Critical role of solvent-modulated hydrogen-binding strength in the catalytic hydrogenation of benzaldehyde on palladium

Cheng, Guanhua; Jentys, Andreas; Gutiérrez, Oliver Y.; Liu, Yue; Chin, Ya-Huei; Lercher, Johannes A.

doi:10.1038/s41929-021-00701-2

Critical role of solvent-modulated hydrogen-binding strength in the catalytic hydrogenation of benzaldehyde on palladium

Journal Article · Thu Nov 18 00:00:00 EST 2021 · Nature Catalysis

DOI:https://doi.org/10.1038/s41929-021-00701-2· OSTI ID:1842503

Cheng, Guanhua ^[1]; ^[1]; ^[2]; ^[1]; Chin, Ya-Huei ^[3]; ^[4]

Technical Univ. of Munich (Germany)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Technical Univ. of Munich (Germany); Univ. of Toronto, ON (Canada)
Technical Univ. of Munich (Germany); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Protic and non-protic solvents influence the rate of benzaldehyde hydrogenation on Pd by one order of magnitude in the following sequence of increasing reactivity, dioxane < tetrahydrofuran < water < methanol. Despite these differences, the reaction pathway does not change; the majority of turnovers occurs via a Langmuir-Hinshelwood mechanism by stepwise addition of sorbed H to sorbed benzaldehyde, first to the carbonyl O and then to the C atom of the formyl group, forming benzyl alcohol. An analysis of the solvation energies shows that both ground and transition states are destabilized by the solvents compared to the same reaction at the gas-solid interface. The destabilization extent of the reacting organic substrates in both states are similar and, therefore, compensate each other, making the net kinetic effects inconsequential. In consequence, the marked reactivity differences arise solely from the differences in the surface stabilization of adsorbed hydrogen adatoms moderated by the four solvents-more weakly bound hydrogen adatoms, because of their solvation by solvent, exhibit higher rates of their hydrogenation reaction in kinetically relevant attack on the C atom.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: Chinese Scholarship Council; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1842503

