mo species susceptible of activation by sulfiding (H{sub 2}S/H{sub 2} at 400 °C) over our ternary carrier. Limiting the concentration of zirconia-titania (at 40–60 mol ratio) to 20 mol% in the mixed oxides support allowed the preparation of highly active promoted (by cobalt, at Co/(Co + Mo) = 0.3) MoS{sub 2} phase (at 2.8 atoms/nm{sup 2}), that formulation showing excellent properties in hydrodesulfurization (HDS) of both dibenzothiophene and highly-refractory 4,6-dimethyl-dibenzothiophene. Due to alike yields to various HDS products over CoMo/(ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3} and the corresponding Al{sub 2}O{sub 3}-supported formulation, presence of similar actives sites over those catalysts was strongly suggested. It seemed that enhanced concentration of octahedral Mo{sup 6+} over the oxidic impregnated precursor with (ZrO{sub 2}–TiO{sub 2})/Al{sub 2}O{sub 3

Synthesis of MnFe2O4@Mn-Co oxide core-shell nanoparticles and their excellent performance for heavy metal removal.

Science.gov (United States)

Ma, Zichuan; Zhao, Dongyuan; Chang, Yongfang; Xing, Shengtao; Wu, Yinsu; Gao, Yuanzhe

2013-10-21

Magnetic nanomaterials that can be easily separated and recycled due to their magnetic properties have received considerable attention in the field of water treatment. However, these nanomaterials usually tend to aggregate and alter their properties. Herein, we report an economical and environmentally friendly method for the synthesis of magnetic nanoparticles with core-shell structure. MnFe2O4 nanoparticles have been successfully coated with amorphous Mn-Co oxide shells. The synthesized MnFe2O4@Mn-Co oxide nanoparticles have highly negatively charged surface in aqueous solution over a wide pH range, thus preventing their aggregation and enhancing their performance for heavy metal cation removal. The adsorption isotherms are well fitted to a Langmuir adsorption model, and the maximal adsorption capacities of Pb(II), Cu(II) and Cd(II) on MnFe2O4@Mn-Co oxide are 481.2, 386.2 and 345.5 mg g(-1), respectively. All the metal ions can be completely removed from the mixed metal ion solutions in a short time. Desorption studies confirm that the adsorbent can be effectively regenerated and reused.

Copper-promoted methylene C-H oxidation to a ketone derivative by O2.

Science.gov (United States)

Deville, Claire; McKee, Vickie; McKenzie, Christine J

2017-01-17

The methylene group of the ligand 1,2-di(pyridin-2-yl)-ethanone oxime (dpeo) is slowly oxygenated by the O 2 in air under ambient conditions when [Cu(dpeo) 2 ](ClO 4 ) 2 is dissolved in ethanol or acetonitrile. An initial transient ketone product, 2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone, (hidpe) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO 4 ). The co-ligand in this complex, N-(2'-pyridylcarbonyl)pyridine-2-carboximidate (bpca - ), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water is present in reaction mixtures copper complexes of dpeo, hidpe and bpca - are not recovered and [Cu(pic) 2 H 2 O] is isolated. This occurs since two equivalents of picolinate are ultimately generated from one equivalent of oxidized and hydrolysed dpeo. The copper-dependent O 2 activation and consequent stoichiometric dpeo C-H oxidation is reminiscent of the previously observed catalysis of dpeo oxidation by Mn(ii) [C. Deville, S. K. Padamati, J. Sundberg, V. McKee, W. R. Browne, C. J. McKenzie, Angew. Chem., Int. Ed., 2016, 55, 545-549]. By contrast dpeo oxidation is not observed during complexation reactions with other late transition metal(ii) ions (M = Fe, Co, Ni, Zn) under aerobic conditions. In these cases bis and tris complexes of bidentate dpeo are isolated in good yields. It is interesting to note that dpeo is not oxidised by H 2 O 2 in the absence of Cu or Mn, suggesting that metal-based oxidants capable of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O 2 . The metastable copper complexes [Cu(dpeo) 2 ](ClO 4 ) 2 and [Cu(bpca)(hidpe)](ClO 4 ), along with [NiX 2 (dpeo) 2 ] (X = Cl, Br), [Ni(dpeo) 3 ](ClO 4 ) 2 , [Co(dpeo) 3 ](ClO 4 ) 3 and the mixed valence complex [Fe III Fe(dpeo-H) 3 (dpeo) 3 ](PF 6 ) 4 , have been structurally characterized.

