Phosphorization-Induced “Fence Effect” on the Active Hydrogen Species Migration Enables Tunable CO<sub>2</sub> Hydrogenation Selectivity
Chunpeng Wu, Jiahui Shen, Xingda An, Zhiyi Wu, Shuairen Qian, Shumin Zhang, Zhiqiang Wang, Bin Song, Yi Cheng, Binhang Yan, Tsun‐Kong Sham, Xiaohong Zhang, Chaoran Li, Kai Feng, Le He
Abstract
Incorporating phosphorus (P) into the active metals of a catalyst is an effective strategy to enhance the catalytic performance. However, the mechanisms underlying the influence of the introduced phosphorus species on catalytic performance remain largely unknown. Herein, we observe a pronounced shift in the product selectivity of the CO 2 hydrogenation from CH 4 to CO upon introducing P into the Ru/SiO 2 catalysts. This alteration in product selectivity is attributed to the role of introduced P as a “fence” hindering the migration of active H species. The adsorbed CO, a key intermediate species for CO 2 methanation, is preferentially desorbed before H species cross the “fence” for further hydrogenation, thereby weakening the H 2 -assisted CO activation process and consequently inhibiting CH 4 generation. Our findings provide in-depth insights into the origin of phosphorization-induced modulation of product selectivity in CO 2 hydrogenation. Furthermore, the concept of phosphorization-induced “fence effect” opens a promising avenue for catalyst design in various industrial hydrogenation processes.