Electrochemical and photochemical hydrogen (H2) evolution activities of a 6-fluoro-2-hydroxypyridinate (fhp−)-bridged paddlewheel-type dirhodium (Rh2) complex, [Rh2(fhp)4], were investigated through experimental and theoretical approaches. In DMF, the [Rh2(fhp)4] underwent a one-electron reduction (assigned to Rh24+/3+) at −1.31 V vs SCE in the cathodic region. Adding trifluoroacetic acid as a proton source to the electrochemical cell containing [Rh2(fhp)4], the significant catalytic current, i.e., electrochemical H2 evolution, was observed; the turnover frequency and overpotential of electrochemical H2 evolution were 18 244 s−1 and 732 mV, respectively. The reaction mechanism of electrochemical H2 evolution catalyzed by [Rh2(fhp)4] in DMF was examined in detail by theoretically predicting the redox potentials and pKa values of the reaction intermediates using density functional theory calculations. The calculations revealed that (i) the formation of a one-electron reduced species, [Rh2(fhp)4]−, triggered for H2 evolution and (ii) the protonation and reduction processes of [Rh2(fhp)4]− to further reduced hydride intermediates proceeded directly via a concerted proton–electron transfer mechanism. Moreover, [Rh2(fhp)4] was shown to be a highly efficient H2 evolution catalyst (HEC) for photochemical proton reduction reactions when combined with an artificial photosynthetic (AP) system containing [Ir(ppy)2(dtbbpy)]PF6 and triethylamine, which served as a photosensitizer and a sacrificial electron donor, respectively. Under visible light irradiation, the total amount of H2 evolved and its turnover number (per Rh ion) were 1361.0 µmol and 13 610, respectively, which are superior to those of previously reported AP systems with rhodium complexes as HEC.
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28 November 2023
Research Article|
November 28 2023
Hydroxypyridinate-bridged paddlewheel-type dirhodium complex as a catalyst for photochemical and electrochemical hydrogen evolution Available to Purchase
Special Collection:
The Physical Chemistry of Solar Fuels Catalysis
Yusuke Kataoka
;
Yusuke Kataoka
a)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Supervision, Validation, Visualization, Writing – original draft, Writing – review & editing)
Department of Chemistry, Natural Science of Technology, Shimane University
, 1060, Nishikawatsu, Matsue, Shimane 690-8504, Japan
a)Author to whom correspondence should be addressed: [email protected]
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Kozo Sato;
Kozo Sato
(Formal analysis, Investigation, Validation, Writing – review & editing)
Department of Chemistry, Natural Science of Technology, Shimane University
, 1060, Nishikawatsu, Matsue, Shimane 690-8504, Japan
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Natsumi Yano
Natsumi Yano
(Data curation, Formal analysis, Funding acquisition, Investigation, Validation, Visualization, Writing – review & editing)
Department of Chemistry, Natural Science of Technology, Shimane University
, 1060, Nishikawatsu, Matsue, Shimane 690-8504, Japan
Search for other works by this author on:
Yusuke Kataoka
Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Supervision, Validation, Visualization, Writing – original draft, Writing – review & editing
a)
Department of Chemistry, Natural Science of Technology, Shimane University
, 1060, Nishikawatsu, Matsue, Shimane 690-8504, Japan
Kozo Sato
Formal analysis, Investigation, Validation, Writing – review & editing
Department of Chemistry, Natural Science of Technology, Shimane University
, 1060, Nishikawatsu, Matsue, Shimane 690-8504, Japan
Natsumi Yano
Data curation, Formal analysis, Funding acquisition, Investigation, Validation, Visualization, Writing – review & editing
Department of Chemistry, Natural Science of Technology, Shimane University
, 1060, Nishikawatsu, Matsue, Shimane 690-8504, Japan
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 159, 204304 (2023)
Article history
Received:
August 26 2023
Accepted:
November 03 2023
Citation
Yusuke Kataoka, Kozo Sato, Natsumi Yano; Hydroxypyridinate-bridged paddlewheel-type dirhodium complex as a catalyst for photochemical and electrochemical hydrogen evolution. J. Chem. Phys. 28 November 2023; 159 (20): 204304. https://doi.org/10.1063/5.0173976
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