郑州大学臧双全团队揭示了电催化硝酸还原中离子化界面水诱导的局部H*富集。相关研究成果发表在2024年9月4日出版的《德国应用化学》。

电催化硝酸盐还原反应（NO₃RR）是一个需要八个电子和九个质子参与的过程。调节活性氢（H*）供应和深入了解相关过程对于提高氨收率和法拉第效率（FE）是必要的。

该文中，研究人员合成了一系列原子级精确的卤化铜簇Cu₂X₂（BINAP）₂（X=Cl，Br，I），其中Cu₂Cl₂（BINAP”2簇的最佳氨FE为94.0%，氨产率为373μmol h^-1 cm^-2。原位实验和理论计算表明，卤素原子，特别是Cu₂Cl₂（BIANP）₂中的Cl，可以显著影响碱金属离子水在催化剂表面的距离，促进水的解离，增强局部H*富集，使硝酸盐继续氢化成氨。

该项工作解释了H*在NO₃RR加氢过程中的作用，以及局部H*富集策略对提高FEs的重要性。

附：英文原文

Title: Unveiling Ionized Interfacial Water-Induced Localized H* Enrichment for Electrocatalytic Nitrate Reduction

Author: Su-Jun Zheng, Xiao-Yu Dong, Hong Chen, Ren-Wu Huang, Jinmeng Cai, Shuang-Quan Zang

Issue&Volume: 2024-09-04

Abstract: Electrocatalytic nitrate reduction reaction (NO3RR) is a process that requires the participation of eight electrons and nine protons. The regulation of active hydrogen (H*) supply and a deep understanding of related processes are necessary for improving the ammonia yield rate and Faradaic efficiency (FE). Herein, we synthesized a series of atomically precise copper-halide clusters Cu2X2(BINAP)2 (X = Cl, Br, I), among which the Cu2Cl2(BINAP)2 cluster shows the optimal ammonia FE of 94.0% and an ammonia yield rate of 373 μmol h-1 cm-2. In situ experiments and theoretical calculations reveal that halogen atoms, especially Cl in Cu2Cl2(BIANP)2, can significantly affect the distance of alkali metal-ionized water on the catalyst surface, which can promote the water dissociation to enhance the localized H* enrichment for the continues hydrogenation of nitrate to ammonia. This work explains the role of H* in the hydrogenation process of NO3RR and the importance of localized H* enrichment strategy for improving the FEs.

DOI: 10.1002/anie.202413033

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202413033