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

doi:10.1016/j.cattod.2017.05.062

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

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

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.

Original language	English
Pages (from-to)	75-81
Number of pages	7
Journal	Catalysis Today
Volume	295
DOIs	https://doi.org/10.1016/j.cattod.2017.05.062
State	Published - 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.

Keywords

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

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10.1016/j.cattod.2017.05.062

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@article{1f180e0a940640ed9bf1447c4935946a,

title = "New cyclopentadienyl rhodium catalysts for electrochemical hydrogen production",

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.",

keywords = "(pyridyl)benzothiazole, Electrocatalytic reduction, Hydrogen production, Molecular rhodium complex, Trifluoroacetic acid",

author = "Jinheung Kim and Eswaran Rajkumar and Soojin Kim and Park, {Yu Mi} and Youngmee Kim and Kim, {Sung Jin} and Lee, {Hye Jin}",

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: {\textcopyright} 2017 Elsevier B.V.",

year = "2017",

doi = "10.1016/j.cattod.2017.05.062",

language = "English",

volume = "295",

pages = "75--81",

journal = "Catalysis Today",

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TY - JOUR

T1 - New cyclopentadienyl rhodium catalysts for electrochemical hydrogen production

AU - Kim, Jinheung

AU - Rajkumar, Eswaran

AU - Kim, Soojin

AU - Park, Yu Mi

AU - Kim, Youngmee

AU - Kim, Sung Jin

AU - Lee, Hye Jin

N1 - 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.

PY - 2017

Y1 - 2017

N2 - 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.

AB - 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.

KW - (pyridyl)benzothiazole

KW - Electrocatalytic reduction

KW - Hydrogen production

KW - Molecular rhodium complex

KW - Trifluoroacetic acid

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U2 - 10.1016/j.cattod.2017.05.062

DO - 10.1016/j.cattod.2017.05.062

M3 - Article

AN - SCOPUS:85020389117

SN - 0920-5861

VL - 295

SP - 75

EP - 81

JO - Catalysis Today

JF - Catalysis Today

ER -

New cyclopentadienyl rhodium catalysts for electrochemical hydrogen production

Abstract

Bibliographical note

Keywords

UN SDGs

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