CO_2 adsorption performance of different amine-based siliceous MCM-41 materials

A series of amine-based adsorbents were synthesized using siliceous MCM-41 individually impregnated with four different amines（ethylenediamine（EDA）,diethylenetriamine（DETA）,tetraethylenepentamine（TEPA） and pentaethylenehexamine（PEHA）） to study the effect of amine chain length and loading weight on their CO2 adsorption performances in detail.The adsorbents were characterized by FT-IR,elemental analysis,and thermo-gravimetric analysis to confirm their structure properties.Thermo-gravimetric analysis was also used to evaluate the CO2 adsorption performance of adsorbents.Longer chain amine-based materials can achieve higher amine loadings and show better thermal stability.The CO2 adsorption capacities at different temperatures indicate that the CO2 adsorption is thermodynamically controlled over EDAMCM41 and DETA-MCM41,while the adsorption over TEPA-MCM41 and PEHA-MCM41 is under kinetic control at low temperature.The chain length of amines affects the CO2 adsorption performance and the adsorption mechanism significantly.The results also indicate that CO2 adsorption capacity can be enhanced despite of high operation temperatures,if appropriate amines（TEPA and PEHA） are applied.However,adsorbents with short chain amine exhibit higher adsorption and desorption rates due to the collaborative effect of rapid reaction mechanisms of primary amines and less diffusion resistance of shorter chain length amines.

Molten salts-modified MgO-based adsorbents for intermediate-temperature CO_2 capture: A review

Carbon dioxide（CO2） capture using magnesium oxide（MgO）-based adsorbents at intermediate temperatures has been regarded as a very prospective technology for their relatively high adsorption capacity,low cost, and wide availability. During the past few years, great effort has been devoted to the fabrication of molten salts-modified MgO-based adsorbents. The extraordinary progress achieved by coating with molten salts greatly promotes the COcapture capacity of MgO-based adsorbents. Therefore, we feel it necessary to deliver a timely review on this type of COcapturing materials, which will benefit the researchers working in both academic and industrial areas. In this work, we classified the molten saltsmodified MgO adsorbents into four categories:（1） homogenous molten salt-modified MgO adsorbents,（2） molten salt-modified double salts-based MgO adsorbents,（3） mixed molten salts-modified MgO adsorbents, and（4） molten salts-modified MgO-based mixed oxides adsorbents. This contribution critically reviews the recent developments in the synthetic method, adsorption capacity, reaction kinetics, promotion mechanism, operational conditions and regenerability of the molten salts-modified MgO COadsorbents. The challenges and prospects in this promising field of molten salts-modified MgO COadsorbents in real applications are also briefly mentioned.

Enhancement of CO_2 adsorption on nanoporous chromium terephthalate(MIL-101) by amine modification

Carbon dioxide （CO2） adsorption on a standard metal-organic framework MIL-101 and a pentaethylenehexamine modified MIL-101 （PEHA- MIL-101） are investigated and compared in this study. The adsorbent samples were characterized by XRD, FT-IR and nitrogen adsorption- desorption isotherms analysis. CO2 adsorption capacity was measured by a volumetric method. MIL-101 and PEHA-MIL-101 exhibited CO2 adsorption capacities of 0.85 and 1.3 mmO1CO2/gadsorbent at 10 bar and 298 K, respectively. It is observed that CO2 adsorption capacity was fairly improved about 50% after amine modification.

Construction of a Pillared-layer Framework Based on Charge Balance:CO2 Adsorption and Luminescence

Via the strategy of charge balance,one new pillared layered metal-organic framework [Zn2（TNB）（2-nim）]（H3TNB = 4,4？,4？？-nitrilotribenzoicacid,2-nim = 2-nitroimidazole）（1） was successfully synthesized based on mixed ligands,where binuclear [Zn2（CO2）3]~＋ cluster-based cationic layers [Zn2（TNB）]~＋ are connected by deprotonated 2-nitroimidazole.Meanwhile,CO2 adsorption bahaviors and luminescent property of compound 1 were investigated.

