Dataset Information

Water Enables Efficient CO₂ Capture from Natural Gas Flue Emissions in an Oxidation-Resistant Diamine-Appended Metal-Organic Framework.

ABSTRACT: Supported by increasingly available reserves, natural gas is achieving greater adoption as a cleaner-burning alternative to coal in the power sector. As a result, carbon capture and sequestration from natural gas-fired power plants is an attractive strategy to mitigate global anthropogenic CO₂ emissions. However, the separation of CO₂ from other components in the flue streams of gas-fired power plants is particularly challenging due to the low CO₂ partial pressure (∼40 mbar), which necessitates that candidate separation materials bind CO₂ strongly at low partial pressures (≤4 mbar) to capture ≥90% of the emitted CO₂. High partial pressures of O₂ (120 mbar) and water (80 mbar) in these flue streams have also presented significant barriers to the deployment of new technologies for CO₂ capture from gas-fired power plants. Here, we demonstrate that functionalization of the metal-organic framework Mg₂(dobpdc) (dobpdc^4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) with the cyclic diamine 2-(aminomethyl)piperidine (2-ampd) produces an adsorbent that is capable of ≥90% CO₂ capture from a humid natural gas flue emission stream, as confirmed by breakthrough measurements. This material captures CO₂ by a cooperative mechanism that enables access to a large CO₂ cycling capacity with a small temperature swing (2.4 mmol CO₂/g with ΔT = 100 °C). Significantly, multicomponent adsorption experiments, infrared spectroscopy, magic angle spinning solid-state NMR spectroscopy, and van der Waals-corrected density functional theory studies suggest that water enhances CO₂ capture in 2-ampd-Mg₂(dobpdc) through hydrogen-bonding interactions with the carbamate groups of the ammonium carbamate chains formed upon CO₂ adsorption, thereby increasing the thermodynamic driving force for CO₂ binding. In light of the exceptional thermal and oxidative stability of 2-ampd-Mg₂(dobpdc), its high CO₂ adsorption capacity, and its high CO₂ capture rate from a simulated natural gas flue emission stream, this material is one of the most promising adsorbents to date for this important separation.

SUBMITTER: Siegelman RL

PROVIDER: S-EPMC8256444 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Similar Datasets

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

Water Enables Efficient CO₂ Capture from Natural Gas Flue Emissions in an Oxidation-Resistant Diamine-Appended Metal-Organic Framework.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Dataset Information

Water Enables Efficient CO2 Capture from Natural Gas Flue Emissions in an Oxidation-Resistant Diamine-Appended Metal-Organic Framework.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Water Enables Efficient CO₂ Capture from Natural Gas Flue Emissions in an Oxidation-Resistant Diamine-Appended Metal-Organic Framework.