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Homogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single‐electron transfer on the electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, the problems of this chemistry still exist such as high dosage, difficult recovery, and low catalytic efficiency. Single‐atom catalysts (SACs) exhibit high atom utilization and excellent catalytic activity, hold great promise in addressing the limitations of homogeneous catalysts. In view of this, we have employed Fe‐SA@NC as an advanced redox mediator to try to change this situation. Fe‐SA@NC was synthesized using an encapsulation‐pyrolysis method, and it demonstrated remarkable performance as a redox mediator in a range of reported organic electrosynthesis reactions, and enabling the construction of various C−C/C−X bonds. Moreover, Fe‐SA@NC demonstrated a great potential in exploring new synthetic method for organic electrosynthesis. We employed it to develop a new electro‐oxidative ring‐opening transformation of cyclopropyl amides. In this new reaction system, Fe‐SA@NC showed good tolerance to drug molecules with complex structures, as well as enabling flow electrochemical syntheses and gram‐scale transformations. This work highlights the great potential of SACs in organic electrosynthesis, thereby opening a new avenue in synthetic chemistry. [ABSTRACT FROM AUTHOR]

The oxygen evolution reaction (OER), characterized by a four‐electron transfer kinetic process, represents a significant bottleneck in improving the efficiency of hydrogen production from water electrolysis. Consequently, extensive research efforts have been directed towards identifying single‐atom electrocatalysts with exceptional OER performance. Despite the comprehensive understanding of the OER mechanism, its application to other valuable synthetic reactions has been limited. Herein, we leverage the MOOH intermediate, a key species in the Mn−N−C single‐atom catalyst (Mn‐SA@NC), which can be cyclically delivered in the OER. We exploit this intermediate' s capability to facilitate electrophilic transfer with silane, enabling efficient silane oxidation under electrochemical conditions. The SAC electrocatalytic system exhibits remarkable performance with catalyst loadings as low as 600 ppm and an exceptional turnover number of 9132. Furthermore, the catalytic method demonstrates stability under a 10 mmol flow chemistry setup. By serving as an OER electrocatalyst, the Mn‐SA@NC drives the entire reaction, establishing a practical Mn SAC‐catalyzed organic electrosynthesis system. This synthesis approach not only presents a promising avenue for the utilization of electrocatalytic OER but also highlights the potential of SACs as an attractive platform for organic electrosynthesis investigations. [ABSTRACT FROM AUTHOR]

The exploitation of highly efficient carbon dioxide reduction (CO2RR) electrocatalyst for methane (CH4) electrosynthesis has attracted great attention for the intermittent renewable electricity storage but remains challenging. Here, N‐heterocyclic carbene (NHC)‐ligated copper single atom site (Cu SAS) embedded in metal–organic framework is reported (2Bn‐Cu@UiO‐67), which can achieve an outstanding Faradaic efficiency (FE) of 81 % for the CO2 reduction to CH4 at −1.5 V vs. RHE with a current density of 420 mA cm−2. The CH4 FE of our catalyst remains above 70 % within a wide potential range and achieves an unprecedented turnover frequency (TOF) of 16.3 s−1. The σ donation of NHC enriches the surface electron density of Cu SAS and promotes the preferential adsorption of CHO* intermediates. The porosity of the catalyst facilitates the diffusion of CO2 to 2Bn‐Cu, significantly increasing the availability of each catalytic center. [ABSTRACT FROM AUTHOR]