Chen Jian, Wang Xin, Sun Chang, Li Zheng, Zhou Yangen, Li Zhenhua, Qian Yumin, Wang Mengran, Li Simin, Lai Yanqing, Wang Shuangyin
School of Metallurgy and Environment, National Energy Metal Resources and New Materials Key Laboratory, Hunan Provincial Key Laboratory of Nonferrous Value-Added Metallurgy, Central South University, Changsha, China.
Yuyao Innovation Institute, Zhejiang Wanli University, Ningbo, PR China.
Nat Commun. 2025 Jul 28;16(1):6932. doi: 10.1038/s41467-025-62293-w.
Electrooxidation of pollutants at potentials near or below the thermodynamic hydrogen evolution potential offers transformative opportunities for energy-efficient pollutant valorization and diverse energy devices. However, existing catalysts suffer from rapid deactivation due to the inevitable overoxidation. Herein, we present an amorphous phosphorus-doped CoFe₂O₄ catalyst that achieves industrial-level current densities (1 A cm⁻²) at ultralow potentials (0.06, 0.65, and -0.17 V vs. reversible hydrogen electrode) for hydrazine, sulfion, and borohydride electrooxidation, respectively, along with 400-hour stability at 300 mA cm⁻² in a hydrazine-assisted electrolyzer. Mechanistic studies reveal electron transfer from Co-P ligands to Co-O ligands, which enhances the involvement of Co-O ligands in low-potential electrooxidation while protecting Co-P ligands from overoxidation. Furthermore, more positive charges on Co centers lower the activation barrier for such pollutant electrooxidation. This work opens a paradigm for designing robust electrocatalysts by decoupling catalytic activity from oxidative deactivation.
在接近或低于热力学析氢电位的电势下对污染物进行电氧化，为高效节能的污染物增值和各种能量装置提供了变革性机遇。然而，由于不可避免的过度氧化，现有催化剂会迅速失活。在此，我们展示了一种非晶态磷掺杂的CoFe₂O₄催化剂，该催化剂分别在超低电势（相对于可逆氢电极，肼为0.06 V、硫离子为0.65 V、硼氢化物为 -0.17 V）下实现了肼、硫离子和硼氢化物电氧化的工业级电流密度（1 A cm⁻²），并且在肼辅助电解槽中于300 mA cm⁻²下具有400小时的稳定性。机理研究表明电子从Co-P配体转移到Co-O配体，这增强了Co-O配体在低电势电氧化中的参与度，同时保护Co-P配体不被过度氧化。此外，Co中心上更多的正电荷降低了此类污染物电氧化的活化能垒。这项工作通过将催化活性与氧化失活解耦，为设计稳健的电催化剂开辟了一种范例。
