Integration of theory prediction and experimental electrooxidation of glycerol on NiCo2O4 nanosheets

Abstract

Electrocatalytic refinery of low-value biomass-based glycerol into value-added chemicals formic acid (FA) is an attractive alternative to traditional thermochemical refineries. However, constructing non-precious catalysts with abundant active hydroxyl (OH*) is the main obstacle to the electrocatalytic glycerol oxidation reaction (EGOR). Herein, we combine density functional theory (DFT) and experiments to investigate EGOR over the finely constructed NiCo2O4 nanosheets. DFT results firstly indicate that the NiCo2O4 nanosheets exhibit the highly hydroxylated (311)-OH* surface with the lowest Gibbs free energy, which significantly improves the electrochemical reaction kinetics and can achieve desirable FA yield by adjusting the adsorption energy of the adsorption intermediate. Following the theoretical prediction, ultrathin NiCo2O4 nanosheets (~1.70 nm) are fabricated by a facile electrodeposition method with sufficient OH* on the surface. The charge-transfer resistance of NiCo2O4 nanosheets in EGOR is only 0.94 Ω and the anode power consumption can be reduced by up to 320 mV at 10 mA cm−2, keeping the high glycerol conversion (89%) and FA selectivity (70%) during the 120-h stability test. DFT calculations and experimental tools (e.g., multi-potential step experiments, operational electrochemical impedance spectroscopy) confirm that OH* in-situ generated on the thin nanosheets structure is essential in facilitating charge transfer between catalysts and adsorbed molecules to enhance C–C bond cleavage. This work offers a guideline for the rational design of robust catalysts for the selective upgrading of biomass-derived chemicals.