US EPA

7425415 

Journal Article 

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

Siegelman, RL; Milner, PJ; Forse, AC; Lee, JH; Colwell, KA; Neaton, JB; Reimer, JA; Weston, SC; Long, , JR; , 

2019 

Yes 

Journal of the American Chemical Society
ISSN: 0002-7863
EISSN: 1520-5126 

AMER CHEMICAL SOC 

WASHINGTON 

141 

33 

13171-13186 

English 

31348649 

10.1021/jacs.9b05567 

WOS:000482546400034 

https://pubs.acs.org/doi/10.1021/jacs.9b05567
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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) (dobpdc4- = 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. 

Amines; Carbon capture; Carbon dioxide; Carboxylation; Crystalline materials; Density functional theory; Flues; Fossil fuel power plants; Gas adsorption; Gas emissions; Gas plants; Hydrogen bonds; Infrared spectroscopy; Magic angle spinning; Natural gas; Natural gasoline plants; Nuclear magnetic resonance spectroscopy; Organometallics; Oxidation resistance; Partial pressure; Proven reserves; Rivers; Separation; Van der Waals forces; Carbon capture and sequestrations; Density functional theory studies; Hydrogen bonding interactions; Magic-angle spinning solid-state NMR spectroscopy; Metal organic framework; Multicomponent adsorption; Natural gas fired power plants; Thermodynamic driving forces; Magnesium compounds; 4,4' dioxidobiphenyl 3,3' dicarboxylate; adsorbent; ammonium carbamate; carbamic acid; carbon dioxide; diamine 2 (aminomethyl)piperidine; diamine derivative; metal organic framework; natural gas; unclassified drug; water; carbon dioxide; diamine; metal organic framework; natural gas; water; adsorption; Article; carbon footprint; chemical binding; chemical parameters; concentration (parameter); controlled study; density functional theory; electric power plant; humidity; hydrogen bond; infrared spectroscopy; magic angle effect; molecular interaction; molecular stability; nuclear magnetic resonance spectroscopy; oxidation; partial pressure; physical parameters; simulation; solid state; technology; temperature; thermodynamics; thermostability; Van der Waals force; chemistry; isolation and purification; molecular model; X ray crystallography; Adsorption; Carbon Dioxide; Crystallography, X-Ray; Diamines; Metal-Organic Frameworks; Models, Molecular; Natural Gas; Thermodynamics; Water