Adsorption Behavior Of Carbon Dioxide Research Articles

Thermodynamic analysis of gate-opening carbon dioxide adsorption behavior of metal-organic frameworks.

Thermodynamic analysis of gate-opening carbon dioxide (CO2) adsorption behavior of metal-organic frameworks (MOFs) was investigated using differential scanning calorimetry (DSC). Unlike measurements under nitrogen atmosphere, obvious exothermic and endothermic peaks were observed in DSC curves under CO2 flow. In situ heating X-ray diffraction and thermogravimetric analyses under CO2 revealed that reversible crystal structure and weight changes occurred upon CO2 adsorption/desorption. The thermodynamic parameters of the CO2 adsorption process by MOFs were determined by DSC analysis at various CO2 partial pressures.

Molecular simulation of the impact of surface roughness on carbon dioxide adsorption in organic-rich shales

This study investigates the adsorption behavior of carbon dioxide in organic nanopores with different surface roughness. The nanopores are constructed by sinusoidally corrugating the graphite slit pore walls. By computing the density distributions, adsorption quantities and orientation of carbon dioxide under various pressure and roughness conditions, we elucidate the impacts of surface roughness on carbon dioxide adsorption in organic nanopores. The Langmuir-Freundlich adsorption model is utilized to fit the isotherms of CO2 adsorption under three different roughness conditions. the results show that increasing surface roughness led to the increase in the adsorption of carbon dioxide, as the relative roughness increased from 0% to 12.92%, the average CO2 adsorption capacity increased by 0.003 mmol/m2. Both the adsorbed layer density and monolayer maximum adsorption capacity increased concurrently with escalating roughness. Moreover, carbon dioxide molecules preferentially aligned parallel to the rough organic surface within the adsorption layer, consistent with the smooth graphitic wall configuration. All simulations, observations, and calculations were performed through grand canonical Monte Carlo (GCMC) simulations. These findings provide insights into the influence of surface roughness on CO2 adsorption, especially in organic nanopores, which has substantial implications for carbon capture and geological sequestration applications. The results could facilitate optimization of strategies for efficient, secure geological CO2 storage.

Carbon dioxide adsorption to 40 MPa on extracted shale from Sichuan Basin, southwestern China

CO2-enhanced shale gas recovery is a promising technology for promoting shale gas production and ideally for CO2 geological sequestration through sorption. Despite this, research studies to date have solely been performed at pressures and temperatures substantially lower than those that actually occur in shale formations. The thrust of this work is to measure and model the carbon dioxide adsorption behavior for the full spectrum of in situ pressure range up to 40 MPa with an intention to provide the baseline values of carbon sequestration planning for the Longmaxi shale formation, Sichuan China. In this study, CO2 adsorption isotherms were measured up to 40 MPa for one sample for five different temperatures (40, 60, 80, 100, and 120 °C) by using the gravimetric method. In the experimental program, we uniquely treated the shale with supercritical CO2 to extract the extractable components to eliminate the high-pressure CO2 extraction effect on adsorption. This pre-extraction was found to significantly reduce the specific surface area of the shale. All excess adsorption trends increased rapidly to maxima followed by the decline to a plateau. The negative excess (Gibbs) adsorptions were observed for two samples at 60 °C and at 40 and 60 °C. At 60 °C, maxima were observed near the critical pressure of CO2 (7.38 MPa) for all samples, which is attributed to the rapid increase of CO2 density near the critical pressure. Adsorption data were fit using several models and the Dubinin-Radushkevich model modified with k times the gas density (MDR + k model) was found to most closely describe the experimental results above 30 MPa. The model-fitted carbon-dioxide maximum absolute adsorption capacities (n0) were 0.150–0.272 mmol/g at 60 °C. Further, n0 decreased with increasing temperature. Thermodynamic data such as heats of adsorption were calculated and used to evaluate CO2 adsorption properties under various conditions. The data also showed that the total organic carbon content of the shale was the primary factor determining CO2 adsorption. The results of this work provide useful knowledge regarding the adsorption characteristics of actual shale formations and are expected to assist in future gas extraction and sequestration projects.

Linking Fluid Densimetry and Molecular Simulation: Adsorption Behavior of Carbon Dioxide on Planar Gold Surfaces

Phase equilibria of fluid substances and their mixtures are important in numerous scientific as well as industrial applications and are, therefore, a major focus of thermophysical property research...

Poly(ionic liquid)-Modified Metal Organic Framework for Carbon Dioxide Adsorption.

