Title: Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity

Journal Article · · Chemistry of Materials
 [1];  [1];  [2];  [1];  [3];  [4];  [1]; ORCiD logo [3];  [3];  [5];  [6];  [6];  [4]; ORCiD logo [4];  [7]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Manchester (United Kingdom)
  2. Novosibirsk State Univ. (Russian Federation); Russian Academy of Sciences (RAS), Novosibirsk (Russian Federation)
  3. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab., ISIS Neutron Source
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Univ. of Nottingham (United Kingdom)
  6. School of Chemistry, University of Nottingham, Nottingham NG7 2RD, U.K.
  7. Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.
+ Show Author Affiliations

Owing to their inherent pore structure, porous metal–organic frameworks (MOFs) can undergo postsynthetic modification, such as loading extra-framework proton carriers. However, strategies for improving the proton conductivity for nonporous MOFs are largely lacking, although increasing numbers of nonporous MOFs exhibit promising proton conductivities. Often, high humidity is required for nonporous MOFs to achieve high conductivities, but to date no clear mechanisms have been experimentally identified. Here we describe the new materials MFM-550(M), [M(HL1)], (H4L1 = biphenyl-4,4'-diphosphonic acid; M = La, Ce, Nd, Sm, Gd, Ho), MFM-550(Ba), [Ba(H2L1)], and MFM-555(M), [M(HL2)], (H4L2 = benzene-1,4-diphosphonic acid; M = La, Ce, Nd, Sm, Gd, Ho), and report enhanced proton conductivities in these nonporous materials by (i) replacing the metal ion to one with a lower oxidation state, (ii) reducing the length of the organic ligand, and (iii) introducing additional acidic protons on the MOF surface. Increased framework proton density in these materials can lead to an enhancement in proton conductivity of up to 4 orders of magnitude. Additionally, we report a comprehensive investigation using in situ 2H NMR and neutron spectroscopy, coupled with molecular dynamic modeling, to elucidate the role of humidity in assembling interconnected networks for proton hopping. This study constructs a relationship between framework proton density and the corresponding proton conductivity in nonporous MOFs, and directly explains the role of both surface protons and external water in assembling the proton conduction pathways.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1486933
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 21 Vol. 30; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (6)

Metal‐Organic Frameworks for Hydrogen Energy Applications: Advances and Challenges journal March 2019
Coordination polymer-based conductive materials: ionic conductivity vs. electronic conductivity journal January 2019
Strategic hierarchical improvement of superprotonic conductivity in a stable metal–organic framework system journal January 2019
Lamellar columnar liquid-crystalline mesophases as a 2D platform for anhydrous proton conduction journal January 2019
Ligand substitution induced single-crystal-to-single-crystal transformations in two Ni( ii ) coordination compounds displaying consequential changes in proton conductivity journal January 2020
A Co( ii )-coordination polymer for ultrahigh superprotonic conduction: an atomistic insight through molecular simulations and QENS experiments journal January 2020

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