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.

Oxidation of atomically thin MoS2 on SiO2

Science.gov (United States)

Yamamoto, Mahito; Cullen, William; Einstein, Theodore; Fuhrer, Michael

2013-03-01

Surface oxidation of MoS2 markedly affects its electronic, optical, and tribological properties. However, oxidative reactivity of atomically thin MoS2 has yet to be addressed. Here, we investigate oxidation of atomic layers of MoS2 using atomic force microscopy and Raman spectroscopy. MoS2 is mechanically exfoliated onto SiO2 and oxidized in Ar/O2 or Ar/O3 (ozone) at 100-450 °C. MoS2 is much more reactive to O2 than an analogous atomic membrane of graphene and monolayer MoS2 is completely etched very rapidly upon O2 treatment above 300 °C. Thicker MoS2 (> 15 nm) transforms into MoO3 after oxidation at 400 °C, which is confirmed by a Raman peak at 820 cm-1. However, few-layer MoS2 oxidized below 400 °C exhibits no MoO3 Raman mode but etch pits are formed, similar to graphene. We find atomic layers of MoS2 shows larger reactivity to O3 than to O2 and monolayer MoS2 transforms chemically upon O3 treatment even below 100 °C. Work supported by the U. of Maryland NSF-MRSEC under Grant No. DMR 05-20741.

Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

Directory of Open Access Journals (Sweden)

J. N. Crowley

2012-01-01

Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

Structural studies of five layer Aurivillius oxides: A2Bi4Ti5O18 (A=Ca, Sr, Ba and Pb)

International Nuclear Information System (INIS)

Ismunandar; Kamiyama, T.; Hoshikawa, A.; Zhou, Q.; Kennedy, B.J.; Kubota, Y.; Kato, K.

2004-01-01

The room temperature structures of the five layer Aurivillius phases A 2 Bi 4 Ti 5 O 18 , (A=Ca, Sr, Ba and Pb) have been refined from powder neutron diffraction data using the Rietveld method. The structures consist of [Bi 2 O 2 ] 2+ layers interleaved with perovskite-like [A 2 Bi 2 Ti 5 O 16 ] 2- blocks. The structures were refined in the orthorhombic space group B2eb (SG. No. 41), Z=4, and the unit cell parameters of the oxides are a=5.4251(2), b=5.4034(1), c=48.486(1); a=5.4650(2), b=5.4625(3), c=48.852(1); a=5.4988(3), b=5.4980(4), c=50.352(1); a=5.4701(2), b=5.4577(2), c=49.643(1) for A=Ca, Sr, Ba and Pb, respectively. The structural features of the compounds were found similar to n=2-4 layers bismuth oxides. The strain caused by mismatch of cell parameter requirements for the [Bi 2 O 2 ] 2+ layers and perovskite-like [A 2 Bi 2 Ti 5 O 16 ] 2- blocks were relieved by tilting of the TiO 6 octahedra. Variable temperature synchrotron X-ray studies for Ca and Pb compounds showed that the orthorhombic structure persisted up to 675 and 475K, respectively. Raman spectra of the compounds are also presented

Hydrolysis of Letrozole catalyzed by macrocyclic Rhodium (I) Schiff-base complexes.

Science.gov (United States)

Reddy, P Muralidhar; Shanker, K; Srinivas, V; Krishna, E Ravi; Rohini, R; Srikanth, G; Hu, Anren; Ravinder, V

2015-03-15

Ten mononuclear Rhodium (I) complexes were synthesized by macrocyclic ligands having N4 and N2O2 donor sites. Square planar geometry is assigned based on the analytical and spectral properties for all complexes. Rh(I) complexes were investigated as catalysts in hydrolysis of Nitrile group containing pharmaceutical drug Letrozole. A comparative study showed that all the complexes are efficient in the catalysis. The percent yields of all the catalytic reaction products viz. drug impurities were determined by spectrophotometric procedures and characterized by spectral studies. Copyright © 2014 Elsevier B.V. All rights reserved.

Initial Stages in the Rhodium(III)-Catalyzed C-H Bond Activation of Primary Alcohols in Aqueous Solution

DEFF Research Database (Denmark)

Eriksen, J.; Monsted, L.; Monsted, O.

