New cyclopentadienyl rhodium catalysts for electrochemical hydrogen production

Jinheung Kim, Eswaran Rajkumar, Soojin Kim, Yu Mi Park, Youngmee Kim, Sung Jin Kim, Hye Jin Lee

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5 Scopus citations


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.

Original languageEnglish
Pages (from-to)75-81
Number of pages7
JournalCatalysis Today
StatePublished - 2017

Bibliographical note

Funding Information:
This work is supported by a National Research Foundation of Korea (NRF) grant funded by the Korean government (MEST) (NRF-2016R1A2B4012488). This study was supported by the New & Renewable Energy Core Technology Program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) which was granted financial resources from the Ministry of Trade, Industry & Energy, Republic of Korea (20153030031720, to H. J. Lee).

Publisher Copyright:
© 2017 Elsevier B.V.


  • (pyridyl)benzothiazole
  • Electrocatalytic reduction
  • Hydrogen production
  • Molecular rhodium complex
  • Trifluoroacetic acid


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