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Title: Structural reversibility of Cu doped NU-1000 MOFs under hydrogenation conditions

Abstract

The metal-organic framework (MOF), NU-1000, and its metalated counterparts have found proof-of-concept application in heterogeneous catalysis and hydrogen storage amongst others. A vapor-phase technique, akin to atomic layer deposition (ALD), is used to selectively deposit divalent Cu ions on oxo, hydroxo-bridged hexa-zirconium(IV) nodes capped with terminal –OH and -OH2 ligands. Subsequent reaction with steam yields node-anchored, CuII-oxo,hydroxo clusters. We find that cluster installation via AIM (= ALD In MOFs) is accompanied by an expansion of MOF mesopore (channel) diameter . We investigated the behavior of the cluster-modified material, termed Cu-AIM-NU-1000, to heat treatment up to 325 °C, at atmospheric pressure with a low flow of H2 into the reaction cell. The response under these conditions revealed two important results: (1) Above 200 °C, the initially installed few-metal-ion clusters reduce to neutral Cu atoms. The neutral atoms migrate from the nodes and aggregate into Cu nanoparticles. While the size of particles formed in the MOF interior is constrained by the width of mesopores (ca. 3 nm), those formed on the exterior surface of the MOF can grow as large as ca. 8 nm. (2) Reduction and release of Cu atoms from the MOFs nodes is accompanied NU-1000 undergoes dynamic structural transformationmore » as it reverts back to its original dimension following the release. These results show while the MOF framework itself remains intact at 325 °C in an H2 atmosphere, the small, AIM-installed CuII-oxo,hydroxo clusters are stable with respect to reduction and conversion to metallic nanoparticles only up to ~200 °C.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [1];  [3];  [4]; ORCiD logo [4];  [4]; ORCiD logo [4]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Univ. of Chicago, IL (United States); Czech Academy of Sciences, Prague (Czech Republic). Dept. of Nanocatalysis, J. Heyrovský Inst. of Physical Chemistry
  4. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1603347
Alternate Identifier(s):
OSTI ID: 1601316
Grant/Contract Number:  
AC02-06CH11357; SC0012702
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Atomic layer deposition; Crystalline solids; Catalysis; Ions and properties; X-ray absorption spectroscopy; Nanoparticles; X-ray scattering

Citation Formats

Halder, Avik, Lee, Sungsik, Yang, Bing, Pellin, Michael J., Vajda, Stefan, Li, Zhanyong, Yang, Ying, Farha, Omar K., and Hupp, Joseph T.. Structural reversibility of Cu doped NU-1000 MOFs under hydrogenation conditions. United States: N. p., 2020. Web. https://doi.org/10.1063/1.5130600.
Halder, Avik, Lee, Sungsik, Yang, Bing, Pellin, Michael J., Vajda, Stefan, Li, Zhanyong, Yang, Ying, Farha, Omar K., & Hupp, Joseph T.. Structural reversibility of Cu doped NU-1000 MOFs under hydrogenation conditions. United States. https://doi.org/10.1063/1.5130600
Halder, Avik, Lee, Sungsik, Yang, Bing, Pellin, Michael J., Vajda, Stefan, Li, Zhanyong, Yang, Ying, Farha, Omar K., and Hupp, Joseph T.. Mon . "Structural reversibility of Cu doped NU-1000 MOFs under hydrogenation conditions". United States. https://doi.org/10.1063/1.5130600. https://www.osti.gov/servlets/purl/1603347.
@article{osti_1603347,
title = {Structural reversibility of Cu doped NU-1000 MOFs under hydrogenation conditions},
author = {Halder, Avik and Lee, Sungsik and Yang, Bing and Pellin, Michael J. and Vajda, Stefan and Li, Zhanyong and Yang, Ying and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {The metal-organic framework (MOF), NU-1000, and its metalated counterparts have found proof-of-concept application in heterogeneous catalysis and hydrogen storage amongst others. A vapor-phase technique, akin to atomic layer deposition (ALD), is used to selectively deposit divalent Cu ions on oxo, hydroxo-bridged hexa-zirconium(IV) nodes capped with terminal –OH and -OH2 ligands. Subsequent reaction with steam yields node-anchored, CuII-oxo,hydroxo clusters. We find that cluster installation via AIM (= ALD In MOFs) is accompanied by an expansion of MOF mesopore (channel) diameter . We investigated the behavior of the cluster-modified material, termed Cu-AIM-NU-1000, to heat treatment up to 325 °C, at atmospheric pressure with a low flow of H2 into the reaction cell. The response under these conditions revealed two important results: (1) Above 200 °C, the initially installed few-metal-ion clusters reduce to neutral Cu atoms. The neutral atoms migrate from the nodes and aggregate into Cu nanoparticles. While the size of particles formed in the MOF interior is constrained by the width of mesopores (ca. 3 nm), those formed on the exterior surface of the MOF can grow as large as ca. 8 nm. (2) Reduction and release of Cu atoms from the MOFs nodes is accompanied NU-1000 undergoes dynamic structural transformation as it reverts back to its original dimension following the release. These results show while the MOF framework itself remains intact at 325 °C in an H2 atmosphere, the small, AIM-installed CuII-oxo,hydroxo clusters are stable with respect to reduction and conversion to metallic nanoparticles only up to ~200 °C.},
doi = {10.1063/1.5130600},
journal = {Journal of Chemical Physics},
number = 8,
volume = 152,
place = {United States},
year = {2020},
month = {2}
}

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