Investigation of Polyol Adsorption on Ru, Pd, and Re Using vdW Density Functionals

Cortese, Remedios; Schimmenti, Roberto; Armata, Nerina; Ferrante, Francesco; Prestianni, Antonio; Duca, Dario; Murzin, Dmitry Yu.

doi:10.1021/acs.jpcc.5b04007

Cited by 21 publications

(18 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Because of the complexity in modeling water layers near the metal surface, water has often been approximated as having a hexagonal ice‐like bilayer structure . Another approach is to only model a few water molecules close to the solute . Ab initio molecular dynamics (AIMD) simulations have also been used to generate equilibrium water solvation structures around reaction intermediates over periodic solid surfaces .…”

Section: Introductionmentioning

confidence: 99%

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

Iyemperumal

Deskins

2017

ChemPhysChem

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 99%

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

Iyemperumal

Deskins

2017

ChemPhysChem

View full text Add to dashboard Cite

show abstract

“…For the most stable triplet state of the Pd 7 cluster the energy of BZ adsorption was found to be about 26-29 kcal/mol. It is noteworthy that B3LYP is the most popular density functional [36][37][38][39][40][41], which fits well for geometry optimization. At the same time, it was mentioned [42] that B3LYP is not fully suitable for energetic calculations.…”

Section: Introductionmentioning

confidence: 94%

“…DFT modeling is widely used to describe polymers and metal clusters [28][29][30][31][32]. Many works describe DFT modeling of Pd n clusters [33][34][35][36] as well as adsorption of different compounds on them [37][38][39]. Duca et al [40] have calculated the geometry of HPS and Pd n (n ≤ 9) clusters using the CAM-B3LYP functional joined with the LANL2-DZ basis set and found that hosting HPS deforms when Pd atoms are added to growing cluster.…”

Section: Introductionmentioning

confidence: 99%

Hyper-Cross-Linked Polystyrene as a Stabilizing Medium for Small Metal Clusters

et al. 2021

View full text Add to dashboard Cite

Among different polymers nanostructured cross-linked aromatics have the greatest potential as catalytic supports due to their exceptional thermal and chemical stability and preservation of the active phase morphology. This work studies the ability of hyper-cross-linked polystyrene (HPS) to stabilize small Pdn and Ptn (n = 4 or 9) clusters. Unrestricted DFT calculations were carried out for benzene (BZ) adsorption at the BP level of theory using triple-zeta basis sets. The adsorption of BZ rings (stepwise from one to four) was found to result in noticeable gain in energy and stabilization of resulting adsorption complexes. Moreover, the interaction of metal clusters with HPS micropores was also addressed. For the first time, the incorporation of small clusters in the HPS structure was shown to influences its geometry resulting in the stabilization of polymer due to its partial relaxation.

show abstract

“…One of the most interesting implication of this approach is the possibility to study how molecules of high industrial interest interact with the different metallic planes of the supported metal cluster. To the best of our knowledge the few computational studies already performed in literature, on these kind of systems, mainly concern the adsorption of small molecules, such as hydrogen, onto BNNT supported metallic clusters [41], while oxygenates such as a-D-glucopyranose, despite their high catalytic interest in the biomass conversion technology, were rarely treated [3,8]. Moreover, a-D-glucopyranose is also a representative molecule suitable to capture the main chemical features of oxygenates in the biomass.…”

Section: Introductionmentioning

confidence: 99%

α-d-Glucopyranose Adsorption on a Pd30 Cluster Supported on Boron Nitride Nanotube

et al. 2016

Self Cite

View full text Add to dashboard Cite

Boron nitride nanotube (BNNT) as an innovative support for carbohydrate transformation processes was evaluated, using density functional theory. The a-D-glucopyranose adsorption on a Pd 30 cluster, supported on BNNT, was used to check both the local activity of topologically different metallic sites and the effects of the proximity of the BNNT surface to the same metallic sites. Detailed geometrical and electronic analyses performed on Pd 30 /BNNT and a-D-glucopyranose/Pd 30 /BNNT systems were discussed. It was observed that the deposition of the Pd 30 cluster onto the BNNT support gives rise to an electronic rearrangement, determining a charge transfer from the support to the adsorbed metal cluster. The charge transfer, as shown by the analysis of molecular electrostatic potential, seems to generate electron-rich and electron-poor zones in the Pd 30 cluster. The a-D-glucopyranose species, regardless the interaction geometry experienced, acts as an electron donor and preferentially adsorbs close to the electron-poor metal/support interface.

show abstract

Investigation of Polyol Adsorption on Ru, Pd, and Re Using vdW Density Functionals

Cited by 21 publications

References 55 publications

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

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

Hyper-Cross-Linked Polystyrene as a Stabilizing Medium for Small Metal Clusters

α-d-Glucopyranose Adsorption on a Pd30 Cluster Supported on Boron Nitride Nanotube

Contact Info

Product

Resources

About