Abstract
Supported metal catalysts, which are composed of metal nanoparticles dispersed on metal oxides or other high-surface-area materials, are ubiquitous in industrially catalysed reactions. Identifying and characterizing the catalytic active sites on these materials still remains a substantial challenge, even though it is required to guide rational design of practical heterogeneous catalysts. Metal–support interactions have an enormous impact on the chemistry of the catalytic active site and can determine the optimum support for a reaction; however, few direct probes of these interactions are available. Here we show how benzyl alcohol oxidation Hammett studies can be used to characterize differences in the catalytic activity of Au nanoparticles hosted on various metal-oxide supports. We combine reactivity analysis with density functional theory calculations to demonstrate that the slope of experimental Hammett plots is affected by electron donation from the underlying oxide support to the Au particles.
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Acknowledgements
The authors thank J.B. Miller and A. Gellman at Carnegie Mellon University for their attempts to measure oxide work functions and S.L.J. Lau at Pennsylvania State University for assistance with work function calculations. The authors acknowledge the US National Science Foundation (NSF, grant nos. CBET-1160217 and CHE-1012395) for financial support of this work. G.K. and M.J.J. acknowledge support from NSF DMREF grant no. 1436206. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported NSF grant no. ACI-1053575. A.M. and R.M.R. acknowledge the Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division, Catalysis Sciences Program (grant no. DE-SC0016192) for partial funding of this research. L.T. thanks the Robert A. Welch Foundation (departmental grant no. W-0031) for summer support.
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L.T., J.N., B.P., B.D.C. and C.J.P. designed the catalysis experiments. L.T. and J.N. performed the catalysis experiments and analysed the data. B.P. prepared the Au/SiO2 catalyst and performed the thiol poisoning experiments. A.M. designed the transmission electron microscopy (TEM) and XPS experiments. A.M. and R.M.R. performed the TEM and XPS experiments and analysed data. G.K. and M.J. designed the computational work. G.K. built the Au/support model and calculated the BA reaction energetics. G.K. calculated the oxide work functions. B.D.C., G.K. and M.J. wrote the paper with assistance from C.J.P. and R.M.R.
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Kumar, G., Tibbitts, L., Newell, J. et al. Evaluating differences in the active-site electronics of supported Au nanoparticle catalysts using Hammett and DFT studies. Nature Chem 10, 268–274 (2018). https://doi.org/10.1038/nchem.2911
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DOI: https://doi.org/10.1038/nchem.2911