Cobalt Single‐Atom Reverse Hydrogen Spillover for Efficient Electrochemical Water Dissociation and Dechlorination

Abstract Efficient water dissociation to atomic hydrogen (H*) with restrained recombination of H* is crucial for improving the H* utilization for electrochemical dechlorination, but is currently limited by the lack of feasible electrodes. Herein, we developed a monolithic single‐atom electrode with Co single atoms anchored on the inherent oxide layer of titanium foam (Co 1 −TiO x /Ti), which can efficiently dissociate water into H* and simultaneously inhibit the recombination of H*, by taking advantage of the single‐atom reverse hydrogen spillover effect. Experimental and theoretical calculations demonstrated that H* could be rapidly generated on the oxide layer of titanium foam, and then overflowed to the adjacent Co single atom for the reductive dechlorination. Using chloramphenicol as a proof‐of‐concept verification, the resulting Co 1 −TiO x /Ti monolithic electrode exhibited an unprecedented performance with almost 100 % dechlorination at −1.0 V, far superior to that of traditional indirect reduction‐driven commercial Pd/C (52 %) and direct reduction‐driven Co 1 −N−C (44 %). Moreover, its dechlorination rate constant of 1.64 h −1 was 4.3 and 8.6 times more active than those of Pd/C (0.38 h −1 ) and Co 1 −N−C (0.19 h −1 ), respectively. Our research sheds light on the rational design of hydrogen spillover‐related electrocatalysts to simultaneously improve the H* generation, transfer, and utilization for environmental and energy applications.