2010-01-01

The mechanism of the catalytic HID exchange in primary alcohol substrates derived from aldopentoses, promoted by a macrocyclic rhodium(III) complex, has been shown to occur by a reversible redox reaction that gives aldehyde and a rhodium hydride complex. Hydride exchange in the latter complex...... promotes the introduction of solvent hydrogen in the primary alcohol formed by the reverse reaction. The hydride complex has been crystallographically characterized as a trifluoromethanesulfonate salt that contains the trans-[Rh(cycb)(H)(OH2)](2+) (cycb = rac-5,5,7,12,12,14-hexamethyl-1......,4,8,11-tetraazacyclotetradecane) cation. The hydride complex is stable for extended periods of time in acidic solution in the absence of oxidants. In basic solutions a series of base-catalyzed reactions take place to yield ultimately the same mixture of [Rh(cycb)(OH)(2)](+) isomers as produced by base hydrolysis of the trans...

Synthesis and electromagnetic absorption properties of Ag-coated reduced graphene oxide with MnFe{sub 2}O{sub 4} particles

Energy Technology Data Exchange (ETDEWEB)

Wang, Yan, E-mail: wangyan287580632@126.com; Wu, Xinming; Zhang, Wenzhi; Huang, Shuo

2016-04-15

A ternary composite of Ag/MnFe{sub 2}O{sub 4}/reduced graphene oxide (RGO) was synthesized by a facile hydrothermal method. The morphology, microstructure, magnetic and electromagnetic properties of as-prepared Ag/MnFe{sub 2}O{sub 4}/RGO composite were characterized by means of XRD, TEM, XPS, VSM and vector network analyzer. The maximum reflection loss (R{sub L}) of Ag/ MnFe{sub 2}O{sub 4}/RGO composite shows maximum absorption of −38 dB at 6 GHz with the thickness of 3.5 mm, and the absorption bandwidth with the R{sub L} below −10 dB is up to 3.5 GHz (from 3.7 to 7.2 GHz). The result demonstrates that the introduction of Ag significantly leads to the multiple absorbing mechanisms. It is believed that such composite could serve as a powerful candidate for microwave absorber. - Highlights: • A ternary composite of Ag/MnFe{sub 2}O{sub 4}/reduced graphene oxide (RGO) was synthesized by a facile method. • The morphology, microstructure, magnetic and electromagnetic properties were characterized. • The maximum reflection loss of Ag/MnFe{sub 2}O{sub 4}/RGO is −38 dB at 6 GHz with a thickness of 3.5 mm. • The composite shows a wide absorption band.

RuO4-mediated oxidation of secondary amines: Part 1. Are hydroxylamines main intermediates?

Directory of Open Access Journals (Sweden)

Florea Cristina A.

2016-01-01

Full Text Available The RuO4-catalyzed oxidation of secondary amines Bn-NH-CH2R (1a-b; R=H, Me gave mainly amides, but minute amounts of nitrones PhCH=N(O-CH2R (9a-b and traces of Bn-N(OH-CH2R (R=H, 4a were also detected. In the presence of cyanide, up to 22 reaction products were identified, but mainly α-aminonitriles. Comparison of the oxidation products of 1a-b with those of 4a-b, 9a-b, and Bn-N(O=CHR (10a-b showed that 4a-b cannot be main reaction intermediates formed from 1a-b.

Photocatalytic oxidation of low concentration 2,4-D solution with new TiO2 fiber catalyst in a continuous flow reactor.

Science.gov (United States)

Terashima, Y; Ozaki, H; Giri, R R; Tano, T; Nakatsuji, S; Takanami, R; Taniguchi, S

