Cobalt Carbonyl Clusters Enable Independent Control of Two Proton Transfer Rates in the Mechanism for Hydrogen Evolution

Pattanayak, Santanu; Berben, Louise A.

doi:10.1002/celc.202100402

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Title: Cobalt Carbonyl Clusters Enable Independent Control of Two Proton Transfer Rates in the Mechanism for Hydrogen Evolution

Journal Article · 30 June 2021 · ChemElectroChem

DOI: https://doi.org/10.1002/celc.202100402 · OSTI ID:1804982

Pattanayak, Santanu ^[1];

^[1]

The University of California 1 Shields Ave Davis CA 95616 USA

Abstract Metal carbonyl clusters (MCC's) are atomically defined nanomaterials which can be characterized using the precise tools of molecular (electro)chemistry. HER mechanisms involve two proton transfer (PT) steps in the catalytic cycle. For HER catalyzed by [Co ₁₁ C ₂ (CO) ₂₃ ] ³⁻ ( 1 ³⁻ ), cyclic voltammetry measurements were used to determine the rate for PT1 as k _PT1 =3×10 ⁸ M ⁻¹ s ⁻¹ , whereas the rate for PT2 is k _PT2 =3.7×10 ³ M ⁻¹ s ⁻¹ . The fast, diffusion‐limited rate for PT1 is consistent with a previous report describing [Co ₁₃ C ₂ (CO) ₂₄ ] ⁴⁻ ( 2 ⁴⁻ ), with PT=2.9×10 ⁹ M ⁻¹ s ⁻¹ . In both cases rate enhancement in PT1 is promoted by the many Co−Co bonds on the surface of the MCC that serve as PT sites: a statistical enhancement of rate akin to the effects of proton relays. In contrast, k _PT2 varies and is five orders of magnitude slower for 1 ²⁻ compared with 2 ⁴⁻ . Thus, MCC's and nanomaterials offer an opportunity to enhance the rate for PT1 while maintaining thermochemical or kinetic control of PT2.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0016395

OSTI ID:: 1804982

Journal Information:: ChemElectroChem, Journal Name: ChemElectroChem Journal Issue: 13 Vol. 8; ISSN 2196-0216

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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