Selective Capture Of Carbon Dioxide Research Articles

Selective capture of carbon dioxide under humid conditions by hydrophobic chabazite-type zeolitic imidazolate frameworks.

Hydrophobic zeolitic imidazolate frameworks (ZIFs) with the chabazite (CHA) topology are synthesized by incorporating two distinct imidazolate links. Zn(2-mIm)0.86 (bbIm)1.14 (ZIF-300), Zn(2-mIm)0.94 (cbIm)1.06 (ZIF-301), and Zn(2-mIm)0.67 (mbIm)1.33 (ZIF-302), where 2-mIm = 2-methylimidazolate, bbIm = 5(6)-bromobenzimidazolate, cbIm = 5(6)-chlorobenzimidazolate, and mbIm = 5(6)-methylbenzimidazolate, were prepared by reacting zinc nitrate tetrahydrate and 2-mIm with the respective bIm link in a mixture of N,N-dimethylformamide (DMF) and water. Their structures were determined by single-crystal X-ray diffraction and their permanent porosity shown. All of these structures are hydrophobic as confirmed by water adsorption isotherms. All three ZIFs are equally effective at the dynamic separation of CO2 from N2 under both dry and humid conditions without any loss of performance over three cycles and can be regenerated simply by using a N2 flow at ambient temperature.

Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite‐Type Zeolitic Imidazolate Frameworks

AbstractHydrophobic zeolitic imidazolate frameworks (ZIFs) with the chabazite (CHA) topology are synthesized by incorporating two distinct imidazolate links. Zn(2‐mIm)0.86(bbIm)1.14 (ZIF‐300), Zn(2‐mIm)0.94(cbIm)1.06 (ZIF‐301), and Zn(2‐mIm)0.67(mbIm)1.33 (ZIF‐302), where 2‐mIm=2‐methylimidazolate, bbIm=5(6)‐bromobenzimidazolate, cbIm=5(6)‐chlorobenzimidazolate, and mbIm=5(6)‐methylbenzimidazolate, were prepared by reacting zinc nitrate tetrahydrate and 2‐mIm with the respective bIm link in a mixture of N,N‐dimethylformamide (DMF) and water. Their structures were determined by single‐crystal X‐ray diffraction and their permanent porosity shown. All of these structures are hydrophobic as confirmed by water adsorption isotherms. All three ZIFs are equally effective at the dynamic separation of CO2 from N2 under both dry and humid conditions without any loss of performance over three cycles and can be regenerated simply by using a N2 flow at ambient temperature.

Metal-organic frameworks with precisely designed interior for carbon dioxide capture in the presence of water.

The selective capture of carbon dioxide in the presence of water is an outstanding challenge. Here, we show that the interior of IRMOF-74-III can be covalently functionalized with primary amine (IRMOF-74-III-CH2NH2) and used for the selective capture of CO2 in 65% relative humidity. This study encompasses the synthesis, structural characterization, gas adsorption, and CO2 capture properties of variously functionalized IRMOF-74-III compounds (IRMOF-74-III-CH3, -NH2, -CH2NHBoc, -CH2NMeBoc, -CH2NH2, and -CH2NHMe). Cross-polarization magic angle spinning (13)C NMR spectra showed that CO2 binds chemically to IRMOF-74-III-CH2NH2 and -CH2NHMe to make carbamic species. Carbon dioxide isotherms and breakthrough experiments show that IRMOF-74-III-CH2NH2 is especially efficient at taking up CO2 (3.2 mmol of CO2 per gram at 800 Torr) and, more significantly, removing CO2 from wet nitrogen gas streams with breakthrough time of 610 ± 10 s g(-1) and full preservation of the IRMOF structure.

Copper(I)-Catalyzed Synthesis of Nanoporous Azo-Linked Polymers: Impact of Textural Properties on Gas Storage and Selective Carbon Dioxide Capture

A new facile method for synthesis of porous azo-linked polymers (ALPs) is reported. The synthesis of ALPs was accomplished by homocoupling of aniline-like building units in the presence of copper(I) bromide and pyridine. The resulting ALPs exhibit high surface areas (SABET = 862–1235 m2 g–1), high physiochemical stability, and considerable gas storage capacity especially at high-pressure settings. Under low pressure conditions, ALPs have remarkable CO2 uptake (up to 5.37 mmol g–1 at 273 K and 1 bar), as well as moderate CO2/N2 (29–43) and CO2/CH4 (6–8) selectivity. Low pressure gas uptake experiments were used to calculate the binding affinities of small gas molecules and revealed that ALPs have high heats of adsorption for hydrogen (7.5–8 kJ mol–1), methane (18–21 kJ mol–1), and carbon dioxide (28–30 kJ mol–1). Under high pressure conditions, the best performing polymer, ALP-1, stores significant amounts of H2 (24 g L–1, 77 K/70 bar), CH4 (67 g L–1, 298 K/70 bar), and CO2 (304 g L–1, 298 K/40 bar).

