Computational screening of MOF-supported transition metal catalysts for activity and selectivity in ethylene dimerization

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Abstract

Deposition of small metal-oxide clusters on the Zr-based nodes of a metal-organic framework has been demonstrated to provide access to a variety of single-site catalysts. Well-defined catalytic active sites are amenable to detailed computational studies of potential catalytic pathways, and they invite screening a wide range of metals to assess their expected activity. Here we report the application of density functional theory to a variety of transition metals (in particular TiIV, VII, VIV, CrII, CrIII, MnII, MnIV, FeII, FeIII, NiII, CoII, CoIII, CuII, CuIII, PdII, MoII, and WII) supported on NU-1000 inorganometallic nodes to evaluate their activity for ethylene dimerization. We found that the rate-determining step varies between different catalysts, which illustrates the importance of considering more than a single step when comparing catalytic cycles across a variety of metals. Our calculations are consistent with the known good activity of supported NiII for ethylene dimerization, and they predict that CrII and PdII are also potentially useful catalysts for this process. We also screen modifications to the organic linker of NiII-NU-1000 by considering the addition of Me, iPr, tBu, CF3 and NH2 groups to study the influence of sterically demanding and, the case of CF3 and NH2, respectively, electron-donating and -withdrawing, substituents on the activity for ethylene dimerization; we predict no improvements in activity or selectivity (for 1-butene) with such substitutions.

Original languageEnglish (US)
Pages (from-to)160-167
Number of pages8
JournalJournal of Catalysis
Volume360
DOIs
StatePublished - Apr 1 2018

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Dimerization
Catalyst selectivity
dimerization
Transition metals
Catalyst activity
Screening
Ethylene
ethylene
screening
selectivity
Metals
transition metals
catalysts
Catalysts
metals
Butenes
Oxides
Density functional theory
butenes
Substitution reactions

Keywords

  • Density functional theory
  • Ethylene dimerization
  • Linker functionalization
  • Metal-organic framework
  • Transition metal catalysts

Cite this

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title = "Computational screening of MOF-supported transition metal catalysts for activity and selectivity in ethylene dimerization",
abstract = "Deposition of small metal-oxide clusters on the Zr-based nodes of a metal-organic framework has been demonstrated to provide access to a variety of single-site catalysts. Well-defined catalytic active sites are amenable to detailed computational studies of potential catalytic pathways, and they invite screening a wide range of metals to assess their expected activity. Here we report the application of density functional theory to a variety of transition metals (in particular TiIV, VII, VIV, CrII, CrIII, MnII, MnIV, FeII, FeIII, NiII, CoII, CoIII, CuII, CuIII, PdII, MoII, and WII) supported on NU-1000 inorganometallic nodes to evaluate their activity for ethylene dimerization. We found that the rate-determining step varies between different catalysts, which illustrates the importance of considering more than a single step when comparing catalytic cycles across a variety of metals. Our calculations are consistent with the known good activity of supported NiII for ethylene dimerization, and they predict that CrII and PdII are also potentially useful catalysts for this process. We also screen modifications to the organic linker of NiII-NU-1000 by considering the addition of Me, iPr, tBu, CF3 and NH2 groups to study the influence of sterically demanding and, the case of CF3 and NH2, respectively, electron-donating and -withdrawing, substituents on the activity for ethylene dimerization; we predict no improvements in activity or selectivity (for 1-butene) with such substitutions.",
keywords = "Density functional theory, Ethylene dimerization, Linker functionalization, Metal-organic framework, Transition metal catalysts",
author = "Jingyun Ye and Laura Gagliardi and Cramer, {Christopher J.} and Truhlar, {Donald G.}",
year = "2018",
month = "4",
day = "1",
doi = "10.1016/j.jcat.2017.12.007",
language = "English (US)",
volume = "360",
pages = "160--167",
journal = "Journal of Catalysis",
issn = "0021-9517",
publisher = "Academic Press Inc.",

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TY - JOUR

T1 - Computational screening of MOF-supported transition metal catalysts for activity and selectivity in ethylene dimerization

AU - Ye, Jingyun

AU - Gagliardi, Laura

AU - Cramer, Christopher J.

AU - Truhlar, Donald G.

PY - 2018/4/1

Y1 - 2018/4/1

N2 - Deposition of small metal-oxide clusters on the Zr-based nodes of a metal-organic framework has been demonstrated to provide access to a variety of single-site catalysts. Well-defined catalytic active sites are amenable to detailed computational studies of potential catalytic pathways, and they invite screening a wide range of metals to assess their expected activity. Here we report the application of density functional theory to a variety of transition metals (in particular TiIV, VII, VIV, CrII, CrIII, MnII, MnIV, FeII, FeIII, NiII, CoII, CoIII, CuII, CuIII, PdII, MoII, and WII) supported on NU-1000 inorganometallic nodes to evaluate their activity for ethylene dimerization. We found that the rate-determining step varies between different catalysts, which illustrates the importance of considering more than a single step when comparing catalytic cycles across a variety of metals. Our calculations are consistent with the known good activity of supported NiII for ethylene dimerization, and they predict that CrII and PdII are also potentially useful catalysts for this process. We also screen modifications to the organic linker of NiII-NU-1000 by considering the addition of Me, iPr, tBu, CF3 and NH2 groups to study the influence of sterically demanding and, the case of CF3 and NH2, respectively, electron-donating and -withdrawing, substituents on the activity for ethylene dimerization; we predict no improvements in activity or selectivity (for 1-butene) with such substitutions.

AB - Deposition of small metal-oxide clusters on the Zr-based nodes of a metal-organic framework has been demonstrated to provide access to a variety of single-site catalysts. Well-defined catalytic active sites are amenable to detailed computational studies of potential catalytic pathways, and they invite screening a wide range of metals to assess their expected activity. Here we report the application of density functional theory to a variety of transition metals (in particular TiIV, VII, VIV, CrII, CrIII, MnII, MnIV, FeII, FeIII, NiII, CoII, CoIII, CuII, CuIII, PdII, MoII, and WII) supported on NU-1000 inorganometallic nodes to evaluate their activity for ethylene dimerization. We found that the rate-determining step varies between different catalysts, which illustrates the importance of considering more than a single step when comparing catalytic cycles across a variety of metals. Our calculations are consistent with the known good activity of supported NiII for ethylene dimerization, and they predict that CrII and PdII are also potentially useful catalysts for this process. We also screen modifications to the organic linker of NiII-NU-1000 by considering the addition of Me, iPr, tBu, CF3 and NH2 groups to study the influence of sterically demanding and, the case of CF3 and NH2, respectively, electron-donating and -withdrawing, substituents on the activity for ethylene dimerization; we predict no improvements in activity or selectivity (for 1-butene) with such substitutions.

KW - Density functional theory

KW - Ethylene dimerization

KW - Linker functionalization

KW - Metal-organic framework

KW - Transition metal catalysts

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U2 - 10.1016/j.jcat.2017.12.007

DO - 10.1016/j.jcat.2017.12.007

M3 - Article

VL - 360

SP - 160

EP - 167

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -