Atomically dispersed catalysts have been widely explored for some reactions, but it remains a challenge to modulate the electronic structure of the center metal for enhancing the electrochemical activity. Herein, the electrochemical activity of copper single-atom catalyst (Cu SAC) was significantly improved by doping secondary heteroatomic phosphorus to engineer the d-band center of Cu atoms, which was named Cu SAC/P. In alkaline media, the Cu SAC/P-700 catalyst exhibited excellent oxygen reduction reaction (ORR) performance with a higher half-wave potential than Cu SAC-700, even better than the state-of-the-art 20 wt% Pt/C 20 mV. The oxygen electroactivity coefficient was only 0.76 V, achieving good performance in zinc-air battery tests. Density functional theory calculations suggested that phosphorus effectively modulated the density of states and the d-band center of Cu atoms. It improved the adsorption of the reaction intermediates and facilitated to trap them on Cu atoms, thus boosting the ORR activity of the catalyst.

原子分散的催化剂已被广泛探索用于一些反应，但调节中心金属的电子结构以增强电化学活性仍然是一个挑战。在此，通过掺杂二级杂原子磷来设计d，显着提高了铜单原子催化剂（Cu SAC）的电化学活性。Cu原子的-能带中心，命名为Cu SAC/P。在碱性介质中，Cu SAC/P-700催化剂表现出优异的氧还原反应（ORR）性能，其半波电位比Cu SAC-700更高，甚至优于最先进的20 wt% Pt/ C 20毫伏。氧电活系数仅为0.76 V，在锌空气电池测试中取得了良好的性能。密度泛函理论计算表明，磷有效地调节了铜原子的态密度和d带中心。它改善了反应中间体的吸附并有利于将它们捕获在铜原子上，从而提高了催化剂的ORR活性。