Effects of co-adsorbed water on different bond cleavages involved in acetic acid decomposition on Pt (111)

Chukwu, Kingsley C.; Árnadóttir, Líney

doi:10.1016/j.susc.2025.122721

Effects of co-adsorbed water on different bond cleavages involved in acetic acid decomposition on Pt (111)

Journal Article · Fri Feb 21 00:00:00 EST 2025 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2025.122721· OSTI ID:2565864

Chukwu, Kingsley C. ^[1]; ^[2]

Oregon State University, Corvallis, OR (United States)
Oregon State University, Corvallis, OR (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Acetic acid decomposition on Pt (111) in the presence of co-adsorbed water is a good model system for oxygenate decomposition on Pt (111) in aqueous phase, with application in hydrogen production and biomass conversion. Here, in this study, we present a density functional theory (DFT) theory calculation of how co-adsorbed water affects different bond cleavages of acetic acid decomposition on Pt (111). The presence of co-adsorbed water generally enhances O$$-$$H bond cleavage while inhibiting OC$$-$$O and OC$$-$$OH bond cleavage. The influence of co-adsorbed water on C$$-$$H bond cleavage varies the most and depends on the nature of the transition state and how co-adsorbed water stabilizes the initial and final state. Although these trends are useful as general guidance, they are not sufficient to predict the effect on a complex reaction network such as acetic acid decomposition on Pt (111) which has several parallel reaction paths with similar energies. In the absence of co-adsorbed water, the two lowest energy pathways are decarboxylation (DCX) and decarbonylation (DCN) pathways through a common CH₂COO intermediate, in which the DCX pathway (C$$-$$H bond cleavage of CH₂COO) is more favorable than DCN pathway (OC$$-$$O bond cleavage of CH₂COO). In the presence of co-adsorbed water, the energy difference between Csingle bondH bond cleavage and OC$$-$$O bond cleavage of CH₂COO increases, suggesting an increase in the favorability of acetic acid decarboxylation (formation of carbon dioxide) over acetic acid decarbonylation (formation of carbon monoxide) on Pt (111).

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2565864

Report Number(s):: PNNL-SA--208494

Journal Information:: Surface Science, Journal Name: Surface Science Vol. 756; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

