Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water

Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water


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ABSTRACT Compared to the vapour phase, liquid-phase heterogeneous catalysis provides additional degrees of freedom for reaction engineering, but the multifaceted solvent effects complicate


analysis of the reaction mechanism. Here, using furfural as an example, we reveal the important role of water-mediated protonation in a typical hydrogenation reaction over a supported Pd


catalyst. Depending on the solvent, we have observed different reaction orders with respect to the partial pressure of H2, as well as distinct selectivity towards hydrogenation of the


conjugated C=O and C=C double bonds. Free energy calculations show that H2O participates directly in the kinetically relevant reaction step and provides an additional channel for


hydrogenation of the aldehyde group, in which hydrogen bypasses the direct surface reaction via a hydrogen-bonded water network. This solution-mediated reaction pathway shows the potential


role of the solvent for tuning the selectivity of metal-catalysed hydrogenation when charge separation on the metal surface is feasible. Access through your institution Buy or subscribe This


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SOLVENT-MODULATED HYDROGEN-BINDING STRENGTH IN THE CATALYTIC HYDROGENATION OF BENZALDEHYDE ON PALLADIUM Article 18 November 2021 CATALYST-FREE SELECTIVE OXIDATION OF C(SP3)-H BONDS IN


TOLUENE ON WATER Article Open access 20 July 2024 IMPACT OF HYDRONIUM IONS ON THE PD-CATALYZED FURFURAL HYDROGENATION Article Open access 22 November 2022 DATA AVAILABILITY Any data that


support the plots within this paper and other findings of the study are available from the corresponding author upon reasonable request. The following files are available in the


Supplementary Information: catalyst particle size calculations, FAL conversion and product yields in water at varying times and H2 pressures, H/D exchange experiment, derivation of rate


equations, AIMD calculations of FAL in water, atomic structures along the reaction pathway, free energy diagram for furanyl ring hydrogenation and maximum rate analysis data. REFERENCES *


Carpenter, B. K., Harvey, J. N. & Orr-Ewing, A. J. The study of reactive intermediates in condensed phases. _J. Am. Chem. Soc._ 138, 4695–4705 (2016). Article  CAS  Google Scholar  *


Chheda, J. N., Huber, G. W. & Dumesic, J. A. Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals. _Angew. Chem. Int. Ed._ 46, 7164–7183


(2007). Article  CAS  Google Scholar  * Struebing, H. et al. Computer-aided molecular design of solvents for accelerated reaction kinetics. _Nat. Chem._ 5, 952–957 (2013). Article  CAS 


Google Scholar  * Mellmer, M. A. et al. Solvent-enabled control of reactivity for liquid-phase reactions of biomass-derived compounds. _Nat. Catal._ 1, 199–207 (2018). Article  Google


Scholar  * Crossley, S., Faria, J., Shen, M. & Resasco, D. E. Solid nanoparticles that catalyze biofuel upgrade reactions at the water/oil. _Science_ 327, 68–72 (2010). Article  CAS 


Google Scholar  * Franck, J. & Rabinowitsch, E. Some remarks about free radicals and the photochemistry of solutions. _Trans. Faraday Soc._ 30, 120–130 (1934). Article  CAS  Google


Scholar  * Madon, R. J. & Iglesia, E. Catalytic reaction rates in thermodynamically non-ideal systems. _J. Mol. Catal. A_ 163, 189–204 (2000). Article  CAS  Google Scholar  * Mellmer, M.


A. et al. Solvent effects in acid-catalyzed biomass conversion reactions. _Angew. Chem. Int. Ed._ 53, 11872–11875 (2014). Article  CAS  Google Scholar  * Sicinska, D., Truhlar, D. G. &


Paneth, P. Solvent-dependent transition states for decarboxylations. _J. Am. Chem. Soc._ 123, 7683–7686 (2001). Article  CAS  Google Scholar  * Hibbitts, D. D., Loveless, B. T., Neurock, M.


