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

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...

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Detalles Bibliográficos
Autores principales: Zhu, Botao, Dong, Bo, Wang, Feng, Yang, Qifeng, He, Yunpeng, Zhang, Cunjin, Jin, Peng, Feng, Lai
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10042884/
https://www.ncbi.nlm.nih.gov/pubmed/36973279
http://dx.doi.org/10.1038/s41467-023-37441-9
Descripción
Sumario: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 Ni(II)-(OH)(2)/Ni(III)-OOH and a concomitant MOR. More importantly, it is proved that the Ni(III)-OOH provides combined active sites including Ni(III) 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 Ni(III)-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.