For nearly a century, the Fischer–Tropsch (FT) reaction has been subject of intense debate. Various molecular views on the active sites and on the reaction mechanism have been presented for both Co- and Fe-based FT reactions. In the last 15 years, the emergence of a surface-science- and molecular-modeling-based bottom-up approach has brought this molecular picture a step closer. Theoretical models provided a structural picture of the Co catalyst particles. Recent surface science experiments and density functional theory (DFT) calculations highlighted the importance of realistic surface coverages, which can induce surface reconstruction and impact the stability of reaction intermediates. For Co-based FTS, detailed microkinetic simulations and mechanistic experiments are moving toward a consensus about the active sites and the reaction mechanism. The dynamic phase evolution of Fe-based catalysts under the reaction conditions complicates identification of the surface structure and the active sites. New techniques can help tackle the combinatorial complexity in these systems. Experimental and DFT studies have addressed the mechanism for Fe-based catalysts; the absence of a clear molecular picture of the active sites, however, limits the development of a molecular view of the mechanism. Finally, direct CO₂ hydrogenation to long-chain hydrocarbons could present a sustainable pathway for FT synthesis.

中文翻译：

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费托合成的分子观点

近一个世纪以来，费托 (FT) 反应一直是激烈争论的主题。对于钴基和铁基费托反应，已经提出了关于活性位点和反应机制的各种分子观点。在过去的 15 年中，基于表面科学和分子建模的自下而上方法的出现使这种分子图更近了一步。理论模型提供了 Co 催化剂颗粒的结构图。最近的表面科学实验和密度泛函理论 (DFT) 计算强调了真实表面覆盖的重要性，它可以诱导表面重建并影响反应中间体的稳定性。对于基于 Co 的 FTS，详细的微观动力学模拟和机械实验正在朝着对活性位点和反应机制达成共识的方向发展。铁基催化剂在反应条件下的动态相演化使表面结构和活性位点的鉴定变得复杂。新技术可以帮助解决这些系统中的组合复杂性。实验和 DFT 研究已经解决了铁基催化剂的机理；然而，缺乏活性位点的清晰分子图限制了该机制的分子观点的发展。最后，直接CO 限制了该机制的分子观点的发展。最后，直接CO 限制了该机制的分子观点的发展。最后，直接CO₂氢化成长链碳氢化合物可以为 FT 合成提供可持续的途径。