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The catalytic transformation of biomass‐derived volatile carboxylic acids in an aqueous environment is crucial to developing a sustainable biorefinery. To date, Kolbe electrolysis remains arguably the most effective means to convert energy‐diluted aliphatic carboxylic acids (carboxylate) to alkane for biofuel production. This paper reports the use of a structurally disordered amorphous RuO2 (a‐RuO2) that is synthesized facilely in a hydrothermal method. The a‐RuO2 is highly effective towards electrocatalytic oxidative decarboxylation of hexanoic acid and is able to produce the Kolbe product, decane, with a yield 5.4 times greater than that of commercial RuO2. A systematic study of the reaction temperature, current intensity, and electrolyte concentration reveals the enhanced Kolbe product yield is attributable to the more efficient oxidation of the carboxylate anions for the alkane dimer formation. Our work showcases a new design idea for establishing an efficient electrocatalysts for decarboxylation coupling reaction, providing a new electrocatalyst candidate for Kolbe electrolysis. [ABSTRACT FROM AUTHOR]

The development of an active earth-abundant metal electrocatalyst for biomass-derived organic materials valorization can greatly benefit the growth of a sustainable biorefinery. Herein, we report a transition metal dichalcogenide catalyst, MoS2, as a great electrocatalytic hydrogenation catalyst in converting a highly versatile platform chemical furfural to furfuryl alcohol, with over 82.4% yield and 92.1% selectivity, and its catalytic performance surpassed those of 11 other base metal electrocatalysts. The durable layer of 1T-rich MoS2 was fabricated on a carbon cloth support via a novel seeded-solvothermal deposition, followed by a thermal treatment. Reaction mechanistic investigation via underpotential hydrogen desorption (HUPD) studies and substrate scope expansion showed that MoS2 delivered the mechanism in a stage-wise manner, where the reduction of the carbonyl occurred to yield a radical intermediate in the vicinity of the MoS2 catalyst, followed by an abstraction of a surface adsorbed hydrogen (Hads). The conversion of reactants benefited from the presence of electron-withdrawing substituents, and the product selectivity was inert to the influence of the substituents. The MoS2 can be prepared easily through electrocatalytic and solvothermal deposition. The resulting catalyst layer demonstrated great stability throughout the repeated application in bulk electrolysis. [ABSTRACT FROM AUTHOR]

The catalytic transformation of biomass-derived volatile carboxylic acids in an aqueous environment is crucial to developing a sustainable biorefinery. To date, Kolbe electrolysis remains arguably the most effective means to convert energy-diluted aliphatic carboxylic acids (carboxylate) to alkane for biofuel production. This paper reports the use of a structurally disordered amorphous RuO 2 (a-RuO 2 ) that is synthesized facilely in a hydrothermal method. The a-RuO 2 is highly effective towards electrocatalytic oxidative decarboxylation of hexanoic acid and is able to produce the Kolbe product, decane, with a yield 5.4 times greater than that of commercial RuO 2 . A systematic study of the reaction temperature, current intensity, and electrolyte concentration reveals the enhanced Kolbe product yield is attributable to the more efficient oxidation of the carboxylate anions for the alkane dimer formation. Our work showcases a new design idea for establishing an efficient electrocatalysts for decarboxylation coupling reaction, providing a new electrocatalyst candidate for Kolbe electrolysis., (© 2023 Wiley-VCH GmbH.)