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:

Webber, Thomas E.  ^[1];

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Liu, Wei-Guang  ^[2];

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Desai, Sai Puneet ^[1]; Lu, Connie C.  ^[1];

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Truhlar, Donald G.  ^[2];

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Penn, R. Lee  ^[1]

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+ Show Author Affiliations

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:

2017-11-01

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)