Mahnaz Fatima, Iovine Andrew, Shetty Manish
Artie McFerrin Department of Chemical Engineering, Texas A&M University College Station TX 77843 USA
Chem Sci. 2025 May 15;16(23):10106-10118. doi: 10.1039/d5sc01653c. eCollection 2025 Jun 11.
The tandem hydrogenation of CO to fuels and chemicals using bifunctional oxide/zeolite catalysts offers a promising strategy for reducing anthropogenic CO emissions while generating sustainable alternatives to fossil fuels. Despite significant advancements in this field, fundamental gaps remain in understanding the inflence of active site-proximity, intermediate transport rates, and the metal oxide migration and their ion-exchange with zeolitic Brønsted acid sites (BAS) on the reaction rates and hydrocarbon (HC) product selectivities. Challenges also include high CO selectivity and understanding the complexities of hydrocarbon pool (HCP) propagation in zeolite pore channels. This perspective integrates insights from analogous bifunctional catalytic systems, such as alkane hydrocracking and isomerization, to refine our understanding of site-proximity and transport artifacts on reaction rates and product selectivities. We examine diffusion-reaction formalisms for elucidating site-proximity effects on rates and HC selectivity, discuss methods to suppress CO selectivity using surface organometallic chemistry (SOMC) approaches, and explore strategies for suppressing ion-exchange and tuning HCP dynamics. By addressing these challenges, we outline a conceptual roadmap for advancing tandem CO hydrogenation chemistry, providing potential strategies to enhance catalytic efficiency of bifunctional oxide/zeolite systems.
使用双功能氧化物/沸石催化剂将一氧化碳串联加氢转化为燃料和化学品，为减少人为一氧化碳排放同时生成化石燃料的可持续替代品提供了一种很有前景的策略。尽管该领域取得了重大进展，但在理解活性位点邻近性、中间产物传输速率、金属氧化物迁移及其与沸石布朗斯台德酸位点（BAS）的离子交换对反应速率和烃类（HC）产物选择性的影响方面，仍存在基本差距。挑战还包括一氧化碳选择性高以及理解沸石孔道中烃池（HCP）传播的复杂性。本文整合了来自类似双功能催化体系（如烷烃加氢裂化和异构化）的见解，以深化我们对活性位点邻近性和传输假象对反应速率和产物选择性的理解。我们研究了扩散 - 反应形式，以阐明活性位点邻近性对反应速率和烃类选择性的影响，讨论了使用表面有机金属化学（SOMC）方法抑制一氧化碳选择性的方法，并探索了抑制离子交换和调节烃池动力学的策略。通过应对这些挑战，我们勾勒出推进串联一氧化碳加氢化学的概念路线图，提供了提高双功能氧化物/沸石体系催化效率的潜在策略。
