Davies Bernadette, Garcia-Martinez Fernando, Goodwin Christopher M, Degerman David, Soldemo Markus, Lömker Patrick, Grigorev Vladimir, Bibi Sara Boscolo, Ali-Löytty Harri, Engel Robin Y, Stenlid Joakim Halldin, Rodrigues Gabriel L S, Hansson Tony, Schlueter Christoph, Zou Xiaodong, Nilsson Anders, Koroidov Sergey
Department of Chemistry, Stockholm University, Svante Arrhenius väg 16C, 114 18, Stockholm, Sweden.
Department of Physics, Stockholm University, AlbaNova University Center, Stockholm, SE-106 91, Sweden.
Angew Chem Int Ed Engl. 2025 Aug 11;64(33):e202506402. doi: 10.1002/anie.202506402. Epub 2025 Jul 16.
In this work, we introduce a modified dip-and-pull electrochemical X-ray photoelectron spectroscopy (ECXPS) approach that offers new mechanistic insight into the alkaline carbon monoxide reduction reaction (CORR) over a Cu(111) single crystal surface. We tackle two major unresolved questions in the CORR mechanism that persist in the literature. Firstly, we address the mechanism for methane formation on Cu(111) and show that the mechanism likely proceeds via atomic carbon, which subsequently couples, leading to the accumulation of amorphous carbon on the surface. Secondly, we provide insight into whether the mechanism for acetate formation occurs entirely on the surface or partially within the solution phase, showing that acetate is present on the surface, indicating a surface-based reaction. These insights into surface-based mechanisms provide a handle for designing future catalysts that can efficiently target the binding of specific intermediates. Furthermore, we expect that our modified approach to dip-and-pull ECXPS - in which we have changed the electrode geometry, the method of introducing the reactant gas and used hard x-rays - will significantly expand the technique's applicability, enabling studies of the CORR and beyond.
在这项工作中，我们介绍了一种改进的浸提式电化学X射线光电子能谱（ECXPS）方法，该方法为在Cu(111)单晶表面上的碱性一氧化碳还原反应（CORR）提供了新的机理见解。我们解决了CORR机理中在文献中一直存在的两个主要未解决问题。首先，我们研究了Cu(111)上甲烷形成的机理，并表明该机理可能通过原子碳进行，随后原子碳耦合，导致表面上无定形碳的积累。其次，我们深入了解了醋酸盐形成的机理是完全发生在表面还是部分发生在溶液相中，结果表明醋酸盐存在于表面，表明这是一个基于表面的反应。这些对基于表面的机理的见解为设计未来能够有效靶向特定中间体结合的催化剂提供了方法。此外，我们预计我们改进的浸提式ECXPS方法——我们改变了电极几何形状、引入反应气体的方法并使用了硬X射线——将显著扩大该技术的适用性，从而能够研究CORR及其他反应。