2006-01-01

Environmental pollution by low concentrations of 2,4-Dichlorophenoxyacetic acid (2,4-D) is a concern these days due to ever increasingly stringent regulations. Photocatalysis with immobilized TiO2 fiber is a promising oxidation method. Laboratory experiments on photocatalytic degradation of 0.045 mmol l(-1) 2,4-D with the world's first high-strength TiO2 fiber catalyst were carried out in a continuous flow reactor in which the degradations were, in general, similar to those with high 2,4-D concentrations investigated elsewhere. Degradation and mineralization of 2,4-D were significantly enhanced with no initial pH adjustments. The rate constants for total organic carbon (TOC) without pH adjustment were about two-fold bigger than the pH adjustment cases. CO2 gas measurement and carbon mass-balance were carried out for the first time, where about 34% organic carbon converted into CO2 gas during four-hour oxidation. 2,4-Dichlorophenol (2,4-DCP), phenol, benzyl alcohol and two unknowns (RT = 2.65 and 3.78 min.) were detected as aromatic intermediates while Phenol was the new aromatic in HPLC analysis. Dechlorination efficiencies were high (> 70%) in all the cases, and more than 90% efficiencies were observed in chloride mass balance. Bigger flow rates and solution temperature fixed at 20 degrees C without pH adjustment greatly enhanced 2,4-D mineralization. These results can be an important basis in applying the treatment method for dioxin-contaminated water and wastewater.

Designing MgFe{sub 2}O{sub 4} decorated on green mediated reduced graphene oxide sheets showing photocatalytic performance and luminescence property

Energy Technology Data Exchange (ETDEWEB)

Shetty, Krushitha [Department of Nanotechnology, PG Center, Bangalore Region, VIAT, VTU, Muddenahalli, Chikkaballapur 562101 (India); Dr. D. Premachandrasagar Centre for Advanced Materials, DSCE, Bangalore 560078 (India); Lokesh, S.V. [Department of Nanotechnology, PG Center, Bangalore Region, VIAT, VTU, Muddenahalli, Chikkaballapur 562101 (India); Rangappa, Dinesh, E-mail: dineshrangappa@gmail.com [Department of Nanotechnology, PG Center, Bangalore Region, VIAT, VTU, Muddenahalli, Chikkaballapur 562101 (India); Nagaswarupa, H.P., E-mail: nagaswarupa77@gmail.com [Research Center, Department of Science, East West Institute of Technology, Bangalore 560091 (India); Nagabhushana, H., E-mail: bhushanvlc@gmail.com [Prof. CNR Rao Centre for Advanced Materials, Tumkur University, Tumkur 572103 (India); Anantharaju, K.S., E-mail: iamananthkurupalya@gmail.com [Department of Chemistry, Dayananda Sagar College of Engineering, Shavige Malleshwara Hills, Kumaraswamy Layout, Bangalore 560078 (India); Dr. D. Premachandrasagar Centre for Advanced Materials, DSCE, Bangalore 560078 (India); Prashantha, S.C. [Research Center, Department of Science, East West Institute of Technology, Bangalore 560091 (India); Vidya, Y.S. [Department of Physics, Lal Bahadur Shastri Government First Grade College, Bangalore, 560032 (India); Sharma, S.C. [Dr. D. Premachandrasagar Centre for Advanced Materials, DSCE, Bangalore 560078 (India); Department of Mechanical Engineering, DSCE, Bangalore-560078 (India)

2017-02-15

Here, a green route has been reported to convert Graphene Oxide (GO) to reduced graphene oxide (RGO) using clove extract. A modest and eco-accommodating sol-gel strategy has been employed to prepare MgFe{sub 2}O{sub 4} nanoparticles, MgFe{sub 2}O{sub 4}–RGO nanocomposite samples. The samples were analyzed by Powder X-ray diffraction (PXRD), Fourier Transform Infrared Spectroscopy (FTIR), UV–Visible Spectroscopy, Scanning Electron Microcopy (SEM), Transmission Electron Microscopy (TEM), Photoluminescence (PL) and Electrochemical Impedance Spectroscopy (EIS). PXRD result revealed that the prepared samples were cubic spinel in nature. SEM results uncovered flake like surface morphology of the prepared nanomaterial. Better PL emission signature was observed when excited at 329 nm. PL studies demonstrated that the present samples were potential for the fabrication of white component of white light emitting diodes (WLEDs). Further, MgFe{sub 2}O{sub 4}–RGO nanocomposite showed enhanced photocatalytic movement (PCM) and photostability under Sunlight in the decomposition of Malachite Green (MG) compared to MgFe{sub 2}O{sub 4}. This can be attributed to the interaction of MgFe{sub 2}O{sub 4} surface with RGO sheets which results in PL quenching, demonstrates that the recombination of photo-induced electrons and holes in MgFe{sub 2}O{sub 4}–RGO nanocomposite is more effectively inhibited. A possible mechanism for the enhanced properties of MgFe{sub 2}O{sub 4}–RGO nanocomposite was discussed. Moreover, MgFe{sub 2}O{sub 4}–RGO photocatalyst also showed easy magnetic separation with high reusability. These results unveil that the synthesized sample can be used in display applications and also as a potential photocatalyst. - Graphical abstract: Green mediated reduced graphene oxide with MgFe{sub 2}O{sub 4} for display applications and also as a potential photocatalyst. - Highlights: • Synthesized GO was reduced to RGO by green route using clove extract. • Mg

Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols.

