Organic Linker Effect on the Growth and Diffusion of Cu Clusters in a Metal-Organic Framework

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Abstract

One reason that metal nanoparticles encapsulated in metal-organic frameworks are of interest is that confinement effects on the particle size and shape may lead to superior catalytic activity. The interior of a metal-organic framework has the potential to influence nucleation and aggregation of metal nanoparticles and to strongly affect their in situ shape and electronic properties. We apply density functional theory and ab initio molecular dynamics (AIMD) to model the nucleation and diffusion of Cun (n = 1-19) clusters on the tetratopic 1,3,6,8-(p-benzoate)pyrene (TBAPy4-) linkers of NU-1000 frameworks. We find that Cu atoms and Cu clusters are stabilized by the TBAPy linker, especially by the edge site of aromatic rings. The stabilization increases when the Cu cluster interacts with two linkers. We identified the most favorable site for Cu cluster adsorption as the window site that connects the c pore and the triangular pore. A Pt atom is found to bind much more strongly than a Cu atom on the TBAPy linker, and AIMD simulations show that this promotes Pt atom diffusion from the center of a Cu15 cluster to the interface between the linker and the cluster. The strong interaction between a Pt atom and a linker is attributed to the greater metal-to-linker charge transfer.

Original languageEnglish (US)
Pages (from-to)26987-26997
Number of pages11
JournalJournal of Physical Chemistry C
Volume122
Issue number47
DOIs
StatePublished - Nov 29 2018

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Metals
Atoms
metals
Metal nanoparticles
atoms
Molecular dynamics
Nucleation
nucleation
molecular dynamics
Benzoates
Pyrene
porosity
nanoparticles
Electronic properties
Density functional theory
pyrenes
Charge transfer
Catalyst activity
Agglomeration
Stabilization

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title = "Organic Linker Effect on the Growth and Diffusion of Cu Clusters in a Metal-Organic Framework",
abstract = "One reason that metal nanoparticles encapsulated in metal-organic frameworks are of interest is that confinement effects on the particle size and shape may lead to superior catalytic activity. The interior of a metal-organic framework has the potential to influence nucleation and aggregation of metal nanoparticles and to strongly affect their in situ shape and electronic properties. We apply density functional theory and ab initio molecular dynamics (AIMD) to model the nucleation and diffusion of Cun (n = 1-19) clusters on the tetratopic 1,3,6,8-(p-benzoate)pyrene (TBAPy4-) linkers of NU-1000 frameworks. We find that Cu atoms and Cu clusters are stabilized by the TBAPy linker, especially by the edge site of aromatic rings. The stabilization increases when the Cu cluster interacts with two linkers. We identified the most favorable site for Cu cluster adsorption as the window site that connects the c pore and the triangular pore. A Pt atom is found to bind much more strongly than a Cu atom on the TBAPy linker, and AIMD simulations show that this promotes Pt atom diffusion from the center of a Cu15 cluster to the interface between the linker and the cluster. The strong interaction between a Pt atom and a linker is attributed to the greater metal-to-linker charge transfer.",
author = "Jingyun Ye and Chris Cramer and Truhlar, {Donald G}",
year = "2018",
month = "11",
day = "29",
doi = "10.1021/acs.jpcc.8b09178",
language = "English (US)",
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TY - JOUR

T1 - Organic Linker Effect on the Growth and Diffusion of Cu Clusters in a Metal-Organic Framework

AU - Ye, Jingyun

AU - Cramer, Chris

AU - Truhlar, Donald G

PY - 2018/11/29

Y1 - 2018/11/29

N2 - One reason that metal nanoparticles encapsulated in metal-organic frameworks are of interest is that confinement effects on the particle size and shape may lead to superior catalytic activity. The interior of a metal-organic framework has the potential to influence nucleation and aggregation of metal nanoparticles and to strongly affect their in situ shape and electronic properties. We apply density functional theory and ab initio molecular dynamics (AIMD) to model the nucleation and diffusion of Cun (n = 1-19) clusters on the tetratopic 1,3,6,8-(p-benzoate)pyrene (TBAPy4-) linkers of NU-1000 frameworks. We find that Cu atoms and Cu clusters are stabilized by the TBAPy linker, especially by the edge site of aromatic rings. The stabilization increases when the Cu cluster interacts with two linkers. We identified the most favorable site for Cu cluster adsorption as the window site that connects the c pore and the triangular pore. A Pt atom is found to bind much more strongly than a Cu atom on the TBAPy linker, and AIMD simulations show that this promotes Pt atom diffusion from the center of a Cu15 cluster to the interface between the linker and the cluster. The strong interaction between a Pt atom and a linker is attributed to the greater metal-to-linker charge transfer.

AB - One reason that metal nanoparticles encapsulated in metal-organic frameworks are of interest is that confinement effects on the particle size and shape may lead to superior catalytic activity. The interior of a metal-organic framework has the potential to influence nucleation and aggregation of metal nanoparticles and to strongly affect their in situ shape and electronic properties. We apply density functional theory and ab initio molecular dynamics (AIMD) to model the nucleation and diffusion of Cun (n = 1-19) clusters on the tetratopic 1,3,6,8-(p-benzoate)pyrene (TBAPy4-) linkers of NU-1000 frameworks. We find that Cu atoms and Cu clusters are stabilized by the TBAPy linker, especially by the edge site of aromatic rings. The stabilization increases when the Cu cluster interacts with two linkers. We identified the most favorable site for Cu cluster adsorption as the window site that connects the c pore and the triangular pore. A Pt atom is found to bind much more strongly than a Cu atom on the TBAPy linker, and AIMD simulations show that this promotes Pt atom diffusion from the center of a Cu15 cluster to the interface between the linker and the cluster. The strong interaction between a Pt atom and a linker is attributed to the greater metal-to-linker charge transfer.

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