Study of Hydrothermal Stability and Water Sorption Characteristics of 3‑Dimensional Zn-Based Trimesate

Zinc trimesate material with high hydrothermal stability was studied for water adsorption/desorption dynamics, and we explained the reason for material’s stability in water. A zinc trimesate Zn2(BTC)(OH)(H2O)·1.67H2O with the three-dimensional framework contains [Zn2O6(OH)(H2O)] chains with ZnO2(OH)...

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Veröffentlicht in:Journal of physical chemistry. C 2013-07, Vol.117 (28), p.14608-14617
Hauptverfasser: Birsa Čelič, Tadeja, Mazaj, Matjaž, Guillou, Nathalie, Elkaïm, Erik, El Roz, Mohamad, Thibault-Starzyk, Frederic, Mali, Gregor, Rangus, Mojca, Čendak, Tomaž, Kaučič, Venčeslav, Zabukovec Logar, Nataša
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container_end_page 14617
container_issue 28
container_start_page 14608
container_title Journal of physical chemistry. C
container_volume 117
creator Birsa Čelič, Tadeja
Mazaj, Matjaž
Guillou, Nathalie
Elkaïm, Erik
El Roz, Mohamad
Thibault-Starzyk, Frederic
Mali, Gregor
Rangus, Mojca
Čendak, Tomaž
Kaučič, Venčeslav
Zabukovec Logar, Nataša
description Zinc trimesate material with high hydrothermal stability was studied for water adsorption/desorption dynamics, and we explained the reason for material’s stability in water. A zinc trimesate Zn2(BTC)(OH)(H2O)·1.67H2O with the three-dimensional framework contains [Zn2O6(OH)(H2O)] chains with ZnO2(OH)2 tetrahedra and ZnO4(OH)(H2O) octahedra corner-shared through μ3-OH group. Inorganic chains are linked with 1,3,5-benzenetricarboxylates forming two types of parallel channels (open and closed) containing adsorbed water in different environments. Closed channels are occupied by free water molecules connected through strong hydrogen-bonds with coordinated water, whereas open-type channels contain water molecules with partially occupied oxygen atom sites. The dynamics of water adsorption/desorption was evaluated by complementary techniques of thermogravimetric (TG), infrared (IR), water sorption, and different magic-angle spinning nuclear magnetic resonance (MAS NMR) techniques. The removal of water from open channels occurs below 100 °C, whereas hydrogen-bonded water molecules and coordinated water are expelled at higher temperatures. 2H MAS NMR was employed to prove that the removal of water from closed channels is not entirely simultaneous and that adsorbed water begins to diffuse at slightly lower temperatures than the coordinated one. The investigated material shows high hydrothermal stability and withstands 40-cycle hydrothermal-stability test without any significant loss of the structure integrity. It also shows complete structural reversibility upon dehydration/rehydration process at 200 °C. The reason for high stability in water mainly lies in the stabilization of the inorganic chains established by the interaction between the adsorbed water molecules and coordinated ones (framework water) via hydrogen bonds. The material also exhibits notable sorption capacity for water (208 mg·g–1) adsorbed in a stepwise process.
doi_str_mv 10.1021/jp4036327
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A zinc trimesate Zn2(BTC)(OH)(H2O)·1.67H2O with the three-dimensional framework contains [Zn2O6(OH)(H2O)] chains with ZnO2(OH)2 tetrahedra and ZnO4(OH)(H2O) octahedra corner-shared through μ3-OH group. Inorganic chains are linked with 1,3,5-benzenetricarboxylates forming two types of parallel channels (open and closed) containing adsorbed water in different environments. Closed channels are occupied by free water molecules connected through strong hydrogen-bonds with coordinated water, whereas open-type channels contain water molecules with partially occupied oxygen atom sites. The dynamics of water adsorption/desorption was evaluated by complementary techniques of thermogravimetric (TG), infrared (IR), water sorption, and different magic-angle spinning nuclear magnetic resonance (MAS NMR) techniques. The removal of water from open channels occurs below 100 °C, whereas hydrogen-bonded water molecules and coordinated water are expelled at higher temperatures. 2H MAS NMR was employed to prove that the removal of water from closed channels is not entirely simultaneous and that adsorbed water begins to diffuse at slightly lower temperatures than the coordinated one. The investigated material shows high hydrothermal stability and withstands 40-cycle hydrothermal-stability test without any significant loss of the structure integrity. It also shows complete structural reversibility upon dehydration/rehydration process at 200 °C. The reason for high stability in water mainly lies in the stabilization of the inorganic chains established by the interaction between the adsorbed water molecules and coordinated ones (framework water) via hydrogen bonds. 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The reason for high stability in water mainly lies in the stabilization of the inorganic chains established by the interaction between the adsorbed water molecules and coordinated ones (framework water) via hydrogen bonds. 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The dynamics of water adsorption/desorption was evaluated by complementary techniques of thermogravimetric (TG), infrared (IR), water sorption, and different magic-angle spinning nuclear magnetic resonance (MAS NMR) techniques. The removal of water from open channels occurs below 100 °C, whereas hydrogen-bonded water molecules and coordinated water are expelled at higher temperatures. 2H MAS NMR was employed to prove that the removal of water from closed channels is not entirely simultaneous and that adsorbed water begins to diffuse at slightly lower temperatures than the coordinated one. The investigated material shows high hydrothermal stability and withstands 40-cycle hydrothermal-stability test without any significant loss of the structure integrity. It also shows complete structural reversibility upon dehydration/rehydration process at 200 °C. The reason for high stability in water mainly lies in the stabilization of the inorganic chains established by the interaction between the adsorbed water molecules and coordinated ones (framework water) via hydrogen bonds. The material also exhibits notable sorption capacity for water (208 mg·g–1) adsorbed in a stepwise process.</abstract><cop>Columbus, OH</cop><pub>American Chemical Society</pub><doi>10.1021/jp4036327</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0002-8095-0860</orcidid><oa>free_for_read</oa></addata></record>
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subjects Chemical Sciences
Condensed matter: structure, mechanical and thermal properties
Exact sciences and technology
Material chemistry
Physics
Solid surfaces and solid-solid interfaces
Surfaces and interfaces
thin films and whiskers (structure and nonelectronic properties)
title Study of Hydrothermal Stability and Water Sorption Characteristics of 3‑Dimensional Zn-Based Trimesate
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