Synergistically Improving the Activity, Antipoisonous Ability, and Long-Term Stability of Pt to Methanol Oxidation through Developing Favorable Graphene-Based Supports.

An interconnected framework of reduced graphene oxide/phenyl formaldehyde polymer composites was synthesized by a one-pot hydrothermal reaction followed by carbonizing under different conditions. Then, the obtained porous materials with varied surface properties were used to disperse ultrasmall Pt nanoparticles. The catalyst with the optimized support demonstrates superior achievements to methanol oxidation reaction (MOR): distinctive improved mass activity (MA) and specific activity at both forward peak position and at the potential range near the operation of fuel cells, best antipoisonous ability revealed by 17 times MA and 7 times the retaining rate of commercial Pt/C in chronoamperometric evaluations, and outstanding long-term stability verified by 3-4 times MA and the retaining rate of Pt/C in the accelerated duration tests. By analyzing the performances of all studied catalysts, we proposed that fruitful oxygen groups and defects on the surface of supporting materials play a key role in boosting the MOR fulfillments through strengthening the Pt-substrate interaction or facilitating the removal of CO from the Pt surface. Elimination of surface oxygen groups and defects may promote the conductivity and mechanical strength of the catalysts but could result in a serious deterioration of antipoisonous ability, which means that only if the deliberate balance is achieved in the preparation of supporting materials can the MOR performances of Pt be improved synergistically.