A Doubly Interpenetrated Co(Ⅱ) Framework：Synthesis,Crystal Structure and Selective Adsorption of CO_2

A novel,porous and doubly interpenetrated MOF（FJU-29） was synthesized and characterized by FT-IR,TGA and X-ray single-crystal/powder diffraction.FJU-29 crystallizes in monoclinic,space group C2/c with a = 22.2890（7）,b = 10.9175（2）,c = 21.5601（7） ？,β = 112.908（4）o,V = 4832.7（3） ？~3,Z = 8,Mr = 450.26,D_c = 1.238 g/cm^3,F（000） = 1832,μ（CuKα） = 5.885 mm^（-1）,R = 0.0585 and wR = 0.1544 for 4789 observed reflections（I 〉 2s（I））,and R = 0.0726 and wR = 0.1627 for all data.FJU-29 possesses paddle-wheel {Co_2（COO）_4} clusters bridged by bi-pyrazolate naphthalene diimide ligands（H_2NDI） and H_2BDC to from a 3D framework with a pcu-topology.The desolvated FJU-29a shows the BET surface area of 560.44 m^2·g^（-1） accompanies with discriminating uptakes in CO_2 and N_2.The adsorption selectivity determined by ideal adsorbed solution theory（IAST） indicated that FJU-29 a has high CO_2/N_2（18/85） selectivity（75.5） at 296 K and 100 kPa.The relatively high selectivity further implies that FJU-29 a is a potential material for practical flue gas purification.

MgO-decorated carbon nanotubes for CO_2 adsorption:first principles calculations

The global greenhouse effect makes it urgent to deal with the increasing greenhouse gases. In this paper the performance of MgO-decorated carbon nanotubes for CO2 adsorption is investigated through first principles calculations. The results show that the MgO-decorated carbon nanotubes can adsorb CO2 well and are relatively insensitive to O2 and N2 at the same time. The binding energy arrives at 1.18 eV for the single-MgO-decorated carbon nanotube adsorbing one CO2 molecule, while the corresponding values for O2 and N2 are 0.55 eV and 0.06 eV, respectively. In addition, multi-molecule adsorption is also proved to be very satisfactory. These results indicate that MgO-decorated carbon nanotubes have great potential applications in industrial and environmental processes.

Breakthrough CO_2 adsorption in bio-based activated carbons

In this work, the effects of different methods of activation on CO2 adsorption performance of activated carbon were studied. Activated carbons were prepared from biochar, obtained from fast pyrolysis of white wood, using three different activation methods of steam activation, CO2 activation and Potassium hydroxide（KOH） activation. CO2 adsorption behavior of the produced activated carbons was studied in a fixed-bed reactor set-up at atmospheric pressure, temperature range of 25–65°C and inlet CO2 concentration range of10–30 mol% in He to determine the effects of the surface area, porosity and surface chemistry on adsorption capacity of the samples. Characterization of the micropore and mesopore texture was carried out using N2 and CO2 adsorption at 77 and 273 K, respectively.Central composite design was used to evaluate the combined effects of temperature and concentration of CO2 on the adsorption behavior of the adsorbents. The KOH activated carbon with a total micropore volume of 0.62 cm3/g and surface area of 1400 m2/g had the highest CO2 adsorption capacity of 1.8 mol/kg due to its microporous structure and high surface area under the optimized experimental conditions of 30 mol% CO2 and 25°C. The performance of the adsorbents in multi-cyclic adsorption process was also assessed and the adsorption capacity of KOH and CO2 activated carbons remained remarkably stable after50 cycles with low temperature（160°C） regeneration.

