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Title: A porous, electrically conductive hexa-zirconium(IV) metal–organic framework

Journal Article · · Chemical Science
DOI: https://doi.org/10.1039/c8sc00961a · OSTI ID:1433741
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Northwestern Univ., Evanston, IL (United States); King Abdulaziz Univ., Jeddah (Saudi Arabia)

Engendering electrical conductivity in high-porosity metal–organic frameworks (MOFs) promises to unlock the full potential of MOFs for electrical energy storage, electrocatalysis, or integration of MOFs with conventional electronic materials. Here we report that a porous zirconium-node-containing MOF, NU-901, can be rendered electronically conductive by physically encapsulating C60, an excellent electron acceptor, within a fraction (ca. 60%) of the diamond-shaped cavities of the MOF. The cavities are defined by node-connected tetra-phenyl-carboxylated pyrene linkers, i.e. species that are excellent electron donors. The bulk electrical conductivity of the MOF is shown to increase from immeasurably low to 10-3 S cm-1, following fullerene incorporation. The observed conductivity originates from electron donor–acceptor interactions, i.e. charge-transfer interactions – a conclusion that is supported by density functional theory calculations and by the observation of a charge-transfer-derived band in the electronic absorption spectrum of the hybrid material. Notably, the conductive version of the MOF retains substantial nanoscale porosity and continues to display a sizable internal surface area, suggesting potential future applications that capitalize on the ability of the material to sorb molecular species.

Research Organization:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
SC0008688; FG02-17ER16362
OSTI ID:
1433741
Alternate ID(s):
OSTI ID: 1506652
Journal Information:
Chemical Science, Vol. 9, Issue 19; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 132 works
Citation information provided by
Web of Science

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Rendering High Surface Area, Mesoporous Metal–Organic Frameworks Electronically Conductive journal March 2017
Computational Design of Functionalized Metal–Organic Framework Nodes for Catalysis journal December 2017
Rational Design, Synthesis, Purification, and Activation of Metal−Organic Framework Materials journal August 2010
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Solvothermal Preparation of an Electrocatalytic Metalloporphyrin MOF Thin Film and its Redox Hopping Charge-Transfer Mechanism journal January 2014
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Metal–Organic Frameworks for Electrocatalytic Reduction of Carbon Dioxide journal October 2015
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Metal–organic framework materials as catalysts journal January 2009
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A Dual Threat: Redox‐Activity and Electronic Structures of Well‐Defined Donor–Acceptor Fulleretic Covalent‐Organic Materials journal February 2020
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Strategies to Improve Electrical and Ionic Conductivities of Metal–Organic Frameworks journal December 2019
Metal–Organic Frameworks Toward Electrocatalytic Applications journal June 2019
Charge-transfer interactions between fullerenes and a mesoporous tetrathiafulvalene-based metal–organic framework journal January 2019
A Dual Threat: Redox‐Activity and Electronic Structures of Well‐Defined Donor–Acceptor Fulleretic Covalent‐Organic Materials journal February 2020
Direct grafting-from of PEDOT from a photoreactive Zr-based MOF – a novel route to electrically conductive composite materials text January 2019
Toward Metal-Organic-Framework-Based Supercapacitors: Room-Temperature Synthesis of Electrically Conducting MOF-Based Nanocomposites Decorated with Redox-Active Manganese: Toward Metal-Organic-Framework-Based Supercapacitors: Room-Temperature Synthesis of Electrically Conducting MOF-Based Nanocomposites Decorated with Re journal June 2019
Charge-transfer interactions between fullerenes and a mesoporous tetrathiafulvalene-based metal–organic framework journal January 2019