Molybdenum-sulfur dimers as electrocatalysts for the production of hydrogen at low overpotentials.
作者： Aaron M. Appel , Daniel L. DuBois , M. Rakowski DuBois
DOI: 10.1021/JA054034O
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摘要: (CpMoμ-S)2S2CH2, 2, and related derivatives serve as electrocatalysts for the reduction of protons with current efficiencies near 100%. The kinetics electrochemical process has been studied, effects varying proton source, solvent, cyclopentadienyl substituents, sulfur substituents on catalyst have examined. excess p-cyanoanilinium tetrafluoroborate under a hydrogen atmosphere in 0.3 M Et4NBF4/acetonitrile buffered at pH 7.6 is catalyzed by 2 −0.64 V versus ferrocene, an overpotential 120 mV. Protonation sulfido ligand initial step catalytic process, rate-determining high acid concentrations appears to be elimination dihydrogen. may occur either from adjacent hydrosulfido sites or hydrosulfido−molybdenum hydride intermediate.
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Alfred B. Anderson, Zeki Y. Al-Saigh, W. Keith Hall, Hydrogen on molybdenum disulfide: theory of its heterolytic and homolytic chemisorption The Journal of Physical Chemistry. ,vol. 92, pp. 803- 809 ,(1988) , 10.1021/J100314A042
Masato Ito, Makoto Hirakawa, Kunihiko Murata, Takao Ikariya, Hydrogenation of aromatic ketones catalyzed by (η5-C5(CH3)5)Ru complexes bearing primary amines Organometallics. ,vol. 20, pp. 379- 381 ,(2001) , 10.1021/OM000912+
Linda L. Lopez, P. Bernatis, J. Birnbaum, R. C. Haltiwanger, M. Rakowski DuBois, Mechanistic study of hydrogen activation by cationic dinuclear (.mu.-sulfido)molybdenum complexes Organometallics. ,vol. 11, pp. 2424- 2435 ,(1992) , 10.1021/OM00043A025
R. S. Nicholson, Irving. Shain, Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems. Analytical Chemistry. ,vol. 36, pp. 706- 723 ,(1964) , 10.1021/AC60210A007
Tamara E. Hanna, Ivan Keresztes, Emil Lobkovsky, Wesley H. Bernskoetter, Paul J. Chirik, Synthesis of a base-free titanium imido and a transient alkylidene from a titanocene dinitrogen complex. Studies on Ti=NR hydrogenation, nitrene group transfer, and comparison of 1,2-addition rates Organometallics. ,vol. 23, pp. 3448- 3458 ,(2004) , 10.1021/OM049817H
Tianshu Li, Raphaël Churlaud, Alan J. Lough, Kamaluddin Abdur-Rashid, Robert H. Morris, Dihydridoamine and Hydridoamido Complexes of Ruthenium(II) with a Tetradentate P−N−N−P Donor Ligand Organometallics. ,vol. 23, pp. 6239- 6247 ,(2004) , 10.1021/OM049565K
C. Thomas, L. Vivier, A. Travert, F. Maugé, S. Kasztelan, G. Pérot, Deuterium Tracer Studies on Hydrotreating Catalysts. 2. Contribution of the Hydrogen of the Alumina Support to H-D Exchange☆ Journal of Catalysis. ,vol. 179, pp. 495- 502 ,(1998) , 10.1006/JCAT.1998.2218
Yasuhiro Ohki, Nobuo Matsuura, Tadashi Marumoto, Hiroyuki Kawaguchi, Kazuyuki Tatsumi, Heterolytic Cleavage of Dihydrogen Promoted by Sulfido-Bridged Tungsten−Ruthenium Dinuclear Complexes Journal of the American Chemical Society. ,vol. 125, pp. 7978- 7988 ,(2003) , 10.1021/JA029941X
R. T. Weberg, R. C. Haltiwanger, J. C. V. Laurie, Mary Rakowski. DuBois, Activation of hydrogen by cationic cyclopentadienylmolybdenum dimers with sulfido ligands. 2. Cationic complexes derived from reactions with vinyl halides Journal of the American Chemical Society. ,vol. 108, pp. 6242- 6250 ,(1986) , 10.1021/JA00280A022
Frédéric Gloaguen, Joshua D. Lawrence, Thomas B. Rauchfuss, Biomimetic Hydrogen Evolution Catalyzed by an Iron Carbonyl Thiolate Journal of the American Chemical Society. ,vol. 123, pp. 9476- 9477 ,(2001) , 10.1021/JA016516F