An Zhidong, Yang Piaoping, Duan Delong, Li Jiang, Wan Tong, Kong Yue, Caratzoulas Stavros, Xiang Shuting, Liu Jiaxing, Huang Lei, Frenkel Anatoly I, Jiang Yuan-Ye, Long Ran, Li Zhenxing, Vlachos Dionisios G
College of New Energy and Materials, China University of Petroleum (Beijing), Beijing, 102249, China.
Department of Chemical and Biomolecular Engineering and Catalysis Center for Energy Innovation, University of Delaware, 221 Academy St., Newark, DE, 19716, USA.
Nat Commun. 2023 Oct 20;14(1):6666. doi: 10.1038/s41467-023-42337-9.
Highly effective and selective noble metal-free catalysts attract significant attention. Here, a single-atom iron catalyst is fabricated by saturated adsorption of trace iron onto zeolitic imidazolate framework-8 (ZIF-8) followed by pyrolysis. Its performance toward catalytic transfer hydrogenation of furfural is comparable to state-of-the-art catalysts and up to four orders higher than other Fe catalysts. Isotopic labeling experiments demonstrate an intermolecular hydride transfer mechanism. First principles simulations, spectroscopic calculations and experiments, and kinetic correlations reveal that the synthesis creates pyrrolic Fe(II)-plN as the active center whose flexibility manifested by being pulled out of the plane, enabled by defects, is crucial for collocating the reagents and allowing the chemistry to proceed. The catalyst catalyzes chemoselectively several substrates and possesses a unique trait whereby the chemistry is hindered for more acidic substrates than the hydrogen donors. This work paves the way toward noble-metal free single-atom catalysts for important chemical reactions.
高效且选择性的无贵金属催化剂备受关注。在此，通过将痕量铁饱和吸附到沸石咪唑酯骨架-8（ZIF-8）上，随后进行热解，制备出一种单原子铁催化剂。其对糠醛催化转移氢化的性能与最先进的催化剂相当，比其他铁催化剂高出多达四个数量级。同位素标记实验证明了分子间氢化物转移机制。第一性原理模拟、光谱计算与实验以及动力学关联表明，该合成过程产生吡咯型Fe(II)-plN作为活性中心，其因缺陷而从平面中拉出所表现出的灵活性，对于试剂的配位以及化学反应的进行至关重要。该催化剂对几种底物具有化学选择性催化作用，并且具有一个独特特性，即对于比氢供体酸性更强的底物，化学反应受到阻碍。这项工作为重要化学反应的无贵金属单原子催化剂铺平了道路。