The design and synthesis of solid sorbents for effective carbon dioxide adsorption are essential for practical applications regarding carbon emissions. Herein, we report the synthesis of composite materials consisting of amine-functionalized imidazolium-type poly(ionic liquid) (PIL) and metal organic frameworks (MOFs) through complexation of amino groups and metal ions. The carbon dioxide adsorption behavior of the synthesized composite materials was evaluated using the temperature-programmed desorption (TPD) technique. Benefiting from the large surface area of metal organic frameworks and high carbon dioxide diffusivity in ionic liquid moieties, the carbon dioxide adsorption capacity of the synthesized composite material reached 19.5 cm3·g−1, which is much higher than that of pristine metal organic frameworks (3.1 cm3·g−1) under carbon dioxide partial pressure of 0.2 bar at 25 °C. The results demonstrate that the combination of functionalized poly(ionic liquid) with metal organic frameworks can be a promising solid sorbent for carbon dioxide adsorption.

Investigation of the carbon dioxide adsorption behavior and the heterogeneous catalytic efficiency of a novel Ni-MOF with nitrogen-rich channels.

MOFs have attracted remarkable attention as solid sorbents in CO2 capture processes for their low-energy post-combustion. In this paper, a new Ni-based MOF, Ni4(TATB)1.5(EtO)3.5(NEt3)4, was synthesized and characterized using various physicochemical techniques. The efficiency of the as-prepared Ni-MOF as a solid sorbent for CO2 capture was investigated, and acceptable adsorption was exhibited. Furthermore, this Ni-MMOF was used as a catalyst in toluene selective oxidation, for eliminating a volatile organic compound, with tert-butyl hydroperoxide as an oxidant in the absence of organic solvents. The obtained results indicated that Ni-MOF has good catalytic activity and could be reused three times without considerable loss of its catalytic activity. This study highlights the great potential of developing MOFs to achieve green chemistry goals with the removal of hazardous liquid and gas compounds such as toluene and CO2.

Study of Thermal Stability of Hydrotalcite and Carbon Dioxide Adsorption Behavior on Hydrotalcite-Derived Mixed Oxides Using Atomistic Simulations.

Hydrotalcites (HTlcs) or layered double hydroxides (LDHs) have been used in a wide range of applications such as catalysis, electrochemical sensors, wastewater treatment, and carbon dioxide (CO2) capture. In the current study, molecular dynamics simulation was employed to investigate carbon dioxide adsorption behavior on amorphous layered double oxides (LDOs) derived from LDHs at elevated temperatures. The thermal stability of LDHs was first examined by heating the sample up to T = 1700 K. Radial distribution functions confirmed the structural evolution upon heating and the obtained structures were in good agreement with experiments, where periclase was confirmed to be the stable phase in the recrystallized mixed oxides above T = 1200 K. Further, CO2 adsorption was studied as a function of amorphous HTlc-derived oxide composition, where static and dynamic atomistic measures have been employed to characterize the CO2 adsorption behavior. The simulation results showed that the CO2 dynamic residence time on LDH-derived LDOs was sensitive to the Mg/Al molar ratio and the average amount of residence time of CO2 on the surface of LDOs reached maximum when the Mg/Al molar ratio was equal to 3.0. Meanwhile, the activation energy for diffusion also showed local maximum when the Mg/Al molar ratio was 3.0, suggesting that this particular ratio of Mg/Al mixed oxides possessed the highest CO2 adsorption capacity. This is consistent with experimental results. Examination of the binding between CO2 and mixed oxides revealed that both magnesium and oxygen in amorphous LDOs contributed to CO2 adsorption. Further analysis suggested that the interaction between Mg–O and O(LDO)–C were the most important interactions for the physisorption of CO2 on amorphous surface and different CO2 adsorption behavior on different Mg/Al molar ratio surfaces was directly related to their amorphous local structure.

Molecular simulations of competitive adsorption of carbon dioxide – methane mixture on illitic clay surfaces

Molecular dynamics and Monte Carlo simulation studies were carried out to investigate adsorption behavior of carbon dioxide and methane mixtures on illitic clay surfaces under dry conditions. Various compositions of the mixtures and distributions of isomorphic substitutions in clay layers were chosen to explore competitive adsorption depending on component concentration and charge localization. The simulations show that carbon dioxide is preferentially sorbed on the illitic surface and is capable to promote methane desorption. Density distributions of the molecular species in pore space reveal formation of multilayers on the clay surfaces at elevated pressures. Mixed adsorption isotherms were compared with adsorption isotherms of pure compounds and thermodynamic quantities were reported to characterize the interaction of the carbon dioxide and methane with the clay surface.

Effect of Pore Size on the Carbon Dioxide Adsorption Behavior of Porous Liquids Based on Hollow Silica.

