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 III, Mengning Ding
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 (ΔθOH∗/θOH∗OER) and the changes in adsorption energy of vital oxygenated intermediates (ΔGOH∗EOOR−ΔGOH∗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.
Group Members
Tian, B., Wang, F., Ran, P., Dai, L., Lv, Y., Sun, Y., Mu, Z., Sun, Y., Tang, L., III, W. A. G., & Ding, M. (2024). Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation. *Nature Communications*, *15*(1), 10145. https://doi.org/10.1038/s41467-024-54318-7