Li Kailang, Li Lulu, Chang Xin, Shi Xiangcheng, Li Xianghong, Pei Chunlei, Zhao Zhi-Jian, Gong Jinlong
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering & Technology, Collaborative Innovation Center for Chemical Science & Engineering, Tianjin University, Tianjin 300072, China.
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, China.
Chem Bio Eng. 2024 Feb 26;1(3):274-282. doi: 10.1021/cbe.3c00124. eCollection 2024 Apr 25.
Water plays a significant role in CO hydrogenation, which is capable of accelerating the reaction in an autocatalytic manner, but the reason for water promotion in the system is still controversial. This work dissects the mechanisms behind the autocatalytic behavior of water in CO hydrogenation. Based on the stable structure of CuZn(211) alloy under the reaction condition, density functional theory is employed to systematically explore all possible autocatalytic modes of water. We find that the influence of water on the reaction is mainly reflected in O-H bonding, in which water tends to facilitate the O-H bond formation by a direct participator mechanism. The nature of the facilitating effect is attributed to the nucleophilic property of O-H bonding. Due to the involvement of water, the reaction activity is enhanced with the improvement of CO selectivity. This work can provide a paradigm for investigating the origin of the autocatalytic behavior of water in heterogeneous catalysis.
水在CO加氢反应中起着重要作用，它能够以自催化的方式加速反应，但水在该体系中促进反应的原因仍存在争议。这项工作剖析了水在CO加氢反应中自催化行为背后的机制。基于反应条件下CuZn(211)合金的稳定结构，采用密度泛函理论系统地探索了水的所有可能自催化模式。我们发现水对反应的影响主要体现在O-H键上，其中水倾向于通过直接参与机制促进O-H键的形成。促进作用的本质归因于O-H键的亲核性质。由于水的参与，反应活性随着CO选择性的提高而增强。这项工作可为研究多相催化中水的自催化行为起源提供一个范例。
