He Fan, Liu Yingnan, Peng Xianyun, Chen Yaqi, Zheng Qiang, Yang Bin, Li Zhongjian, Zhou Qiang, Zhang Qinghua, Lu Jianguo, Lei Lecheng, Wu Gang, Hou Yang
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, China.
Institute of Zhejiang University - Quzhou, Quzhou, China.
Nat Commun. 2025 Jul 29;16(1):6974. doi: 10.1038/s41467-025-62290-z.
Selective electrochemical water oxidation via a 2e pathway represents a sustainable HO electrosynthesis route. However, the low activity and selectivity due to competing 4e oxygen evolution and challenges in separating in-situ-generated HO for subsequent reactions. Herein, we develop an unsaturated coordinative bismuth-benzene tricarboxylic acid metal-organic framework using a hetero-linker doping strategy. The catalyst demonstrates enhanced performance in selective HO synthesis, achieving a low overpotential of 0.98 V and high selectivity with a Faradaic efficiency of 79.1%. The accumulated ~6.17 wt.% HO enables an efficient direct conversion of butanone ammoximation to butanone oxime, showing a high conversion rate of 80.2% and a selectivity of 81.1%. Structural characterizations reveal the unsaturated coordination in the central bismuth atoms. These unsaturated coordinative bismuth sites modulate the OH* intermediate adsorption and optimize the free energy of OH* → HO, as revealed by in-situ attenuated total reflection Fourier transform infrared spectroscopy and theoretical calculations. This work provides a strategy for rationalizing selective 2e water oxidation catalysts and advances the industrially valuable reaction for value-added chemicals production.
通过2e途径进行的选择性电化学水氧化代表了一种可持续的HO电合成路线。然而，由于竞争性的4e析氧反应，其活性和选择性较低，并且在分离原位生成的HO以用于后续反应方面存在挑战。在此，我们采用杂连接体掺杂策略开发了一种不饱和配位的铋-苯三甲酸金属有机框架。该催化剂在选择性HO合成中表现出增强的性能，实现了0.98 V的低过电位和79.1%的法拉第效率的高选择性。累积的约6.17 wt.%的HO能够实现丁酮氨肟化高效直接转化为丁酮肟，转化率高达80.2%，选择性为81.1%。结构表征揭示了中心铋原子的不饱和配位。原位衰减全反射傅里叶变换红外光谱和理论计算表明，这些不饱和配位的铋位点调节了OH中间体的吸附，并优化了OH→HO的自由能。这项工作为合理设计选择性2e水氧化催化剂提供了一种策略，并推动了用于生产高附加值化学品的具有工业价值的反应。
