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

Abstract

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 (CoOh 3+) in Co3O4, facilitating the generation of reactive hydroxyl species (OH*) at adjacent tetrahedral Co sites (CoTd 2+). 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.

In Situ Immobilizing Atomically Dispersed Ru on Oxygen-Defective Co3O4 for Efficient Oxygen Evolution

“…Raman spectra of pure Co 3 O 4 , Co 3 O 4– x , and Ru/Co 3 O 4– x display similar patterns, hence suggesting their identical same structure information. Figure d presents three obvious evident Raman peaks located at 467, 510, and 675 cm –1 , corresponding to E g , F 2g , and A 1g modes of crystalline Co 3 O 4 , respectively. − Strikingly, the peaks of Co 3 O 4– x and Ru/Co 3 O 4– x are slightly shifted and broadened (Figure e) due to the existence of oxygen vacancies and Ru doping. , From Brunauer–Emmett–Teller (BET) analysis (Figure f), Co 3 O 4 , Co 3 O 4– x , and Ru/Co 3 O 4– x samples possess specific surface areas of 54.7, 63.2, and 65.7 m 2 /g, respectively. The large surface area of Ru/Co 3 O 4– x is due to the continuous ultrasonication and stirring treatment, illustrating that this synthetic strategy could not alter the surface areas greatly.…”

Selective Valorization of Glycerol to Formic Acid on a BiVO4 Photoanode through NiFe Phenolic Networks

“…Thus, FA is detected as the main product with a high selectivity of 85% (Scheme a, red dashed box). The unique bonding mode, full conversion of C2–C3 intermediates, and retarded overoxidation of BVO/TANF result in highly selective FA generation on BVO/TANF (Scheme b) …”

“…The unique bonding mode, full conversion of C2−C3 intermediates, and retarded overoxidation of BVO/TANF result in highly selective FA generation on BVO/TANF (Scheme 3b). 66…”

Conversion of glycerol to acrylic acid: a review of strategies, recent developments and prospects

“…Moreover, the authors also suggested that enhanced product selectivity was due to regioselective oxidation and weak adsorption of the products on the surface of Bi 2 WO 6 . 49…”