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
Reaction Paths in the Hydrogenolysis of Acetic Acid to Ethanol over Pd(111), Re(0001), and PdRe Alloys Pallassana, Venkataraman; Neurock, Matthew Journal of Catalysis, Vol. 209, Issue 2 https://doi.org/10.1006/jcat.2002.3585	journal	July 2002
Chemisorption and thermal decomposition of acetic acid on Pt(111) Gao, Quanyin; Hemminger, John C. Journal of Electron Spectroscopy and Related Phenomena, Vol. 54-55 https://doi.org/10.1016/0368-2048(90)80259-D	journal	January 1990
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Aqueous-phase reforming of methanol and ethylene glycol over alumina-supported platinum catalysts Shabaker, J. Journal of Catalysis, Vol. 215, Issue 2 https://doi.org/10.1016/S0021-9517(03)00032-0	journal	April 2003
CO oxidation on Pt() promoted by coadsorbed H2O Bergeld, Johan; Kasemo, Bengt; Chakarov, Dinko V. Surface Science, Vol. 495, Issue 3 https://doi.org/10.1016/S0039-6028(01)01598-9	journal	December 2001
Catalytic steam reforming of bio-oils for the production of hydrogen: effects of catalyst composition Garcia, Lucı́a; French, Richard; Czernik, Stefan Applied Catalysis A: General, Vol. 201, Issue 2, p. 225-239 https://doi.org/10.1016/S0926-860X(00)00440-3	journal	July 2000
Solvent effects in enantioselective hydrogenation of 1-phenyl-1,2-propanedione Toukoniitty, E.; Mäki-Arvela, P.; Kuusisto, J. Journal of Molecular Catalysis A: Chemical, Vol. 192, Issue 1-2 https://doi.org/10.1016/S1381-1169(02)00415-6	journal	February 2003
Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts Rioche, Cyrille; Kulkarni, Shrikant; Meunier, Frederic C. Applied Catalysis B: Environmental, Vol. 61, Issue 1-2 https://doi.org/10.1016/j.apcatb.2005.04.015	journal	October 2005
An overview of hydrogen production technologies Holladay, J. D.; Hu, J.; King, D. L. Catalysis Today, Vol. 139, Issue 4 https://doi.org/10.1016/j.cattod.2008.08.039	journal	January 2009
The role of water in the initial steps of methanol oxidation on Pt(111) Hartnig, C.; Spohr, E. Chemical Physics, Vol. 319, Issue 1-3 https://doi.org/10.1016/j.chemphys.2005.05.037	journal	December 2005
Water-assisted oxygen activation during selective oxidation reactions Tran, Hung-Vu; Doan, Hieu A.; Chandler, Bert D. Current Opinion in Chemical Engineering, Vol. 13 https://doi.org/10.1016/j.coche.2016.08.010	journal	August 2016
The effect of coadsorbed water on the stability, configuration and interconversion of formyl (HCO) and hydroxymethylidyne (COH) on platinum (111) Árnadóttir, Líney; Stuve, Eric M.; Jónsson, Hannes Chemical Physics Letters, Vol. 541 https://doi.org/10.1016/j.cplett.2012.05.024	journal	July 2012
Theoretical study of solvent effects on the decomposition of formic acid over a Co(111) surface Li, Xinbao; Zhu, Yingying; Chen, Geng International Journal of Hydrogen Energy, Vol. 42, Issue 39 https://doi.org/10.1016/j.ijhydene.2017.08.022	journal	September 2017
Sustainable hydrogen from bio-oil—Steam reforming of acetic acid as a model oxygenate Takanabe, K.; Aika, K.; Seshan, K. Journal of Catalysis, Vol. 227, Issue 1 https://doi.org/10.1016/j.jcat.2004.07.002	journal	October 2004
Steam reforming of biomass based oxygenates—Mechanism of acetic acid activation on supported platinum catalysts Matasguell, B.; Babich, I.; Seshan, K. Journal of Catalysis, Vol. 257, Issue 1 https://doi.org/10.1016/j.jcat.2008.04.019	journal	July 2008
Solvent effects in the liquid phase hydrodeoxygenation of methyl propionate over a Pd(1 1 1) catalyst model Behtash, Sina; Lu, Jianmin; Walker, Eric Journal of Catalysis, Vol. 333 https://doi.org/10.1016/j.jcat.2015.10.027	journal	January 2016
Understanding the influence of solvents on the Pt-catalyzed hydrodeoxygenation of guaiacol Saleheen, Mohammad; Mamun, Osman; Mohan Verma, Anand Journal of Catalysis, Vol. 425 https://doi.org/10.1016/j.jcat.2023.06.009	journal	September 2023
Density functional theory study of trends in water dissociation on oxygen-preadsorbed and pure transition metal surfaces Mäkinen, Mario; Laasonen, Kari Surface Science, Vol. 734 https://doi.org/10.1016/j.susc.2023.122305	journal	August 2023
Density Functional Theory Study of Decarboxylation and Decarbonylation of Acetic Acid on Pd(111) Chukwu, Kingsley C.; Árnadóttir, Líney The Journal of Physical Chemistry C, Vol. 124, Issue 24 https://doi.org/10.1021/acs.jpcc.0c00436	journal	April 2020
Theoretical Investigation of Solvent Effects on the Hydrodeoxygenation of Propionic Acid over a Ni(111) Catalyst Model Zare, Mehdi; Solomon, Rajadurai Vijay; Yang, Wenqiang The Journal of Physical Chemistry C, Vol. 124, Issue 30 https://doi.org/10.1021/acs.jpcc.0c04437	journal	July 2020
