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

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 *

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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

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