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

Abstract

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 amore » 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.« less

Authors:
 [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.
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1486933
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 21; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Pili, Simona, Rought, Peter, Kolokolov, Daniil I., Lin, Longfei, da Silva, Ivan, Cheng, Yongqiang, Marsh, Christopher, Silverwood, Ian P., García Sakai, Victoria, Li, Ming, Titman, Jeremy J., Knight, Lyndsey, Daemen, Luke L., Ramirez-Cuesta, Anibal J., Tang, Chiu C., Stepanov, Alexander G., Yang, Sihai, and Schröder, Martin. Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.chemmater.8b02765.
Pili, Simona, Rought, Peter, Kolokolov, Daniil I., Lin, Longfei, da Silva, Ivan, Cheng, Yongqiang, Marsh, Christopher, Silverwood, Ian P., García Sakai, Victoria, Li, Ming, Titman, Jeremy J., Knight, Lyndsey, Daemen, Luke L., Ramirez-Cuesta, Anibal J., Tang, Chiu C., Stepanov, Alexander G., Yang, Sihai, & Schröder, Martin. Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity. United States. https://doi.org/10.1021/acs.chemmater.8b02765
Pili, Simona, Rought, Peter, Kolokolov, Daniil I., Lin, Longfei, da Silva, Ivan, Cheng, Yongqiang, Marsh, Christopher, Silverwood, Ian P., García Sakai, Victoria, Li, Ming, Titman, Jeremy J., Knight, Lyndsey, Daemen, Luke L., Ramirez-Cuesta, Anibal J., Tang, Chiu C., Stepanov, Alexander G., Yang, Sihai, and Schröder, Martin. Mon . "Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity". United States. https://doi.org/10.1021/acs.chemmater.8b02765. https://www.osti.gov/servlets/purl/1486933.
@article{osti_1486933,
title = {Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity},
author = {Pili, Simona and Rought, Peter and Kolokolov, Daniil I. and Lin, Longfei and da Silva, Ivan and Cheng, Yongqiang and Marsh, Christopher and Silverwood, Ian P. and García Sakai, Victoria and Li, Ming and Titman, Jeremy J. and Knight, Lyndsey and Daemen, Luke L. and Ramirez-Cuesta, Anibal J. and Tang, Chiu C. and Stepanov, Alexander G. and Yang, Sihai and Schröder, Martin},
abstractNote = {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.},
doi = {10.1021/acs.chemmater.8b02765},
journal = {Chemistry of Materials},
number = 21,
volume = 30,
place = {United States},
year = {2018},
month = {9}
}

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Cited by: 7 works
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Figures / Tables:

Figure 1 Figure 1: Views of structures of MFM-550(M) and MFM-555(M) obtained from high resolution synchrotron PXRD data. Views of the structure of MFM-550 (a) and MFM-555 (b) along the $c$-axis. (c) View of the coordination node of the phosphonate group of the ligand. (d) Perspective view of the coordination environment atmore » Ln(III) centres. (e) View of the extended Ln-phosphonate 2D-sheet along the $b$-axis.« less

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