A self-driven seawater splitting system could efficiently produce hydrogen from abundant seawater. However, high Cl− concentrations in seawater lead to catalyst corrosion and deactivation, impairing performance in the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Here, we adopted single-atom Co-N-C-based catalysts, in which the electronic structure around the central Co site can be controlled and adjusted at an atomic level. Experimentally, the target N and S co-doped hollow carbon sphere (Co-N/S-HCS) catalyst, featuring asymmetric Co-N3S1 sites, shows excellent ORR/OER/HER performance. By employing density functional theory and molecular dynamics simulations of real-time simulations, we reveal that the S doped in the asymmetric Co-N3S1 model leads to a customized electronic structure around the central Co site, enabling weakened adsorption of the corrosive Cl− and excellent ORR/OER/HER activities. Moreover, the seawater-based Zn-air batteries (S-ZABs) assembled by the Co-N/S-HCS deliver a cycling performance exceeding 650 h, and the overall seawater splitting system can run continuously for 1,100 h.

中文翻译：

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打破对称性的 CoN3S1 中心可实现惰性氯离子吸附，促进自驱动的整体海水分解


自驱动海水分离系统可以从丰富的海水中高效生产氢气。然而，海水中的高浓度 Cl− 会导致催化剂腐蚀和失活，从而损害氧还原反应 （ORR）、析氧反应 （OER） 和析氢反应 （HER） 的性能。在这里，我们采用了基于单原子 Co-N-C 的催化剂，其中中心钴位周围的电子结构可以在原子水平上控制和调整。实验上，具有不对称 Co-N3S1 位点的靶 N 和 S 共掺杂空心碳球 （Co-N/S-HCS） 催化剂表现出优异的 ORR/OER/HER 性能。通过采用密度泛函理论和实时模拟的分子动力学模拟，我们揭示了不对称 Co-N3S1 模型中掺杂的 S 导致中央 Co 位点周围形成定制的电子结构，从而削弱了腐蚀性 Cl− 的吸附和优异的 ORR/OER/HER 活性。此外，由 Co-N/S-HCS 组装的海水基锌空气电池 （S-ZAB） 可提供超过 650 小时的循环性能，整个海水分解系统可以连续运行 1,100 小时。