Tuning the properties of metal-organic framework nodes as supports of single-site iridium catalysts: Node modification by atomic layer deposition of aluminium

Dong Yang; Mohammad R. Momeni; Hakan Demir; Dale R. Pahls; Martino Rimoldi; Timothy C. Wang; Omar K. Farha; Joseph T. Hupp; Christopher J. Cramer; Bruce C. Gates; Laura Gagliardi

doi:10.1039/c7fd00031f

Tuning the properties of metal-organic framework nodes as supports of single-site iridium catalysts: Node modification by atomic layer deposition of aluminium

Dong Yang, Mohammad R. Momeni, Hakan Demir, Dale R. Pahls, Martino Rimoldi, Timothy C. Wang, Omar K. Farha, Joseph T. Hupp, Christopher J. Cramer, Bruce C. Gates^*, Laura Gagliardi

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Review article › peer-review

31 Scopus citations

Abstract

The metal-organic framework NU-1000, with Zr₆-oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al(iii) ions by ALD-like chemistry with [Al(CH₃)₂(iso-propoxide)]₂ followed by steam (ALD = atomic layer deposition). Al ions were installed to the extent of approximately 7 per node. Single-site iridium diethylene complexes were anchored to the nodes of the modified and unmodified MOFs by reaction with Ir(C₂H₄)₂(acac) (acac = acetylacetonate) and converted to Ir(CO)₂ complexes by treatment with CO. Infrared spectra of these supported complexes show that incorporation of Al weakened the electron donor tendency of the MOF. Correspondingly, the catalytic activity of the initial supported iridium complexes for ethylene hydrogenation increased, as did the selectivity for ethylene dimerization. The results of density functional theory calculations with a simplified model of the nodes incorporating Al(iii) ions are in qualitative agreement with some catalyst performance data.

Original language	English (US)
Pages (from-to)	195-206
Number of pages	12
Journal	Faraday Discussions
Volume	201
DOIs	https://doi.org/10.1039/c7fd00031f
State	Published - 2017

Funding

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, Office of Science, Basic Energy Sciences, under Award DE-SC0012702.

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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10.1039/c7fd00031f

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Yang, D., Momeni, M. R., Demir, H., Pahls, D. R., Rimoldi, M., Wang, T. C., Farha, O. K., Hupp, J. T., Cramer, C. J., Gates, B. C., & Gagliardi, L. (2017). Tuning the properties of metal-organic framework nodes as supports of single-site iridium catalysts: Node modification by atomic layer deposition of aluminium. Faraday Discussions, 201, 195-206. https://doi.org/10.1039/c7fd00031f

@article{1550fcaecfc34a0199023a64e0ae291e,

title = "Tuning the properties of metal-organic framework nodes as supports of single-site iridium catalysts: Node modification by atomic layer deposition of aluminium",

abstract = "The metal-organic framework NU-1000, with Zr6-oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al(iii) ions by ALD-like chemistry with [Al(CH3)2(iso-propoxide)]2 followed by steam (ALD = atomic layer deposition). Al ions were installed to the extent of approximately 7 per node. Single-site iridium diethylene complexes were anchored to the nodes of the modified and unmodified MOFs by reaction with Ir(C2H4)2(acac) (acac = acetylacetonate) and converted to Ir(CO)2 complexes by treatment with CO. Infrared spectra of these supported complexes show that incorporation of Al weakened the electron donor tendency of the MOF. Correspondingly, the catalytic activity of the initial supported iridium complexes for ethylene hydrogenation increased, as did the selectivity for ethylene dimerization. The results of density functional theory calculations with a simplified model of the nodes incorporating Al(iii) ions are in qualitative agreement with some catalyst performance data.",

author = "Dong Yang and Momeni, {Mohammad R.} and Hakan Demir and Pahls, {Dale R.} and Martino Rimoldi and Wang, {Timothy C.} and Farha, {Omar K.} and Hupp, {Joseph T.} and Cramer, {Christopher J.} and Gates, {Bruce C.} and Laura Gagliardi",

note = "Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

year = "2017",

doi = "10.1039/c7fd00031f",

language = "English (US)",

volume = "201",

pages = "195--206",

journal = "Faraday Discussions",

issn = "1359-6640",

publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Tuning the properties of metal-organic framework nodes as supports of single-site iridium catalysts

T2 - Node modification by atomic layer deposition of aluminium

AU - Yang, Dong

AU - Momeni, Mohammad R.

AU - Demir, Hakan

AU - Pahls, Dale R.

AU - Rimoldi, Martino

AU - Wang, Timothy C.

AU - Farha, Omar K.

AU - Hupp, Joseph T.

AU - Cramer, Christopher J.

AU - Gates, Bruce C.

AU - Gagliardi, Laura

PY - 2017

Y1 - 2017

N2 - The metal-organic framework NU-1000, with Zr6-oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al(iii) ions by ALD-like chemistry with [Al(CH3)2(iso-propoxide)]2 followed by steam (ALD = atomic layer deposition). Al ions were installed to the extent of approximately 7 per node. Single-site iridium diethylene complexes were anchored to the nodes of the modified and unmodified MOFs by reaction with Ir(C2H4)2(acac) (acac = acetylacetonate) and converted to Ir(CO)2 complexes by treatment with CO. Infrared spectra of these supported complexes show that incorporation of Al weakened the electron donor tendency of the MOF. Correspondingly, the catalytic activity of the initial supported iridium complexes for ethylene hydrogenation increased, as did the selectivity for ethylene dimerization. The results of density functional theory calculations with a simplified model of the nodes incorporating Al(iii) ions are in qualitative agreement with some catalyst performance data.

AB - The metal-organic framework NU-1000, with Zr6-oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al(iii) ions by ALD-like chemistry with [Al(CH3)2(iso-propoxide)]2 followed by steam (ALD = atomic layer deposition). Al ions were installed to the extent of approximately 7 per node. Single-site iridium diethylene complexes were anchored to the nodes of the modified and unmodified MOFs by reaction with Ir(C2H4)2(acac) (acac = acetylacetonate) and converted to Ir(CO)2 complexes by treatment with CO. Infrared spectra of these supported complexes show that incorporation of Al weakened the electron donor tendency of the MOF. Correspondingly, the catalytic activity of the initial supported iridium complexes for ethylene hydrogenation increased, as did the selectivity for ethylene dimerization. The results of density functional theory calculations with a simplified model of the nodes incorporating Al(iii) ions are in qualitative agreement with some catalyst performance data.

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JO - Faraday Discussions

JF - Faraday Discussions

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Tuning the properties of metal-organic framework nodes as supports of single-site iridium catalysts: Node modification by atomic layer deposition of aluminium

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