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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. In this paper, we demonstrate the saturating reaction of trimethylindium (InMe 3) 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. Finally, we further demonstrate tunable metal loading through controlled number density of the reactive handles (–OH and –OH 2) achieved through node dehydration at elevated temperatures.

Authors:
 [1];  [2];  [3];  [2];  [4];  [5];  [6];  [2];  [3];  [2];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry. Supercomputing Inst. Chemical Theory Center
  3. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  4. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  5. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
Northwestern Univ., Evanston, IL (United States); King Abdulaziz Univ., Jeddah (Saudi Arabia)
OSTI Identifier:
1356617
Grant/Contract Number:  
AC02-06CH11357; SC0012702
Resource Type:
Accepted Manuscript
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:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

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. Thu . "Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition". United States. doi:10.1021/acs.chemmater.5b01560. https://www.osti.gov/servlets/purl/1356617.
@article{osti_1356617,
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. In this paper, we 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. Finally, 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},
number = 13,
volume = 27,
place = {United States},
year = {2015},
month = {7}
}

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