Porous liquids are an expanding class of material that has huge potential in gas separation and gas adsorption. Pore size has a dramatic influence on the gas adsorption of porous liquids. In this article, we chose hollow silica nanoparticles as cores, 3-(trihydroxysilyl)-1-propanesulfonic acid (SIT) as corona, and inexpensive industrial reagent polyether amine (M2070) as canopy to obtain a new type of porous liquids. Hollow silica nanospheres with different pore sizes were chosen to investigate the influence of porosity size on CO2 adsorption capacity of porous liquids. Their chemical structure, morphology, thermal behavior and possible adsorption mechanism are discussed in detail. It was proved that with similar grafting density, porous liquid that has bigger pore size possesses a better CO2 adsorption capacity (2.182 mmol g-1 under 2.5 MPa at 298 K). More than that, this article demonstrates a more facile and low-cost method to obtain porous liquids with good CO2 adsorption capacity, recyclability, and huge variability.

Thermodynamic adsorptive properties of exchanged chabazite-like aluminophosphate SAPO-34

The carbon dioxide adsorption behavior of synthesized chabazite-like M-SAPO-34 and modified with alkali metals (M = Li, Na, K, Cs), processed using volumetric method at different temperatures, was explored. The study allowed to see that the adsorption capacity increases according to the sequence: Na + > Li + > K + > Cs +, and all adsorption isothermal are type I according to Brunauer classification. Thermodynamic studies have been treated by the determination of the adsorption affinity, entropy and isosteric heat of these systems CO2-M-SAPO-34 with temperature variation between 273 and 298 K. The adsorption affinity shows the same trend for all the M-SAPO-34 at low coverage at 273 K. However, at high coverage, the isosteric heats of exchanged (H, Na, Li)-SAPO-34 present a homogeneous profile indicating dominance of adsorbate-adsorbate interaction. The differentials entropies were found to increase slightly with the coverage. Furthermore, the entropy of K-SAPO-34 at 273, exhibits values less than other exchanged M-SAPO-34. This Confirms pore blockage effect in the case of K-SAPO-34 and leads to reduction of free volume, while the Li-SAPO-34 shows the highest values of entropies with large free volume due to small size of Li+ cation.

Study of CO2 adsorption on iron oxide doped MCM-41

Carbon dioxide adsorption behaviors of iron oxide doped mesoporous silica (MCM-41) were investigated. The iron oxide doped on MCM-41 samples were prepared by impregnation method with iron concentrations of 0.10, 0.25, 0.50, 0.75 and 1.0 wt%. The XRD patterns indicate highly dispersed forms of iron oxide on MCM-41. The results from N2 adsorption-desorption showed that there was no difference in mesoporous structure upon the addition of iron oxide and that the morphology of doped adsorbent was slightly distorted from its original spherical shape. Adsorption isotherm indicated that modifying MCM-41 with iron oxide can increase CO2 adsorption with the best result being achieved with 0.50 wt%Fe/MCM-41. Good correlations between the adsorption extent and the surface area were observed. Interaction between CO2 and Fe atoms were studied by X-ray absorption near edge structure (XANES). XANES spectra indicated the transfer of metal d-electrons to CO2 π*-antibonding orbital giving rise to additional adsorption. Stronger bonding between CO2 and the adsorbent was indicated by the increase of the isosteric heat of adsorption.

Adsorption behavior of carbon dioxide and methane in bituminous coal: A molecular simulation study

The adsorption behavior of CO2, CH4 and their mixtures in bituminous coal was investigated in this study. First, a bituminous coal model was built through molecular dynamic (MD) simulations, and it was confirmed to be reasonable by comparing the simulated results with the experimental data. Grand Canonical Monte Carlo (GCMC) simulations were then carried out to investigate the single and binary component adsorption of CO2 and CH4 with the built bituminous coal model. For the single component adsorption, the isosteric heat of CO2 adsorption is greater than that of CH4 adsorption. CO2 also exhibits stronger electrostatic interactions with the heteroatom groups in the bituminous coal model compared with CH4, which can account for the larger adsorption capacity of CO2 in the bituminous coal model. In the case of binary adsorption of CO2 and CH4 mixtures, CO2 exhibits the preferential adsorption compared with CH4 under the studied conditions. The adsorption selectivity of CO2 exhibited obvious change with increasing pressure. At lower pressure, the adsorption selectivity of CO2 shows a rapid decrease with increasing the temperature, whereas it becomes insensitive to temperature at higher pressure. Additionally, the adsorption selectivity of CO2 decreases gradually with the increase of the bulk CO2 mole fraction and the depth of CO2 injection site.

