Fundamental knowledge of the active site requirements for the selective activation of C–O bonds over heterogeneous catalysts is required to design multistep processes for the synthesis of complex chemicals. Here we employ reaction kinetics measurements, extensive catalyst characterization, first principles calculations and microkinetic modelling to reveal metal oxides as a general class of catalysts capable of selectively cleaving C–O bonds with unsaturation at the α position, at a moderate temperature and H2 pressure. Strikingly, metal oxides are considerably more active catalysts than commonly employed VIIIB and IB transition metal catalysts. We identify the normalized Gibbs free energy of oxide formation as both a reactivity and a catalyst stability descriptor and demonstrate the generality of the radical-mediated, reverse Mars–van Krevelen C–O bond activation mechanism on oxygen vacancies, previously established only for RuO2. Importantly, we provide evidence that the substrate plays an equally key role to the catalyst in C–O bond activation.
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The data that support the plots in this paper and other findings are available from the corresponding author upon reasonable request. DFT-optimized geometries of atomistic models of metal oxide surfaces with adsorbates are included as part of the Supplementary Data Set 1.
Melis, A. Solar energy conversion efficiencies in photosynthesis: minimizing the chlorophyll antennae to maximize efficiency. Plant science 177, 272–280 (2009).
Centeno, A., Laurent, E. & Delmon, B. Influence of the support of CoMo sulfide catalysts and of the addition of potassium and platinum on the catalytic performances for the hydrodeoxygenation of carbonyl, carboxyl and guaiacol-type molecules. J. Catal. 154, 288–298 (1995).
Ferrari, M., Bosmans, S., Maggi, R., Delmon, B. & Grange, P. CoMo/carbon hydrodeoxygenation catalysts: influence of the hydrogen sulfide partial pressure and of the sulfidation temperature. Catal. Today 65, 257–264 (2001).
Ferrari, M., Maggi, R., Delmon, B. & Grange, P. Influences of the hydrogen sulfide partial pressure and of a nitrogen compound on the hydrodeoxygenation activity of a CoMo/carbon catalyst. J. Catal. 198, 47–55 (2001).
Laurent, E. & Delmon, B. Study of the hydrodeoxygenation of carbonyl, carboxylic and guaiacyl groups over sulfided CoMo/γ-Al2O3 and NiMo/γ-Al2O3 catalysts. 1. Catalytic reaction schemes. Appl. Catal. A 109, 77–96 (1994).
Balakrishnan, M. et al. Novel pathways for fuels and lubricants from biomass optimized using life-cycle greenhouse gas assessment. Proc. Natl Acad. Sci. USA 112, 7645–7649 (2015).
Sacia, E. R. et al. Highly selective condensation of biomass-derived methyl ketones as a source of aviation fuel. ChemSusChem 8, 1726–1736 (2015).
Laurent, E. & Delmon, B. Influence of oxygen-containing, nitrogen-containing, and sulfur-containing-compounds on the hydrodeoxygenation of phenols over sulfided CoMo/γ-Al2O3 and NiMo/γ-Al2O3 catalysts. Ind. Eng. Chem. Res. 32, 2516–2524 (1993).
Luo, J. et al. Comparison of HMF hydrodeoxygenation over different metal catalysts in a continuous flow reactor. Appl. Catal. A 508, 86–93 (2015).
Luo, J. et al. The H2 pressure dependence of hydrodeoxygenation selectivities for furfural over Pt/C catalysts. Catal. Lett. 146, 711–717 (2016).
Jae, J., Zheng, W., Lobo, R. F. & Vlachos, D. G. Production of dimethylfuran from hydroxymethylfurfural through catalytic transfer hydrogenation with ruthenium supported on carbon. ChemSusChem 6, 1158–1162 (2013).
Jae, J. et al. The role of Ru and RuO2 in the catalytic transfer hydrogenation of 5-hydroxymethylfurfural for the production of 2,5-dimethylfuran. ChemCatChem 6, 848–856 (2014).
Panagiotopoulou, P., Martin, N. & Vlachos, D. G. Effect of hydrogen donor on liquid phase catalytic transfer hydrogenation of furfural over a Ru/RuO2/C catalyst. J. Mol. Catal. A 392, 223–228 (2014).
Panagiotopoulou, P. & Vlachos, D. G. Liquid phase catalytic transfer hydrogenation of furfural over a Ru/C catalyst. Appl. Catal. A 480, 17–24 (2014).
Gilkey, M. J. et al. Mechanistic insights into metal Lewis acid-mediated catalytic transfer hydrogenation of furfural to 2-methylfuran. ACS Catal. 5, 3988–3994 (2015).
