Effect of Oxygen-Containing Functional Groups on the Performance of Palladium/Carbon Catalysts for Electrocatalytic Oxidation of Methanol

The methanol oxidation reaction (MOR) of direct methanol fuel cells (DMFCs) is limited by the slow kinetic process and high reaction energy barrier, significantly restricting the commercial application of DMFCs. Therefore, developing MOR catalysts with high activity and stability is very important. In this paper, oxygen-functionalised activated carbon (FAC) with controllable oxygen-containing functional groups was prepared by adjusting the volume ratio of H2SO3/HNO3 mixed acid, and Pd/AC and Pd/FAC catalysts were synthesised via the hydrazine hydrate reduction method. A series of characterisation techniques and electrochemical performance tests were used to study the catalyst. The results showed that when V(H2SO3):V(HNO3) = 2:3, more defects were generated on the surface of the AC, and more oxygen-containing functional groups represented by C=O and C–OH were attached to the surface of the support, which increased the anchor sites of Pd and improved the dispersion of Pd nanoparticles (Pd NPs) on the support. At the same time, the mass–specific activity of Pd/FAC for MOR was 2320 mA·mgPd, which is 1.5 times that of Pd/AC, and the stability was also improved to a certain extent. In situ infrared spectroscopy further confirmed that oxygen functionalisation treatment promoted the formation and transformation of *COOH intermediates, accelerated the transformation of COL into COB, reduced the poisoning of COads species adsorbed to the catalyst, optimised the reaction path and improved the catalytic kinetic performance.