Single Ni atoms and Ni4 clusters have similar catalytic activity for ethylene dimerization

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Abstract

Atomic layer deposition (ALD) of Ni on the metal–organic framework NU-1000 has been shown to generate a material that serves as a catalyst for ethylene dimerization. However, the precise nature of the active catalytic site or sites remains uncertain. Here we employ periodic density functional calculations to characterize the structure and reactivity of the deposited species. Optimized lattice constants for a sequence of structures incorporating successively more Ni4-hydroxo clusters in the c pore of NU-1000 show good agreement with experimental trends involving multiple ALD cycles; therefore we study the catalytic cycle for this cluster in detail, and we compare it to that for a site with only a single Ni atom. We find that both the atomic Ni catalyst and the Ni4-hydroxo cluster have higher catalytic activity in the singlet state than in the triplet state. We also find that the two catalysts have very similar activity. Thus, precise size control of the active catalytic species is not essential for ethylene dimerization in this system.

Original languageEnglish (US)
Pages (from-to)278-286
Number of pages9
JournalJournal of Catalysis
Volume354
DOIs
StatePublished - Jan 1 2017

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Dimerization
dimerization
catalytic activity
Catalyst activity
Ethylene
ethylene
Atomic layer deposition
atomic layer epitaxy
catalysts
Atoms
Catalysts
atoms
cycles
atomic energy levels
Lattice constants
Density functional theory
reactivity
porosity
trends

Keywords

  • Density functional theory
  • Ethylene dimerization
  • Metal−organic framework
  • Ni catalyst

Cite this

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title = "Single Ni atoms and Ni4 clusters have similar catalytic activity for ethylene dimerization",
abstract = "Atomic layer deposition (ALD) of Ni on the metal–organic framework NU-1000 has been shown to generate a material that serves as a catalyst for ethylene dimerization. However, the precise nature of the active catalytic site or sites remains uncertain. Here we employ periodic density functional calculations to characterize the structure and reactivity of the deposited species. Optimized lattice constants for a sequence of structures incorporating successively more Ni4-hydroxo clusters in the c pore of NU-1000 show good agreement with experimental trends involving multiple ALD cycles; therefore we study the catalytic cycle for this cluster in detail, and we compare it to that for a site with only a single Ni atom. We find that both the atomic Ni catalyst and the Ni4-hydroxo cluster have higher catalytic activity in the singlet state than in the triplet state. We also find that the two catalysts have very similar activity. Thus, precise size control of the active catalytic species is not essential for ethylene dimerization in this system.",
keywords = "Density functional theory, Ethylene dimerization, Metal−organic framework, Ni catalyst",
author = "Jingyun Ye and Laura Gagliardi and Cramer, {Christopher J.} and Truhlar, {Donald G.}",
year = "2017",
month = "1",
day = "1",
doi = "10.1016/j.jcat.2017.08.011",
language = "English (US)",
volume = "354",
pages = "278--286",
journal = "Journal of Catalysis",
issn = "0021-9517",
publisher = "Academic Press Inc.",

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TY - JOUR

T1 - Single Ni atoms and Ni4 clusters have similar catalytic activity for ethylene dimerization

AU - Ye, Jingyun

AU - Gagliardi, Laura

AU - Cramer, Christopher J.

AU - Truhlar, Donald G.

PY - 2017/1/1

Y1 - 2017/1/1

N2 - Atomic layer deposition (ALD) of Ni on the metal–organic framework NU-1000 has been shown to generate a material that serves as a catalyst for ethylene dimerization. However, the precise nature of the active catalytic site or sites remains uncertain. Here we employ periodic density functional calculations to characterize the structure and reactivity of the deposited species. Optimized lattice constants for a sequence of structures incorporating successively more Ni4-hydroxo clusters in the c pore of NU-1000 show good agreement with experimental trends involving multiple ALD cycles; therefore we study the catalytic cycle for this cluster in detail, and we compare it to that for a site with only a single Ni atom. We find that both the atomic Ni catalyst and the Ni4-hydroxo cluster have higher catalytic activity in the singlet state than in the triplet state. We also find that the two catalysts have very similar activity. Thus, precise size control of the active catalytic species is not essential for ethylene dimerization in this system.

AB - Atomic layer deposition (ALD) of Ni on the metal–organic framework NU-1000 has been shown to generate a material that serves as a catalyst for ethylene dimerization. However, the precise nature of the active catalytic site or sites remains uncertain. Here we employ periodic density functional calculations to characterize the structure and reactivity of the deposited species. Optimized lattice constants for a sequence of structures incorporating successively more Ni4-hydroxo clusters in the c pore of NU-1000 show good agreement with experimental trends involving multiple ALD cycles; therefore we study the catalytic cycle for this cluster in detail, and we compare it to that for a site with only a single Ni atom. We find that both the atomic Ni catalyst and the Ni4-hydroxo cluster have higher catalytic activity in the singlet state than in the triplet state. We also find that the two catalysts have very similar activity. Thus, precise size control of the active catalytic species is not essential for ethylene dimerization in this system.

KW - Density functional theory

KW - Ethylene dimerization

KW - Metal−organic framework

KW - Ni catalyst

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DO - 10.1016/j.jcat.2017.08.011

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EP - 286

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

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