Multigrid-Based Methodology for Implicit Solvation Models in Periodic DFT

García-Ratés, Miquel; López, Núria

doi:10.1021/acs.jctc.5b00949

Cited by 63 publications

(76 citation statements)

References 69 publications

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“…Solvation contributions for the molecules in the liquid phase were also considered using the MGCM methodology. 52 The climbing image nudged elastic band (CI-NEB) 53,54 and improved dimer method (IDM) 55 were employed to locate the transition states in the potential surfaces. The transition states were confirmed by having only one imaginary value from frequency analysis.…”

Section: Methodsmentioning

confidence: 99%

Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone

Albani

Vilé

et al. 2017

Green Chem.

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a Gamma-valerolactone (GVL), a versatile renewable compound listed among the top 10 most promising platform chemical by the US Department of Energy, is produced via hydrogenation of levulinic acid (LA). The traditional high-loading ruthenium-on-carbon catalyst (5 wt.% Ru) employed for this transformation suffers from low metal utilisation and poor resistance to deactivation due to the formation of RuO x species. Aiming at an improved catalyst design, we have prepared ruthenium nanoparticles modified with the water-soluble hydroxyethyl-dimethyl ammonium dihydrogen phosphate (HHDMA) ligand and supported on TiSi 2 O 6 . The hybrid catalyst has been characterised by ICP-OES, elemental analysis, TGA, DRIFTS, H 2 -TPR, STEM, EDX, 31 P and 13 C MAS-NMR, and XPS. When evaluated in the continuous-flow hydrogenation of LA, the Ru-HHDMA/TiSi 2 O 6 catalyst (0.24 wt.% Ru) displays a fourfold higher reaction rate than the stateof-the-art Ru/C catalyst, while maintaining a 100% selectivity to GVL and no sign of deactivation after 15 hours on stream. An in-depth molecular analysis by Density Functional Theory demonstrates that the intrinsic acidic properties of the ligand-metal interface under reaction conditions ensure that the less energy demanding path is followed. The reaction does not obey the expected cascade mechanism and intercalates hydrogenation steps, hydroxyl/water eliminations, and ring closings to ensure high selectivity. Moreover, the interfacial acidity increases the robustness of the material against ruthenium oxide formation. These results provide valuable improvements for the sustainable production of GLV and insights for the rationalisation of the exceptional selectivity of Ru-based catalysts.

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Section: Methodsmentioning

confidence: 99%

Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone

Albani

Vilé

et al. 2017

Green Chem.

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“…In computational electrocatalysis adsorbate‐solvent and adsorbate‐electrolyte interactions at the interface can be evaluated implicitly (where the solvent is modelled as a continuum with certain dielectric constant), explicitly, or through combinations of the two . Furthermore, efforts have been devoted to determine the minimal number of explicit water molecules needed to stabilize a given adsorbate .…”

Section: Computational Detailsmentioning

confidence: 99%

Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt‐Based Electrocatalysts

et al. 2019

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Solvation can significantly modify the adsorption energy of species at surfaces, thereby influencing the performance of electrocatalysts and liquid‐phase catalysts. Thus, it is important to understand adsorbate solvation at the nanoscale. Here we evaluate the effect of van der Waals (vdW) interactions described by different approaches on the solvation energy of *OH adsorbed on near‐surface alloys (NSAs) of Pt. Our results show that the studied functionals can be divided into two groups, each with rather similar average *OH solvation energies: (1) PBE and PW91; and (2) vdW functionals, RPBE, PBE‐D3 and RPBE‐D3. On average, *OH solvation energies are less negative by ∼0.14 eV in group (2) compared to (1), and the values for a given alloy can be extrapolated from one functional to another within the same group. Depending on the desired level of accuracy, these concrete observations and our tabulated values can be used to rapidly incorporate solvation into models for electrocatalysis and liquid‐phase catalysis.

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“…Climbing Image Nudged Elastic Band (CI‐NEB) approach, and the improved dimer algorithms were employed to locate the transition states, which were further verified by their single imaginary frequency character. Solvation (toluene) contributions to the reaction network have also been considered via the MGCM method ,. All structures in the present study can be retrieved from ioChem‐BD ,…”

Section: Methodsmentioning

confidence: 99%

Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi‐Hydrogenation

et al. 2018

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Modification of transition metals with p‐block elements is known to be effective to tune the ensemble characteristics of catalysts for the semi‐hydrogenation of alkynes. To further explore this approach, here we prepare two nickel phosphides, namely Ni2P and Ni5P4. Assessment in the semi‐hydrogenation of 1‐hexyne and 2‐methyl‐3‐butyn‐2‐ol shows that the phosphides present higher rate and selectivity than unmodified nickel catalysts. While no activity and selectivity differences are displayed in the semi‐hydrogenation of 1‐hexyne over Ni2P and Ni5P4, in the case of 2‐methyl‐3‐butyn‐2‐ol a higher rate and lower selectivity to 2‐methyl‐3‐buten‐2‐ol are observed over Ni2P. Density functional theory reveals that the hydroxyl group facilitates the reaction, but also increases the barrier for product desorption. Detailed analyses of the ensemble show the potential of phosphorus to create spatially‐isolated nickel trimers that surpass the performance of unmodified nickel, but also its limited ability to modulate the electronic properties and related binding energies of organic intermediates, which is key to preventing undesired side reactions.

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Multigrid-Based Methodology for Implicit Solvation Models in Periodic DFT

Cited by 63 publications

References 69 publications

Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone

Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone

Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt‐Based Electrocatalysts

Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi‐Hydrogenation

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