Report Number(s):: PNNL-SA--166986

Journal Information:: Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 11 Vol. 4; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Mechanistic Role of Water on the Rate and Selectivity of Fischer-Tropsch Synthesis on Ruthenium Catalysts Hibbitts, David D.; Loveless, Brett T.; Neurock, Matthew Angewandte Chemie International Edition, Vol. 52, Issue 47 https://doi.org/10.1002/anie.201304610	journal	October 2013
Electrochemically Tunable Proton‐Coupled Electron Transfer in Pd‐Catalyzed Benzaldehyde Hydrogenation Koh, Katherine; Sanyal, Udishnu; Lee, Mal‐Soon Angewandte Chemie International Edition, Vol. 59, Issue 4 https://doi.org/10.1002/anie.201912241	journal	January 2020
Catalytic Activity of Multiwalled Carbon Nanotubes in Acetylene Hydrogenation Bychko, Igor B.; Abakumov, Alexander A.; Lemesh, Natasha V. ChemCatChem, Vol. 9, Issue 24 https://doi.org/10.1002/cctc.201701234	journal	November 2017
Reduction of Acetophenones over Pd/AlPO4 Catalysts. Linear Free Energy Relationship (LFER) Aramendia, M. A.; Borau, V.; Gomez, J. F. Journal of Catalysis, Vol. 140, Issue 2 https://doi.org/10.1006/jcat.1993.1088	journal	April 1993
Reduction of Benzaldehyde on Metal Oxides Haffad, D.; Kameswari, U.; Bettahar, M. M. Journal of Catalysis, Vol. 172, Issue 1 https://doi.org/10.1006/jcat.1997.1854	journal	November 1997
Solvent effects in catalytic hydrogenation Rajadhyaksha, R. A.; Karwa, S. L. Chemical Engineering Science, Vol. 41, Issue 7 https://doi.org/10.1016/0009-2509(86)87055-5	journal	January 1986
Generation of surface hydronium from water and hydrogen coadsorbed on Pt(111) Wagner, Frederick T.; Moylan, Thomas E. Surface Science, Vol. 206, Issue 1-2 https://doi.org/10.1016/0039-6028(88)90021-0	journal	November 1988
Coadsorption of water and hydrogen on Pt(100): formation of adsorbed hydronium ions Kizhakevariam, N.; Stuve, E. M. Surface Science, Vol. 275, Issue 3 https://doi.org/10.1016/0039-6028(92)90796-9	journal	September 1992
Enantioselective hydrogenation of α-ketoesters with cinchona-modified platinum catalysts: Effect of acidic and basic solvents and additives Blaser, H. U.; Jalett, H. P.; Wiehl, J. Journal of Molecular Catalysis, Vol. 68, Issue 2 https://doi.org/10.1016/0304-5102(91)80076-F	journal	September 1991
Hydrogenation of But-1-yne and But-1-ene on Palladium Catalysts Hub, Serge; Hilaire, Lionel; Touroude, Raymonde Applied Catalysis, Vol. 36 https://doi.org/10.1016/S0166-9834(00)80124-4	journal	January 1988
Particle size effect in the catalytic hydrogenation of 2,4-dinitrotoluene over Pd/C catalysts Neri, Giovanni; Musolino, Maria G.; Milone, C. Applied Catalysis A: General, Vol. 208, Issue 1-2 https://doi.org/10.1016/S0926-860X(00)00717-1	journal	February 2001
Kinetics of liquid-phase hydrogenation reactions over supported metal catalysts — a review Singh, Utpal K.; Vannice, M. Albert Applied Catalysis A: General, Vol. 213, Issue 1 https://doi.org/10.1016/S0926-860X(00)00885-1	journal	May 2001
Selective hydrogenation of acetophenone on chromium promoted Raney nickel catalysts. III. The influence of the nature of the solvent Masson, J.; Cividino, P.; Court, J. Applied Catalysis A: General, Vol. 161, Issue 1-2 https://doi.org/10.1016/S0926-860X(97)00068-9	journal	November 1997
Selectivity modulation in the consecutive hydrogenation of benzaldehyde via functionalization of carbon nanotubes Zhou, Yonghua; Liu, Jing; Li, Xingyun Journal of Natural Gas Chemistry, Vol. 21, Issue 3 https://doi.org/10.1016/S1003-9953(11)60359-9	journal	May 2012
Gas phase hydrogenation of benzaldehyde over supported copper catalysts Saadi, A.; Rassoul, Z.; Bettahar, M. M. Journal of Molecular Catalysis A: Chemical, Vol. 164, Issue 1-2 https://doi.org/10.1016/S1381-1169(00)00199-0	journal	December 2000