& Iglesia, E. Mechanistic role of water on the rate and selectivity of Fischer–Tropsch synthesis on ruthenium catalysts. _Angew. Chem. Int. Ed._ 52, 12273–12278 (2013). Article  CAS 


Google Scholar  * Saavedra, J. et al. Controlling activity and selectivity using water in the Au-catalysed preferential oxidation of CO in H2. _Nat. Chem._ 8, 585–590 (2016). Article  Google


Scholar  * Saavedra, J., Doan, H. A., Pursell, C. J., Grabow, L. C. & Chandler, B. D. The critical role of water at the gold–titania interface in catalytic CO oxidation. _Science_ 345,


1599–1602 (2014). Article  CAS  Google Scholar  * Yoon, Y., Rousseau, R., Weber, R. S., Mei, D. H. & Lercher, J. A. First-principles study of phenol hydrogenation on Pt and Ni catalysts


in aqueous phase. _J. Am. Chem. Soc._ 136, 10287–10298 (2014). Article  CAS  Google Scholar  * Resasco, D. E., Sitthisa, S., Faria, J., Prasomsri, T. & Ruiz, M. P. in _Solid_ _Waste_ _as


a Renewable Resource: Methodologies_ (eds Albanese, J. A. F. & Pilar Ruiz, M.) 103 (CRC Press, 2015). * Lange, J. P., van der Heide, E., van Buijtenen, J. & Price, R. Furfural—a


promising platform for lignocellulosic biofuels. _ChemSusChem_ 5, 150–166 (2012). Article  CAS  Google Scholar  * Resasco, D. E., Wang, B. & Sabatini, D. Distributed processes for


biomass conversion could aid UN sustainable development goals. _Nat. Catal._ 1, 731–735 (2018). Article  Google Scholar  * Sitthisa, S. & Resasco, D. E. Hydrodeoxygenation of furfural


over supported metal catalysts: a comparative study of Cu, Pd and Ni. _Catal. Lett._ 141, 784–791 (2011). Article  CAS  Google Scholar  * 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). Article  CAS  Google Scholar  *


Maldonado, G. M. G., Assary, R. S., Dumesic, J. & Curtiss, L. A. Experimental and theoretical studies of the acid-catalyzed conversion of furfuryl alcohol to levulinic acid in aqueous


solution. _Energy Environ. Sci._ 5, 6981–6989 (2012). Article  Google Scholar  * Corma, A., Iborra, S. & Velty, A. Chemical routes for the transformation of biomass into chemicals.


_Chem. Rev._ 107, 2411–2502 (2007). Article  CAS  Google Scholar  * Serrano-Ruiz, J. C., Luque, R. & Sepulveda-Escribano, A. Transformations of biomass-derived platform molecules: from


high added-value chemicals to fuels via aqueous-phase processing. _Chem. Soc. Rev._ 40, 5266–5281 (2011). Article  CAS  Google Scholar  * Vorotnikov, V., Mpourmpakis, G. & Vlachos, D. G.


DFT study of furfural conversion to furan, furfuryl alcohol, and 2-methylfuran on Pd(111). _ACS Catal._ 2, 2496–2504 (2012). Article  CAS  Google Scholar  * Pang, S. H. & Medlin, J. W.


Adsorption and reaction of furfural and furfuryl alcohol on Pd(111): unique reaction pathways for multifunctional reagents. _ACS Catal._ 1, 1272–1283 (2011). Article  CAS  Google Scholar  *


Wang, S. G., Vorotnikov, V. & Vlachos, D. G. Coverage-induced conformational effects on activity and selectivity: hydrogenation and decarbonylation of furfural on Pd(111). _ACS Catal._


5, 104–112 (2015). Article  CAS  Google Scholar  * Pang, S. H., Schoenbaum, C. A., Schwartz, D. K. & Medlin, J. W. Effects of thiol modifiers on the kinetics of furfural hydrogenation


over Pd catalysts. _ACS Catal._ 4, 3123–3131 (2014). Article  CAS  Google Scholar  * Pang, S. H., Schoenbaum, C. A., Schwartz, D. K. & Medlin, J. W. Directing reaction pathways by


catalyst active-site selection using self-assembled monolayers. _Nat. Commun._ 4, 2448 (2013). Article  Google Scholar  * Sitthisa, S. et al. Conversion of furfural and 2-methylpentanal on


Pd/SiO2 and Pd-Cu/SiO2 catalysts. _J. Catal._ 280, 17–27 (2011). Article  CAS  Google Scholar  * Sitthisa, S., An, W. & Resasco, D. E. Selective conversion of furfural to methylfuran


over silica-supported Ni–Fe bimetallic catalysts. _J. Catal._ 284, 90–101 (2011). Article  CAS  Google Scholar  * Fulajtarova, K. et al. Aqueous phase hydrogenation of furfural to furfuryl


alcohol over Pd–Cu catalysts. _Appl. Catal. A_ 502, 78–85 (2015). Article  CAS  Google Scholar  * Merlo, A. B., Vetere, V., Ruggera, J. F. & Casella, M. L. Bimetallic PtSn catalyst for


the selective hydrogenation of furfural to furfuryl alcohol in liquid-phase. _Catal. Commun._ 10, 1665–1669 (2009). Article  CAS  Google Scholar  * Chen, X. F., Zhang, L. G., Zhang, B., Guo,


