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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 featuring mesoporous channels, has been post-synthetically metalated via atomic layer deposition in MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe2iOPr]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. As a result, the catalytic performance of Al-NU-1000 has been benchmarked against γ-Al2O3, with promising results in terms of selectivity.

Authors:
ORCiD logo [1];  [2];  [2];  [3]; ORCiD logo [4]; ORCiD logo [4];  [4];  [3];  [4]; ORCiD logo [5];  [4]; ORCiD logo [2]; ORCiD logo [2];  [1]; ORCiD logo [6]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); TU Munchen, Garching (Germany)
  6. Northwestern Univ., Evanston, IL (United States); King Abdulaziz Univ., Jeddah (Saudi Arabia)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1356822
Grant/Contract Number:  
AC02-06CH11357; SC0012702
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 3; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alumina; aluminum; ethanol dehydration; metal-organic framework; atomic layer deposition

Citation Formats

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., and Farha, Omar K. Atomic layer deposition in a metal–organic framework: Synthesis, characterization, and performance of a solid acid. United States: N. p., 2017. Web. doi: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. United States. 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., and Farha, Omar K. Thu . "Atomic layer deposition in a metal–organic framework: Synthesis, characterization, and performance of a solid acid". United States. https://doi.org/10.1021/acs.chemmater.6b03880. https://www.osti.gov/servlets/purl/1356822.
@article{osti_1356822,
title = {Atomic layer deposition in a metal–organic framework: Synthesis, characterization, and performance of a solid acid},
author = {Rimoldi, Martino and Bernales, Varinia and Borycz, Joshua and Vjunov, Aleksei 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 Gagliardi, Laura and Hupp, Joseph T. and Farha, Omar K.},
abstractNote = {NU-1000, a zirconium-based metal-organic framework featuring mesoporous channels, has been post-synthetically metalated via atomic layer deposition in MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe2iOPr]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. As a result, the catalytic performance of Al-NU-1000 has been benchmarked against γ-Al2O3, with promising results in terms of selectivity.},
doi = {10.1021/acs.chemmater.6b03880},
journal = {Chemistry of Materials},
number = 3,
volume = 29,
place = {United States},
year = {Thu Jan 05 00:00:00 EST 2017},
month = {Thu Jan 05 00:00:00 EST 2017}
}

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