Fine‐tuning coordination from WO to WN in graphene gel based single‐atom W for hydrogenation of p ‐chloronitrobenzene

Abstract The rational design of single‐atom catalysts (SACs) with controllable coordination environments is indispensable for various target reactions. It is still a challenge due to the difficulty in understanding atomic behavior specifically in complex synthetic processes. Notably, such deep research and structure–activity relationship of tungsten (W) SACs are still unclear because of its variable oxidation states and challenging synthesis. Herein, W single atoms anchored in three‐dimensional N‐doped graphene gel are synthesized through the combined strategy of spatial confinement and coordination design, dispensing with post‐treatment. Systematic research on structural evolution under various synthetic conditions is conducted. The investigation is put forward to uncover the structure–activity relationship toward chemoselective hydrogenation of p ‐chloronitrobenzene. The relatively abundant active sites, WN/C coordination environment, absence of WO, and unique cross‐linking structure promote the reaction synergistically. The experimental results and theoretical calculations verify that the most efficient specific WN 2 C 2 ‐E configuration addresses the trade‐off problem among activity, selectivity, and stability.