Mironenko, A. V. & Vlachos, D. G. Conjugation-driven ‘reverse Mars–van Krevelen’-type radical mechanism for low-temperature C–O bond activation. J. Am. Chem. Soc. 138, 8104–8113 (2016).
Prasomsri, T., Nimmanwudipong, T. & Roman-Leshkov, Y. Effective hydrodeoxygenation of biomass-derived oxygenates into unsaturated hydrocarbons by MoO3 using low H2 pressures. Energy Environ. Sci. 6, 1732–1738 (2013).
Prasomsri, T., Shetty, M., Murugappan, K. & Roman-Leshkov, Y. Insights into the catalytic activity and surface modification of MoO3 during the hydrodeoxygenation of lignin-derived model compounds into aromatic hydrocarbons under low hydrogen pressures. Energy Environ. Sci. 7, 2660–2669 (2014).
Shetty, M., Murugappan, K., Prasomsri, T., Green, W. H. & Román-Leshkov, Y. Reactivity and stability investigation of supported molybdenum oxide catalysts for the hydrodeoxygenation (HDO) of m-cresol. J. Catal. 331, 86–97 (2015).
Nelson, R. C. et al. Experimental and theoretical insights into the hydrogen-efficient direct hydrodeoxygenation mechanism of phenol over Ru/TiO2. ACS Catal. 5, 6509–6523 (2015).
Omotoso, T., Boonyasuwat, S. & Crossley, S. P. Understanding the role of TiO2 crystal structure on the enhanced activity and stability of Ru/TiO2 catalysts for the conversion of lignin-derived oxygenates. Green Chem. 16, 645–652 (2014).
Gilkey, M. J., Mironenko, A. V., Yang, L., Vlachos, D. G. & Xu, B. Insights into the ring-opening of biomass-derived furanics over carbon-supported ruthenium. ChemSusChem 9, 3113–3121 (2016).
Louie, Y. L., Tang, J., Hell, A. M. L. & Bell, A. T. Kinetics of hydrogenation and hydrogenolysis of 2,5-dimethylfuran over noble metals catalysts under mild conditions. Appl. Catal. B 202, 557–568 (2017).
Nørskov, J. K., Clausen, B. S. & Topsøe, H. Understanding the trends in the hydrodesulfurization activity of the transition metal sulfides. Catal. Lett. 13, 1–8 (1992).
Chianelli, R. R., Pecoraro, T. A., Halbert, T. R., Pan, W. H. & Stiefel, E. I. Transition metal sulfide catalysis: relation of the synergic systems to the periodic trends in hydrodesulfurization. J. Catal. 86, 226–230 (1984).
Ugur, D., Storm, A. J., Verberk, R., Brouwer, J. C. & Sloof, W. G. Kinetics of reduction of a RuO2(110) film on Ru(0001) by H2. J. Phys. Chem. C 116, 26822–26828 (2012).
Wöll, C. The chemistry and physics of zinc oxide surfaces. Prog. Surf. Sci. 82, 55–120 (2007).
Werner, K. et al. Toward an understanding of selective alkyne hydrogenation on ceria: on the impact of O vacancies on H2 interaction with CeO2(111). J. Am. Chem. Soc. 139, 17608–17616 (2017).
Knapp, M. et al. Unusual process of water formation on RuO2(110) by hydrogen exposure at room temperature. J. Phys. Chem. B 110, 14007–14010 (2006).
García-Melchor, M. & López, N. Homolytic products from heterolytic paths in H2 dissociation on metal oxides: the example of CeO2. J. Phys. Chem. C 118, 10921–10926 (2014).
Pan, J. M., Maschhoff, B., Diebold, U. & Madey, T. Interaction of water, oxygen, and hydrogen with TiO2(110) surfaces having different defect densities. J. Vac. Sci. Technol. A 10, 2470–2476 (1992).
Yin, X. L. et al. Diffusion versus desorption: complex behavior of H atoms on an oxide surface. Chemphyschem 9, 253–256 (2008).
Getsoian, A. B., Zhai, Z. & Bell, A. T. Band-gap energy as a descriptor of catalytic activity for propene oxidation over mixed metal oxide catalysts. J. Am. Chem. Soc. 136, 13684–13697 (2014).
Christiansen, M. A., Mpourmpakis, G. & Vlachos, D. G. Density functional theory-computed mechanisms of ethylene and diethyl ether formation from ethanol on γ-Al2O3(100). ACS Catal. 3, 1965–1975 (2013).
Hu, Z. & Metiu, H. Halogen adsorption on CeO2: the role of Lewis acid–base pairing. J. Phys. Chem. C 116, 6664–6671 (2012).
