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Title: Role of a Modulator in the Synthesis of Phase-Pure NU-1000

Abstract

NU-1000 is a robust, mesoporous metal–organic framework (MOF) with hexazirconium nodes ([Zr6O16H16]8+, referred to as oxo–Zr6 nodes) that can be synthesized by combining a solution of ZrOCl2·8H2O and a benzoic acid modulator in N,N-dimethylformamide with a solution of linker (1,3,6,8-tetrakis(p-benzoic acid)pyrene, referred to as H4TBAPy) and by aging at an elevated temperature. Typically, the resulting crystals are primarily composed of NU-1000 domains that crystallize with a more dense phase that shares structural similarity with NU-901, which is an MOF composed of the same linker molecules and nodes. Density differences between the two polymorphs arise from the differences in the node orientation: in NU-1000, the oxo–Zr6 nodes rotate 120° from node to node, whereas in NU-901, all nodes are aligned in parallel. Considering this structural difference leads to the hypothesis that changing the modulator from benzoic acid to a larger and more rigid biphenyl-4-carboxylic acid might lead to a stronger steric interaction between the modulator coordinating on the oxo–Zr6 node and misaligned nodes or linkers in the large pore and inhibit the growth of the more dense NU-901-like material, resulting in phase-pure NU-1000. Side-by-side reactions comparing the products of synthesis using benzoic acid or biphenyl-4-carboxylic acid as a modulator produce structurallymore » heterogeneous crystals and phase-pure NU-1000 crystals. It can be concluded that the larger and more rigid biphenyl-4-carboxylate inhibits the incorporation of nodes with an alignment parallel to the neighboring nodes already residing in the crystal.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, and Chemical Theory Center and Minnesota Supercomputing Inst.
Publication Date:
Research Org.:
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:
1470050
Grant/Contract Number:  
SC0012702
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 45; Related Information: ICDC partners with University of Minnesota(lead); Argonne National Laboratory; Clemson University; Dow Chemical Company; Northwestern University; Pacific Northwest National Laboratory; University of California Davis; University of Washington; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); materials and chemistry by design; synthesis (novel materials)

Citation Formats

Webber, Thomas E., Liu, Wei-Guang, Desai, Sai Puneet, Lu, Connie C., Truhlar, Donald G., and Penn, R. Lee. Role of a Modulator in the Synthesis of Phase-Pure NU-1000. United States: N. p., 2017. Web. https://doi.org/10.1021/acsami.7b11348.
Webber, Thomas E., Liu, Wei-Guang, Desai, Sai Puneet, Lu, Connie C., Truhlar, Donald G., & Penn, R. Lee. Role of a Modulator in the Synthesis of Phase-Pure NU-1000. United States. https://doi.org/10.1021/acsami.7b11348
Webber, Thomas E., Liu, Wei-Guang, Desai, Sai Puneet, Lu, Connie C., Truhlar, Donald G., and Penn, R. Lee. Wed . "Role of a Modulator in the Synthesis of Phase-Pure NU-1000". United States. https://doi.org/10.1021/acsami.7b11348. https://www.osti.gov/servlets/purl/1470050.
@article{osti_1470050,
title = {Role of a Modulator in the Synthesis of Phase-Pure NU-1000},
author = {Webber, Thomas E. and Liu, Wei-Guang and Desai, Sai Puneet and Lu, Connie C. and Truhlar, Donald G. and Penn, R. Lee},
abstractNote = {NU-1000 is a robust, mesoporous metal–organic framework (MOF) with hexazirconium nodes ([Zr6O16H16]8+, referred to as oxo–Zr6 nodes) that can be synthesized by combining a solution of ZrOCl2·8H2O and a benzoic acid modulator in N,N-dimethylformamide with a solution of linker (1,3,6,8-tetrakis(p-benzoic acid)pyrene, referred to as H4TBAPy) and by aging at an elevated temperature. Typically, the resulting crystals are primarily composed of NU-1000 domains that crystallize with a more dense phase that shares structural similarity with NU-901, which is an MOF composed of the same linker molecules and nodes. Density differences between the two polymorphs arise from the differences in the node orientation: in NU-1000, the oxo–Zr6 nodes rotate 120° from node to node, whereas in NU-901, all nodes are aligned in parallel. Considering this structural difference leads to the hypothesis that changing the modulator from benzoic acid to a larger and more rigid biphenyl-4-carboxylic acid might lead to a stronger steric interaction between the modulator coordinating on the oxo–Zr6 node and misaligned nodes or linkers in the large pore and inhibit the growth of the more dense NU-901-like material, resulting in phase-pure NU-1000. Side-by-side reactions comparing the products of synthesis using benzoic acid or biphenyl-4-carboxylic acid as a modulator produce structurally heterogeneous crystals and phase-pure NU-1000 crystals. It can be concluded that the larger and more rigid biphenyl-4-carboxylate inhibits the incorporation of nodes with an alignment parallel to the neighboring nodes already residing in the crystal.},
doi = {10.1021/acsami.7b11348},
journal = {ACS Applied Materials and Interfaces},
number = 45,
volume = 9,
place = {United States},
year = {2017},
month = {11}
}

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