3D-printed photopolyacrylate resin (PPAR)-supported copper polyoxometalate catalyst for electrocatalytic oxidative coupling of thiols to disulfides

Cu transition lacunary polyoxometalates Cu-LPOMs@PPAR (20%) based 3D printing have been synthetized, which exhibit outstanding qualities. • The catalyst can reuse for eight cycles. • This synthesis strategy can be easily scaled up to a gram scale. • Various thiols can be used to obtain disulfides in good yields. • The efficient environmental friendliness electrochemical reaction strategy with oxidant-free and low-cost graphite electrodes. Polyoxometalates (POMs) are promising molecular electrocatalysts owing to their rapid and reversible multi-electron transfer properties. However, their practical application is often hindered by poor recyclability and dissolution in polar media. Herein, a 3D-printed photopolyacrylate resin-supported copper-substituted lacunary phosphotungstate (PW 11 Cu) catalyst (Cu-LPOMs@PPAR) was successfully fabricated through a facile additive manufacturing strategy. The resulting macroporous catalyst efficiently promotes the oxidative coupling of thiols to disulfides under external oxidant-free electrochemical conditions. Under optimized conditions, a variety of thiols were converted into the corresponding disulfides in yields of up to 95%, and simultaneous hydrogen evolution. The catalyst exhibited excellent recyclability over eight consecutive cycles without significant loss of activity. Remarkably, in the kilogram-scale experiment, a single batch production yielded 9.77 g of the disulfide product, with a yield as high as 90%. This work demonstrates a practical strategy for integrating POM electrocatalysts into 3D-printed architectures and provides a promising platform for sustainable heterogeneous electrosynthesis. Download: Download high-res image (166KB) Download: Download full-size image