Influence of configuration at dopant sites on catalytic activity of phosphorus-doped graphite

The relationship between catalytic activity and local structure at dopant sites of phosphorus-doped graphite prepared by ion implantation was studied by electrochemical measurements and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The P K-edge NEXAFS spectra of samples doped at room temperature and high temperature showed different polarization dependences, with graphite-like clear polarization dependence observed for the sample prepared by high-temperature doping. NEXAFS spectra were analyzed by density functional theory calculations to reveal the chemical-bonding states of P sites. In electrochemical measurements with an acid solution, samples with relatively small polarization dependence of NEXAFS exhibited marked catalytic activity in oxygen reduction reactions while those with larger polarization dependence showed lower catalytic activity. This indicates the influence of the configuration at dopant sites on catalytic activity and suggests that the introduction of curved structures is one way to design carbon catalysts with high catalytic activity.