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Theoretical Study of an almost Barrier-Free Water Dissociation on a Platinum (111) Surface Alloyed with Ruthenium and Molybdenum.

ABSTRACT: A theoretical study based on density functional theory for H₂O dissociation on the metal surface of Pt(111) alloyed simultaneously with Ru and Mo was performed. The determination of the minimum energy path using the climbing image nudged elastic band (CI-NEB) method shows that the dissociation reaction of H₂O with this catalyst requires almost no energy cost. This dissociation reaction is not only kinetically favored but also almost thermodynamically neutral and somewhat exothermic. The electronic structure analysis showed that much more charge was released in Mo and was used to bind the adsorbed hydroxyl (OH_ad). Further analyses of the density of states (DOS) showed that the large number of orbitals that overlap when OH binds to Mo are responsible for the stabilization of the OH-surface bond. The stability of the OH_ad fragment on the surface is believed to be a descriptor for the dissociation of H₂O with an almost spontaneous process.

SUBMITTER: Cahyanto WT

PROVIDER: S-EPMC8153754 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature

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Theoretical Study of an almost Barrier-Free Water Dissociation on a Platinum (111) Surface Alloyed with Ruthenium and Molybdenum.

Cahyanto Wahyu Tri WT Zulaehah Siti S Widanarto Wahyu W Abdullatif Farzand F Effendi Mukhtar M Kasai Hideaki H

ACS omega 20210416 16

A theoretical study based on density functional theory for H<sub>2</sub>O dissociation on the metal surface of Pt(111) alloyed simultaneously with Ru and Mo was performed. The determination of the minimum energy path using the climbing image nudged elastic band (CI-NEB) method shows that the dissociation reaction of H<sub>2</sub>O with this catalyst requires almost no energy cost. This dissociation reaction is not only kinetically favored but also almost thermodynamically neutral and somewhat ex ...[more]

PMID: 34056231

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Project description:Bimetallic heterogeneous catalysts combining group 9 metals (Rh, Ir) or group 10 metals (Ni, Pd, Pt) with Mo on a silica-based support have been synthesized via surface organometallic chemistry and assessed in their catalytic activity for the hydrodeoxygenation (HDO) of alcohols with particular emphasis on the structural evolution of the catalysts and the role of Mo. The investigation was conducted with an air-free approach to isolate any sample alterations exclusively to those caused by the reaction. Structural analysis was performed using a combination of (S)TEM, IR, and XAS. It was found that Ir-Mo/SiO2, Rh-Mo/SiO2, and Pt-Mo/SiO2 display high activity for primary, secondary, and tertiary alcohol deoxygenation, while Pd-Mo/SiO2 selectively catalyses tertiary alcohol deoxygenation. Other combinations as well as the corresponding monometallic materials do not display the same activity. X-ray absorption spectroscopy confirmed metallic states for M (M = Ni, Rh, Pd, Ir, or Pt), while Mo K-edge XANES showed varying amounts of Mo(0), Mo(iv) and Mo(vi) depending on the metal counterpart in fresh materials, and indicated complete conversion of Mo(vi) to lower oxidation states (IV and 0) during the reaction. For Rh, Pd, Ir, and Pt, alloy formation (M-Mo) was identified via M-Mo paths in EXAFS and supported by CO-IR spectroscopy. In contrast to Ir, Rh, and Pt, where some Mo(0) is present at the nanoparticle surface, Pd-Mo forms an alloy but likely retains Mo in the nanoparticle core, as suggested by CO-IR spectroscopy and CO-chemisorption. Reactivity studies suggest that tertiary alcohols primarily undergo dehydration-hydrogenation, evidenced by olefin formation with MoO x /SiO2, as well as Ir/SiO2 and Ir-Mo/SiO2 under inert conditions. In contrast, primary and secondary alcohols follow a different mechanism, correlated with the presence of metallic Mo species on the nanoparticle surface, highlighting their role in C-O bond activation. These findings provide new insights into the structure-activity relationships of Mo-based bimetallic catalysts, underscoring the influence of Mo in different oxidation states and strong substrate dependence on mechanistic pathways.

Dataset Information

Theoretical Study of an almost Barrier-Free Water Dissociation on a Platinum (111) Surface Alloyed with Ruthenium and Molybdenum.

Publications

Theoretical Study of an almost Barrier-Free Water Dissociation on a Platinum (111) Surface Alloyed with Ruthenium and Molybdenum.

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