Issue 25, 2020

Kinetics of cooperative CO2 adsorption in diamine-appended variants of the metal–organic framework Mg2(dobpdc)

Abstract

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.

Graphical abstract: Kinetics of cooperative CO2 adsorption in diamine-appended variants of the metal–organic framework Mg2(dobpdc)

Supplementary files

Article information

Article type
Edge Article
Submitted
24 Feb 2020
Accepted
23 Mas 2020
First published
31 Mas 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 6457-6471

Kinetics of cooperative CO2 adsorption in diamine-appended variants of the metal–organic framework Mg2(dobpdc)

J. D. Martell, P. J. Milner, R. L. Siegelman and J. R. Long, Chem. Sci., 2020, 11, 6457 DOI: 10.1039/D0SC01087A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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