Catalysis

Electrochemistry

Metallurgy

Materials science

Embedded system

Spinel

Computer science

Inorganic chemistry

Faraday efficiency

Formate

Electrocatalyst

Physical chemistry

Bismuth

Reversible hydrogen electrode

Organic chemistry

Doping

Glycerol

Atom (system on chip)

Chemistry

Electrode

Working electrode

Optoelectronics

ACS Catalysis

The renewable electricity-driven electrocatalytic oxidation of biomass represents a pathway to produce value-added chemicals from waste biomass such as glycerol (a byproduct of industrial biodiesel production). However, it remains difficult to design an efficient electrocatalyst with explicit structure–property relationships. Herein, we report a single-atom bismuth (Bi)-doping strategy to endow Co3O4 with enhanced activity and selectivity toward electrocatalytic glycerol oxidation reaction (GOR). Experimental characterizations and theoretical calculations reveal that single-atom Bi substitutes cobalt at octahedral sites (CoOh3+) in Co3O4, facilitating the generation of reactive hydroxyl species (OH*) at adjacent tetrahedral Co sites (CoTd2+). Mechanism studies demonstrate that OH* accelerates the oxidation of hydroxyl groups and carbon–carbon (C–C) bond cleavage, achieving GOR activity (400 mA cm–2 at 1.446 V vs reversible hydrogen electrode, RHE) and high faradaic efficiency of formate (97.05 ± 2.55%). Our study shows a promising way to promote the electro-oxidation activity of spinel oxides for biomass valorization by a single-atom doping strategy.

Efficient Electrocatalytic Oxidation of Glycerol via Promoted OH* Generation over Single-Atom-Bismuth-Doped Spinel Co<sub>3</sub>O<sub>4</sub>

Efficient Electrocatalytic Oxidation of Glycerol via Promoted OH* Generation over Single-Atom-Bismuth-Doped Spinel Co3O4

Efficient Electrocatalytic Oxidation of Glycerol via Promoted OH* Generation over Single-Atom-Bismuth-Doped Spinel Co₃O₄