Developing highly active single-atom catalysts for electrochemical reactions is a key to future renewable energy technology. Here we present a universal design principle to evaluate the activity of graphene-based single-atom catalysts towards the oxygen reduction, oxygen evolution and hydrogen evolution reactions. Our results indicate that the catalytic activity of single-atom catalysts is highly correlated with the local environment of the metal centre, namely its coordination number and electronegativity and the electronegativity of the nearest neighbour atoms, validated by available experimental data. More importantly, we reveal that this design principle can be extended to metal–macrocycle complexes. The principle not only offers a strategy to design highly active nonprecious metal single-atom catalysts with specific active centres, for example, Fe-pyridine/pyrrole-N₄ for the oxygen reduction reaction; Co-pyrrole-N₄ for the oxygen evolution reaction; and Mn-pyrrole-N₄ for the hydrogen evolution reaction to replace precious Pt/Ir/Ru-based catalysts, but also suggests that macrocyclic metal complexes could be used as an alternative to graphene-based single-atom catalysts.

开发用于电化学反应的高活性单原子催化剂是未来可再生能源技术的关键。在这里，我们提出了一种通用的设计原理，以评估基于石墨烯的单原子催化剂对氧还原，氧释放和氢释放反应的活性。我们的结果表明，单原子催化剂的催化活性与金属中心的局部环境高度相关，即其配位数和电负性以及最近邻原子的电负性，已通过可用的实验数据验证。更重要的是，我们揭示了该设计原理可以扩展到金属-大环配合物。该原理不仅为设计具有特定活性中心的高活性非贵金属单原子催化剂提供了策略，₄用于氧还原反应；Co-吡咯-N ₄用于氧放出反应；Mn-吡咯-N ₄用于氢生成反应以取代珍贵的Pt / Ir / Ru基催化剂，但也表明大环金属配合物可替代石墨烯基单原子催化剂。