Dispersed Strandberg-type polyoxometalate-supported Cu atoms: Boosting molecular activation for efficient electrocatalytic furfural hydrogenation

The electrocatalytic hydrogenation (ECH) of biomass-derived furfural (FF) offers a sustainable route to furfuryl alcohol (FA). However, achieving high FA selectivity in near-neutral reaction systems remains a formidable challenge. Herein, we explore an effective electrostatic assembly strategy to regulate the surface properties and electronic conductivity of the electrocatalyst: Strandberg-type polyoxomolybdate ([Mo 5 P 2 O 23 ]·[Cu(phen)(H 2 O)] 3 ·5 H 2 O, abbreviated as Cu 3 P 2 Mo 5 , which act as electron sponges are anchored onto two-dimensional transition metal carbides (MXenes, specifically Ti 3 C 2 T x ). This unique architecture significantly facilitates electron transfer between the substrate and the catalyst. Under near-neutral aerobic conditions, Cu 3 P 2 Mo 5 @MXenes exhibits exceptional catalytic performance in the electroreduction of FF, achieving full conversion to FA within 6 h. Notably, the dispersed copper atoms display remarkable catalytic activity for FF reduction, delivering a FA yield exceeding 99% with a turnover frequency (TOF) of 559 h −1 . Furthermore, this system achieved enhanced conversion efficiency with a reduced quantity of active centers, highlighting its superior atomic utilization. Based on the results of experimental (control experiments, kinetic isotope effect studies, electrochemical analyses, spectroscopic characterization) and theoretical (DFT calculations) analyses, we systematically elucidate the electronic synergy between Cu-modified Cu 3 P 2 Mo 5 and MXenes. Modulated electronic interactions optimize adsorption of key carbon radical intermediates, thereby boosting FF electrocatalytic hydrogenation efficiency. This study offers critical insights into the rational design of high-performance POMs-based electrocatalysts, advancing their application in efficient biomass conversion.