Melt-Quenched Glass Films of Coordination Polymers as Impermeable Barrier Layers and Protective Anticorrosion Coatings

Abstract

The crystal−liquid−glass phase-transition behavior of coordination polymers (CPs) endows them with unique processing and mechanical properties to prepare functional CP glass films. However, their potential applications are still waiting to be explored. In this study, flawless [Zn(HPO 4 )(H 2 PO 4 ) 2 ](H 2 Im) 2 (abbreviated as ZnP-H 2 Im) glass films are facilely prepared through rapid hot casting coupled with melt quenching. Relying on the grain-boundary-free structure of the film and nonporous structure of the coordination network, undesired diffusion of guest molecules in ZnP-H 2 Im glass films can be effectively prohibited, which is advantageous for gas permeation and liquid leakage prevention. Gas permeation test results indicate that the barrier efficiency of the ZnP-H 2 Im glass film to gas molecules reaches 100%, while polarization curve and EIS results imply that prepared ZnP-H 2 Im glass film possesses excellent corrosion resistance in salt aqueous solution with a protection efficiency up to 99.98% for metallic substrate. Our research demonstrates that CP glasses hold great potential to serve as competent gas barrier layers and corrosion-resistant coatings.

Heterogenous CO2 Reduction Photocatalysis of Transparent Coordination Polymer Glass Membranes Containing Metalloporphyrins

“…57−60 Gas adsorption measurements were performed to estimate the void distributions quantitatively, but negligible nitrogen (N 2 ) and CO 2 were adsorbed in 1g and Fe/1g (Figure S13). 31,61 Photocatalytic CO 2 reduction was evaluated using Fe/1g-9 containing various concentrations of Fe(TPP)Cl. Fe 0.25 /1g-9 and Fe 0.1 /1g-9 were prepared by mixing 1l and Fe(TPP)Cl ([Fe(TPP)Cl]/[1] = 0.25 or 0.1 w/w%), followed by membrane preparation with a thickness of 9 nm (Figure S14).…”

“…Although the experiments indicate the subsurface access of CO 2 and BIH through the voids, the quantitative analyses of the void structure are difficult due to their nonuniform structures. − Gas adsorption measurements were performed to estimate the void distributions quantitatively, but negligible nitrogen (N 2 ) and CO 2 were adsorbed in 1g and Fe/1g (Figure S13). , …”

“…Glasses are strong candidates for transparent and grain boundary-free membranes. Glassy coordination polymers (CPs) or metal-organic frameworks (MOFs) have been of interest as a new class of glasses with high formability. , Their properties are controlled by combining metal ions and bridging ligands, and are distinct from conventional inorganic glasses in many cases. − The CP/MOF glasses have gained research interest in applications such as proton-conductive electrolytes, optics, and drug delivery systems by immobilizing guest molecules during vitrification, − but there has been no report on the immobilization of metal complex catalysts including metalloporphyrins in the CP/MOF glasses. Herein, we elucidate the CP/MOF glasses working as a substrate for molecular catalysts for the first time.…”

Ion transport and conduction in metal–organic framework glasses

“…1c). 9,27 Currently, meltable MOFs mainly stem from the ZIF family as well as metal-phosphate-azolate and metal-amide frameworks. 13,[28][29][30] Further effort should be directed at lowering the melting temperature of MOFs to below their decomposition temperature to expand the types of meltable MOFs.…”

Functions and applications of emerging metal–organic-framework liquids and glasses

“…Overall, the discovery and regulation of MOF liquids and glasses promote new scientific directions in various fields due to their unusual physical properties like porosity, ionic conductivity, and optical and mechanical properties. 26 In this review, we describe the crystal-to-liquid/glass transformation of MOFs, including the phase and structure evolution upon heating and the alternative approaches to promote melting and vitrification. Besides, the attractive properties and potential applications of liquid and glassy MOFs are also comprehensively summarized.…”