Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation

Bailin Tian, Fangyuan Wang, Pan Ran, Luhan Dai, Yang Lv, Yuxia Sun, Zhangyan Mu, Yamei Sun, Lingyu Tang, William A. Goddard and Mengning Ding ()
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Bailin Tian: Nanjing University
Fangyuan Wang: Nanjing University
Pan Ran: Nanjing University
Luhan Dai: Nanjing University
Yang Lv: Nanjing University
Yuxia Sun: Nanjing University
Zhangyan Mu: Nanjing University
Yamei Sun: Nanjing University
Lingyu Tang: Nanjing University
William A. Goddard: California Institute of Technology
Mengning Ding: Nanjing University

Nature Communications, 2024, vol. 15, issue 1, 1-14

Abstract: Abstract Electro-selective-oxidation using water as a green oxygen source demonstrates promising potential towards efficient and sustainable chemical upgrading. However, surface micro-kinetics regarding co-adsorption and reaction between organic and oxygen intermediates remain unclear. Here we systematically study the electro-oxidation of aldehydes, alcohols, and amines on Co/Ni-oxyhydroxides with multiple characterizations. Utilizing Fourier transformed alternating current voltammetry (FTacV) measurements, we show the identification and quantification of two key operando parameters (ΔIharmonics/IOER and ΔVharmonics) that can be fundamentally linked to the altered surface coverage ( $$\Delta {\theta }_{{{{{\rm{OH}}}}}^{*}}/{\theta }_{{{{{\rm{OH}}}}}^{*}}^{{{{\rm{OER}}}}}$$ Δ θ OH * / θ OH * OER ) and the changes in adsorption energy of vital oxygenated intermediates ( $${\Delta G}_{{{{\rm{OH}}}}*}^{{{{\rm{EOOR}}}}}-{\Delta G}_{{{{\rm{OH}}}}*}^{{{{\rm{OER}}}}}$$ Δ G OH * EOOR − Δ G OH * OER ), under the influence of organic adsorption/oxidation. Mechanistic analysis based on these descriptors reveals distinct optimal oxyhydroxide surface states for each organics, and elucidates the critical catalyst design principles: balancing organic and M3+δ−OH* coverages and fine-tuning ΔG for key elementary steps, e.g., via precise modulation of chemical compositions, crystallinity, defects, electronic structures, and/or surface bimolecular interactions.

Date: 2024
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DOI: 10.1038/s41467-024-54318-7

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