Experimental and computational investigation of adsorption performance of TC-5A and PSA-5A for manned spacecraft

Two kinds of molecular sieve materials, TC-5A and PSA-5A, were produced to satisfy with special requirement of manned space flight. Their CO2 adsorption performances were investi- gated and compared through two experiments, the thermo gravimetric analysis （TGA） experiment and packed bed column experiment. Besides, some kinetic equations were compared according to the TGA experimental data, and their errors were analyzed. Finally, the classic linear driving force （LDF） model is improved to the new Avrami＇s model, and two models are analyzed based on the packed bed data. The TGA data shows that the CO2 loading has an approximately linear relation- ship with the CO2 concentration, and the best fit adsorption temperature range is from 283 to 303 K. The packed bed column results show that water vapor in air can affect the CO2 adsorption performance badly. The new Avrami＇s model is proved more suitable to reflect the complex adsorption mechanism for two molecular sieves. The materials are proved having much better adsorption capacity than the other adsorbents with room temperature and low CO2 concentration （≤ 1.0% in volume）, and they can meet the aerospace requirements. This work will benefit the optimal design and simulation of the air revitalization （AR） system for Chinese manned spacecraft.

Enhanced CO_2 adsorptive performance of PEI/SBA-15 adsorbent using phosphate ester based surfactants as additives

In this study,a series of polyetherimide/SBA-15： 2-D hexagonal P6 mm,Santa Barbara USA（PEI/SBA-15） adsorbents modified by phosphoric ester based surfactants（including tri（2-ethylhexyl）phosphate（TEP）,bis（2-ethylhexyl） phosphate（BEP） and trimethyl phosphonoacetate（TMPA））were prepared for CO2 adsorption.Experimental results indicated that the addition of TEP and BEP had positive effects on CO2 adsorption capacity over PEI/SBA-15.In particular,the CO2 adsorption amount could be improved by around 20% for 45PEI-5TEP/SBA-15 compared to the additive-free adsorbent.This could be attributed to the decrease of CO2 diffusion resistance in the PEI bulk network due to the interactions between TEP and loaded PEI molecules,which was further confirmed by adsorption kinetics results.In addition,it was also found that the cyclic performance of the TEP-modified adsorbent was better than the surfactant-free one.This could be due to two main reasons,based on the results of in situ DRIFT and TG-DSC tests.First and more importantly,adsorbed CO2 species could be desorbed more rapidly over TEP-modified adsorbent during the thermal desorption process.Furthermore,the enhanced thermal stability after TEP addition ensured lower degradation of amine groups during adsorption/desorption cycles.

Carbon dioxide adsorption behaviors of aluminum-pillared montmorillonite-supported alkaline earth metals

The Al-pillared montmorillonite-supported alkaline earth metal 5M/Al-PILC(PILC = pillared clay, M = Mg, Ca, Sr, and Ba) and x Mg/Al-PILC( x = 1, 3, 5, and 7 wt.%) samples were prepared using an impregnation method. Physical properties of the materials were determined by means of X-ray diffraction(XRD) and N2 adsorption-desorption, and their CO2 adsorption behaviors were investigated using the thermogravimetric analyzer(TG), CO2 temperatureprogrammed desorption(CO2-TPD), and in situ diffuse reflectance infrared transform spectroscopy(in situ-DRIFTS) techniques. It is shown that 5 Mg/Al-PILC possessed the highest CO2 adsorption capacity(2.559 mmol/g). The characterization results indicate that Alpillaring increased the specific surface area of montmorillonite, which was beneficial for the adsorption of CO2. The CO2 adsorption process on the sample was mainly chemical adsorption, and alkalinity was the main factor influencing its adsorption capacity. The alkalinity of the sample was enhanced by loading an appropriate amount of alkaline earth metal, and the adsorbed CO2 was present in the form of bicarbonate and carbonate. In addition, the 5Mg/Al-PILC sample exhibited an excellent regeneration efficiency. We believe that the outcome of this research would provide a good option for developing highly effective CO2 adsorption materials.

