Dataset Information

Cooperative adsorption of carbon disulfide in diamine-appended metal-organic frameworks.

ABSTRACT: Over one million tons of CS₂ are produced annually, and emissions of this volatile and toxic liquid, known to generate acid rain, remain poorly controlled. As such, materials capable of reversibly capturing this commodity chemical in an energy-efficient manner are of interest. Recently, we detailed diamine-appended metal-organic frameworks capable of selectively capturing CO₂ through a cooperative insertion mechanism that promotes efficient adsorption-desorption cycling. We therefore sought to explore the ability of these materials to capture CS₂ through a similar mechanism. Employing crystallography, spectroscopy, and gas adsorption analysis, we demonstrate that CS₂ is indeed cooperatively adsorbed in N,N-dimethylethylenediamine-appended M₂(dobpdc) (M?=?Mg, Mn, Zn; dobpdc^4-?=?4,4'-dioxidobiphenyl-3,3'-dicarboxylate), via the formation of electrostatically paired ammonium dithiocarbamate chains. In the weakly thiophilic Mg congener, chemisorption is cleanly reversible with mild thermal input. This work demonstrates that the cooperative insertion mechanism can be generalized to other high-impact target molecules.

SUBMITTER: McGuirk CM

PROVIDER: S-EPMC6277438 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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Cooperative adsorption of carbon disulfide in diamine-appended metal-organic frameworks.

McGuirk C Michael CM Siegelman Rebecca L RL Drisdell Walter S WS Runčevski Tomče T Milner Phillip J PJ Oktawiec Julia J Wan Liwen F LF Su Gregory M GM Jiang Henry Z H HZH Reed Douglas A DA Gonzalez Miguel I MI Prendergast David D Long Jeffrey R JR

Nature communications 20181203 1

Over one million tons of CS<sub>2</sub> are produced annually, and emissions of this volatile and toxic liquid, known to generate acid rain, remain poorly controlled. As such, materials capable of reversibly capturing this commodity chemical in an energy-efficient manner are of interest. Recently, we detailed diamine-appended metal-organic frameworks capable of selectively capturing CO<sub>2</sub> through a cooperative insertion mechanism that promotes efficient adsorption-desorption cycling. We ...[more]

PMID: 30510262

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Project description:Carbon capture and sequestration is a key element of global initiatives to minimize anthropogenic greenhouse gas emissions. Although many investigations of new candidate CO2 capture materials focus on equilibrium adsorption properties, it is also critical to consider adsorption/desorption kinetics when evaluating adsorbent performance. Diamine-appended variants of the metal-organic framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising materials for CO2 capture because of their cooperative chemisorption mechanism and associated step-shaped equilibrium isotherms, which enable large working capacities to be accessed with small temperature swings. However, the adsorption/desorption kinetics of these unique materials remain understudied. More generally, despite the necessity of kinetics characterization to advance adsorbents toward commercial separations, detailed kinetic studies of metal-organic framework-based gas separations remain rare. Here, we systematically investigate the CO2 adsorption kinetics of diamine-appended Mg2(dobpdc) variants using a thermogravimetric analysis (TGA) assay. In particular, we examine the effects of diamine structure, temperature, and partial pressure on CO2 adsorption and desorption kinetics. Importantly, most diamine-appended Mg2(dobpdc) variants exhibit an induction period prior to reaching the maximum rate of CO2 adsorption, which we attribute to their unique cooperative chemisorption mechanism. In addition, these materials exhibit inverse Arrhenius behavior, displaying faster adsorption kinetics and shorter induction periods at lower temperatures. Using the Avrami model for nucleation and growth kinetics, we determine rate constants for CO2 adsorption and quantitatively compare rate constants among different diamine-appended variants. Overall, these results provide guidelines for optimizing adsorbent design to facilitate CO2 capture from diverse target streams and highlight kinetic phenomena relevant for other materials in which cooperative chemisorption mechanisms are operative.

Dataset Information

Cooperative adsorption of carbon disulfide in diamine-appended metal-organic frameworks.

Publications

Cooperative adsorption of carbon disulfide in diamine-appended metal-organic frameworks.

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