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Single-atom gold oxo-clusters prepared in alkaline solutions catalyse the heterogeneous methanol self-coupling reactions

Nature Chemistry volume 11, pages 1098–1105 (2019)Cite this article

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Abstract

In an effort to obtain the maximum atom efficiency, research on heterogeneous single-atom catalysts has intensified recently. Anchoring organometallic homogeneous catalysts to surfaces creates issues with retaining mononuclearity and activity, while the several techniques developed to prepare atomically dispersed precious metals on oxide supports are usually complex. Here we report a facile one-pot synthesis of inorganometallic mononuclear gold complexes formed in alkaline solutions as robust and versatile single-atom gold catalysts. The complexes remain intact on impregnation onto supports or after drying in air to give a crystalline powder. They can be used to interrogate the nuclearity of the catalytically active gold site for reactions known to be catalysed by oxidized gold species. We show that the [Au1–Ox]– cluster directs the heterogeneous coupling of two methanol molecules to methyl formate and hydrogen with a 100% selectivity below 180 °C. The reaction is industrially important as well as the key step in methanol steam reforming on gold catalysts.

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Fig. 1: Single-atom gold oxo-clusters in solution, as dried powder and on TiO2 support.
Fig. 2: Non-oxidative methanol self-coupling activity and the stability of the single-atom gold oxo-clusters.
Fig. 3: In situ CH3OH DRIFT spectra of the supported and unsupported Au1–Ox–Na9–(OH)y.
Fig. 4: AIMD-calculated PED for the minimum-energy pathway from methanol to MF + 2H2 on Au1–O3–Na9–(OH)9, starting from the undecorated cluster, followed by the formation of the 1-HCOO spectator on the cluster to form the working active site, and then the catalytic cycle.

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Additional methods and data are provided in the Supplementary Information. All data supporting the findings of this study are available upon request from the corresponding authors.

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Acknowledgements

The financial support by the DOE/BES under Grant no. DE-FG02-05ER15730 is acknowledged. The XAS research is sponsored by the Advanced Photon Source at Argonne National Laboratory under Contract no. DE-AC02-06CH11357. The aberration-corrected microscopy research conducted at Oak Ridge National Laboratory was sponsored by the US DOE Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office, Propulsion Materials Program. This work was also supported by DOE-BES, Office of Chemical Sciences (Grant DE-FG02-05ER15731). Calculations were performed at supercomputing centres located at the Environmental Molecular Sciences Laboratory, which is sponsored by the DOE Office of Biological and Environmental Research at the Pacific Northwest National Laboratory, the Center for Nanoscale Materials at Argonne National Laboratory, supported by DOE contract DE-AC02-06CH11357, the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by DOE contract DE-AC02-05CH11231 and the UW-Madison Center for High Throughput Computing (CHTC), supported by UW-Madison, the Advanced Computing Initiative, the Wisconsin Alumni Research Foundation, the Wisconsin Institutes for Discovery, and the National Science Foundation, and is an active member of the Open Science Grid, which is supported by the National Science Foundation and the US Department of Energy’s Office of Science.

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Author notes

  1. These authors contributed equally: Sufeng Cao, Ming Yang and Ahmed O. Elnabawy.

Authors and Affiliations

  1. Department of Chemical and Biological Engineering, Tufts University, Medford, MA, USA

    Sufeng Cao, Ming Yang, Antonios Trimpalis, Chongyang Wang, Jilei Liu, Junjun Shan, Mengwei Li, Terry Haas & Maria Flytzani-Stephanopoulos

  2. Department of Chemical and Biological Engineering, University of Wisconsin, Madison, WI, USA

    Ahmed O. Elnabawy, Sha Li, Florian Göltl & Manos Mavrikakis

  3. Department of Chemistry, Stony Brook University, Stony Brook, NY, USA

    Zhihengyu Chen & Karena W. Chapman

  4. X-ray Science Division, Argonne National Laboratory, Argonne, IL, USA

    Sungsik Lee

  5. Materials Science & Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Lawrence F. Allard

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Contributions

M.Y. developed the sample synthesis approach with S.C.; S.C., M.Y. and C.W. performed the catalytic tests for methanol self-coupling, WGS and methanol steam reforming reactions. A.O.E., F.G. and S.L. conducted the DFT calculations. S.C. and A.T. conducted the infrared study. S.C., M.Y, S.L., J.S. and M.L. performed the XAS experiments. K.W.C. and Z.C. performed the pair distribution function experiments. L.F.A. performed the microscopy work, S.C. and J.L. conducted the XRD, and T.H. analysed the XRD data. S.C., M.Y., A.O.E., M.M. and M.F.-S. wrote the manuscript. M.M. and M.F.-S. guided the work and coordinated the individual author contributions. All the authors read and commented on the manuscript.

Corresponding authors

Correspondence to Manos Mavrikakis or Maria Flytzani-Stephanopoulos.

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Supplementary information

Supplementary Information

Supplementary experimental methods, X-ray characterization (XRD, XPS and XAS), DFT methods and results, Figs. 1–50 and Tables 1–3.

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Cao, S., Yang, M., Elnabawy, A.O. et al. Single-atom gold oxo-clusters prepared in alkaline solutions catalyse the heterogeneous methanol self-coupling reactions. Nat. Chem. 11, 1098–1105 (2019). https://doi.org/10.1038/s41557-019-0345-3

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