Lömker Patrick, Degerman David, Goodwin Christopher M, Shipilin Mikhail, Amann Peter, Rodrigues Gabriel L S, Garcia-Martinez Fernando, Rameshan Raffael, Gladh Jörgen, Wang Hsin-Yi, Soldemo Markus, Holm Alexander, Tober Steffen, Schober Jan-Christian, Jacobse Leon, Vonk Vedran, Gleißner Robert, Noei Heshmat, Hegedues Zoltan, Stierle Andreas, Schlueter Christoph, Nilsson Anders
Department of Physics, Stockholm University, 10691, Stockholm, Sweden.
Wallenberg Initiative Materials Science for Sustainability, Department of Physics, Stockholm University, 114 28, Stockholm, Sweden.
Nat Commun. 2025 Jan 24;16(1):1005. doi: 10.1038/s41467-025-56082-8.
The surface chemistry of the Fischer-Tropsch catalytic reaction over Co has still several unknows. Here, we report an in-situ X-ray photoelectron spectroscopy study of Co and Co( ), and in-situ high energy surface X-ray diffraction of Co during the Fischer-Tropsch reaction at 0.15 bar - 1 bar and 406 K - 548 K in a H/CO gas mixture. We find that these Co surfaces remain metallic under all conditions and that the coverage of chemisorbed species ranges from 0.4-1.7 monolayers depending on pressure and temperature. The adsorbates include CO on-top, C/-CH and various longer hydrocarbon molecules, indicating a rate-limiting direct CO dissociation pathway and that only hydrocarbon species participate in the chain growth. The accumulation of hydrocarbon species points to the termination step being rate-limiting also. Furthermore, we demonstrate that the intermediate surface species are highly dynamic, appearing and disappearing with time delays after rapid changes in the reactants' composition.
钴上费托催化反应的表面化学仍存在一些未知之处。在此，我们报告了在0.15巴至1巴以及406 K至548 K的H/CO气体混合物中，费托反应期间钴和钴（ ）的原位X射线光电子能谱研究，以及钴的原位高能表面X射线衍射研究。我们发现，在所有条件下这些钴表面均保持金属态，且化学吸附物种的覆盖度根据压力和温度在0.4至1.7单层之间变化。吸附物包括顶位CO、C/-CH以及各种更长的烃分子，这表明存在限速的直接CO解离途径，且只有烃类物种参与链增长。烃类物种的积累也表明终止步骤同样是限速的。此外，我们证明中间表面物种具有高度动态性，在反应物组成快速变化后会随时间延迟出现和消失。