Chemoselective hydrogenation of carbonyl compounds over heterogeneous catalysts Mäki-Arvela, P.; Hájek, J.; Salmi, T. Applied Catalysis A: General, Vol. 292 https://doi.org/10.1016/j.apcata.2005.05.045	journal	September 2005
Solvent effect in the liquid-phase hydrogenation of acetophenone over Ni/SiO2: A comprehensive study of the phenomenon Bertero, Nicolás M.; Trasarti, Andrés F.; Apesteguía, Carlos R. Applied Catalysis A: General, Vol. 394, Issue 1-2 https://doi.org/10.1016/j.apcata.2011.01.003	journal	February 2011
Heterostructured Ni/NiO composite as a robust catalyst for the hydrogenation of levulinic acid to γ-valerolactone Song, Song; Yao, Sikai; Cao, Jiahui Applied Catalysis B: Environmental, Vol. 217 https://doi.org/10.1016/j.apcatb.2017.05.073	journal	November 2017
Fragrance material review on benzyl alcohol Scognamiglio, J.; Jones, L.; Vitale, D. Food and Chemical Toxicology, Vol. 50 https://doi.org/10.1016/j.fct.2011.10.013	journal	September 2012
Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111) Wang, Jian; Lv, Cun-Qin; Liu, Jian-Hong International Journal of Hydrogen Energy, Vol. 46, Issue 2 https://doi.org/10.1016/j.ijhydene.2020.10.066	journal	January 2021
Solvent effects in liquid-phase reactionsI. Activity and selectivity during citral hydrogenation on Pt/SiO2 and evaluation of mass transfer effects Mukherjee, S.; Vannice, M. Journal of Catalysis, Vol. 243, Issue 1 https://doi.org/10.1016/j.jcat.2006.06.021	journal	October 2006
Kinetics and mechanism of hydrogenation of furfural on Cu/SiO2 catalysts Sitthisa, Surapas; Sooknoi, Tawan; Ma, Yuguang Journal of Catalysis, Vol. 277, Issue 1 https://doi.org/10.1016/j.jcat.2010.10.005	journal	January 2011
Solvent effects in the hydrogenation of 2-butanone Akpa, B. S.; D’Agostino, C.; Gladden, L. F. Journal of Catalysis, Vol. 289 https://doi.org/10.1016/j.jcat.2012.01.011	journal	May 2012
Kinetic investigations of unusual solvent effects during Ru/C catalyzed hydrogenation of model oxygenates Wan, Haijun; Vitter, Audrey; Chaudhari, Raghunath V. Journal of Catalysis, Vol. 309 https://doi.org/10.1016/j.jcat.2013.09.020	journal	January 2014
Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals Song, Yang; Sanyal, Udishnu; Pangotra, Dhananjai Journal of Catalysis, Vol. 359 https://doi.org/10.1016/j.jcat.2017.12.026	journal	March 2018
Formation of PdO on Au–Pd bimetallic catalysts and the effect on benzyl alcohol oxidation Wu, Pingping; Cao, Yunxiang; Zhao, Lianming Journal of Catalysis, Vol. 375 https://doi.org/10.1016/j.jcat.2019.05.003	journal	July 2019
Catalytic consequences of hydrogen addition events and solvent-adsorbate interactions during guaiacol-H2 reactions at the H2O-Ru(0 0 0 1) interface Hensley, Alyssa J. R.; Bray, Jacob; Shangguan, Junnan Journal of Catalysis, Vol. 395 https://doi.org/10.1016/j.jcat.2020.09.034	journal	March 2021
Catalytic pathways and mechanistic consequences of water during vapor phase hydrogenation of butanal on Ru/SiO2 Wu, Zhenwei; Chin, Ya-Huei Cathy Journal of Catalysis, Vol. 394 https://doi.org/10.1016/j.jcat.2020.10.022	journal	February 2021
Adsorption and Desorption of Hydrogen by Gas-Phase Palladium Clusters Revealed by In Situ Thermal Desorption Spectroscopy Takenouchi, Masato; Kudoh, Satoshi; Miyajima, Ken The Journal of Physical Chemistry A, Vol. 119, Issue 26 https://doi.org/10.1021/acs.jpca.5b03926	journal	June 2015
The Role of Protons and Hydrides in the Catalytic Hydrogenolysis of Guaiacol at the Ruthenium Nanoparticle–Water Interface Shangguan, Junnan; Hensley, Alyssa J. R.; Gradiski, Matthew V. ACS Catalysis, Vol. 10, Issue 20 https://doi.org/10.1021/acscatal.0c01963	journal	October 2020
Kinetic Significance of Proton–Electron Transfer during Condensed Phase Reduction of Carbonyls on Transition Metal Clusters Shangguan, Junnan; Chin, Ya-Huei Cathy ACS Catalysis, Vol. 9, Issue 3 https://doi.org/10.1021/acscatal.8b03470	journal	January 2019
