Yi Jianhui, Wen Zi, Jiang Qing
Key Laboratory of Automobile Materials, Ministry of Education and School of Materials Science and Engineering, Jilin University, Changchun, 130022, China.
Chemistry. 2025 Jun 6;31(32):e202500965. doi: 10.1002/chem.202500965. Epub 2025 May 3.
Electrocatalytic nitrate reduction reaction (NORR) is an effective way to solve nitrate pollution and a promising strategy for ammonia (NH) synthesis under ambient temperature and pressure. However, NORR is still hindered by the lack of efficient catalysts and an understanding of mechanisms that enhance the catalytic performance. In this study, we propose intermetallic alloying as a promising strategy to optimize the NORR reaction pathway by tuning the adsorption energies and configurations of intermediates, as demonstrated by density functional theory (DFT) calculations comparing NORR performance of Cu (111) and CuZn (110) surfaces. In CuZn alloy, the electron-donating property of Cu weakens the adsorption of NO (x = 1, 2, and 3) intermediates, whereas the electron-accepting property of Zn strengthens the binding of NOH intermediates, thus lowering the protonation reaction energy. Zn sites preferentially promote the removal of O species, whereas Cu sites dominate the protonation of N species. This synergistic effect enables CuZn (110) surface to successfully break the undesirable scaling relationship in traditional metal catalysts, resulting in excellent catalytic activity for NORR, with an ultra-low limiting potential of -0.28 V. This work provides valuable insights and theoretical guidance for NORR.
电催化硝酸盐还原反应（NORR）是解决硝酸盐污染的有效途径，也是在常温常压下合成氨（NH₃）的一种有前景的策略。然而，NORR仍然受到缺乏高效催化剂以及对提高催化性能的机制认识不足的阻碍。在本研究中，我们提出金属间合金化作为一种有前景的策略，通过调整中间体的吸附能和构型来优化NORR反应路径，密度泛函理论（DFT）计算比较Cu(111)和CuZn(110)表面的NORR性能证明了这一点。在CuZn合金中，Cu的供电子性质减弱了NOₓ（x = 1、2和3）中间体的吸附，而Zn的吸电子性质增强了NOH中间体的结合，从而降低了质子化反应能。Zn位点优先促进O物种的去除，而Cu位点主导N物种的质子化。这种协同效应使CuZn(110)表面成功打破了传统金属催化剂中不良的比例关系，从而对NORR具有优异的催化活性，极限电位低至 -0.28 V。这项工作为NORR提供了有价值的见解和理论指导。
