Intrinsic Effect of Carbon Supports on the Activity and Stability of Precious Metal Based Catalysts for Electrocatalytic Alcohol Oxidation in Fuel Cells: A Review

Abstract Electrocatalyst supports, in particular carbonaceous materials, play critical roles in the electrocatalytic activity and stability of precious metal group (PMG)‐based catalysts such as Pt, Pd, and Au for the electrochemical alcohol oxidation reaction (AOR) of fuels such as methanol and ethanol in polymer electrolyte membrane fuel cells (PEMFCs). Carbonaceous supports such as high surface area carbon provide electronic contact throughout the catalyst layer, isolate PMG nanoparticles (NPs) to maintain high electrochemical surface area, and provide hydrophobic properties to avoid flooding of the catalyst layer by liquid water produced. Compared to high surface area carbon, PMG catalysts supported on 1D and 2D carbon materials such as graphene and carbon nanotubes show enhanced activity and durability due to the intrinsic effect of the underlying carbonaceous supports on the electronic states of PMG NPs. The modification of the electronic environment, in particular the d‐band centers of PMG NPs, weakens the adsorption of AOR intermediates, facilitates breaking of the C−C bonds, and thus enhances the electrocatalytic activity of PMG catalysts. The doping of heteroatoms further facilitates the electrocatalytic activity for the AOR through the structural, bifunctional, and electronic effects, in addition to the enhanced dispersion of PMG NPs in the carbon support. The prospects for the development of effective PMG‐based catalysts for high‐performance alcohol‐fuel‐based PEMFCs is discussed.