Reactions of C−H Bonds in Water Herrerías, Clara I.; Yao, Xiaoquan; Li, Zhiping Chemical Reviews, Vol. 107, Issue 6 https://doi.org/10.1021/cr050980b	journal	April 2007
Water: Nature’s Reaction Enforcer—Comparative Effects for Organic Synthesis “In-Water” and “On-Water” Butler, Richard N.; Coyne, Anthony G. Chemical Reviews, Vol. 110, Issue 10 https://doi.org/10.1021/cr100162c	journal	October 2010
Solvent Effect in Liquid-Phase Hydrogenation of Toluene Rautanen, Petri A.; Aittamaa, Juhani R.; Krause, A. Outi I. Industrial & Engineering Chemistry Research, Vol. 39, Issue 11 https://doi.org/10.1021/ie000349v	journal	October 2000
Proton-Coupled Electron Transfer versus Hydrogen Atom Transfer in Benzyl/Toluene, Methoxyl/Methanol, and Phenoxyl/Phenol Self-Exchange Reactions Mayer, James M.; Hrovat, David A.; Thomas, Jennie L. Journal of the American Chemical Society, Vol. 124, Issue 37 https://doi.org/10.1021/ja012732c	journal	September 2002
Solubility of hydrogen in 10 organic solvents at 298.15, 323.15, and 373.15 K Brunner, Erwin Journal of Chemical & Engineering Data, Vol. 30, Issue 3 https://doi.org/10.1021/je00041a010	journal	July 1985
Solubility of Hydrogen, Carbon Monoxide, and 1-Octene in Various Solvents and Solvent Mixtures No authors listed Journal of Chemical & Engineering Data, Vol. 41, Issue 6 https://doi.org/10.1021/je960024e	journal	January 1996
Adsorption and Desorption of Methanol on Pd (111) and on a Pd/V Surface Alloy Schennach, R.; Eichler, A.; Rendulic, K. D. The Journal of Physical Chemistry B, Vol. 107, Issue 11 https://doi.org/10.1021/jp021841q	journal	March 2003
Adsorption Orientation-Induced Selectivity Control of Reactions of Benzyl Alcohol on Pd(111) Pang, Simon H.; Román, Alex M.; Medlin, J. Will The Journal of Physical Chemistry C, Vol. 116, Issue 25 https://doi.org/10.1021/jp303147c	journal	June 2012
Large-Scale Carbonyl Reductions in the Pharmaceutical Industry Magano, Javier; Dunetz, Joshua R. Organic Process Research & Development, Vol. 16, Issue 6 https://doi.org/10.1021/op2003826	journal	April 2012
Selective hydrogenation of ά,β-unsaturated aldehydes and other C=O and C=C bonds containing compounds Claus, Peter Topics In Catalysis, Vol. 5, Issue 1/4, p. 51-62 https://doi.org/10.1023/A:1019177330810	journal	January 1998
Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water Zhao, Zheng; Bababrik, Reda; Xue, Wenhua Nature Catalysis, Vol. 2, Issue 5 https://doi.org/10.1038/s41929-019-0257-z	journal	April 2019
Molecular simulations of palladium catalysed hydrodeoxygenation of 2-hydroxybenzaldehyde using density functional theory Verma, Anand Mohan; Kishore, Nanda Physical Chemistry Chemical Physics, Vol. 19, Issue 37 https://doi.org/10.1039/C7CP05113A	journal	January 2017
Tunable selectivity of phenol hydrogenation to cyclohexane or cyclohexanol by a solvent-driven effect over a bifunctional Pd/NaY catalyst Xia, Heng; Tan, Hongzi; Cui, Hongyou Catalysis Science & Technology, Vol. 11, Issue 5 https://doi.org/10.1039/D0CY02188A	journal	January 2021

Similar Records

Aqueous phase catalytic and electrocatalytic hydrogenation of phenol and benzaldehyde over platinum group metals

Journal Article · Thu Jan 16 19:00:00 EST 2020 · Journal of Catalysis · OSTI ID:1595284

Role of catalyst characteristics in electrocatalytic hydrogenation: Reduction of benzaldehyde and acetophenone on carbon felt/Pd electrodes

Journal Article · Thu Jul 01 00:00:00 EDT 1993 · Industrial and Engineering Chemistry Research; (United States) · OSTI ID:6224748

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalytic mechanisms
heterogeneous catalysis
reaction kinetics and dynamics

Critical role of solvent-modulated hydrogen-binding strength in the catalytic hydrogenation of benzaldehyde on palladium

Citation Formats

References (44)

Similar Records

Related Subjects