Atomic Layer Deposition in a Metal-Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid

Martino Rimoldi; Varinia Bernales; Joshua Borycz; Aleksei Vjunov; Leighanne C. Gallington; Ana E. Platero-Prats; I. S. Kim; John L. Fulton; A. B.F. Martinson; Johannes A. Lercher; Karena W. Chapman; Christopher J. Cramer; Laura Gagli; Joseph T. Hupp; Omar K. Farha

doi:10.1021/acs.chemmater.6b03880

Atomic Layer Deposition in a Metal-Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid

Martino Rimoldi, Varinia Bernales, Joshua Borycz, Aleksei Vjunov, Leighanne C. Gallington, Ana E. Platero-Prats, I. S. Kim, John L. Fulton, A. B.F. Martinson, Johannes A. Lercher, Karena W. Chapman, Christopher J. Cramer, Laura Gagli, Joseph T. Hupp, Omar K. Farha

Chemistry

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

46 Scopus citations

Abstract

NU-1000, a zirconium-based metal-organic framework (MOF) featuring mesoporous channels, has been postsynthetically metalated via atomic layer deposition in a MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe₂OⁱPr]₂, DMAI), a milder precursor than widely used trimethylaluminum (AlMe₃, TMA). The aluminum-modified NU-1000 (Al-NU-1000) has been characterized with a comprehensive suite of techniques that points to the formation of aluminum oxide clusters well dispersed through the framework and stabilized by confinement within small pores intrinsic to the NU-1000 structure. Experimental evidence allows for identification of spectroscopic similarities between Al-NU-1000 and γ-Al₂O₃. Density functional theory modeling provides structures and simulated spectra, the relevance of which can be assessed via comparison to experimental IR and EXAFS data. The catalytic performance of Al-NU-1000 has been benchmarked against γ-Al₂O₃, with promising results in terms of selectivity.

Original language	English (US)
Pages (from-to)	1058-1068
Number of pages	11
Journal	Chemistry of Materials
Volume	29
Issue number	3
DOIs	https://doi.org/10.1021/acs.chemmater.6b03880
State	Published - Feb 14 2017

Funding

This work was supported as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-SC0012702. This work made use of the IMSERC facility supported by the National Science Foundation (NSF, DMR-0521267); the J.B. Cohen X-ray Diffraction Facility at the Materials Research Center of NU supported by the MRSEC (NSF, DMR- 1121262); the EPIC facility of the NUANCE Center at NU, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF, NNCI-1542205); the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Metal analysis was performed at the NU Quantitative Bio-element Imaging Center. Gas flow reactions were performed at the NU CleanCat Core facility. A.V., J.L.F., and J.A.L. acknowledge the support by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Work done at Argonne was performed using the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Authors thank Dr. T. Huthwelker for support during Al XAFS measurements at the Swiss Light Source (PSI, Switzerland). M.R. was supported by the Swiss National Science Foundation with an "Early Postdoc.Mobility Fellowship". A.E.P.-P. acknowledges a Beatriu de Pino´s fellowship (BP-DGR 2014) from the Ministry of Economy and Knowledge (Catalan Government).

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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Rimoldi, M., Bernales, V., Borycz, J., Vjunov, A., Gallington, L. C., Platero-Prats, A. E., Kim, I. S., Fulton, J. L., Martinson, A. B. F., Lercher, J. A., Chapman, K. W., Cramer, C. J., Gagli, L., Hupp, J. T., & Farha, O. K. (2017). Atomic Layer Deposition in a Metal-Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid. Chemistry of Materials, 29(3), 1058-1068. https://doi.org/10.1021/acs.chemmater.6b03880