Science.gov (United States)

Li, Junjun; Liu, Yuxuan; Tang, Weijun; Xue, Dong; Li, Chaoqun; Xiao, Jianliang; Wang, Chao

2017-10-17

The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Study on Production of Carbon Nanotubes by CH4 Decomposition over LaNiO3, La4Ni3O10, La3Ni2O7 and La2NiO4

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

Carbon nanotubes (CNTs) of narrow size distribution can be abundantly produced in the catalytic decomposition of CH4 over pre-reduced LaNiO3, La4Ni3O10, La3Ni2O7 and La2NiO4.The CNTs obtained were characterized by means of transmission electron microscopy (TEM).Thermal oxidation of CNTs in air was monitored thermogravimetrically (TG). The resultsrevealed that a lower La/Ni ratio of the catalysts would lead to a wider diameter distribution and a higher degree of graphitic nature.

An expedient procedure for the oxidative cleavage of olefinic bonds with PhI(OAc)2, NMO, and catalytic OsO4.

Science.gov (United States)

Nicolaou, K C; Adsool, Vikrant A; Hale, Christopher R H

2010-04-02

PhI(OAc)(2) in the presence of OsO(4) (cat.) and 2,6-lutidine cleaves olefinic bonds to yield the corresponding carbonyl compounds, albeit, in some cases, with alpha-hydroxy ketones as byproduct. A more practical and clean protocol to effect oxidative cleavage of olefinic bonds involves NMO, OsO(4) (cat.), 2,6-lutidine, and PhI(OAc)(2).

Colloidal stability, surface characterisation and intracellular accumulation of Rhodium(II) citrate coated superparamagnetic iron oxide nanoparticles in breast tumour: a promising platform for cancer therapy

Energy Technology Data Exchange (ETDEWEB)

Silva Nunes, Eloiza da [Universidade Federal de Goias, Campus Samambaia, Instituto de Quimica (Brazil); Lemos Brettas Carneiro, Marcella; Guirelli Simoes de Oliveira, Ricardo; Nair Bao, Sonia [Universidade de Brasilia (UnB), Instituto de Ciencias Biologicas (Brazil); Ribeiro de Souza, Aparecido, E-mail: ardsouza@quimica.ufg.br [Universidade Federal de Goias, Campus Samambaia, Instituto de Quimica (Brazil)

2013-06-15

The colloidal stability of a rhodium(II) citrate, Rh{sub 2}(H{sub 2}cit){sub 4}, coating on the surface of maghemite ({gamma}-Fe{sub 2}O{sub 3}) nanoparticles was studied and compared in different dispersion media. The adsorption of Rh{sub 2}(H{sub 2}cit){sub 4} at the water-maghemite interface was evaluated as a function of pH and complex concentration. A slight pH-dependent adsorption of the complex was observed with a maximum at pH 3. The colloidal stability of the functionalised nanoparticles with different amounts of Rh{sub 2}(H{sub 2}cit){sub 4} as a function of pH was evaluated using dynamic light scattering measurements. The particles have a mean magnetic core size of 5.6 nm and the hydrodynamic diameters are approximately 60 nm, which remained unchanged in the pH range in which the samples were a stable sol. The tolerance to different dispersion media, which were deionised water, saline, phosphate-buffered saline (PBS), foetal bovine serum (FBS) and NaCl solutions with different concentrations, was investigated. At moderate ionic strength, the colloidal stability of the dispersions was similar in saline and in PBS compared to the stability of dispersions diluted in water. Moreover, the intracellular accumulation of nanoparticles in 4T1 breast tumour was examined by ultrastructural analysis performed by transmission electron microscopy. The rhodium(II) citrate-coated nanoparticles were found mostly in the cytoplasm and nucleus. Thus, we suggest that these SPIO nanoparticles functionalized with Rh{sub 2}(H{sub 2}Cit){sub 4} can be potential tools for anticancer therapy.

