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

Title: 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)

Abstract In this work, 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 (κ ⁴ ‐L)(OH ₂ )] ²⁺ . Further reduction produces [Co ^I (κ ⁴ ‐L)(OH ₂ )] ⁺ , which undergoes a rate‐limiting structural rearrangement to [Co ^I (κ ⁵ ‐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 p K _a values of [Co ^III −H] ²⁺ estimated from PR experiments, we found that while the protonation of [Co ^III −H] ²⁺ is unfavorable, [Co ^II −H] ⁺ reacts with protons to produce H ₂ . The catalytic activity for H ₂ evolution tracks the hydricity of the [Co ^II −H] ⁺ intermediate.

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

Sponsoring Organization:: 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, Vol. 22, Issue 14; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC
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PHYSICAL AND ANALYTICAL CHEMISTRY
cobalt hydrides
electrocatalysis
hydricity
pulse radiolysis
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Title: Structural and Electronic Influences on Rates of Tertpyridine-Amine CoIII-H Formation During Catalytic H2 Evolution in an Aqueous Environment

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References (49)

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