Ethanol chemisorption on core–shell Pt-nanoparticles: an ab initio study

Vagner A. Rigo; Caetano R. Miranda; Francesca Baletto

doi:10.1140/epjb/e2018-90241-3

Ethanol chemisorption on core–shell Pt-nanoparticles: an ab initio study

Vagner A. Rigo, Caetano R. Miranda, Francesca Baletto

Universidade de Sao Paulo - USP

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

102 Downloads (Pure)

Abstract

By means of ab initio calculations, we have investigated the chemisorption properties of ethanol onto segregating binary nanoalloys (NAs). We select nanostructures with icosahedral shape of 55 atoms with a Pt outermost layer over an M-core with M = Ag, Pd, Ni. With respect to nanofilms with equivalent composition, there is an increase of the ethanol binding energy. This is not merely due to observed shortening of the Pt–O distance but depends on the nanoparticle distortion after ethanol adsorption. This geometrical distortion within the nanoparticle can be interpreted as a radial breathing, which is sensitive to the adsorption site, identified by the O-anchor point and the relative positions of the ethyl group. More interestingly, being core-dependent larger in Pd@Pt and smaller in Ni@Pt, it relates to an effective electron transfer from ethanol and the M-core towards the Pt-shell. On the view of this new analysis, Pd@Pt NAs show the most promising features for ethanol oxidation.

Original language	English
Article number	24
Journal	European Physical Journal B
Volume	92
Issue number	2
DOIs	https://doi.org/10.1140/epjb/e2018-90241-3
Publication status	E-pub ahead of print - 4 Feb 2019

Access to Document

10.1140/epjb/e2018-90241-3

Ethanol chemisorption on core_RIGO_Firstonline4February2019_GREEN AAMAccepted author manuscript, 590 KB

https://arxiv.org/pdf/1804.07631.pdf

Cite this

@article{0421eb0861204dac9267184810876467,

title = "Ethanol chemisorption on core–shell Pt-nanoparticles: an ab initio study",

abstract = "By means of ab initio calculations, we have investigated the chemisorption properties of ethanol onto segregating binary nanoalloys (NAs). We select nanostructures with icosahedral shape of 55 atoms with a Pt outermost layer over an M-core with M = Ag, Pd, Ni. With respect to nanofilms with equivalent composition, there is an increase of the ethanol binding energy. This is not merely due to observed shortening of the Pt–O distance but depends on the nanoparticle distortion after ethanol adsorption. This geometrical distortion within the nanoparticle can be interpreted as a radial breathing, which is sensitive to the adsorption site, identified by the O-anchor point and the relative positions of the ethyl group. More interestingly, being core-dependent larger in Pd@Pt and smaller in Ni@Pt, it relates to an effective electron transfer from ethanol and the M-core towards the Pt-shell. On the view of this new analysis, Pd@Pt NAs show the most promising features for ethanol oxidation.",

author = "Rigo, {Vagner A.} and Miranda, {Caetano R.} and Francesca Baletto",

year = "2019",

month = feb,

day = "4",

doi = "10.1140/epjb/e2018-90241-3",

language = "English",

volume = "92",

journal = "European Physical Journal B",

issn = "1434-6028",

publisher = "Springer New York",

number = "2",

}

TY - JOUR

T1 - Ethanol chemisorption on core–shell Pt-nanoparticles

T2 - an ab initio study

AU - Rigo, Vagner A.

AU - Miranda, Caetano R.

AU - Baletto, Francesca

PY - 2019/2/4

Y1 - 2019/2/4

N2 - By means of ab initio calculations, we have investigated the chemisorption properties of ethanol onto segregating binary nanoalloys (NAs). We select nanostructures with icosahedral shape of 55 atoms with a Pt outermost layer over an M-core with M = Ag, Pd, Ni. With respect to nanofilms with equivalent composition, there is an increase of the ethanol binding energy. This is not merely due to observed shortening of the Pt–O distance but depends on the nanoparticle distortion after ethanol adsorption. This geometrical distortion within the nanoparticle can be interpreted as a radial breathing, which is sensitive to the adsorption site, identified by the O-anchor point and the relative positions of the ethyl group. More interestingly, being core-dependent larger in Pd@Pt and smaller in Ni@Pt, it relates to an effective electron transfer from ethanol and the M-core towards the Pt-shell. On the view of this new analysis, Pd@Pt NAs show the most promising features for ethanol oxidation.

AB - By means of ab initio calculations, we have investigated the chemisorption properties of ethanol onto segregating binary nanoalloys (NAs). We select nanostructures with icosahedral shape of 55 atoms with a Pt outermost layer over an M-core with M = Ag, Pd, Ni. With respect to nanofilms with equivalent composition, there is an increase of the ethanol binding energy. This is not merely due to observed shortening of the Pt–O distance but depends on the nanoparticle distortion after ethanol adsorption. This geometrical distortion within the nanoparticle can be interpreted as a radial breathing, which is sensitive to the adsorption site, identified by the O-anchor point and the relative positions of the ethyl group. More interestingly, being core-dependent larger in Pd@Pt and smaller in Ni@Pt, it relates to an effective electron transfer from ethanol and the M-core towards the Pt-shell. On the view of this new analysis, Pd@Pt NAs show the most promising features for ethanol oxidation.

U2 - 10.1140/epjb/e2018-90241-3

DO - 10.1140/epjb/e2018-90241-3

M3 - Article

SN - 1434-6028

VL - 92

JO - European Physical Journal B

JF - European Physical Journal B

IS - 2

M1 - 24

ER -

Ethanol chemisorption on core–shell Pt-nanoparticles: an ab initio study

Abstract

Access to Document

Fingerprint

Cite this