Synthesis and characterization of tetrairidium clusters in the metal organic framework UiO-67: Catalyst for ethylene hydrogenation

Dong Yang; Carlo Alberto Gaggioli; Edward Conley; Melike Babucci; Laura Gagliardi; Bruce C. Gates

doi:10.1016/j.jcat.2019.11.031

Synthesis and characterization of tetrairidium clusters in the metal organic framework UiO-67: Catalyst for ethylene hydrogenation

Dong Yang, Carlo Alberto Gaggioli, Edward Conley, Melike Babucci, Laura Gagliardi, Bruce C. Gates

Chemistry (Twin Cities)

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

26 Scopus citations

Abstract

Clusters that are well approximated as tetrairidium were synthesized from Ir(C₂H₄)₂ complexes anchored to the Zr₆O₈ nodes of the metal organic framework (MOF) UiO-67 by treatment in H₂ at 353 K. The conversion taking place within the porous MOF structure was monitored by infrared and X-ray absorption spectroscopies, which provide evidence of tetrairidium clusters formed from the mononuclear precursors. The supported clusters were tested in a flow reactor as catalysts for ethylene conversion at 298 K and atmospheric pressure with a 1:1 M feed ratio of H₂ to ethylene. The results show that the turnover frequency (per Ir atom) characterizing the clusters is twice that of the mononuclear iridium complexes, with both catalysts being active for hydrogenation and dimerization and the clusters being less selective than the complexes for dimerization. Density functional theory calculations of the reaction energetics are in good accord with experiment, showing that the rate-determining step for the hydrogenation on the isolated iridium complexes is the H₂ activation on iridium, whereas the hydrogenation of an iridium-bound ethyl ligand is rate determining for the cluster.

Original language	English (US)
Pages (from-to)	165-172
Number of pages	8
Journal	Journal of Catalysis
Volume	382
DOIs	https://doi.org/10.1016/j.jcat.2019.11.031
State	Published - Feb 2020

Bibliographical note

Funding Information:
This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (DE-SC0012702). We gratefully acknowledge beam time at Beamline 2-2 at the Stanford Synchrotron Radiation Lightsource supported by the DOE Division of Materials Sciences under Contract No. DE-AC02-76SF00515. We thank the beamline scientists, Nebojsa Marinkovic and Syed Khalid, for valuable support. The computations were performed at the Minnesota Supercomputing Institute.

Funding Information:
This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE) , Office of Science, Basic Energy Sciences ( DE-SC0012702 ). We gratefully acknowledge beam time at Beamline 2-2 at the Stanford Synchrotron Radiation Lightsource supported by the DOE Division of Materials Sciences under Contract No. DE-AC02-76SF00515 . We thank the beamline scientists, Nebojsa Marinkovic and Syed Khalid, for valuable support. The computations were performed at the Minnesota Supercomputing Institute. Appendix A

Publisher Copyright:
© 2019 Elsevier Inc.

Keywords

Density functional theory
Ethylene hydrogenation
Iridium clusters
Metal organic framework
X-ray absorption spectroscopy

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10.1016/j.jcat.2019.11.031

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@article{3b8cc1505d8f4d1ca0f04d09b3183500,

title = "Synthesis and characterization of tetrairidium clusters in the metal organic framework UiO-67: Catalyst for ethylene hydrogenation",

abstract = "Clusters that are well approximated as tetrairidium were synthesized from Ir(C2H4)2 complexes anchored to the Zr6O8 nodes of the metal organic framework (MOF) UiO-67 by treatment in H2 at 353 K. The conversion taking place within the porous MOF structure was monitored by infrared and X-ray absorption spectroscopies, which provide evidence of tetrairidium clusters formed from the mononuclear precursors. The supported clusters were tested in a flow reactor as catalysts for ethylene conversion at 298 K and atmospheric pressure with a 1:1 M feed ratio of H2 to ethylene. The results show that the turnover frequency (per Ir atom) characterizing the clusters is twice that of the mononuclear iridium complexes, with both catalysts being active for hydrogenation and dimerization and the clusters being less selective than the complexes for dimerization. Density functional theory calculations of the reaction energetics are in good accord with experiment, showing that the rate-determining step for the hydrogenation on the isolated iridium complexes is the H2 activation on iridium, whereas the hydrogenation of an iridium-bound ethyl ligand is rate determining for the cluster.",

keywords = "Density functional theory, Ethylene hydrogenation, Iridium clusters, Metal organic framework, X-ray absorption spectroscopy",

author = "Dong Yang and Gaggioli, {Carlo Alberto} and Edward Conley and Melike Babucci and Laura Gagliardi and Gates, {Bruce C.}",

