Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity Научная публикация
Журнал |
Chemistry of Materials
ISSN: 0897-4756 , E-ISSN: 1520-5002 |
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Вых. Данные | Год: 2018, Том: 30, Номер: 21, Страницы: 7593-7602 Страниц : 10 DOI: 10.1021/acs.chemmater.8b02765 | ||||||||||||||||
Ключевые слова | Crystalline materials Metal ions Metals Molecular dynamics Organometallics | ||||||||||||||||
Авторы |
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Организации |
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Информация о финансировании (6)
1 | Engineering and Physical Sciences Research Council | EP/I011870 |
2 | European Research Council | AdG 742041 |
3 | Royal Society | |
4 | University of Manchester | |
5 | Федеральное агентство научных организаций России | 0303-2016-0003 |
6 | Oak Ridge National Laboratory |
Реферат:
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.
Библиографическая ссылка:
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 CAPlusCA OpenAlex
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 CAPlusCA OpenAlex
Файлы:
Полный текст от издателя
Даты:
Поступила в редакцию: | 30 июн. 2018 г. |
Принята к публикации: | 24 сент. 2018 г. |
Опубликована online: | 24 сент. 2018 г. |
Опубликована в печати: | 13 нояб. 2018 г. |
Идентификаторы БД:
Web of science: | WOS:000450696100026 |
Scopus: | 2-s2.0-85056604299 | 2-s2.0-85056358646 |
РИНЦ: | 38630340 | 41783699 |
Chemical Abstracts: | 2018:1778883 |
Chemical Abstracts (print): | 169:480076 |
OpenAlex: | W2892554131 |