Numerous important reactions consisting of combinations of steps (for example, hydrogenation and dehydration) have been found to require bifunctional catalysts with both a late-transition metal component and an acidic component. Here, we develop a method for preparing and controlling bifunctional sites by employing organic acid-functionalized monolayer films tethered to the support as an alternative to traditional ligand-on-metal strategies. This approach was used to create a reactive interface between the phosphonic acid monolayers and metal particles, where active-site properties such as acid strength were manipulated via tuning of the molecular structure of the organic ligands within the monolayer. After surface modification, the resultant catalysts exhibited markedly improved selectivity and activity towards hydrodeoxygenation of aromatic alcohols and phenolics. Moreover, by tuning the ligand of the acidic modifier, the rate of deactivation was significantly reduced.
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The authors acknowledge support from the National Science Foundation (Designing Materials to Revolutionize and Engineer our Future grant 1436206) and the Basic Energy Sciences Program of the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Science at the US Department of Energy under grant DE-SC0005239. We also thank T. Van Cleve, C.-H. Lien, P. Coan and M. V. Rodrigues for useful discussions and assistance with measurements. A portion of the research was performed using computational resources sponsored by the Department of Energy’s Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory.
The authors declare no competing financial interests.
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Zhang, J., Ellis, L.D., Wang, B. et al. Control of interfacial acid–metal catalysis with organic monolayers. Nat Catal 1, 148–155 (2018). https://doi.org/10.1038/s41929-017-0019-8
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