Chemisorption working capacity and kinetics of CO2 and H2O of hydrotalcite-based adsorbents for sorption-enhanced water-gas-shift applications

The adsorption behavior of carbon dioxide and water on a K-promoted hydrotalcite based adsorbent has been studied by thermogravimetric analysis with the aim to better understand the kinetic behavior and mechanism of such material in sorption enhanced water-gas shift reactions.The cyclic adsorption capacity was measured as a function of temperature (300–500°C), pressure (0–8bar) and the cycle time. Both species interact at elevated temperatures with the adsorbent. The history of the adsorbent (pretreatment/desorption conditions) has a profound influence on its sorption capacity. Slow desorption kinetics determine the sorption capacity during cyclic operation, where a high temperature during the desorption and long half-cycle times can increase the cyclic working capacity for both CO2 and H2O significantly. Accounting for the sorbent history and the definition of adsorption capacity are very important features when comparing sorption capacities to values reported in literature. The adsorbent shows very high capacities for H2O compared to CO2 which has not been reported in the literature up to now. The mechanism for H2O and CO2 adsorption seems to be a different one. Whereas H2O adsorption seems to follow the principles of a simple physisorption mechanism, CO2 adsorption can only be explained by a chemical reaction with the adsorbent. Working isotherms (cyclic working capacity at isothermal conditions at different pressures) of both CO2 and H2O were measured up to 8bar total pressure. Higher partial pressures increase the cyclic working capacity of the adsorbent up to 0.47mmol/g for CO2(PCO2=8bar) and 1.06mmol/g for H2O (PH2O=4.2bar) at 400°C after 30min of adsorption followed by 30min of dry regeneration with N2.

다양한 아미노실란을 이용한 이산화탄소 흡착제 합성 및 흡착 특성

The carbon dioxide adsorption behavior of silica with a large specific surface area and pore volume functionalized with aminosilane compounds via in-situ polymerization and functionalization method were investigated. The organosilanes include amino functional group capable of adsorbing carbon dioxide. Elemental analyzer, in situ FT-IR and thermogravimetric analyzer were used to characterize the sorbents and to determine their CO2 adsorption behavior. Comparison of different aminosilane loading in the support revealed that polyaminosilane functionalization of 70% of the pore volume in the support was better in terms of the adsorption capacity and amine efficiency than that of 100% of the pore volume of the support. Furthermore, the sorbents showed a higher adsorption capacity at an adsorption temperature of 75 ℃ than at 30 ℃ due to the thermal expansion of synthesized polyaminosilanes inside the pore of silica. The N-[3-(trimethoxysilyl)propyl]ethylenediamine (2NS) sorbent with 70% of the pore volume functionalized showed the highest adsorption capacity of 9.2 wt% at 75 ℃.

Facile synthesis of nitrogen-enriched mesoporous carbon for carbon dioxide capture

Abstract To investigate carbon dioxide adsorption behaviors, we prepared mesoporous carbon (MC) materials that incorporated framework nitrogen functional groups via a facile polymerization-induced colloid aggregation (PICA) procedure, where the nitrogen content varied as a function of carbonization temperature. The prepared MCs had high specific surface areas (e.g., 974 m2/g) with well-developed mesopores. The highest carbon dioxide adsorption capacity of 106 mg/g at 25 °C was achieved with the MCs-800 sample (carbonization temperature of 800 °C). We found that the materials prepared in this study were highly effective for carbon dioxide capture, because the nitrogenous functional groups in the MCs enhanced their affinities for acidic carbon dioxide.

Synthesis of a honeycomb-like Cu-based metal–organic framework and its carbon dioxide adsorption behaviour

Herein, we report on a new Cu-based MOF material, Cu(2)(dhtp), structurally homologous to the honeycomb-like M(2)(dhtp) series. This has been crystallized under solvothermal conditions using copper nitrate and 2,5-dihydroxyterephthalic acid as an organic linker, being the nature of the co-solvent in the synthesis media an important variable over the final physical properties of the material. The presence of isopropanol as a co-solvent leads to the formation of a pure crystalline phase with textural properties comparable to M(2)(dhtp) homologues. The interesting results in CO(2) adsorption properties of this new material, especially its isosteric heat of adsorption, make it a suitable MOF to be further evaluated under real conditions of industrial CO(2) capture.

