Selective Electrooxidation of Biomass-Derived Alcohols to Aldehydes in a Neutral Medium: Promoted Water Dissociation over a Nickel-Oxide-Supported Ruthenium Single-Atom Catalyst

Ruixiang Ge; Ye Wang; Zezhou Li; Ming Xu; Si-Min Xu; Hua Zhou; Kaiyue Ji; Fengen Chen; Jihan Zhou; Haohong Duan

doi:10.1002/anie.202200211

Selective Electrooxidation of Biomass-Derived Alcohols to Aldehydes in a Neutral Medium: Promoted Water Dissociation over a Nickel-Oxide-Supported Ruthenium Single-Atom Catalyst

Angew Chem Int Ed Engl. 2022 May 2;61(19):e202200211. doi: 10.1002/anie.202200211. Epub 2022 Feb 25.

Authors

Ruixiang Ge¹, Ye Wang¹, Zezhou Li², Ming Xu³, Si-Min Xu³, Hua Zhou¹, Kaiyue Ji¹, Fengen Chen¹, Jihan Zhou², Haohong Duan¹

Affiliations

¹ Department of Chemistry, Tsinghua University, Beijing, 100084, China.
² Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100091, China.
³ State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029, China.

PMID: 35170172
DOI: 10.1002/anie.202200211

Abstract

The biomass-derived alcohol oxidation reaction (BDAOR) holds great promise for sustainable production of chemicals. However, selective electrooxidation of alcohols to value-added aldehyde compounds is still challenging. Herein, we report the electrocatalytic BDAORs to selectively produce aldehydes using single-atom ruthenium on nickel oxide (Ru₁ -NiO) as a catalyst in the neutral medium. For electrooxidation of 5-hydroxymethylfurfural (HMF), Ru₁ -NiO exhibits a low potential of 1.283 V at 10 mA cm^-2 , and an optimal 2,5-diformylfuran (DFF) selectivity of 90 %. Experimental studies reveal that the neutral electrolyte plays a critical role in achieving a high aldehyde selectivity, and the single-atom Ru boosts HMF oxidation in the neutral medium by promoting water dissociation to afford OH*. Furthermore, Ru₁ -NiO can be extended to selective electrooxidation of a series of biomass-derived alcohols to corresponding aldehydes, which are conventionally difficult to obtain in the alkaline medium.

Keywords: Aldehydes; Biomass Upgrading; Electrocatalysis; Neutral Medium; Single-Atom Catalysts.

Abstract

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