Active Hydroxyl‐Mediated Preferential Cleavage of Carbon‐Carbon Bonds in Electrocatalytic Glycerol Oxidation

Electrocatalytic glycerol oxidation reaction (GOR) to produce high-value formic acid (FA) is hindered by high formation potential of active species and sluggish C-C bond cleavage kinetics. Herein, Ni single-atom (NiSA) and Co single-atom (CoSA) dual sites anchored on nitrogen-doped carbon nanotubes embedded with Ni0.1Co0.9 alloy (Ni0.1Co0.9@NiSACoSA-NCNTs) are constructed for electrochemical GOR. Remarkably, it can reach 10 mA cm-2 at a low potential of 1.15 V versus the reversible hydrogen electrode (vs. RHE) and realize a high formate selectivity of 93.27 % even at high glycerol conversion of 98.81 % at 1.45 V vs. RHE. The GOR mechanism and pathway are systematically elucidated via experimental analyses and theoretical calculations. It is revealed that the active hydroxyl (*OH) can be produced during the GOR. The NiSA, CoSA, and Ni0.1Co0.9 synergistically optimizes the electronic structure of CoSA active sites, reducing the energy barriers of *OH-mediated cleavage of C-C bonds and dehydrogenation of C1 intermediates. This decreases the number of reaction intermediates and reaction steps of GOR-to-FA, thus increasing the formate production efficiency. After coupling GOR with hydrogen evolution reaction in a membrane electrode assembly cell, 14.26 g of formate and 23.10 L of H2 are produced at 100 mA cm-2 for 108 h.