Liu Kui, Li Hongmei, Xie Minghao, Wang Pengfei, Jin Zhaoyu, Liu Yuanting, Zhou Min, Li Panpan, Yu Guihua
College of Materials Science and Engineering, Sichuan University, Chengdu 610065, China.
Materials Science and Engineering Program and Walker Department of Mechanical Engineering, the University of Texas at Austin, Austin, Texas 78712, United States.
J Am Chem Soc. 2024 Mar 20;146(11):7779-7790. doi: 10.1021/jacs.4c00429. Epub 2024 Mar 11.
The electrochemical nitrate reduction reaction (NORR) holds promise for converting nitrogenous pollutants to valuable ammonia products. However, conventional electrocatalysis faces challenges in effectively driving the complex eight-electron and nine-proton transfer process of the NORR while also competing with the hydrogen evolution reaction. In this study, we present the thermally enhanced electrocatalysis of nitrate-to-ammonia conversion over nickel-modified copper oxide single-atom alloy oxide nanowires. The catalyst demonstrates improved ammonia production performance with a Faradaic efficiency of approximately 80% and a yield rate of 9.7 mg h cm at +0.1 V versus a reversible hydrogen electrode at elevated cell temperatures. In addition, this thermally enhanced electrocatalysis system displays impressive stability, interference resistance, and favorable energy consumption and greenhouse gas emissions for the simulated industrial wastewater treatment. Complementary in situ analyses confirm that the significantly superior relay of active hydrogen species formed at Ni sites facilitates the thermal-field-coupled electrocatalysis of Cu surface-adsorbed *NO hydrogenation. Theoretical calculations further support the thermodynamic and kinetic feasibility of the relay catalysis mechanism for the NORR over the NiCu model catalyst. This study introduces a conceptual thermal-electrochemistry approach for the synergistic regulation of complex catalytic processes, highlighting the potential of multifield-coupled catalysis to advance sustainable-energy-powered chemical synthesis technologies.
电化学硝酸盐还原反应（NORR）有望将含氮污染物转化为有价值的氨产品。然而，传统电催化在有效驱动NORR复杂的八电子和九质子转移过程方面面临挑战，同时还会与析氢反应竞争。在本研究中，我们展示了在镍改性的氧化铜单原子合金氧化物纳米线上热增强电催化硝酸盐转化为氨的过程。该催化剂在电池温度升高时，相对于可逆氢电极在+0.1 V时表现出改善的产氨性能，法拉第效率约为80%，产率为9.7 mg h cm 。此外，这种热增强电催化系统在模拟工业废水处理中表现出令人印象深刻的稳定性、抗干扰性以及良好的能耗和温室气体排放。互补的原位分析证实，在镍位点形成的活性氢物种的显著优越的接力促进了铜表面吸附的*NO加氢的热场耦合电催化。理论计算进一步支持了NiCu模型催化剂上NORR接力催化机制的热力学和动力学可行性。本研究引入了一种概念性的热电化学方法来协同调节复杂的催化过程，突出了多场耦合催化在推进可持续能源驱动的化学合成技术方面的潜力。
