Issue 5, 2024

Fe-based “electron pump” involving NiCo-LDH enables robust and highly-selective electrocatalytic methanol oxidation to formic acid

Abstract

Nucleophile oxidation reactions, represented by the incomplete methanol oxidation reaction (i-MOR) to formic acid, can effectively lower the potential of electrolytic hydrogen production while generating high-value products. In order to achieve an industrial grade i-MOR coupled with hydrogen production, designing efficient catalysts toward the i-MOR becomes crucial. In this work, a nickel–cobalt-layered double hydroxide (NiCo-LDH) catalyst incorporating an Fe-based “electron pump” is developed in accordance with the classic two-step NOR mechanism of Ni-based active sites. The coordinating effect of Co effectively reduces the oxidation potential of Ni(II/III) in NiCo-LDH, thus reducing the potential differential between it and the oxidation potential of Fe(II/III), consequently establishing an efficient electron transport pathway from Ni to Fe. Owing to the spontaneous dehydrogenation of methanol, elemental Fe can achieve a valence change during the i-MOR catalytic process. The “electron pump” composed of valence-change Fe effectively enhances the electron transfer, thus ensuring the efficient utilization of electron-deficient active Ni sites throughout the catalytic process. Therefore, FeEP-NiCo-LDH demonstrates outstanding i-MOR catalytic activity, with a potential requirement of 1.349 V (vs. RHE) and 1.430 V to deliver current densities of 10 mA cm−2 and 100 mA cm−2, respectively, while maintaining a Faraday efficiency of ca. 95%.

Graphical abstract: Fe-based “electron pump” involving NiCo-LDH enables robust and highly-selective electrocatalytic methanol oxidation to formic acid

Supplementary files

Article information

Article type
Paper
Submitted
22 12月 2023
Accepted
05 1月 2024
First published
09 1月 2024

Green Chem., 2024,26, 2638-2644

Fe-based “electron pump” involving NiCo-LDH enables robust and highly-selective electrocatalytic methanol oxidation to formic acid

J. Shi, H. He, S. Zhou, J. Li and W. Cai, Green Chem., 2024, 26, 2638 DOI: 10.1039/D3GC05086F

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