Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches

Mefford, J. Tyler; Zhao, Zhenghang; Bajdich, Michal; Chueh, William C.

doi:10.1039/c9ee02697e

Title: Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches

Journal Article · 16 January 2020 · Energy & Environmental Science

DOI: https://doi.org/10.1039/c9ee02697e · OSTI ID:1608944

^[1]; Zhao, Zhenghang ^[2];

^[3];

^[1]

Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Notre Dame, IN (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Assessing the reaction pathway of multi-electron-transfer reactions is an essential yet difficult task for the rational design of electrocatalysts. In this work, we develop a heuristic approach that combines thermodynamic adsorption energetics calculated through density functional theory with microkinetic modeling using the steady state approximation to interpret the potential-dependent Tafel behavior of consecutive electrochemical reactions. In doing so, we introduce a kinetic framework for ab initio calculations that ensures self-consistent adsorption energetics based on kinetically limited adsorbate coverages. The approach is applied to experimental results on CoO_x(OH)_2-x single crystal electrocatalyst particles yielding coverage dependent mechanistic information and identification of the rate-limiting step with standard rate constants for the oxygen evolution reaction on the ($$11\bar{2}0$$) surfaces of the β-Co(OH)₂, β-CoOOH, and CoO₂ bulk phases. Finally, this generalizable method enables catalyst benchmarking based on determining the active species involved and associated intrinsic reaction rate constants in consecutive multi-electron-transfer reactions.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; SC0008685

OSTI ID:: 1608944

Journal Information:: Energy & Environmental Science, Journal Name: Energy & Environmental Science Journal Issue: 2 Vol. 13; ISSN EESNBY; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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