Chen Tianxiang, Li Yunong, Ho Ping-Luen, Leung Kwan Chee, Liu Jinjie, Wun Ching Kit Tommy, Li Zehao, Tang Chiu Chung, Kawaguchi Shogo, Wu Tai-Sing, Soo Yun-Liang, Yin Jun, Edman Tsang Shik Chi, Lo Tsz Woon Benedict
State Key Laboratory of Chemical Biology and Drug Discovery, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon 516083, Hong Kong, China.
The Hong Kong Polytechnic University Shenzhen Research Institute, The Hong Kong Polytechnic University, Shenzhen 518057, China.
J Am Chem Soc. 2025 May 21;147(20):17170-17180. doi: 10.1021/jacs.5c02706. Epub 2025 May 7.
A precise understanding of the structure-activity relationship of catalysts is crucial for catalysis research and is essential for rationalizing next-generation catalysts. As the size of catalysts decreases from nanometric to atomic dimensions, the focus on structure-activity relationship correlation has shifted from the "size effect" to the much more challenging "metal nuclearity effect". However, precise synthesis and reliable characterization for structurally related solid atomic catalysts, such as single-, dual-, and triatom catalysts, still remain extremely challenging. Here, we present the controlled assembly of single-atomic Cu, dual-atomic Cu, and triatomic Cu supported on zeolites through an innovative atomically choreographed approach. For the first time, we have directly visualized the atomic features of Cu with respect to the zeolitic channels using double aberration-corrected scanning transmission electron microscopy (STEM). The structural and electronic properties of the catalysts have been characterized using synchrotron X-ray absorption spectroscopy, high-resolution synchrotron powder X-ray diffraction (PXRD), and density functional theory (DFT) calculations. We revealed the interplay among surface structures, adsorption configurations, catalytic reactivities (showing a significant 25-fold improvement), and product selectivity across structurally related species using a model methanol reforming reaction. We have successfully elucidated the relationship between the metal nuclearity effect and its activity and selectivity in a complex catalytic reaction. Our findings offer an unprecedented opportunity for the catalysis and materials community to finely manipulate the physicochemical properties of this category of solid atomic catalysts to achieve the desired reactivities and selectivities.
精确理解催化剂的构效关系对于催化研究至关重要，也是设计下一代催化剂的关键。随着催化剂尺寸从纳米级减小到原子级，对构效关系相关性的关注已从“尺寸效应”转向更具挑战性的“金属核数效应”。然而，对于结构相关的固体原子催化剂，如单原子、双原子和三原子催化剂，精确合成和可靠表征仍然极具挑战性。在此，我们通过一种创新的原子编排方法，展示了负载在沸石上的单原子铜、双原子铜和三原子铜的可控组装。我们首次使用双像差校正扫描透射电子显微镜（STEM）直接观察了铜相对于沸石通道的原子特征。利用同步辐射X射线吸收光谱、高分辨率同步辐射粉末X射线衍射（PXRD）和密度泛函理论（DFT）计算对催化剂的结构和电子性质进行了表征。我们使用甲醇重整反应模型揭示了表面结构、吸附构型、催化活性（显著提高了25倍）和产物选择性在结构相关物种之间的相互作用。我们成功阐明了在复杂催化反应中金属核数效应与其活性和选择性之间的关系。我们的研究结果为催化和材料领域提供了前所未有的机会，可精细调控这类固体原子催化剂的物理化学性质，以实现所需的反应活性和选择性。
