Indirect Electrocatalysis S─N/S─S Bond Construction by Robust Polyoxometalate Based Foams

Abstract Indirect electrocatalytic conversion of cheap organic raw materials via the activation of S─H and N─H bonds into the value‐added S─N/S─S bonds chemicals for industrial rubber production is a promising strategy to realize the atomic economic reaction, during which the kinetic inhibition that is associated with the electron transfer at the electrode/electrolyte interface in traditional direct electrocatalysis can be eliminated to achieve higher performance. In this work, a series of di‐copper‐substituted phosphotungstatebased foams (PW 10 Cu 2 @CMC) are fabricated with tunable loadings (17 to 44 wt%), which can be successfully applied in indirect electrocatalytic syntheses of sulfenamides and disulfides. Specifically, the optimal PW 10 Cu 2 @CMC (44 wt%) exhibits excellent electrocatalytic performance for the construction of S─N/S─S bonds (yields up to 99%) coupling with the efficient production of H 2 (≈50 µmol g −1 h −1 ). Remarkably, it enables the scale‐up production (≈14.4 g in a batch experiment) and the obtained products can serve as rubber vulcanization accelerators with superior properties to traditional industrial rubber additives in real industrial processes. This powerful catalysis system that can simultaneously produce rubber vulcanization accelerator and H 2 may inaugurate a new electrocatalytic avenue to explore polyoxometalate‐based foam catalysts in electrocatalysis field.