Ambient-Pressure X-ray Photoelectron Spectroscopy Study of Acetic Acid Thermal Decomposition on Pd(111) Nguyen, Hoan K. K.; Addou, Rafik; Chukwu, Kingsley C. The Journal of Physical Chemistry C, Vol. 127, Issue 24 https://doi.org/10.1021/acs.jpcc.2c05539	journal	June 2023
Evaluating Adsorbate–Solvent Interactions: Are Dispersion Corrections Necessary? Romeo, Eleonora; Illas, Francesc; Calle-Vallejo, Federico The Journal of Physical Chemistry C, Vol. 127, Issue 21 https://doi.org/10.1021/acs.jpcc.3c02934	journal	May 2023
Molecular-Level Details about Liquid H ₂ O Interactions with CO and Sugar Alcohol Adsorbates on Pt(111) Calculated Using Density Functional Theory and Molecular Dynamics Bodenschatz, Cameron J.; Sarupria, Sapna; Getman, Rachel B. The Journal of Physical Chemistry C, Vol. 119, Issue 24 https://doi.org/10.1021/acs.jpcc.5b02333	journal	June 2015
Decomposition of Acetic Acid on Model Pt/CeO ₂ Catalysts: The Effect of Surface Crowding Neitzel, Armin; Lykhach, Yaroslava; Johánek, Viktor The Journal of Physical Chemistry C, Vol. 119, Issue 24 https://doi.org/10.1021/acs.jpcc.5b03079	journal	June 2015
Solvation Effects on Methanol Decomposition on Pd(111), Pt(111), and Ru(0001) Garcia-Ratés, Miquel; García-Muelas, Rodrigo; López, Núria The Journal of Physical Chemistry C, Vol. 121, Issue 25 https://doi.org/10.1021/acs.jpcc.7b05545	journal	June 2017
Computational Investigation of Aqueous Phase Effects on the Dehydrogenation and Dehydroxylation of Polyols over Pt(111) Saleheen, Mohammad; Zare, Mehdi; Faheem, Muhammad The Journal of Physical Chemistry C, Vol. 123, Issue 31 https://doi.org/10.1021/acs.jpcc.9b04994	journal	July 2019
Effects of Co-adsorbed Water on Different Bond Cleavages of Oxygenates on Pd (111) Chukwu, Kingsley C.; Árnadóttir, Líney ACS Catalysis, Vol. 12, Issue 1 https://doi.org/10.1021/acscatal.1c03764	journal	December 2021
How to Gain Atomistic Insights on Reactions at the Water/Solid Interface? Steinmann, Stephan N.; Michel, Carine ACS Catalysis, Vol. 12, Issue 11 https://doi.org/10.1021/acscatal.2c00594	journal	May 2022
Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites Hensley, Alyssa J. R.; Wang, Yong; Mei, Donghai ACS Catalysis, Vol. 8, Issue 3 https://doi.org/10.1021/acscatal.7b02576	journal	January 2018
C–H versus O–H Bond Dissociation for Alcohols on a Rh(111) Surface: A Strong Assistance from Hydrogen Bonded Neighbors Michel, Carine; Auneau, Florian; Delbecq, Françoise ACS Catalysis, Vol. 1, Issue 10 https://doi.org/10.1021/cs200370g	journal	September 2011
Liquid-Phase Effects on Adsorption Processes in Heterogeneous Catalysis Zare, Mehdi; Saleheen, Mohammad S.; Singh, Nirala JACS Au, Vol. 2, Issue 9 https://doi.org/10.1021/jacsau.2c00389	journal	August 2022
A Periodic Density Functional Theory Analysis of the Effect of Water Molecules on Deprotonation of Acetic Acid over Pd(111) Desai, Sanket K.; Pallassana, Venkataraman; Neurock, Matthew The Journal of Physical Chemistry B, Vol. 105, Issue 38 https://doi.org/10.1021/jp002797m	journal	September 2001
First-Principles Based Kinetic Simulations of Acetic Acid Temperature Programmed Reaction on Pd(111) Hansen, Eric; Neurock, Matthew The Journal of Physical Chemistry B, Vol. 105, Issue 38 https://doi.org/10.1021/jp0103427	journal	September 2001
New Implicit Solvation Scheme for Solid Surfaces Faheem, Muhammad; Suthirakun, Suwit; Heyden, Andreas The Journal of Physical Chemistry C, Vol. 116, Issue 42 https://doi.org/10.1021/jp308212h	journal	October 2012
Role of Oxygen in Acetic Acid Decomposition on Pt(111) Neitzel, Armin; Lykhach, Yaroslava; Johánek, Viktor The Journal of Physical Chemistry C, Vol. 118, Issue 26 https://doi.org/10.1021/jp502017t	journal	June 2014
Mechanism of the Water Gas Shift Reaction on Pt: First Principles, Experiments, and Microkinetic Modeling Grabow, Lars C.; Gokhale, Amit A.; Evans, Steven T. The Journal of Physical Chemistry C, Vol. 112, Issue 12 https://doi.org/10.1021/jp7099702	journal	March 2008
Density Functional Theory Comparison of Water Dissociation Steps on Cu, Au, Ni, Pd, and Pt Phatak, Abhijit A.; Delgass, W. Nicholas; Ribeiro, Fabio H. The Journal of Physical Chemistry C, Vol. 113, Issue 17 https://doi.org/10.1021/jp810216b	journal	April 2009
Decomposition of Ethanol on Pd(111): A Density Functional Theory Study Li, Ming; Guo, Wenyue; Jiang, Ruibin Langmuir, Vol. 26, Issue 3 https://doi.org/10.1021/la902641t	journal	February 2010
Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents Mellmer, Max A.; Sanpitakseree, Chotitath; Demir, Benginur Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09090-4	journal	March 2019
