Unraveling a bifunctional mechanism for methanol-to-formate electro-oxidation on nickel-based hydroxides

Botao Zhu, Bo Dong, Feng Wang, Qifeng Yang, Yunpeng He, Cunjin Zhang, Peng Jin () and Lai Feng ()
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Botao Zhu: Soochow University
Bo Dong: Soochow University
Feng Wang: Soochow University
Qifeng Yang: Soochow University
Yunpeng He: Soochow University
Cunjin Zhang: Hebei University of Technology
Peng Jin: Hebei University of Technology
Lai Feng: Soochow University

Nature Communications, 2023, vol. 14, issue 1, 1-9

Abstract: Abstract For nickel-based catalysts, in-situ formed nickel oxyhydroxide has been generally believed as the origin for anodic biomass electro-oxidations. However, rationally understanding the catalytic mechanism still remains challenging. In this work, we demonstrate that NiMn hydroxide as the anodic catalyst can enable methanol-to-formate electro-oxidation reaction (MOR) with a low cell-potential of 1.33/1.41 V at 10/100 mA cm−2, a Faradaic efficiency of nearly 100% and good durability in alkaline media, remarkably outperforming NiFe hydroxide. Based on a combined experimental and computational study, we propose a cyclic pathway that consists of reversible redox transitions of NiII-(OH)2/NiIII-OOH and a concomitant MOR. More importantly, it is proved that the NiIII-OOH provides combined active sites including NiIII and nearby electrophilic oxygen species, which work in a cooperative manner to promote either spontaneous or non-spontaneous MOR process. Such a bifunctional mechanism can well account for not only the highly selective formate formation but also the transient presence of NiIII-OOH. The different catalytic activities of NiMn and NiFe hydroxides can be attributed to their different oxidation behaviors. Thus, our work provides a clear and rational understanding of the overall MOR mechanism on nickel-based hydroxides, which is beneficial for advanced catalyst design.

Date: 2023
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DOI: 10.1038/s41467-023-37441-9

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