Boosting Electrocatalytic Performance of Sulfide Oxidation on Polyoxomolybdates with Synergistic Effects of CNT‐Doped Aerogel Foams

Abstract The meticulous design of highly efficient indirect electrocatalysts with value‐added conversion properties remains a substantial challenge within the realm of organic catalysis. While polyoxometalates (POMs) serve as crucial active centers in catalytic modeling systems for chemical materials, their exploration in electrocatalytic organic molecular transformations is hindered by kinetic barriers. Therefore, an efficient protocol is established for the synthesis of electrocatalysts utilizing polyoxomolybdates (CuMo 6 ) immobilized on aerogel foams (CMC). The electrical conductivity and electrocatalytic activities of the electrocatalyst (CuMo 6 /CNT@CMC) can be readily enhanced by adjusting the microenvironment between the CuMo 6 and CMC using carbon nanotubes (CNT). Controlled experiments demonstrate that the CuMo 6 /CNT@CMC electrocatalyst for the oxidation of sulfide achieves an impressive Faradaic Efficiency (FE) exceeding 95% under ambient conditions, while the working potential is markedly lower than that of reported heterogeneous electrocatalysts. Combined experimental and theoretical analyses suggest that the modulated electronic synergistic interaction between the Cu‐assisted Mo sites and CNT within foam favors the appropriate binding of PhCH 3 S +• intermediates, thereby promoting the selective oxidation of sulfides. This study paves the way for the utilization of polyoxometalate‐based materials with simple synthesis methods for various electrocatalytic applications.