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Title: Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition

Abstract

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. We here demonstrate the saturating reaction of trimethylindium (InMe3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOF node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. We further demonstrate tunable metal loading through controlled number density of the reactive handles (-OH and -OH2) achieved through node dehydration at elevated temperatures.

Authors:
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Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1391834
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 27; Journal Issue: 13; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
atomic layer deposition in MOF; catalysis; metal organic framework; post-synthetic modification

Citation Formats

Kim, In Soo, Borycz, Joshua, Platero-Prats, Ana E., Tussupbayev, Samat, Wang, Timothy C., Farha, Omar K., Hupp, Joseph T., Gagliardi, Laura, Chapman, Karena W., Cramer, Christopher J., and Martinson, Alex B. F. Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition. United States: N. p., 2015. Web. doi:10.1021/acs.chemmater.5b01560.
Kim, In Soo, Borycz, Joshua, Platero-Prats, Ana E., Tussupbayev, Samat, Wang, Timothy C., Farha, Omar K., Hupp, Joseph T., Gagliardi, Laura, Chapman, Karena W., Cramer, Christopher J., & Martinson, Alex B. F. Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition. United States. doi:10.1021/acs.chemmater.5b01560.
Kim, In Soo, Borycz, Joshua, Platero-Prats, Ana E., Tussupbayev, Samat, Wang, Timothy C., Farha, Omar K., Hupp, Joseph T., Gagliardi, Laura, Chapman, Karena W., Cramer, Christopher J., and Martinson, Alex B. F. Tue . "Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition". United States. doi:10.1021/acs.chemmater.5b01560.
@article{osti_1391834,
title = {Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition},
author = {Kim, In Soo and Borycz, Joshua and Platero-Prats, Ana E. and Tussupbayev, Samat and Wang, Timothy C. and Farha, Omar K. and Hupp, Joseph T. and Gagliardi, Laura and Chapman, Karena W. and Cramer, Christopher J. and Martinson, Alex B. F.},
abstractNote = {Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. We here demonstrate the saturating reaction of trimethylindium (InMe3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOF node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. We further demonstrate tunable metal loading through controlled number density of the reactive handles (-OH and -OH2) achieved through node dehydration at elevated temperatures.},
doi = {10.1021/acs.chemmater.5b01560},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 13,
volume = 27,
place = {United States},
year = {2015},
month = {7}
}

Works referencing / citing this record:

Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015

  • Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng
  • Angewandte Chemie International Edition, Vol. 54, Issue 49
  • DOI: 10.1002/anie.201505625

Assembly of dicobalt and cobalt–aluminum oxide clusters on metal–organic framework and nanocast silica supports
journal, January 2017

  • Desai, Sai Puneet; Malonzo, Camille D.; Webber, Thomas
  • Faraday Discussions, Vol. 201
  • DOI: 10.1039/c7fd00055c