Mesoporous Mn promoted Co3O4 oxides as an efficient and stable catalyst for low temperature oxidation of CO

Science.gov (United States)

Liu, Changxiang; Gong, Lei; Dai, Runying; Lu, Meijuan; Sun, Tingting; Liu, Qian; Huang, Xigen; Huang, Zhong

2017-09-01

Mesoporous Mn-doped Co3O4 catalysts were successfully prepared via a dry soft reactive grinding method based on solid state reaction, and their catalytic performances on CO oxidation were evaluated at a high space velocity of 49,500 mL g-1 h-1. A significant promoted effect was observed once the atomic ratios of Mn/(Co+Mn) were lower than 10%, for instance, the temperature for 50% conversion decreased to about -60 °C, showing superior catalytic performance compared to the single metal oxide. Especially, the Mn-promoted Co3O4 catalyst with a Mn/(Co+Mn) molar ratio of 10% could convert 100% CO after 3000 min of time-on-steam without any deactivation at room temperature. As prepared catalysts were characterized by XRD, N2-adsorption/desorption, TEM, H2-TPR, O2-TPD and CO-titration analysis. The significant enhancement of performance for oxidation of CO over Mn-Co-O mixed oxides was associated with the high active oxygen species concentrations formed during the pretreatment in O2 atmosphere.

Decolorization of methylene blue in layered manganese oxide suspension with H2O2

International Nuclear Information System (INIS)

Zhang Lili; Nie Yulun; Hu Chun; Hu Xuexiang

2011-01-01

Highlights: → Layered birnessite-type manganese oxides exhibited a well-crystallized octahedral layer (OL) structure with β-MnOOH, α-MnOOH and γ-Mn 3 O 4 . → The catalyst was highly effective for the decolorization and degradation of methylene blue in the presence of H 2 O 2 at neutral pH. → The 1 O 2 and O 2 · - were the main reactive oxygen species in the reaction. - Abstract: Layered birnessite-type manganese oxides (Na-OL-1) were prepared via a redox reaction involving MnO 4 - and Mn 2+ under markedly alkaline conditions. According to the XRD analysis, the resulting material exhibited a well-crystallized octahedral layer (OL) structure with several different phases, including β-MnOOH, α-MnOOH and γ-Mn 3 O 4 . The catalyst was highly effective for the decolorization and degradation of methylene blue (MB) in the presence of H 2 O 2 at neutral pH. The tested MB was completely decolorized in Na-OL-1 suspension by the fraction dosing of H 2 O 2 (556.5 mM at the beginning and then 183.8 mM at 40 min). Based on the studies of electron spin resonance and the effect of radical scavengers, the 1 O 2 and O 2 · - were the main reactive oxygen species (ROS) in the reaction. It was found that both oxygen and ROS were generated from the decomposition of H 2 O 2 in Na-OL-1 suspension, wherein the decomposition pathways were proposed. The generation of H 2 O 2 in Na-OL-1 suspension at air atmosphere indicated that the existence of multivalent manganese oxides greatly enhanced the interfacial electron transfer, leading to the high activity of Na-OL-1.

High-temperature oxidation of Zircaloy-2 and Zircaloy-4 in steam

International Nuclear Information System (INIS)

Urbanic, V.F.; Heidrick, T.R.

1978-01-01

At temperatures above the (α + β)/β transformation temperature for zirconium alloys, steam reacts with β-Zr to form a superficial layer of zirconium oxide (ZrO 2 ) and an intermediate layer of oxygen-stabilized α-Zr. Reaction kinetics and the rate of growth of the combined (ZrO 2 + α-Zr) layer for Zircaloy-2 and Zircaloy-4 oxidation in steam were measured over the temperature range 1050-1850 o C. The reaction rates for both alloys were similar, obeyed parabolic kinetics and were not limited by gas phase diffusion. The parabolic rate constants were consistently less than those given by the Baker and Just correlation for zirconium oxidation in steam. A discontinuity was found in the temperature dependence of both the reaction rate and the rate of growth of the combined (ZrO 2 + α-Zr) layer. The discontinuity is attributed to a change in the oxide microstructure at the discontinuity temperature, an observation which is consistent with the zirconium-oxygen phase diagram. (author)