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 Gagliardi, Joseph T. Hupp, Omar K. Farha

Research output: Contribution to journalArticle

20 Citations (Scopus)

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 languageEnglish (US)
Pages (from-to)1058-1068
Number of pages11
JournalChemistry of Materials
Volume29
Issue number3
DOIs
StatePublished - Feb 14 2017

Fingerprint

Atomic layer deposition
Aluminum
Metals
Acids
Aluminum Oxide
Density functional theory
Zirconium
Oxides

Cite this

Rimoldi, M., Bernales, V., Borycz, J., Vjunov, A., Gallington, L. C., Platero-Prats, A. E., ... 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

Atomic Layer Deposition in a Metal-Organic Framework : Synthesis, Characterization, and Performance of a Solid Acid. / Rimoldi, Martino; Bernales, Varinia; Borycz, Joshua; Vjunov, Aleksei; Gallington, Leighanne C.; Platero-Prats, Ana E.; Kim, I. S.; Fulton, John L.; Martinson, A. B F; Lercher, Johannes A.; Chapman, Karena W.; Cramer, Christopher J.; Gagliardi, Laura; Hupp, Joseph T.; Farha, Omar K.

In: Chemistry of Materials, Vol. 29, No. 3, 14.02.2017, p. 1058-1068.

Research output: Contribution to journalArticle

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, Gagliardi, 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
Rimoldi, Martino ; Bernales, Varinia ; Borycz, Joshua ; Vjunov, Aleksei ; Gallington, Leighanne C. ; Platero-Prats, Ana E. ; Kim, I. S. ; Fulton, John L. ; Martinson, A. B F ; Lercher, Johannes A. ; Chapman, Karena W. ; Cramer, Christopher J. ; Gagliardi, Laura ; Hupp, Joseph T. ; Farha, Omar K. / Atomic Layer Deposition in a Metal-Organic Framework : Synthesis, Characterization, and Performance of a Solid Acid. In: Chemistry of Materials. 2017 ; Vol. 29, No. 3. pp. 1058-1068.
@article{e09704053c89469f855bbf87efcf34d6,
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 Gagliardi and Hupp, {Joseph T.} and Farha, {Omar K.}",
year = "2017",
month = "2",
day = "14",
doi = "10.1021/acs.chemmater.6b03880",
language = "English (US)",
volume = "29",
pages = "1058--1068",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "3",

}

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 - Gagliardi, 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.

UR - http://www.scopus.com/inward/record.url?scp=85012994933&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85012994933&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.6b03880

DO - 10.1021/acs.chemmater.6b03880

M3 - Article

VL - 29

SP - 1058

EP - 1068

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 3

ER -