note = "Funding Information: This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (DE-SC0012702). We gratefully acknowledge beam time at Beamline 2-2 at the Stanford Synchrotron Radiation Lightsource supported by the DOE Division of Materials Sciences under Contract No. DE-AC02-76SF00515. We thank the beamline scientists, Nebojsa Marinkovic and Syed Khalid, for valuable support. The computations were performed at the Minnesota Supercomputing Institute. Funding Information: This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE) , Office of Science, Basic Energy Sciences ( DE-SC0012702 ). We gratefully acknowledge beam time at Beamline 2-2 at the Stanford Synchrotron Radiation Lightsource supported by the DOE Division of Materials Sciences under Contract No. DE-AC02-76SF00515 . We thank the beamline scientists, Nebojsa Marinkovic and Syed Khalid, for valuable support. The computations were performed at the Minnesota Supercomputing Institute. Appendix A Publisher Copyright: {\textcopyright} 2019 Elsevier Inc.",

year = "2020",

month = feb,

doi = "10.1016/j.jcat.2019.11.031",

language = "English (US)",

volume = "382",

pages = "165--172",

journal = "Journal of Catalysis",

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TY - JOUR

T1 - Synthesis and characterization of tetrairidium clusters in the metal organic framework UiO-67

T2 - Catalyst for ethylene hydrogenation

AU - Yang, Dong

AU - Gaggioli, Carlo Alberto

AU - Conley, Edward

AU - Babucci, Melike

AU - Gagliardi, Laura

AU - Gates, Bruce C.

N1 - Funding Information: This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (DE-SC0012702). We gratefully acknowledge beam time at Beamline 2-2 at the Stanford Synchrotron Radiation Lightsource supported by the DOE Division of Materials Sciences under Contract No. DE-AC02-76SF00515. We thank the beamline scientists, Nebojsa Marinkovic and Syed Khalid, for valuable support. The computations were performed at the Minnesota Supercomputing Institute. Funding Information: This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE) , Office of Science, Basic Energy Sciences ( DE-SC0012702 ). We gratefully acknowledge beam time at Beamline 2-2 at the Stanford Synchrotron Radiation Lightsource supported by the DOE Division of Materials Sciences under Contract No. DE-AC02-76SF00515 . We thank the beamline scientists, Nebojsa Marinkovic and Syed Khalid, for valuable support. The computations were performed at the Minnesota Supercomputing Institute. Appendix A Publisher Copyright: © 2019 Elsevier Inc.

PY - 2020/2

Y1 - 2020/2

N2 - Clusters that are well approximated as tetrairidium were synthesized from Ir(C2H4)2 complexes anchored to the Zr6O8 nodes of the metal organic framework (MOF) UiO-67 by treatment in H2 at 353 K. The conversion taking place within the porous MOF structure was monitored by infrared and X-ray absorption spectroscopies, which provide evidence of tetrairidium clusters formed from the mononuclear precursors. The supported clusters were tested in a flow reactor as catalysts for ethylene conversion at 298 K and atmospheric pressure with a 1:1 M feed ratio of H2 to ethylene. The results show that the turnover frequency (per Ir atom) characterizing the clusters is twice that of the mononuclear iridium complexes, with both catalysts being active for hydrogenation and dimerization and the clusters being less selective than the complexes for dimerization. Density functional theory calculations of the reaction energetics are in good accord with experiment, showing that the rate-determining step for the hydrogenation on the isolated iridium complexes is the H2 activation on iridium, whereas the hydrogenation of an iridium-bound ethyl ligand is rate determining for the cluster.

AB - Clusters that are well approximated as tetrairidium were synthesized from Ir(C2H4)2 complexes anchored to the Zr6O8 nodes of the metal organic framework (MOF) UiO-67 by treatment in H2 at 353 K. The conversion taking place within the porous MOF structure was monitored by infrared and X-ray absorption spectroscopies, which provide evidence of tetrairidium clusters formed from the mononuclear precursors. The supported clusters were tested in a flow reactor as catalysts for ethylene conversion at 298 K and atmospheric pressure with a 1:1 M feed ratio of H2 to ethylene. The results show that the turnover frequency (per Ir atom) characterizing the clusters is twice that of the mononuclear iridium complexes, with both catalysts being active for hydrogenation and dimerization and the clusters being less selective than the complexes for dimerization. Density functional theory calculations of the reaction energetics are in good accord with experiment, showing that the rate-determining step for the hydrogenation on the isolated iridium complexes is the H2 activation on iridium, whereas the hydrogenation of an iridium-bound ethyl ligand is rate determining for the cluster.

KW - Density functional theory

KW - Ethylene hydrogenation

KW - Iridium clusters

KW - Metal organic framework

KW - X-ray absorption spectroscopy

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JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Synthesis and characterization of tetrairidium clusters in the metal organic framework UiO-67: Catalyst for ethylene hydrogenation

Abstract

Bibliographical note

Keywords

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