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

Creators: Tian, Bailin¹; Wang, Fangyuan¹; Ran, Pan¹; Dai, Luhan¹; Lv, Yang¹; Sun, Yuxia¹; Mu, Zhangyan¹; Sun, Yamei¹; Tang, Lingyu¹; Goddard, William A.²; Ding, Mengning¹

1. Nanjing University
2. California Institute of Technology

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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 (ΔI_harmonics/I_OER and ΔV_harmonics) that can be fundamentally linked to the altered surface coverage () and the changes in adsorption energy of vital oxygenated intermediates (), 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 M^3+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.

Copyright and License

© 2024, The Author(s). This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, which permits any non-commercial use, sharing, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if you modified the licensed material. You do not have permission under this licence to share adapted material derived from this article or parts of it. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

Acknowledgement

B.T., F.W., P.R., L.D., Y.L., Yu.S., Z.M., Ya.S., L.T., and M.D. acknowledge the support by the Natural Science Foundation of China (22172075 and 92156024), the Fundamental Research Funds for the Central Universities in China (14380273), the Natural Science Foundation of Jiangsu Province (BK20220765) and Beijing National Laboratory for Molecular Sciences (BNLMS202107). W.A.G. acknowledges support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award Number DE-SC0021266.

Contributions

These authors contributed equally: Bailin Tian, Fangyuan Wang.

M.D. and W.A.G. supervised the research. B.T. and M.D. designed the research. B.T. conducted the various in situ measurements (ETS, Raman, FTacV, and EIS). F.W. conducted the potentiostatic electrolysis and products HPLC, GC quantification. P.R., Y.L., Yu.S., Ya.S., and L.T. participated in catalysts synthesis and characterization. B.T., L.D., P.R. and Z.M. performed the micro-kinetics simulation. B.T. and M.D. analyzed the data. B.T., F.W., W.A.G., and M.D. co-wrote the paper. All authors have given approval to the final version of the manuscript.

Supplemental Material

Supplementary Information

Data Availability

The authors declare that the data supporting the conclusions of this study are available within the paper and its supplementary materials. Source data of figures are provided in this paper. Additional data are available from the corresponding author upon request.

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