Xu Guangyuan, Peng Xingjie, Wu Chuanqiang, Xi Shibo, Xiang Huixin, Feng Lei, Liu Zhendong, Duan Yi, Gan Lijin, Chen Si, Kong Yuan, Ma Yanzhe, Nie Fujing, Zhao Jie, Hai Xiao, Wei Wei, Zhou Meng, Wang Tianfu, Yao Chuanhao, Zhou Wu, Yan Huan
State Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui, PR China.
School of Physical Sciences and CAS Key Laboratory of Vacuum Physics, University of Chinese Academy of Sciences, Beijing, PR China.
Nat Commun. 2025 Apr 22;16(1):3774. doi: 10.1038/s41467-025-59079-5.
CO electroreduction to CO promises to give an efficient strategy for CO fixation and transformation. However, current reported active sites fail to deliver sufficient activity with high CO Faradic efficiency (FEco) over a wide range of potential. Here, we show a general synthetic protocol to fabricate a batch of highly pure and active NiN catalysts with precise engineering of the uniform-large (UL) vacancy around the active sites, which is accomplished through the 'pre-deposition + pyrolysis' of various atomically precise Ni clusters (Ni) and in-situ etching of the support by the 'nano bomb' (sulfur-ligand in the clusters). The NiN sites with UL vacancies could achieve a high turnover frequency (TOF) of 350000 h with ~100% FEco in a wide potential range of 1500 mV. In-situ infrared spectra and theoretical calculations reveal that a highly pure NiN site with UL vacancy contributes to this remarkable catalytic performance compared to the counterparts. This general synthetic strategy enables us to simultaneously engineer active sites and surrounding vacancies with the employment of atomically precise metal clusters, thereby enhancing catalytic performance for other specific reactions.
将CO电还原为CO有望为CO固定和转化提供一种高效策略。然而，目前报道的活性位点在很宽的电位范围内无法以高CO法拉第效率（FEco）提供足够的活性。在此，我们展示了一种通用的合成方案，通过对活性位点周围均匀大（UL）空位进行精确工程设计，制备出一批高纯度且活性高的NiN催化剂，这是通过各种原子精确的Ni簇（Ni）的“预沉积+热解”以及“纳米炸弹”（簇中的硫配体）对载体进行原位蚀刻来实现的。具有UL空位的NiN位点在1500 mV的宽电位范围内可实现350000 h的高周转频率（TOF），FEco约为100%。原位红外光谱和理论计算表明，与同类位点相比，具有UL空位的高纯度NiN位点有助于实现这种卓越的催化性能。这种通用的合成策略使我们能够通过使用原子精确的金属簇同时对活性位点和周围空位进行工程设计，从而提高其他特定反应的催化性能。
