Solvent effects in the liquid phase hydrodeoxygenation of methyl propionate over a Pd(1 1 1) catalyst model

Behtash, Sina; Lü, Jianmin; Walker, Eric A.; Mamun, Osman; Heyden, Andreas

doi:10.1016/j.jcat.2015.10.027

Cited by 37 publications

(34 citation statements)

References 52 publications

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“…We assess the influence of PCM on ethanol aqueous reforming, including water-gas shift reactions, by considering the corresponding standard Gibbs free energy of reactions in gas-phase (gp) and solution (aq): (13) where the reaction involves species i with the stoichiometric coefficient νi with νi >0 if i is a product. To assess the change in the standard Gibbs free energy of reaction upon solvation, we further define Λsol as the change of a reaction energy upon solvation:…”

Section: Influence Of the Solvation On Reactionsmentioning

confidence: 99%

“…10 Despite the wide use of solvent in biomass conversion, only a limited number of theoretical studies have explicitly addressed solvation effects. [11][12][13][14][15][16][17][18][19] This shortcoming is due to the methodology: there are no computationally affordable, broadly validated and general methods to include solvent effects in heterogeneous catalysis. The most rigorous way to describe reactivity in condensed phases is to perform thermodynamic integration at the ab initio molecular dynamics (AIMD) level.…”

Section: Introductionmentioning

confidence: 99%

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Group Additivity for Aqueous Phase Thermochemical Properties of Alcohols on Pt(111)

Schweitzer

Michel

et al. 2017

J. Phys. Chem. C

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International audienceDespite progress in theoretical tools, the influence of solvation in heterogeneous catalysis remains poorly understood and predicted due to the large computational burden. In this work, we show that the inclusion of the solvation by water using a continuum model thermodynamically inhibits the O–H bond scissions involved in the ethanol aqueous phase reforming reaction over Pt(111), while it tends to favor the C–H, C–C, and C–O scissions. Then, we present a novel group additivity scheme for the free energy of adsorbates at the Pt/water interface that is able to capture this solvent effect. The mean absolute error (MeanAE) for the Gibbs free energy of formation is 3.3 kcal/mol over the investigated set of 200 species at the interface and the MeanAE for the 151 reaction free energies of ethanol aqueous phase reforming is 2.8 kcal/mol. Regarding the effect of solvation, our scheme is able to predict it with a MeanAE of about 1 kcal/mol. Together, the scheme promises to be accurate enough for narrowing down the most important reaction pathways in complex reaction networks as encountered in biomass conversion

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Section: Influence Of the Solvation On Reactionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Group Additivity for Aqueous Phase Thermochemical Properties of Alcohols on Pt(111)

Schweitzer

Michel

et al. 2017

J. Phys. Chem. C

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“…We are particularly interested in heterogeneously catalyzed reactions that are carried out under liquid water. Water molecules have significant influence on catalytic phenomena, such as interacting with catalytic species (e.g., via dispersion forces and hydrogen bonding) 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23 , participating in catalytic reactions 1,7,8,9,15,21,22,24,25,26,27 , and influencing reaction pathways and/or catalytic rates 1,11,12,15,18,23,25,27,28,29,30,31 . Modeling of these phenomena has been performed using QM and/or ab initio molecular dynamics (AIMD) 1,2,…”

Section: Introductionmentioning

confidence: 99%

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

Bodenschatz

Zhang

Xie

et al. 2019

JoVE

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A significant number of heterogeneously-catalyzed chemical processes occur under liquid conditions, but simulating catalyst function under such conditions is challenging when it is necessary to include the solvent molecules. The bond breaking and forming processes modeled in these systems necessitate the use of quantum chemical methods. Since molecules in the liquid phase are under constant thermal motion, simulations must also include configurational sampling. This means that multiple configurations of liquid molecules must be simulated for each catalytic species of interest. The goal of the protocol presented here is to generate and sample trajectories of configurations of liquid water molecules around catalytic species on flat transition metal surfaces in a way that balances chemical accuracy with computational expense. Specifically, force field molecular dynamics (FFMD) simulations are used to generate configurations of liquid molecules that can subsequently be used in quantum mechanics-based methods such as density functional theory or ab initio molecular dynamics. To illustrate this, in this manuscript, the protocol is used for catalytic intermediates that could be involved in the pathway for the decomposition of glycerol (C 3 H 8 O 3). The structures that are generated using FFMD are modeled in DFT in order to estimate the enthalpies of solvation of the catalytic species and to identify how H 2 O molecules participate in catalytic decompositions.

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“…Several recent reports have described catalysis results with implicit solvation models over metal surfaces. Heyden and co‐workers used their iSMS approach and found that the solvation effects on Pd(111) and Pd(211) surfaces were small (not more than 0.25 eV compared to vacuum) in studies involving C−C cleavage of ethylene glycol, and hydrodeoxygenation of propanoic acid and methyl propionate . Over the Pt(111) surface, Bodenschatz et al .…”

Section: Introductionmentioning

confidence: 99%

Evaluating Solvent Effects at the Aqueous/Pt(111) Interface

Iyemperumal

Deskins

2017

ChemPhysChem

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Liquid-metal interfaces occur in a number of surface processes, and it is fundamentally important to accurately model them. Herein, it is systematically determined how the presence of water affects several processes by using density functional theory with implicit solvation models. Adsorption of 41 common adsorbates and four catalytic reactions in both vacuum and water over the Pt(111) surface were modeled. The results show that adsorption energies for some species can change significantly in the presence of water (by up to 0.44 eV). It is further shown that solvation effects can be explained and predicted by analyzing simple chemical descriptors such as dipole moment and adsorbate charge. Models from artificial neural networks involving several potential descriptors, including gas-phase solvation energy, adsorbate charge, dipole moment, and surface area, are also reported. When water is present, reaction energies change by up to 0.23 eV, although it appears that water solvent negligibly affects several elementary reaction steps. The results show that hydrogen bonding can be important for a number of reactions, but is largely absent in the implicit solvation models. Furthermore, other solvents besides water were also modeled, and if a solvent has a small dielectric constant, then small solvation effects occur. This work provides guidelines on when solvation effects may be important for surface chemistry, and also provides valuable insights into modeling such effects.

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Solvent effects in the liquid phase hydrodeoxygenation of methyl propionate over a Pd(1 1 1) catalyst model

Cited by 37 publications

References 52 publications

Group Additivity for Aqueous Phase Thermochemical Properties of Alcohols on Pt(111)

Group Additivity for Aqueous Phase Thermochemical Properties of Alcohols on Pt(111)

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

Evaluating Solvent Effects at the Aqueous/Pt(111) Interface

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