Delineating Catalyst Deactivation Mechanisms in Electrocatalytic Glycerol Oxidation toward Biodiesel Wastewater/CO2 Co-valorization

Biodiesel plays a key role in achieving economy-wide decarbonization but its production discharges significant amounts of CO2 and glycerol-laden wastewater. Given the increasing abundance of biodiesel wastewater and low redox potential of glycerol, coupling the glycerol oxidation reaction (GOR) with CO2 electrolysis has emerged as an attractive strategy to achieve sustainable wastewater management, CO2 utilization, and green chemical synthesis in a single unit process. Despite the need for highly stable catalysts, few studies have examined electrocatalyst deactivation in environmental waste streams. Here, we present a first-of-a-kind diagnostic study that investigates nickel (Ni) catalyst stability during the GOR in synthetic biodiesel wastewaters. A current decline of 99.7% was observed within 24 h of operation. This coincided with an 80% decrease in surface active Ni(II)/Ni(III) concentrations, 190-fold increases in interfacial impedance, and the appearance of electrode C-bonds that suggested surface coverage by GOR reactants and intermediates was likely a main contributor to loss in catalytic activity. Analyses in more complex electrolytes containing methanol and oleate suggested the emergence of distinct deactivation mechanisms through restricted NiOOH formation. Altogether, this study details several previously unreported catalyst deactivation mechanisms. These findings can ultimately help inform future catalyst design toward more practical and sustainable waste valorization.