Chrétien, S. & Metiu, H. Acid–base interaction and its role in alkane dissociative chemisorption on oxide surfaces. J. Phys. Chem. C 118, 27336–27342 (2014).
Deshlahra, P. & Iglesia, E. Reactivity and selectivity descriptors for the activation of C–H bonds in hydrocarbons and oxygenates on metal oxides. J. Phys. Chem. C 120, 16741–16760 (2016).
Derk, A. R. et al. Methane oxidation by lanthanum oxide doped with Cu, Zn, Mg, Fe, Nb, Ti, Zr, or Ta: the connection between the activation energy and the energy of oxygen-vacancy formation. Catal. Lett. 143, 406–410 (2013).
Moses, P. G. et al. Trends in hydrodesulfurization catalysis based on realistic surface models. Catal. Lett. 144, 1425–1432 (2014).
Wendt, S. et al. Formation and splitting of paired hydroxyl groups on reduced TiO2(110). Phys. Rev. Lett. 96, 066107 (2006).
Wang, H. & Iglesia, E. Thiophene hydrodesulfurization catalysis on supported Ru clusters: mechanism and site requirements for hydrogenation and desulfurization pathways. J. Catal. 273, 245–256 (2010).
Yik, E. S. Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C–S Bond Activation and Consequences of Bifunctional Synergies PhD thesis, UC Berkeley (2015).
Janik, M. J., Macht, J., Iglesia, E. & Neurock, M. Correlating acid properties and catalytic function: a first-principles analysis of alcohol dehydration pathways on polyoxometalates. J. Phys. Chem. C 113, 1872–1885 (2009).
Greeley, J. Theoretical heterogeneous catalysis: scaling relationships and computational catalyst design. Ann. Rev. Chem. Biomol. Eng. 7, 605–635 (2016).
Vojvodic, A. & Nørskov, J. K. New design paradigm for heterogeneous catalysts. Natl Sci. Rev. 2, 140–149 (2015).
Li, G. J. & Kawi, S. High-surface-area SnO2: a novel semiconductor-oxide gas sensor. Mater. Lett. 34, 99–102 (1998).
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Dudarev, S., Botton, G., Savrasov, S., Humphreys, C. & Sutton, A. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA+U study. Phys. Rev. B 57, 1505 (1998).
Selcuk, S. & Selloni, A. Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces. Nat. Mater. 15, 1107 (2016).
Singh, A. K., Janotti, A., Scheffler, M. & Van de Walle, C. G. Sources of electrical conductivity in SnO2. Phys. Rev. Lett. 101, 055502 (2008).
Janotti, A. & Van de Walle, C. G. Native point defects in ZnO. Phys. Rev. B 76, 165202 (2007).
Agarwal, V. & Metiu, H. Oxygen vacancy formation on α-MoO3 slabs and ribbons. J. Phys. Chem. C 120, 19252–19264 (2016).
Sun, L., Huang, X., Wang, L. & Janotti, A. Disentangling the role of small polarons and oxygen vacancies in CeO2. Phys. Rev. B 95, 245101 (2017).
Andersson, D. A., Simak, S., Johansson, B., Abrikosov, I. & Skorodumova, N. V. Modeling of CeO2, Ce2O3, and CeO2−x in the LDA+U formalism. Phys. Rev. B 75, 035109 (2007).
Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).
Acharya, D. P. et al. Site-specific imaging of elemental steps in dehydration of diols on TiO2(110). ACS Nano 7, 10414–10423 (2013).
Ressler, T., Wienold, J., Jentoft, R. E. & Neisius, T. Bulk structural investigation of the reduction of MoO3 with propene and the oxidation of MoO2 with oxygen. J. Catal. 210, 67–83 (2002).
Tanemura, S. et al. Optical properties of polycrystalline and epitaxial anatase and rutile TiO2 thin films by RF magnetron sputtering. Appl. Surf. Sci. 212, 654–660 (2003).
This material is based on work supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award no. DE-SC0001004. Portions of this work were performed at the DuPont–Northwestern–Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the APS. DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co. and The Dow Chemical Company. This research used resources of the Advanced Photon Source, a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. The authors also acknowledge the use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, which is supported by the US DOE, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. NSF award no. 1428149 is acknowledged for supporting the XPS instrumentation. We also acknowledge the resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the US DOE under contract no. DE-AC02-05CH11231 for computational time. Additional computational capacity was supported in part by the Information Technologies resources at the University of Delaware, specifically the high-performance computing resources.
The authors declare no competing interests.
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Goulas, K.A., Mironenko, A.V., Jenness, G.R. et al. Fundamentals of C–O bond activation on metal oxide catalysts. Nat Catal 2, 269–276 (2019). https://doi.org/10.1038/s41929-019-0234-6
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