Structural and Electronic Influences on Rates of Tertpyridine-Amine CoIII-H Formation During Catalytic H2 Evolution in an Aqueous Environment

DiMarco, Brian N.; Polyansky, Dmitry E.; Grills, David C.; Wang, Ping; Kuwahara, Yutaka; Zhao, Xuan; Fujita, Etsuko

doi:10.1002/cphc.202100295

Structural and Electronic Influences on Rates of Tertpyridine-Amine Co^III-H Formation During Catalytic H₂ Evolution in an Aqueous Environment

Journal Article · Fri May 14 00:00:00 EDT 2021 · ChemPhysChem

DOI:https://doi.org/10.1002/cphc.202100295· OSTI ID:1784482

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Brookhaven National Lab. (BNL), Upton, NY (United States)
University of Memphis, TN (United States)
Kumamoto University (Japan)

In this paper, the differences in catalytic performance for a series of Co hydrogen evolution catalysts with different pentadentate polypyridyl ligands (L), have been rationalized by examining elementary steps of the catalytic cycle using a combination of electrochemical and transient pulse radiolysis (PR) studies in aqueous solution. Solvolysis of the [Co^II-Cl]⁺ species results in the formation of [Co^II(κ⁴-L)(OH₂)]²⁺. Further reduction produces [Co^I κ⁴-L)(OH₂)]⁺, which undergoes a rate-limiting structural rearrangement to [Co^I(κ⁵-L)]⁺ before being protonated to form [Co^III -H]²⁺. The rate of [Co^III-H]²⁺ formation is similar for all complexes in the series. Using E_1/2 values of various Co species and pKa values of [Co^III-H]²⁺ estimated from PR experiments, we found that while the protonation of [Co^III-H]²⁺ is unfavorable, [CoII-H]+ reacts with protons to produce H₂. The catalytic activity for H₂ evolution tracks the hydricity of the [Co^II-H]⁺ intermediate.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1784482

Alternate ID(s):: OSTI ID: 1787711

Report Number(s):: BNL--221417-2021-JAAM

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 14 Vol. 22; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Structural and Electronic Influences on Rates of Tertpyridine-Amine CoIII-H Formation During Catalytic H2 Evolution in an Aqueous Environment

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Structural and Electronic Influences on Rates of Tertpyridine-Amine Co^III-H Formation During Catalytic H₂ Evolution in an Aqueous Environment