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Highly Efficient Assembly-Line Production of Long-Chain Hydrocarbons via Fischer–Tropsch Synthesis over Ru/TiO2 Catalysts
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2025-06-04 , DOI: 10.1021/jacs.5c02684
Dejian Zhao, Shuaishuai Lyu, Qingpeng Cheng, Yunhao Liu, Pengwei Zhao, Qicheng Zhang, Yingtian Zhang, Yu Pan, Xiaoshen Li, Shaohui Xiong, Zhihong Wang, Xingang Li

The assembly-line strategy serves as an effective way for optimizing tandem steps in the fields of enzyme catalysis and homogeneous catalysis. Herein, we rationally construct efficient Ru/TiO2 catalysts for an important industrial heterogeneous reaction of Fischer–Tropsch synthesis (FTS), involving CO dissociation, hydrogenation, and C–C coupling complex processes. These catalysts feature an “assembly-line” structure composed of oxygen vacancies (Ov), interfacial Ru (RuIδ+ at RuIδ+–Ov–Ti3+), and exposed Ru (RuE0) sites. Both experimental and theoretical results demonstrate that RuIδ+ sites with the assistance of Ov primarily contribute to CO dissociation and hydrogenation to C1 monomers (workshop 1), while RuE0 sites predominantly drive the above intermediates to C–C coupling for carbon chain growth (workshop 2). We interestingly discover that besides the performance of the two workshops themselves, their efficient coordination is key to improve the activity and long-chain hydrocarbon selectivity in FTS. Optimizing this trisite catalytic system via tuning the prereduction time of the TiO2 support robustly achieves an ultrahigh FTS activity (180.8 molCO molRu–1 h–1) while maintaining an impressive C5+ selectivity (90.1%), outperforming the vast majority of state-of-the-art Ru-based FTS catalysts. This work not only clearly clarifies the synergistic mechanisms of multiple active sites but also offers valuable guidance for the application of the assembly-line strategy in complex heterogeneous catalysis reactions.

中文翻译:

通过 Ru/TiO2 催化剂的费托合成实现长链碳氢化合物的高效流水线生产

流水线策略是优化酶催化和均相催化领域串联步骤的有效方法。在此,我们合理构建了高效的 Ru/TiO2 催化剂,用于费托合成 (FTS) 的重要工业非均相反应,涉及 CO 解离、加氢和 C-C 耦合复杂过程。这些催化剂具有由氧空位 (Ov)、界面 Ru(Ruδ+ 在 Ruδ+–Ov–Ti3+)和暴露的 Ru (RuE0) 位点组成的“流水线”结构。实验和理论结果表明,在 Ov 的帮助下,Ruδ+ 位点主要有助于 CO 解离和氢化为 C1 单体(车间 1),而 RuE0 位点主要驱动上述中间体与 C-C 偶联以促进碳链生长(车间 2)。有趣的是,除了两个车间本身的性能外,它们的有效协调是提高 FTS 中活性和长链烃选择性的关键。通过调整 TiO2 载体的预还原时间来优化这种三元催化系统,稳健地实现了超高的 FTS 活性 (180.8 molCO molRu–1 h–1),同时保持了令人印象深刻的 C5+ 选择性 (90.1%),优于绝大多数最先进的基于 Ru 的 FTS 催化剂。这项工作不仅清楚地阐明了多个活性位点的协同机制,而且为流水线策略在复杂的多相催化反应中的应用提供了有价值的指导。
更新日期:2025-06-04
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