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New cyclopentadienyl rhodium catalysts for electrochemical hydrogen production

Title
New cyclopentadienyl rhodium catalysts for electrochemical hydrogen production
Authors
Kim J.Rajkumar E.Kim S.Park Y.M.Kim Y.Kim S.-J.Lee H.J.
Ewha Authors
김진흥
SCOPUS Author ID
김진흥scopus
Issue Date
2017
Journal Title
Catalysis Today
ISSN
0920-5861JCR Link
Citation
vol. 295, pp. 75 - 81
Keywords
(pyridyl)benzothiazoleElectrocatalytic reductionHydrogen productionMolecular rhodium complexTrifluoroacetic acid
Publisher
Elsevier B.V.
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
The electrocatalytic activity of two new molecular rhodium catalysts was investigated in a hydrogen evolution system in the presence of a proton source using glassy carbon electrodes in acetonitrile and water. Rhodium complexes supported by pbi and pbt ligands, i.e., [Cp*Rh(pbt)Cl](PF6) (1) and [Cp*Rh(pbi)Cl] (2) (where Cp* is pentamethylcyclopentadienyl, pbt is 2-(2′-pyridyl)benzothiazole, and pbi is 2-(2′-pyridyl)benzimidazole), were observed to electrocatalytically evolve H2 at potential of −0.90 V vs Ag/AgCl in CH3CN and CH3CN/H2O. Cyclic voltammetry of 1 and 2 in the presence of acid revealed redox waves consistent with the Rh(III)/Rh(I) couple. Bulk electrolysis were used to confirm the catalytic nature of the process for complexes 1 and 2, with turnover numbers in excess of 100 and essentially quantitative faradaic yields for H2 production. The potentials at which these Rh complexes catalyzed H2 evolution were close to the thermodynamic potentials for the production of H2 from protons in CH3CN and CH3CN/H2O, with the small overpotential being 50 mV for 1 as determined by electrochemistry. The complex 1 with more positive Rh(III/I) redox potentials exhibited higher activity for H2 production. © 2017 Elsevier B.V.
DOI
10.1016/j.cattod.2017.05.062
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자연과학대학 > 화학·나노과학전공 > Journal papers
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