Liu, Jia; Yang, Chengguang; Li, Shenggang; Zhang, Jian; Bu, Xianni; Wang, Hao; Ji, Te; Li, Jiong; Chang, Chun-Ran; Shi, Yanyong; Liu, Jianguo; Xu, Zhisheng; Gao, Peng

APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY

2025, ,

Liu, Jia; Yang, Chengguang; Li, Shenggang; Zhang, Jian; Bu, Xianni; Wang, Hao; Ji, Te; Li, Jiong; Chang, Chun-Ran; Shi, Yanyong; Liu, Jianguo; Xu, Zhisheng; Gao, Peng

Direct CO2 hydrogenation to value-added aromatics has attracted considerable attention in recent years. Nevertheless, designing highly efficient and highly stable catalysts for low-temperature CO2 hydrogenation to aromatics remains a significant challenge. Herein, boron-modified ZSM-5 zeolites with a stacked lamellar morphology are synthesized through a simple one-step solid-state crystallization method, and are subsequently integrated with ZnZrOx to obtain a highly active bifunctional catalyst for CO2 hydrogenation to aromatics. B incorporation is found to effectively tune the framework Al placement and to increase the proportion of Al species in the intersection channels, which are beneficial to the formation of aromatics. In addition, B modification also increases the number of Br & oslash;nsted acid sites and weakens the acid strength of zeolite. The synergy of Al distribution, acidity and morphology promotes the facile formation and diffusion of aromatics in the bifunctional catalysts, significantly improving the aromatic selectivity and stability. Under the mild reaction conditions of 300 degrees C and 3 MPa, the ZnZrOx/B-modified ZSM-5 catalyst enables an unprecedented performance with an aromatic selectivity of 88.0 % at a CO2 conversion of 14.3 %. Among them, > 99 % are C-8-C-10 aromatics, which are important precursors for producing kerosene-based aviation fuels. Notably, the as-synthesized bifunctional catalyst exhibits an ultra-high stability of over 1000 h. In situ DRIFTS analysis indicates that oxygen-containing species and light olefins are the key intermediates in the CO2 hydrogenation to aromatics reaction. This work offers a promising new route and a highly efficient bifunctional catalyst system for the low-temperature CO2 hydrogenation into aromatics.