Effect of Elevated Air Humidity on the Structure and Proton Conductivity of Porphyrin-Based Zr(IV)-MOFs

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389013%3A_____%2F25%3A00637946" target="_blank" >RIV/61389013:_____/25:00637946 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388980:_____/25:00637946 RIV/00216275:25310/25:39923298 RIV/00216208:11320/25:10511231

Výsledek na webu

<a href="https://hdl.handle.net/11104/0368741" target="_blank" >https://hdl.handle.net/11104/0368741</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.5c02165" target="_blank" >10.1021/acs.inorgchem.5c02165</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Effect of Elevated Air Humidity on the Structure and Proton Conductivity of Porphyrin-Based Zr(IV)-MOFs

Popis výsledku v původním jazyce

Metal-organic frameworks (MOFs) based on Zr6(mu 3-O)8 oxometallic clusters are attracting attention as potential proton conductors due to their high surface area, ease of further substitution, and exceptional chemical stability. We hereby present an examination of two Zr(IV)-MOFs with a tetrakis(4-carboxyphenyl)porphyrin (TCPP4-) linker, PCN-222 and PCN-224, as proton conductors. It was found that, in spite of their excellent stability in aqueous suspensions, in the environment of elevated air humidity, serious changes in their bonding system occur, mainly involving breakage of the carboxylate coordination bonds and hydration of the Zr6(mu 3-O)8 clusters, which leads to gradual amorphization and loss of porous character. The stability of the structures can be improved by postsynthetic modification with diphenylphosphinic acid (DPPA) to some extent. Inclusion of host imidazole molecules facilitates proton mobility in the pore system of the MOFs, further accelerating the structural degradation. Even though the original structures of the MOFs collapse under the conditions of proton conductivity measurement, the resulting amorphous solids still reveal a proton conductivity up to 6.7 x 10-6 S<middle dot>cm-1 at ambient temperature and a 92% relative humidity, which is comparable to that of other Zr(IV)-MOFs with well-preserved structures. The presented study demonstrates an important phenomenon that has to be considered with any investigation using MOFs as proton conductors.

Název v anglickém jazyce

Effect of Elevated Air Humidity on the Structure and Proton Conductivity of Porphyrin-Based Zr(IV)-MOFs

Popis výsledku anglicky

Metal-organic frameworks (MOFs) based on Zr6(mu 3-O)8 oxometallic clusters are attracting attention as potential proton conductors due to their high surface area, ease of further substitution, and exceptional chemical stability. We hereby present an examination of two Zr(IV)-MOFs with a tetrakis(4-carboxyphenyl)porphyrin (TCPP4-) linker, PCN-222 and PCN-224, as proton conductors. It was found that, in spite of their excellent stability in aqueous suspensions, in the environment of elevated air humidity, serious changes in their bonding system occur, mainly involving breakage of the carboxylate coordination bonds and hydration of the Zr6(mu 3-O)8 clusters, which leads to gradual amorphization and loss of porous character. The stability of the structures can be improved by postsynthetic modification with diphenylphosphinic acid (DPPA) to some extent. Inclusion of host imidazole molecules facilitates proton mobility in the pore system of the MOFs, further accelerating the structural degradation. Even though the original structures of the MOFs collapse under the conditions of proton conductivity measurement, the resulting amorphous solids still reveal a proton conductivity up to 6.7 x 10-6 S<middle dot>cm-1 at ambient temperature and a 92% relative humidity, which is comparable to that of other Zr(IV)-MOFs with well-preserved structures. The presented study demonstrates an important phenomenon that has to be considered with any investigation using MOFs as proton conductors.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10404 - Polymer science

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

1520-510X

Svazek periodika

64

Číslo periodika v rámci svazku

31

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

15993-16004

Kód UT WoS článku

001539119000001

EID výsledku v databázi Scopus

2-s2.0-105013405773