Exploring the Potential Energy Surface of Pt<sub>6</sub> Sub-Nano Clusters Deposited over Graphene
Catalytic systems based on sub-nanoclusters deposited over different supports are promising for very relevant chemical transformations such as many electrocatalytic processes as the ORR. These systems have been demonstrated to be very fluxional, as they are able to change shape and interconvert betw...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-01-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/24/1/870 |
| _version_ | 1797625566844682240 |
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| author | Daniel Barrena-Espés Sergio Boneta Victor Polo Julen Munárriz |
| author_facet | Daniel Barrena-Espés Sergio Boneta Victor Polo Julen Munárriz |
| author_sort | Daniel Barrena-Espés |
| collection | DOAJ |
| description | Catalytic systems based on sub-nanoclusters deposited over different supports are promising for very relevant chemical transformations such as many electrocatalytic processes as the ORR. These systems have been demonstrated to be very fluxional, as they are able to change shape and interconvert between each other either alone or in the presence of adsorbates. In addition, an accurate representation of their catalytic activity requires the consideration of ensemble effects and not a single structure alone. In this sense, a reliable theoretical methodology should assure an accurate and extensive exploration of the potential energy surface to include all the relevant structures and with correct relative energies. In this context, we applied DFT in conjunction with global optimization techniques to obtain and analyze the characteristics of the many local minima of Pt<sub>6</sub> sub-nanoclusters over a carbon-based support (graphene)—a system with electrocatalytic relevance. We also analyzed the magnetism and the charge transfer between the clusters and the support and paid special attention to the dependence of dispersion effects on the ensemble characteristics. We found that the ensembles computed with and without dispersion corrections are qualitatively similar, especially for the lowest-in-energy clusters, which we attribute to a (mainly) covalent binding to the surface. However, there are some significant variations in the relative stability of some clusters, which would significantly affect their population in the ensemble composition. |
| first_indexed | 2024-03-11T09:58:12Z |
| format | Article |
| id | doaj.art-bee5cb1ca75f4423a61357b06fd3c328 |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-11T09:58:12Z |
| publishDate | 2023-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-bee5cb1ca75f4423a61357b06fd3c3282023-11-16T15:39:38ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672023-01-0124187010.3390/ijms24010870Exploring the Potential Energy Surface of Pt<sub>6</sub> Sub-Nano Clusters Deposited over GrapheneDaniel Barrena-Espés0Sergio Boneta1Victor Polo2Julen Munárriz3Departamento de Química Física y Analítica, Universidad de Oviedo, 33006 Oviedo, SpainDepartamento de Bioquímica y Biología Molecular y Celular, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza, SpainInstituto de Biocomputación y Física de Sistemas Complejos (BIFI), Universidad de Zaragoza, 50009 Zaragoza, SpainDepartamento de Química Física y Analítica, Universidad de Oviedo, 33006 Oviedo, SpainCatalytic systems based on sub-nanoclusters deposited over different supports are promising for very relevant chemical transformations such as many electrocatalytic processes as the ORR. These systems have been demonstrated to be very fluxional, as they are able to change shape and interconvert between each other either alone or in the presence of adsorbates. In addition, an accurate representation of their catalytic activity requires the consideration of ensemble effects and not a single structure alone. In this sense, a reliable theoretical methodology should assure an accurate and extensive exploration of the potential energy surface to include all the relevant structures and with correct relative energies. In this context, we applied DFT in conjunction with global optimization techniques to obtain and analyze the characteristics of the many local minima of Pt<sub>6</sub> sub-nanoclusters over a carbon-based support (graphene)—a system with electrocatalytic relevance. We also analyzed the magnetism and the charge transfer between the clusters and the support and paid special attention to the dependence of dispersion effects on the ensemble characteristics. We found that the ensembles computed with and without dispersion corrections are qualitatively similar, especially for the lowest-in-energy clusters, which we attribute to a (mainly) covalent binding to the surface. However, there are some significant variations in the relative stability of some clusters, which would significantly affect their population in the ensemble composition.https://www.mdpi.com/1422-0067/24/1/870sub-nano clustersglobal optimizationcatalysisDFTdispersion interactionsensemble effects |
| spellingShingle | Daniel Barrena-Espés Sergio Boneta Victor Polo Julen Munárriz Exploring the Potential Energy Surface of Pt<sub>6</sub> Sub-Nano Clusters Deposited over Graphene International Journal of Molecular Sciences sub-nano clusters global optimization catalysis DFT dispersion interactions ensemble effects |
| title | Exploring the Potential Energy Surface of Pt<sub>6</sub> Sub-Nano Clusters Deposited over Graphene |
| title_full | Exploring the Potential Energy Surface of Pt<sub>6</sub> Sub-Nano Clusters Deposited over Graphene |
| title_fullStr | Exploring the Potential Energy Surface of Pt<sub>6</sub> Sub-Nano Clusters Deposited over Graphene |
| title_full_unstemmed | Exploring the Potential Energy Surface of Pt<sub>6</sub> Sub-Nano Clusters Deposited over Graphene |
| title_short | Exploring the Potential Energy Surface of Pt<sub>6</sub> Sub-Nano Clusters Deposited over Graphene |
| title_sort | exploring the potential energy surface of pt sub 6 sub sub nano clusters deposited over graphene |
| topic | sub-nano clusters global optimization catalysis DFT dispersion interactions ensemble effects |
| url | https://www.mdpi.com/1422-0067/24/1/870 |
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