@article{92323241de504828a56c142f517b57c5,

title = "Atomic Layer Deposition in a Metal-Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid",

abstract = "NU-1000, a zirconium-based metal-organic framework (MOF) featuring mesoporous channels, has been postsynthetically metalated via atomic layer deposition in a MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe2OiPr]2, DMAI), a milder precursor than widely used trimethylaluminum (AlMe3, TMA). The aluminum-modified NU-1000 (Al-NU-1000) has been characterized with a comprehensive suite of techniques that points to the formation of aluminum oxide clusters well dispersed through the framework and stabilized by confinement within small pores intrinsic to the NU-1000 structure. Experimental evidence allows for identification of spectroscopic similarities between Al-NU-1000 and γ-Al2O3. Density functional theory modeling provides structures and simulated spectra, the relevance of which can be assessed via comparison to experimental IR and EXAFS data. The catalytic performance of Al-NU-1000 has been benchmarked against γ-Al2O3, with promising results in terms of selectivity.",

author = "Martino Rimoldi and Varinia Bernales and Joshua Borycz and Aleksei Vjunov and Gallington, {Leighanne C.} and Platero-Prats, {Ana E.} and Kim, {I. S.} and Fulton, {John L.} and Martinson, {A. B.F.} and Lercher, {Johannes A.} and Chapman, {Karena W.} and Cramer, {Christopher J.} and Laura Gagli and Hupp, {Joseph T.} and Farha, {Omar K.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.chemmater.6b03880",

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Rimoldi, M, Bernales, V, Borycz, J, Vjunov, A, Gallington, LC, Platero-Prats, AE, Kim, IS, Fulton, JL, Martinson, ABF, Lercher, JA, Chapman, KW, Cramer, CJ, Gagli, L, Hupp, JT & Farha, OK 2017, 'Atomic Layer Deposition in a Metal-Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid', Chemistry of Materials, vol. 29, no. 3, pp. 1058-1068. https://doi.org/10.1021/acs.chemmater.6b03880

TY - JOUR

T1 - Atomic Layer Deposition in a Metal-Organic Framework

T2 - Synthesis, Characterization, and Performance of a Solid Acid

AU - Rimoldi, Martino

AU - Bernales, Varinia

AU - Borycz, Joshua

AU - Vjunov, Aleksei

AU - Gallington, Leighanne C.

AU - Platero-Prats, Ana E.

AU - Kim, I. S.

AU - Fulton, John L.

AU - Martinson, A. B.F.

AU - Lercher, Johannes A.

AU - Chapman, Karena W.

AU - Cramer, Christopher J.

AU - Gagli, Laura

AU - Hupp, Joseph T.

AU - Farha, Omar K.

PY - 2017/2/14

Y1 - 2017/2/14

N2 - NU-1000, a zirconium-based metal-organic framework (MOF) featuring mesoporous channels, has been postsynthetically metalated via atomic layer deposition in a MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe2OiPr]2, DMAI), a milder precursor than widely used trimethylaluminum (AlMe3, TMA). The aluminum-modified NU-1000 (Al-NU-1000) has been characterized with a comprehensive suite of techniques that points to the formation of aluminum oxide clusters well dispersed through the framework and stabilized by confinement within small pores intrinsic to the NU-1000 structure. Experimental evidence allows for identification of spectroscopic similarities between Al-NU-1000 and γ-Al2O3. Density functional theory modeling provides structures and simulated spectra, the relevance of which can be assessed via comparison to experimental IR and EXAFS data. The catalytic performance of Al-NU-1000 has been benchmarked against γ-Al2O3, with promising results in terms of selectivity.

AB - NU-1000, a zirconium-based metal-organic framework (MOF) featuring mesoporous channels, has been postsynthetically metalated via atomic layer deposition in a MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe2OiPr]2, DMAI), a milder precursor than widely used trimethylaluminum (AlMe3, TMA). The aluminum-modified NU-1000 (Al-NU-1000) has been characterized with a comprehensive suite of techniques that points to the formation of aluminum oxide clusters well dispersed through the framework and stabilized by confinement within small pores intrinsic to the NU-1000 structure. Experimental evidence allows for identification of spectroscopic similarities between Al-NU-1000 and γ-Al2O3. Density functional theory modeling provides structures and simulated spectra, the relevance of which can be assessed via comparison to experimental IR and EXAFS data. The catalytic performance of Al-NU-1000 has been benchmarked against γ-Al2O3, with promising results in terms of selectivity.

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Atomic Layer Deposition in a Metal-Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid

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