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Control of interfacial acid–metal catalysis with organic monolayers


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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Fig. 1: Characterization of catalyst materials.
Fig. 2: HDO of benzyl alcohol and furfuryl alcohol.
Fig. 3: Acid-site characterization and HDO performance of modified and unmodified catalysts.
Fig. 4: Correlation of HDO selectivity and catalyst stability with Brønsted acid strength.
Fig. 5: HDO of phenolics using modified and unmodified catalysts.


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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.

Author information




J.Z. conducted the material synthesis, reaction tests and characterizations except for the STEM-EDS, XPS and 31P nuclear magnetic resonance analysis. L.D.E developed the acid deposition method and performed the density functional theory calculations. B.W. and E.N. conducted the STEM-EDS analysis. M.J.D. and S.P. conducted the XPS analysis. C.S. conducted the 31P nuclear magnetic resonance analysis. All authors discussed the results and commented on the manuscript. J.W.M. supervised the project.

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Correspondence to J. Will Medlin.

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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).

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