X. C. & Mu, X. D. Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water. _Sci. Rep._ 6, 28558 (2016).


Article  Google Scholar  * Vaidya, P. D. & Mahajani, V. V. Kinetics of liquid-phase hydrogenation of furfuraldehyde to furfuryl alcohol over a Pt/C catalyst. _Ind. Eng. Chem. Res._ 42,


3881–3885 (2003). Article  CAS  Google Scholar  * Lee, J. C., Xu, Y. & Huber, G. W. High-throughput screening of monometallic catalysts for aqueous-phase hydrogenation of biomass-derived


oxygenates. _Appl. Catal. B_ 140, 98–107 (2013). Google Scholar  * Frainier, L. J. & Fineberg, H. H. Copper chromite catalyst for preparation of furfuryl alcohol from furfural. US


patent 4,251,396A (1979). * Villaverde, M. M., Bertero, N. M., Garetto, T. F. & Marchi, A. J. Selective liquid-phase hydrogenation of furfural to furfuryl alcohol over Cu-based


catalysts. _Catal. Today_ 213, 87–92 (2013). Article  CAS  Google Scholar  * Singh, U. K. & Vannice, M. A. Kinetics of liquid-phase hydrogenation reactions over supported metal


catalysts—a review. _Appl. Catal. A_ 213, 1–24 (2001). Article  CAS  Google Scholar  * Nakagawa, Y., Takada, K., Tamura, M. & Tomishige, K. Total hydrogenation of furfural and


5-hydroxymethylfurfural over supported Pd–Ir alloy catalyst. _ACS Catal._ 4, 2718–2726 (2014). Article  CAS  Google Scholar  * Dumesic, J. A., Rudd, D. F., Aparicio, L. M., Rekoske, J. E.


& Trevino, A. A. _The Microkinetics of Heterogeneous Catalysis_ (American Chemical Society, Washington DC, 1993). * Loffreda, D., Delbecq, F., Vigne, F. & Sautet, P.


Chemo-regioselectivity in heterogeneous catalysis: competitive routes for C=O and C=C hydrogenations from a theoretical approach. _J. Am. Chem. Soc._ 128, 1316–1323 (2006). Article  CAS 


Google Scholar  * Maroncelli, M., MacInnis, J. & Fleming, G. R. Polar solvent dynamics and electron-transfer reactions. _Science_ 243, 1674–1681 (1989). Article  CAS  Google Scholar  *


Henriksen, N. E. & Hansen, F. Y. _Theories of Molecular Reaction Dynamics: The Microscopic Foundation of Chemical Kinetics_ (Oxford University Press, Oxford, 2018). * Kibler, L. A.


Hydrogen electrocatalysis. _Chemphyschem_ 7, 985–991 (2006). Article  CAS  Google Scholar  * Agmon, N. The Grotthuss mechanism. _Chem. Phys. Lett._ 244, 456–462 (1995). Article  CAS  Google


Scholar  * Cukier, R. I. & Nocera, D. G. Proton-coupled electron transfer. _Annu. Rev. Phys. Chem._ 49, 337–369 (1998). Article  CAS  Google Scholar  * Farberow, C. A., Dumesic, J. A.


& Mavrikakis, M. Density functional theory calculations and analysis of reaction pathways for reduction of nitric oxide by hydrogen on Pt(111). _ACS Catal._ 4, 3307–3319 (2014). Article


  CAS  Google Scholar  * Mukherjee, S. & Vannice, M. A. Solvent effects in liquid-phase reactions II. Kinetic modeling for citral hydrogenation. _J. Catal._ 243, 131–148 (2006). Article


  CAS  Google Scholar  * Norskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. _Nat. Chem._ 1, 37–46 (2009). Article  CAS


  Google Scholar  * Zhang, L., Pham, T. N., Faria, J. & Resasco, D. E. Improving the selectivity to C4 products in the aldol condensation of acetaldehyde in ethanol over faujasite


zeolites. _Appl. Catal. A_ 504, 119–129 (2015). Article  CAS  Google Scholar  * Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a


plane-wave basis set. _Phys. Rev. B_ 54, 11169–11186 (1996). Article  CAS  Google Scholar  * Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple.


_Phys. Rev. Lett._ 77, 3865–3868 (1996). Article  CAS  Google Scholar  * Blochl, P. E. Projector augmented-wave method. _Phys. Rev. B_ 50, 17953–17979 (1994). Article  CAS  Google Scholar  *


Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. _Phys. Rev. B_ 59, 1758–1775 (1999). Article  CAS  Google Scholar  * Grimme, S., Antony,


J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. _J. Chem. Phys._ 132,


154104 (2010). Article  Google Scholar  * Henkelman, G., Uberuaga, B. P. & Jonsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. _J.


