Abstract
Developing highly effective catalysts for ammonia (NH3) synthesis is a challenging task. Even the current, prevalent iron-derived catalysts used for industrial NH3 synthesis require harsh reaction conditions and involve massive energy consumption. Here we show that anchoring buckminsterfullerene (C60) onto non-iron transition metals yields cluster-matrix co-catalysts that are highly efficient for NH3 synthesis. Such co-catalysts feature separate catalytic active sites for hydrogen and nitrogen. The ‘electron buffer’ behaviour of C60 balances the electron density at catalytic transition metal sites and enables the synergistic activation of nitrogen on transition metals in addition to the activation and migration of hydrogen on C60 sites. As demonstrated in long-term, continuous runs, the C60-promoting transition metal co-catalysts exhibit higher NH3 synthesis rates than catalysts without C60. With the involvement of C60, the rate-determining step in the cluster-matrix co-catalysis is found to be the hydrogenation of *NH2. C60 incorporation exemplifies a practical approach for solving hydrogen poisoning on a wide variety of oxide-supported Ru catalysts.
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Acknowledgements
The work was supported by the National Natural Science Foundation of China (22221005, L.J.; 22222801, X.W.; 92361303, S.X.; 22038002, L.J.; 92061204, S.X.; 22322302, B.Y.; 21721001, Y.Z.), the National Key Research and Development Program (2021YFB4000400, L.J.; and 2022YFA1604101, X.W.) and the Key R&D plan of the Shanghai Science and Technology Commission (21DZ1209002, L.J.). We thank Y. Gong from Northwestern Polytechnical University for providing electride supports. Moreover, we acknowledge the facility resources from the Electron Microscopy Center of Fuzhou University.
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L.J. conceived the project and organized experiments as well as participated in paper revision. X.W. proposed the detail research idea and supervised the entire project including designing the research scheme and the interpretation of results as well as wrote the manuscript. Y.Zhang and X.P. performed the synthesis of samples. Y.Zhang, X.P., T.Z. and M.Z. performed characterization and catalytic measurements. H.-R.T. performed mass spectra measurements. L.Z. provided the instrument platform for XAS. J.L., B.Y. and Z.-C.C. carried out the model construction and density functional theory calculations. X.W. and Y.Zhou performed in situ X-ray absorption fine-structure measurements. Y.T. performed the fitting of XAFS data, X.L. and Z.Y. carried out the AC–TEM and AC–STEM as well as iDPC measurements. J.-W.Z. and C.-t.A. participated in discussion and revision. S.-Y.X. provided the raw C60 and proposed the concept of cluster matrix, and participated in interpretation of results and made comments on the manuscript. All authors participated in the interpretation of results and made comments on the manuscript.
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Zhang, Y., Peng, X., Tian, HR. et al. Fullerene on non-iron cluster-matrix co-catalysts promotes collaborative H2 and N2 activation for ammonia synthesis. Nat. Chem. 16, 1781–1787 (2024). https://doi.org/10.1038/s41557-024-01626-6
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DOI: https://doi.org/10.1038/s41557-024-01626-6
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