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

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

doi:10.1021/acs.chemmater.8b02765

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

Journal Article · Mon Sep 24 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b02765· OSTI ID:1486933

Pili, Simona ^[1]; Rought, Peter ^[1]; Kolokolov, Daniil I. ^[2]; Lin, Longfei ^[1]; da Silva, Ivan ^[3]; Cheng, Yongqiang ^[4]; Marsh, Christopher ^[1];

^[3]; García Sakai, Victoria ^[3]; Li, Ming ^[5]; Titman, Jeremy J. ^[6]; Knight, Lyndsey ^[6]; Daemen, Luke L. ^[4];

^[4]; Tang, Chiu C. ^[7];

^[2];

^[1];

^[1]

Univ. of Manchester (United Kingdom)
Novosibirsk State Univ. (Russian Federation); Russian Academy of Sciences (RAS), Novosibirsk (Russian Federation)
Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab., ISIS Neutron Source
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Nottingham (United Kingdom)
School of Chemistry, University of Nottingham, Nottingham NG7 2RD, U.K.
Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.

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.

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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, Vol. 30, Issue 21; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 45 works

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