New insights into carbon dioxide interactions with benzimidazole-linked polymers

A synergistic experimental and theoretical study (DFT) highlights the impact of material design at the molecular and electronic levels on the binding affinity and interaction sites of CO2 with benzimidazole-linked polymers (BILPs); CO2 is stabilized by benzimidazole units through Lewis acid-base (N···CO2) and aryl C-H···O=C=O interactions.

Designed amyloid fibers as materials for selective carbon dioxide capture

New materials capable of binding carbon dioxide are essential for addressing climate change. Here, we demonstrate that amyloids, self-assembling protein fibers, are effective for selective carbon dioxide capture. Solid-state NMR proves that amyloid fibers containing alkylamine groups reversibly bind carbon dioxide via carbamate formation. Thermodynamic and kinetic capture-and-release tests show the carbamate formation rate is fast enough to capture carbon dioxide by dynamic separation, undiminished by the presence of water, in both a natural amyloid and designed amyloids having increased carbon dioxide capacity. Heating to 100 °C regenerates the material. These results demonstrate the potential of amyloid fibers for environmental carbon dioxide capture.

Low‐Energy Selective Capture of Carbon Dioxide by a Pre‐designed Elastic Single‐Molecule Trap

Einzelmolekülfalle: Die einfache Aktivierung der wasserbeständigen Metall-organischen Gerüststruktur PCN-200 öffnet eine neue Route für die selektive CO2-Einlagerung durch responsive Adsorption. Der elastische CO2-Einfang wurde anhand von Adsorptionsisothermen für einzelne Komponenten und binäre Gasmischung sowie kristallographische Studien bestätigt. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Low‐Energy Selective Capture of Carbon Dioxide by a Pre‐designed Elastic Single‐Molecule Trap

Single-molecule trap: Easy activation of the water-stable metal-organic framework PCN-200 provides a new route to low-energy selective CO(2) capture through stimuli-responsive adsorption behavior. This elastic CO(2) trapping effect was confirmed by single-component and binary gas-adsorption isotherms and crystallographic determination.

A partially interpenetrated metal–organic framework for selective hysteretic sorption of carbon dioxide

The selective capture of carbon dioxide in porous materials has potential for the storage and purification of fuel and flue gases. However, adsorption capacities under dynamic conditions are often insufficient for practical applications, and strategies to enhance CO(2)-host selectivity are required. The unique partially interpenetrated metal-organic framework NOTT-202 represents a new class of dynamic material that undergoes pronounced framework phase transition on desolvation. We report temperature-dependent adsorption/desorption hysteresis in desolvated NOTT-202a that responds selectively to CO(2). The CO(2) isotherm shows three steps in the adsorption profile at 195 K, and stepwise filling of pores generated within the observed partially interpenetrated structure has been modelled by grand canonical Monte Carlo simulations. Adsorption of N(2), CH(4), O(2), Ar and H(2) exhibits reversible isotherms without hysteresis under the same conditions, and this allows capture of gases at high pressure, but selectively leaves CO(2) trapped in the nanopores at low pressure.

Hydrogen storage and selective carbon dioxide capture in a new chromium(iii)-based infinite coordination polymer

A new chromium(III)-based infinite coordination polymer (ICP) was synthesized under solvothermal conditions. The morphology, particle size and the textural porosity of the resulting solids could be monitored and controlled by adjusting the volume ratio of the solvent mixture (1,4-dioxane/N,N′-dimethylformamide). Two differently textured samples were further compared using powder X-ray diffraction, scanning electron microscopy, FT-IR spectroscopy, solid-state UV-Vis spectroscopy and thermogravimetric analysis. Their sorption capacities for H2, CO2 and CH4 were measured by using volumetric gas adsorption, while the isosteric heats of adsorption for the same gasses were calculated based on gas sorption data at different temperatures. Both samples showed a remarkable selectivity for CO2 over CH4 at 273 K. H2 and CO2 sorption capacities, (respectively 16.9 mg g−1 at 77 K and 817 mm Hg and 168 mg g−1 at 273 K and 760 mm Hg) of the sample composed of the nanosized particles, are comparable or even superior to values reported for most MOFs and ZIFs under similar conditions.