Dependency of solvation effects on metal identity in surface reactions Zare, Mehdi; Saleheen, Mohammad; Kundu, Subrata Kumar Communications Chemistry, Vol. 3, Issue 1 https://doi.org/10.1038/s42004-020-00428-4	journal	December 2020
Solvent effects on the hydrodeoxygenation of propanoic acid over Pd(111) model surfaces Behtash, Sina; Lu, Jianmin; Faheem, Muhammad Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/C3GC41368C	journal	January 2014
Role of water in metal catalyst performance for ketone hydrogenation: a joint experimental and theoretical study on levulinic acid conversion into gamma-valerolactone Michel, Carine; Zaffran, Jérémie; Ruppert, Agnieszka M. Chem. Commun., Vol. 50, Issue 83 https://doi.org/10.1039/C4CC04401K	journal	January 2014
Trends in water-promoted oxygen dissociation on the transition metal surfaces from first principles Yan, Ming; Huang, Zheng-Qing; Zhang, Yu Physical Chemistry Chemical Physics, Vol. 19, Issue 3 https://doi.org/10.1039/C6CP06974F	journal	January 2017
Insights into how the aqueous environment influences the kinetics and mechanisms of heterogeneously-catalyzed COH* and CH ₃ OH* dehydrogenation reactions on Pt(111) Bodenschatz, Cameron J.; Xie, Tianjun; Zhang, Xiaohong Physical Chemistry Chemical Physics, Vol. 21, Issue 19 https://doi.org/10.1039/C9CP00824A	journal	January 2019
Investigation of solvent effects on the hydrodeoxygenation of guaiacol over Ru catalysts Saleheen, Mohammad; Verma, Anand Mohan; Mamun, Osman Catalysis Science & Technology, Vol. 9, Issue 22 https://doi.org/10.1039/C9CY01763A	journal	January 2019
Aqueous-phase effects on ethanol decomposition over Ru-based catalysts Zare, Mehdi; Saleheen, Mohammad; Mamun, Osman Catalysis Science & Technology, Vol. 11, Issue 20 https://doi.org/10.1039/D1CY01057C	journal	January 2021
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Comparison of methods for finding saddle points without knowledge of the final states Olsen, R. A.; Kroes, G. J.; Henkelman, G. The Journal of Chemical Physics, Vol. 121, Issue 20 https://doi.org/10.1063/1.1809574	journal	November 2004
Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method Heyden, Andreas; Bell, Alexis T.; Keil, Frerich J. The Journal of Chemical Physics, Vol. 123, Issue 22 https://doi.org/10.1063/1.2104507	journal	December 2005
Optimization methods for finding minimum energy paths Sheppard, Daniel; Terrell, Rye; Henkelman, Graeme The Journal of Chemical Physics, Vol. 128, Issue 13 https://doi.org/10.1063/1.2841941	journal	April 2008
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 111, Issue 15 https://doi.org/10.1063/1.480097	journal	October 1999
Beyond single-crystal surfaces: The GAL21 water/metal force field Clabaut, Paul; Beisert, Matthieu; Michel, Carine The Journal of Chemical Physics, Vol. 157, Issue 19 https://doi.org/10.1063/5.0130368	journal	November 2022
Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation Perdew, John P.; Yue, Wang Physical Review B, Vol. 33, Issue 12 https://doi.org/10.1103/PhysRevB.33.8800	journal	June 1986
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/PhysRevB.46.6671	journal	September 1992
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Implementation of gradient-corrected exchange-correlation potentials in Car-Parrinello total-energy calculations White, J. A.; Bird, D. M. Physical Review B, Vol. 50, Issue 7 https://doi.org/10.1103/PhysRevB.50.4954	journal	August 1994
XSEDE: Accelerating Scientific Discovery Towns, John; Cockerill, Timothy; Dahan, Maytal Computing in Science & Engineering, Vol. 16, Issue 5 https://doi.org/10.1109/MCSE.2014.80	journal	September 2014
The critical role of water at the gold-titania interface in catalytic CO oxidation Saavedra, J.; Doan, H. A.; Pursell, C. J. Science, Vol. 345, Issue 6204 https://doi.org/10.1126/science.1256018	journal	September 2014

Similar Records

Effect of sodium loading on Pt/ZrO₂ during ethanol steam reforming

Journal Article · Fri Dec 04 19:00:00 EST 2020 · Applied Catalysis. A, General · OSTI ID:1829997

Theoretical Investigation of Solvent Effects on the Hydrodeoxygenation of Propionic Acid over a Ni(111) Catalyst Model

Journal Article · Mon Jul 06 20:00:00 EDT 2020 · Journal of Physical Chemistry. C · OSTI ID:3001231

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Acetic acid decomposition pt(111)
Density functional theory water
Heterogeneous catalysis
Reaction mechanism

Effects of co-adsorbed water on different bond cleavages involved in acetic acid decomposition on Pt (111)

Citation Formats

References (62)

Similar Records

Related Subjects