Ethanol, O, and CO adsorption on Pt nanoparticles: effects of nanoparticle size and graphene support

Verga, Lucas Garcia; Russell, Andrea E.; Skylaris, Chris Kriton

doi:10.1039/c8cp04798g

Cited by 32 publications

(31 citation statements)

References 94 publications

(153 reference statements)

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“…The bridge sites are found to be the most favourable on isolated Pt 13 . This is in contrast to binding energies calculated with frozen nanoparticles 27,45 , where the hollow (HCP) site is favourable. The Pt 13 nanoparticle undergoes a significant shift in Pt-Pt bond lengths and structure upon oxygen deposition on the atop and especially bridge sites, in a way that is not seen with the hollow site.…”

Section: Oxygen On Pt 13contrasting

confidence: 80%

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Modification of O and CO binding on Pt nanoparticles due to electronic and structural effects of titania supports

Ellaby

Briquet

Sarwar

et al. 2019

The Journal of Chemical Physics

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Metal oxide supports often play an active part in heterogeneous catalysis by moderating both the structure and the electronic properties of the metallic catalyst particle. In order to provide some fundamental understanding on these effects, we present here a DFT investigation of the binding of O and CO on Pt nanoparticles supported on titania (anatase) surfaces. These systems are complex and in order to develop realistic models here we needed to perform DFT calculations with up to ∼1000 atoms. By performing full geometry relaxations at each stage, we avoid any effects of "frozen geometry" approximations. In terms of the interaction of the Pt nanoparticles with the support, we find that the surface deformation of the anatase support contributes greatly to the adsorption of each nanoparticle, especially for the anatase (001) facet. We attempt to separate geometric and electronic effects, and find a larger contribution to ligand binding energy arising from the former. Overall, we show an average weakening (compared to the isolated nanoparticle) of ∼0.1 eV across atop, bridge and hollow binding sites on supported Pt 55 for O and CO, and a preservation of site preference. Stronger effects are seen for O on Pt 13 , which is heavily deformed by anatase supports. In order to rationalise our results and examine methods for faster characterisation of metal catalysts, we make use of electronic descriptors, including the d-band centre and our electronic density based descriptor. We expect that the approach followed in this study could be applied to study other supported metal catalysts.

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Section: Oxygen On Pt 13contrasting

confidence: 80%

“…Both the geometric and electronic properties are affected by the support material, even for weakly interacting metals and supports like Pt on graphene 27 . A graphene support weakens the adsorption energies of O and CO on Pt, although this effect is diminished as the size of the nanoparticle increases.…”

Section: Introductionmentioning

confidence: 99%

Modification of O and CO binding on Pt nanoparticles due to electronic and structural effects of titania supports

Ellaby

Briquet

Sarwar

et al. 2019

The Journal of Chemical Physics

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“…However, support effects weaken the adsorption energies, which are lower for larger NPs, but are signicant for smaller NPs. 40 Assuming a cuboctahedron structure for all Pt NPs, to calculate the population of surface sites of Pt NPs, the relative IR intensities of the Pt:PVP samples were used, as was the equation…”

Section: Surface Structure Of Pt Npsmentioning

confidence: 99%

Preference for low-coordination sites by adsorbed CO on small platinum nanoparticles

2020

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“…In addition, more recent HAADF-STEM measurements have even observed single Pt atoms dispersed on undoped [15,16] and nitrogendoped [17] graphene, which show high catalytic activities and CO tolerance. Theoretically, on the other hand, firstprinciples calculations based on density functional theory (DFT) have been performed extensively to clarify the properties of graphene-supported Pt clusters from viewpoints of geometric [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] and magnetic [35][36][37][38][39][40][41][42][43][44] structures, molecular adsorptions [45][46][47][48][49][50], CO tolerance [51][52][53][54], and catalytic reactions such as CO oxidation [55][56][57][58][59][60], decomposition of O 3…”

Section: Introductionmentioning

confidence: 99%

Enhanced CO tolerance of Pt clusters supported on graphene with lattice vacancies

et al. 2020

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The adsorption of CO on Pt 4 clusters supported on graphene with lattice vacancies is studied theoretically using the first-principles calculation. Our results show that the electronic structure of the graphene-supported Pt 4 clusters is significantly modified by the interaction with carbon dangling bonds. As a result the adsorption energy of CO at a Pt site decreases almost linearly with the lowering of the Pt d-band center, in analogy with the linear law previously reported for CO adsorption on various Pt surfaces. An exceptional behavior is found for Pt 4 supported on graphene with a tetravacancy, where CO adsorption is noticeably weaker than predicted by the shift in the d-band center. Detailed electronic structure analyses reveal that the deviation from the linear scaling can be attributed to lack of Pt d states near the Fermi level that hybridize with CO molecular orbitals. The weakening of CO adsorption on the Pt 4 clusters is considered as a manifestation of the support effect of graphene, and leads to the enhancement of CO poisoning tolerance that is crucial for developing high-performance Pt cluster catalysts.

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Ethanol, O, and CO adsorption on Pt nanoparticles: effects of nanoparticle size and graphene support

Abstract: DFT calculations reveal aspects of size and support effects for Pt nanoparticles on graphene interacting with O, CO and ethanol.

Cited by 32 publications

References 94 publications

Modification of O and CO binding on Pt nanoparticles due to electronic and structural effects of titania supports

Modification of O and CO binding on Pt nanoparticles due to electronic and structural effects of titania supports

Preference for low-coordination sites by adsorbed CO on small platinum nanoparticles

Enhanced CO tolerance of Pt clusters supported on graphene with lattice vacancies

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