Chem. Phys._ 113, 9901–9904 (2000). Article  CAS  Google Scholar  * Henkelman, G. & Jonsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy


paths and saddle points. _J. Chem. Phys._ 113, 9978–9985 (2000). Article  CAS  Google Scholar  * Henkelman, G. & Jonsson, H. A dimer method for finding saddle points on high dimensional


potential surfaces using only first derivatives. _J. Chem. Phys._ 111, 7010–7022 (1999). Article  CAS  Google Scholar  * Campbell, C. T. & Sellers, J. R. V. The entropies of adsorbed


molecules. _J. Am. Chem. Soc._ 134, 18109–18115 (2012). Article  CAS  Google Scholar  Download references ACKNOWLEDGEMENTS This work was supported by the US Department of Energy, Basic


Energy Sciences (grant no. DE-SC0018284). The computational research used the supercomputer resources of the National Energy Research Scientific Computing Centre (NERSC), the OU


Supercomputing Centre for Education & Research (OSCER) at the University of Oklahoma and the Tandy Supercomputing Centre (TSC). The authors thank T. Sooknoi (King Mongkut’s Institute of


Technology Ladkrabang, Thailand) for valuable discussions. AUTHOR INFORMATION Author notes * These authors contributed equally: Zheng Zhao, Reda Bababrik, Wenhua Xue. AUTHORS AND


AFFILIATIONS * Center for Interfacial Reaction Engineering and School of Chemical, Biological and Materials Engineering, The University of Oklahoma, Norman, OK, USA Zheng Zhao, Reda


Bababrik, Nicholas M. Briggs, Dieu-Thy Nguyen, Umi Nguyen, Steven P. Crossley, Bin Wang & Daniel E. Resasco * Department of Physics and Engineering Physics, The University of Tulsa,


Tulsa, OK, USA Wenhua Xue, Yaping Li & Sanwu Wang Authors * Zheng Zhao View author publications You can also search for this author inPubMed Google Scholar * Reda Bababrik View author


publications You can also search for this author inPubMed Google Scholar * Wenhua Xue View author publications You can also search for this author inPubMed Google Scholar * Yaping Li View


author publications You can also search for this author inPubMed Google Scholar * Nicholas M. Briggs View author publications You can also search for this author inPubMed Google Scholar *


Dieu-Thy Nguyen View author publications You can also search for this author inPubMed Google Scholar * Umi Nguyen View author publications You can also search for this author inPubMed Google


Scholar * Steven P. Crossley View author publications You can also search for this author inPubMed Google Scholar * Sanwu Wang View author publications You can also search for this author


inPubMed Google Scholar * Bin Wang View author publications You can also search for this author inPubMed Google Scholar * Daniel E. Resasco View author publications You can also search for


this author inPubMed Google Scholar CONTRIBUTIONS Z.Z. conducted material synthesis, reaction tests and the H/D exchange experiment. R.B. completed the DFT calculations, the free energy


calculations and the micro kinetic analysis. W.X., Y.L. and S.W. performed the DFT calculations. N.M.B. and S.P.C. conducted the catalyst characterization and analysed the data. D.-T.N. and


U.N. performed the AIMD calculations. All authors discussed the results and commented on the manuscript. B.W. and D.E.R supervised the project. CORRESPONDING AUTHORS Correspondence to Bin


Wang or Daniel E. Resasco. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. ADDITIONAL INFORMATION PUBLISHER’S NOTE: Springer Nature remains neutral with


regard to jurisdictional claims in published maps and institutional affiliations. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary Figures 1–17, Supplementary Table 1,


Supplementary Methods, Supplementary Notes 1–4, Supplementary References SUPPLEMENTARY DATA 1 DFT structure of FAL*+H* on Pd in H2O SUPPLEMENTARY DATA 2 AIMD simulation of FAL at the


water/Pd interface RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Zhao, Z., Bababrik, R., Xue, W. _et al._ Solvent-mediated charge separation drives


alternative hydrogenation path of furanics in liquid water. _Nat Catal_ 2, 431–436 (2019). https://doi.org/10.1038/s41929-019-0257-z Download citation * Received: 26 June 2017 * Accepted: 20


February 2019 * Published: 01 April 2019 * Issue Date: May 2019 * DOI: https://doi.org/10.1038/s41929-019-0257-z SHARE THIS ARTICLE Anyone you share the following link with will be able to


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