Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation
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<sub>harmonics</sub>/I<sub>OER</sub> and ΔV<sub>harmonics</sub>) that can be fundamentally linked to the altered surface coverage ( <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mi>Δ</mml:mi> <mml:msub><mml:mrow><mml:mi>θ</mml:mi></mml:mrow> <mml:mrow> <mml:msup><mml:mrow><mml:mi>OH</mml:mi></mml:mrow> <mml:mrow><mml:mo>*</mml:mo></mml:mrow> </mml:msup> </mml:mrow> </mml:msub> <mml:mo>/</mml:mo> <mml:msubsup><mml:mrow><mml:mi>θ</mml:mi></mml:mrow> <mml:mrow> <mml:msup><mml:mrow><mml:mi>OH</mml:mi></mml:mrow> <mml:mrow><mml:mo>*</mml:mo></mml:mrow> </mml:msup> </mml:mrow> <mml:mrow><mml:mi>OER</mml:mi></mml:mrow> </mml:msubsup> </mml:math> ) and the changes in adsorption energy of vital oxygenated intermediates ( <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msubsup><mml:mrow><mml:mi>Δ</mml:mi> <mml:mi>G</mml:mi></mml:mrow> <mml:mrow><mml:mi>OH</mml:mi> <mml:mo>*</mml:mo></mml:mrow> <mml:mrow><mml:mi>EOOR</mml:mi></mml:mrow> </mml:msubsup> <mml:mo>-</mml:mo> <mml:msubsup><mml:mrow><mml:mi>Δ</mml:mi> <mml:mi>G</mml:mi></mml:mrow> <mml:mrow><mml:mi>OH</mml:mi> <mml:mo>*</mml:mo></mml:mrow> <mml:mrow><mml:mi>OER</mml:mi></mml:mrow> </mml:msubsup> </mml:math> ), 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<sup>3+δ</sup>-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.
Authors
- Pan Ran (ORCID: https://orcid.org/0009-0000-2009-5754)
- Mengning Ding (ORCID: https://orcid.org/0000-0001-6581-3385)
- William A. Goddard (ORCID: https://orcid.org/0000-0003-0097-5716)
- Lingyu Tang
- Bailin Tian (ORCID: https://orcid.org/0000-0002-4200-5825)
- Zhangyan Mu
- Fangyuan Wang (ORCID: https://orcid.org/0009-0004-0536-2382)
- Yuxia Sun (ORCID: https://orcid.org/0000-0002-9402-8279)
- Luhan Dai
- Yamei Sun
- Yang Lv
Institutions
- California Institute of Technology (US)
- Ministry of Education and Child Care (CA)
- Nanjing University (CN)
Publication Details
- Journal
- Nature Communications
- Published
- 2024-11-22
- DOI
- https://doi.org/10.1038/s41467-024-54318-7
- Citations
- 11
- Primary Topic
- Electrocatalysts for Energy Conversion
- Type
- article
- Field-Weighted Citation Impact
- 1.13
Funders
- U.S. Department of Energy
- National Natural Science Foundation of China
- Government of Jiangsu Province
- Natural Science Foundation of Jiangsu Province
- Office of Science
- Fundamental Research Funds for the Central Universities
- Basic Energy Sciences
- Beijing National Laboratory for Molecular Sciences