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 (Ni-SA) and Co single-atom (Co-SA) 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 10mAcm(-2) at a low potential of 1.15V 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 1.45V 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 Ni-SA, Co-SA, and Ni0.1Co0.9 synergistically optimizes the electronic structure of Co-SA active sites, reducing the energy barriers of *OH-mediated cleavage of C-C bonds and dehydrogenation of C-1 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, 14.26g of formate and 23.10L of H-2 are produced at 100mAcm(-2) for 108h.