A Microporous Metal–Organic Framework for Highly Selective Separation of Acetylene, Ethylene, and Ethane from Methane at Room Temperature

Abstract

A novel three-dimensional microporous metal-organic framework Zn(4)L(DMA)(4) (UTSA-33, H(8) L=1,2,4,5-tetra(5-isophthalic acid)benzene, DMA=N,N'-dimethylacetamide) with small pores of about 4.8 to 6.5 Å was synthesized and structurally characterized as a non-interpenetrated (4,8)-connected network with the flu topology (Schläfli symbol: (4(12)6(12)8(4))(4(6))(2)). The activated UTSA-33a exhibits highly selective separation of acetylene, ethylene, and ethane from methane with the adsorption selectivities of 12 to 20 at 296 K, which has been established exclusively by the sorption isotherms and simulated breakthrough experiments, thus methane can be readily separated from their binary and even ternary mixtures at room temperature.

Modeling adsorption properties of structurally deformed metal–organic frameworks using structure–property map

“…To examine whether the trend found from the computational structure-property map agrees with the experimental data of crystalline MOFs, 13 experimental data points (1,(28)(29)(30)(31)(32)(33) were selected and placed on top of the structure-property map in the 2D view (Fig. 1B).…”

“…1B). The selected experimental data were extracted from recent review papers on methane storage in MOFs (1,28) and several source papers of the CoRE MOF database (29)(30)(31)(32)(33). Except for NU-111, all of the experimental data showed consistent placement within the computational structure-property map.…”

Highly selective separation of small hydrocarbons and carbon dioxide in a metal–organic framework with open copper(ii) coordination sites

“…Compared with traditional porous materials such as zeolites and activated carbon, MOFs are very unique in terms of their (1) systematically tuned micropores by choosing the different organic linkers or the diverse metal-containing secondary building units (SBUs) or by the framework interpenetration, and (2) modied pore surfaces by organic and/or inorganic functional recognition sites on the pore surfaces, enabling them as very promising materials for gas separations. [30][31][32][33][34][35][36][37][38][39][40][41] For instance, coordinatively unsaturated metal centers (UMCs), which are oen produced through the removal of terminally coordinated solvent molecules to the metal centers, can enhance gas adsorption and separation properties. [41][42][43] Indeed, a number of MOF materials have been reported to selectively separate methane from mixtures including hydrocarbons (ethane, ethylene, and acetylene) and carbon dioxide for the purication of natural gas, though MOF materials for simultaneous purication of the individual component of ethane, ethylene, acetylene and carbon dioxide from their mixture are still rare.…”

A new MOF-5 homologue for selective separation of methane from C2 hydrocarbons at room temperature

“…2), which is typical for microporous materials. UTSA-10a can adsorb 282 cm 3 (STP) g −1 of N 2 at 77 K. Based on the N 2 adsorption isotherms, the Brunauer-Emmett-Teller (BET) and Langmuir surface areas are calculated to be 1090 12,13,[23][24][25][26][27][28][29][30] Given the fact the pore size within UTSA-10a tuned by the methyl group in the organic linker falls in the range of the kinetic diameters of C 1 and C 2 hydrocarbons (3.3-4.4 Å), the low-pressure single-component C 2 H 2 , C 2 H 4 , C 2 H 6 , and CH 4 adsorption properties were examined accordingly at two different temperatures of 273 and 296 K. As shown in Fig. 3, all isotherms, except the C 2 H 2 one, show good reversible sorption behavior.…”