Abstract
Understanding gas–surface reaction dynamics, such as the rupture and formation of bonds in vibrationally and translationally excited (‘hot’) molecules, is important to provide mechanistic insight into heterogeneous catalytic processes. Although it has been established that such excitation can affect the reactions occurring via dissociative mechanisms, for associative mechanisms—in which the gas-phase reactant collides directly with a surface-adsorbed species—only translational excitation has been observed to affect reactivity. Here we report a bond-formation reaction that is driven by the vibrational energy of reactant molecules and occurs via an (associative) Eley–Rideal-type mechanism, in which the reaction takes place in a single collision. Hot CO2 in a molecular beam is found to react with pre-adsorbed hydrogen atoms directly on cold Cu(111) and Cu(100) surfaces to form formate adspecies. The vibrational energy of CO2 is more effective at promoting the reaction than translational energy, the reaction rate is independent of the surface temperature and the experimental results are consistent with density functional theory calculations.
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Acknowledgements
Financial support was provided by the Advanced Catalytic Transformation Program for Carbon Utilization (ACT-C) of the Japan Science and Technology Agency (JST). The numerical calculations were performed with computer resources at the Institute for Solid State Physics (ISSP), University of Tokyo, with HPCI systems provided by Nagoya University, the University of Tokyo and Tohoku University through the HPCI System Research Project (project nos. hp130112, hp140166 and hp150201). Theoretical calculations were partly supported by Grants-in-Aid for Scientific Research on Innovative Areas 3D Active-Site Science (nos. 26105010 and 26105011) from the Japan Society for the Promotion of Science (JSPS), and the Elements Strategy Initiative for Catalysts and Batteries (ESICB) supported by the Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT). J.Q. thanks Y. Horiike and M. Kitajima for fruitful discussions.
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J.N. and Y.M. conceived and designed the project. J.Q., T.Kon, T.Koz., T.M. and T.I. performed experiments. J.Q., T.Kon., T.Koz., T.M., T.I. and J.N. analysed experimental results. F.M. performed calculations and data analysis, with contributions from Y.H., K.I. and I.H. J.N. supervised experiments. Y.M. supervised calculations. J.Q., F.M., T.Kon., I.H., Y.M. and J.N. wrote the manuscript. All authors contributed to the scientific discussion and helped in writing the manuscript.
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Supplementary methods, Supplementary Figs. 1–25, Supplementary Tables 1–4
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Quan, J., Muttaqien, F., Kondo, T. et al. Vibration-driven reaction of CO2 on Cu surfaces via Eley–Rideal-type mechanism. Nat. Chem. 11, 722–729 (2019). https://doi.org/10.1038/s41557-019-0282-1
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DOI: https://doi.org/10.1038/s41557-019-0282-1
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