Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity | Sciact - CRIS-system of Boreskov Institute of Catalysis

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

Journal

Chemistry of Materials
ISSN: 0897-4756 , E-ISSN: 1520-5002

Output data

Year: 2018, Volume: 30, Number: 21, Pages: 7593-7602 Pages count : 10 DOI: 10.1021/acs.chemmater.8b02765

Tags

Crystalline materials Metal ions Metals Molecular dynamics Organometallics

Authors

Pili Simona ¹ , Rought Peter ¹ , Kolokolov Daniil I. ^2,3 , Lin Longfei ¹ , da Silva Ivan ⁴ , Cheng Yongqiang ⁵ , Marsh Christopher ¹ , Silverwood Ian P. ⁴ , García Sakai Victoria ⁴ , Li Ming ⁶ , Titman Jeremy J. ⁷ , Knight Lyndsey ⁷ , Daemen Luke L. ⁵ , Ramirez-Cuesta Anibal J. ⁵ , Tang Chiu C. ⁸ , Stepanov Alexander G. ^2,3 , Yang Sihai ¹ , Schröder Martin ¹

Affiliations

1	School of Chemistry, University of Manchester, Manchester M13 9PL, U.K.
2	Novosibirsk State University, Novosibirsk, 630090, Russia
3	Siberian Branch of Russian Academy of Sciences, Boreskov Institute of Catalysis, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
4	Rutherford Appleton Laboratory, ISIS Pulsed Neutron and Muon Source, Rutherford Appleton Laboratory, Oxfordshire OX11 0QX, U.K.
5	Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
6	School of Engineering, University of Nottingham, Nottingham NG7 2RD, U.K.
7	School of Chemistry, University of Nottingham, Nottingham NG7 2RD, U.K.
8	Diamond Light Source, Harwell Science and Innovation Campus, Oxfordshire OX11 0DE, U.K.

Funding (6)

1	Engineering and Physical Sciences Research Council	EP/I011870
2	European Research Council	AdG 742041
3	Royal Society
4	University of Manchester
5	Federal Agency for Scientific Organizations	0303-2016-0003
6	Oak Ridge National Laboratory

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.

Pili S. , Rought P. , Kolokolov D.I. , Lin L. , da Silva I. , Cheng Y. , Marsh C. , Silverwood I.P. , García Sakai V. , Li M. , Titman J.J. , Knight L. , Daemen L.L. , Ramirez-Cuesta A.J. , Tang C.C. , Stepanov A.G. , Yang S. , Schröder M.
Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity

Chemistry of Materials. 2018. V.30. N21. P.7593-7602. DOI: 10.1021/acs.chemmater.8b02765 WOS Scopus Scopus РИНЦ РИНЦ ANCAN OpenAlex

Full text from publisher

Submitted:	Jun 30, 2018
Accepted:	Sep 24, 2018
Published online:	Sep 24, 2018
Published print:	Nov 13, 2018

Web of science:	WOS:000450696100026
Scopus:	2-s2.0-85056604299 \| 2-s2.0-85056358646
Elibrary:	38630340 \| 41783699
Chemical Abstracts:	2018:1778883
Chemical Abstracts (print):	169:480076
OpenAlex:	W2892554131

DB	Citing
Scopus	62
Web of science	61
Elibrary	2 59
OpenAlex	67