Effect of Ion-Exchange Modification on Hydrogen and Carbon Dioxide Adsorption Behaviour of RhoZMOF Material

Zeolite-like metal-organic frameworks (ZMOFs) can adsorb hydrogen and carbon dioxide because of their negatively charged structures, being able to be ion exchanged with metal cations to further increase the electrostatic field inside the framework cavities. Ion exchange of RhoZMOF with alkaline and alkaline-earth metal cations was performed up to stoichiometric levels with one single ion-exchange step. Screen effect caused by water-coordinated molecules around the exchanged cations hindered the hydrogen uptake, although slightly higher heats of hydrogen adsorption were observed for Na+, Li+, Mg2+ and Ca2+ exchanged samples. Conversely, the same exchange treatment produced a very interesting enhancement in CO2 adsorption of RhoZMOF at 303 K. Moreover, because there are no water molecules surrounding the metallic cations, RhoZMOF material was exchanged with an Li+–crown–ether complex in the nitrobenzene/acetonitrile mixture, free of water. Nitrogen and hydrogen adsorption isotherms at 77 K showed higher specific surface area and hydrogen adsorption capacity than the material with hydrated cations.

Influence of nickel oxide on carbon dioxide adsorption behaviors of activated carbons

In this work, the adsorption behaviors of nickel oxide loaded activated carbons were studied in carbon dioxide capture. The nickel oxides were introduced onto the activated carbons using a post-oxidation method including nickel electroless plating at 573K in an air stream. The structure of the nickel oxide loaded activated carbons was characterized by XRD. The nickel oxide contents on the activated carbons were verified by XPS, and the textural properties were analyzed by N2/77K isotherms. The carbon dioxide adsorption behaviors of the nickel oxide loaded activated carbons were observed in the amounts of carbon dioxide adsorptions at 298K and 1.0atm. As the post-oxidation time increased, the carbon dioxide adsorption capacity was enhanced. From the results, it was found that the nickel oxide on the activated carbons led to an increase in the carbon dioxide adsorption capacity of the activated carbons.

Influence of Amine Grafting on Carbon Dioxide Adsorption Behaviors of Activated Carbons

In this work, the amine grafting treated activated carbons were studied for carbon dioxide adsorbent. The surfaces of activated carbon were functionalized by 3-chloropropyltrimethoxysilane, which was subsequently grafted with amine compounds tris-(2-aminoethyl)amine and tri-ethylenetetramine and subjected to comparison. The surface functional groups of the amine grafted activated carbons were characterized using XPS. The textural properties of the amine grafted activated carbons were analyzed by <TEX>$N_2$</TEX>/77 K isotherms. Carbon dioxide adsorption behaviors of the amine grafted activated carbons were examined via the amounts of carbon dioxide adsorption at 298 K and 1.0 atm. From the results, tris-(2-aminoethyl)amine grafted activated carbons showed 43.8 <TEX>$cm^3$</TEX>/g of carbon dioxide adsorption while non-treated activated carbons and triethylenetetramine grafted activated carbons showed less carbon dioxide adsorption. These results were thought to be due to the presence of isolated amine groups in the amine compounds. Tris-(2-aminoethyl)amine grafted activated carbons have basic features that result in the enhancement of adsorption capacity of the carbon dioxide molecules, which have an acidic feature.

Solvo- or hydrothermal fabrication and excellent carbon dioxide adsorption behaviors of magnesium oxides with multiple morphologies and porous structures

MgO nano/microparticles with multiple morphologies and porous structures have been fabricated via the surfactant (poly( N-vinyl-2-pyrrolidone, poly(ethylene glycol) (PEG), cetyltrimethylammonium bromide, oleylamine or triblock copolymer P123 or F127) assisted solvo- or hydrothermal route in a dodecylamine or oleic acid solvent. The as-fabricated MgO samples were characterized by means of numerous techniques. It is shown that the obtained MgO samples were single-phase and of cubic in crystal structure; the particle morphology and pore architecture mainly depended upon the surfactant, solvent, and solvo- or hydrothermal temperature adopted. The solvothermal process resulted in polycrystalline MgO, whereas the hydrothermal one gave rise to single-crystalline MgO. Surface areas (8–169 m 2 g −1) of the MgO samples derived solvothermally were lower than those (181–204 m 2 g −1) of the MgO counterparts derived hydrothermally, with the mesoporous MgO generated after the PEG-assisted hydrothermal treatment at 240 °C for 72 h possessing the highest surface area. CO 2 adsorption capacities of the MgO samples were in good agreement with their surface areas, and the mesoporous MgO derived hydrothermally with PEG at 240 °C for 72 h exhibited the largest CO 2 uptake (368 μmol g −1) below 350 °C. We believe that such a high low-temperature adsorption capacity renders the mesoporous magnesia material useful in the utilization of acidic gas adsorption.