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Vibration-driven reaction of CO2 on Cu surfaces via Eley–Rideal-type mechanism

Nature Chemistry volume 11, pages 722–729 (2019)Cite this article

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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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Fig. 1: Four prototypes of thermal non-equilibrium gas–surface reaction.
Fig. 2: Formation of formate by a CO2 beam colliding with Ha/Cu(111) at various CO2 exposures (collision numbers of CO2 per Cu atom: [CO2]/Cu atom) traced by IRAS and TPD.
Fig. 3: Effects of Tsurf, Etrans and \({\bar{\boldsymbol E}}_{{\mathrm{vib}}}\) on P0 for formate formation with an incident angle of θi = 0° on Cu(111) and Cu(100).
Fig. 4: Effect of normal component of the translational energy En of CO2 on P0 for formate formation on Cu(111) at 180 K.
Fig. 5: Reaction pathway of the E–R-type mechanism for CO2 hydrogenation to form formate on Cu(111).

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All results are reported in the main paper and Supplementary Information, and all data are available from the authors upon reasonable request.

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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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Authors and Affiliations

  1. Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki, Japan

    Jiamei Quan, Takahiro Kondo & Junji Nakamura

  2. Department of Precision Science and Technology, Graduate School of Engineering, Osaka University, Suita, Osaka, Japan

    Fahdzi Muttaqien, Yuji Hamamoto, Kouji Inagaki, Ikutaro Hamada & Yoshitada Morikawa

  3. Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, Tsukuba, Ibaraki, Japan

    Takahiro Kondo & Junji Nakamura

  4. Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki, Japan

    Taijun Kozarashi, Tomoyasu Mogi & Takumi Imabayashi

  5. Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto, Japan

    Yuji Hamamoto, Kouji Inagaki, Ikutaro Hamada & Yoshitada Morikawa

  6. Research Center for Ultra-Precision Science and Technology, Graduate School of Engineering, Osaka University, Suita, Osaka, Japan

    Yoshitada Morikawa

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Contributions

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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Correspondence to Junji Nakamura.

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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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