Coordination Polymer Glasses with Lava and Healing Ability for High‐Performance Gas Sieving

Abstract

Coordination polymer (CP) glasses offer aw ay to tackle the fabrication challenges encountered by inorganic porous membranes and showgreat potentials for size-exclusive gas separation. However,their processability and performance still cannot simultaneously meet the requirements for highperformance membrane separation. Herein, we have developed aseries of CP glasses (M-P-dmbIm, M = Zn, Cd, Cu, and Mn), whichpossess low vitrification temperature as well as low viscosity (h)a nd lave capability above the transition temperatures.T he derived glass (a g M-P-dmbIm) membranes show outstanding performances for H 2 /CO 2 ,H 2 /N 2 ,a nd H 2 /CH 4 separation, whicha ll far surpass the Robeson upper bound and even rival against the best of the state-of-the-art gas separation membranes.The low viscosities not only allowusto hot-cast or hot-press the CP glasses into thin membranes within 5min without sacrificing their selectivity and permeability,but also endowt he resulted glass membranes with healing ability.

Quantification of gas-accessible microporosity in metal-organic framework glasses

“…above their melting temperature, T m ) and vitrification to a MOF glass after cooling below their glass transition temperature (T g ) [21][22][23][24][25] . MOF glasses propose unique opportunities for solid-state ion conduction 20,26,27 and gas separation membranes [28][29][30] because of improved performance as a result of their monolithic structure and the absence of mass transport limiting grain boundaries 31 . However, compared to their structurally well-defined crystalline parent materials, it is very difficult to predict and design the functionally relevant porosity features (pore volume and pore size) of the MOF glasses.…”

“…ZIF-76, lta topology; ZIF-8, sod topology) [40][41][42] . Given that the crystalline ZIF precursors are typically microporous solids with porosity features interesting for gas storage and separation [43][44][45][46][47] , their melt-quenched glasses are deemed to exhibit similar potential for gas adsorption and separation processes 28,29 . Nevertheless, gas-accessible microporosity in MOF glasses has only been poorly investigated and was just demonstrated for a few ZIF glasses 30,37,38,48 .…”

Quantification of gas-accessible microporosity in metal-organic framework glasses

“…above their melting temperature, Tm) and vitrification to a MOF glass after cooling below their glass transition temperature (Tg). [21][22][23][24][25] MOF glasses propose unique opportunities for solid state ion conduction 20,26,27 and gas separation membranes [28][29][30] because of improved performance as a result of their monolithic structure and the absence of mass transport limiting grain boundaries. 31 However, compared to their structurally well-defined crystalline parent materials, it is extremely difficult to predict and design the functionally relevant porosity features (pore volume and pore size) of the MOF glasses.…”

“…[40][41][42] Given that the crystalline ZIF precursors are typically microporous solids with porosity features interesting for gas storage and separation, [43][44][45][46][47] their melt-quenched glasses are deemed to exhibit similar potential for gas adsorption and separation processes. 28,29 Nevertheless, gas-accessible microporosity in MOF glasses has been only poorly investigated and was just demonstrated for ZIF glasses obtained from ZIFs with cag topology. 30,37,38 A quantification of the total gas-accessible pore volume of the ZIF glasses as well as a comprehensive comparison of the porosity of the glasses in relation to their crystalline precursors has not yet been reported.…”

A hybrid ZIF-8/ZIF-62 glass membrane for gas separation

“…It was confirmed that the in situ melting of ZIF-62 within the polyimide matrix was very effective in reducing meso- and macroscale defects at the MOF/polymer interface, resulting in a 23.7% increase in CO 2 /N 2 selectivity. Except for the a g ZIF-62 and a g (ZIF-62) 0.2 (6FDA-DAM) 0.8 membrane, other MOF glass membranes such as M-P-dmbIm 17 and TIF-4 membranes 18 also showed outstanding CO 2 separation performance.…”