Synthesis of a Rare Doubly-interpenetrating Zinc(II) Coordination Polymer for Applications in Photocatalysis

A rare doubly-interpenetrating Zn-MOF(complex 1),formulated as{Zn(tci)-(bpy)(NO3)·DMF·0.5CH3CN}n(H3tci=tri(2-carboxyethyl)isocyanurate,bpy=4,4-bipyridine),has been constructed under solvothermal conditions and characterized by single-crystal X-ray diffraction,infrared spectroscopy(IR)and powder X-ray diffraction(PXRD).1 crystallizes in monoclinic system,space group C2/c with a=21.5759(4),b=12.87221(18),c=26.4917(5)Å,β=109.462(2)°,V=6937.1(2)Å3,C50H56N14O27Zn4,Mr=1546.56,Z=4,Dc=1.481 g·cm-3,μ=2.325 mm-1λ=1.54178Å,F(000)=3160,S=1.041,R=0.0621 and wR=0.1773.1 features a two-fold interpenetrating 3D hms topology.Moreover,the thermal stabilities,fluorescent and CO2 adsorption properties were investigated.Complex 1 showed highly encoura-ging photocatalytic degradation of toxic dye molecules with a potential application in wastewater purification.

Novel Porous Aromatic Framework with Excellent Separation Capability of CO2 in N2 or CH4

A novel porous aromatic framework, PAF-52, was obtained via the polymerization of tetrahedral mono- mer tetrakis（4-cyanodiphenyl） methane（TCDPM） with the aid of a facile ionothermal method. PAF-52 has a surface area of 1159 m2/g（BET）, and shows a considerable high separation ability of CO2 in N2 or CH4 respectively at room temperature, using gas-chromatography experiments as evidence,

Targeted synthesis of novel porous aromatic frameworks with selective separation of CO_2/CH_4and CO_2/N_2

Novel porous aromatic frameworks（PAF-53 and PAF-54） have been obtained by the polymerization of amino compound（p-phenylenediamine and melamine） and cyanuric chloride. They display a certain amount of CO2 adsorption capacity and highly selective separation of CO2/CH4 and CO2/N2 as 18.1 and83 by Henry Law respectively. They may be applied as ideal adsorbents to separate and capture CO2.

Hyper-crosslinked Porous Polymer Based on Bulk Rigid Monomer for Gas and Dye Absorptions

Using the rigid 3,3-bis（4-hydroxyphenyl）-2-（4-tritylphenyl）isoindolin-l-one with polar functional groups as a building block and formaldehyde dimethyl acetal（FDA） as crossinglinker, a new hyper-crosslinked polymer （HCP） was synthesized via Friedel-Crafts alkylation reaction promoted by anhydrous FeC13. The synthesized HCP is insoluble in boiled water and common organic solvents. Moreover, it shows a good CO2 capture capacity even if its surface area is not very high, and the absolute COz uptake capacity of it is 3.05 mmol/g. This can be attributed to the introduction of polar hydroxyl and lactam groups into the skeleton of the polymer, which provides effective adsorp- tion sites for COz. In addition, the synthesized HCP also exhibits good adsorption capacity for organic dyes in water, especially for crystal violet.

Synthesis of porous aromatic framework with Friedel–Crafts alkylation reaction for CO_2 separation

A novel porous aromatic framework, PAF-8, derived from tetraphenylsilane as basic building unit, was successfully synthesized via Friedel-Crafts alkylation reaction. This PAF material had high thermal stability as well as high surface area （785 m^2 g^-1） calculated from the Brunauer-Emmett-Teller （BET） model. Meanwhile, PAF-8 possessed high performances in gas sorption and especially for CO2 separation.

Mesoporous carbon adsorbents from melamine–formaldehyde resin using nanocasting technique for CO_2 adsorption

Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine-formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction（XRD）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, thermogravimetric analysis（TGA）, elemental（CHN） analysis, Fourier transform infrared（FTIR） spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO2 capture.The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO2 adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO2 adsorption capacity among the synthesized adsorbents. Breakthrough time and CO2 equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent-CO2 system was found to be reversible with stable adsorption capacity over four consecutive adsorption-desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.

Adsorption of carbon dioxide on amine-modified TiO_2 nanotubes

TiO2 nanotubes （TiNT） were prepared by a hydrothermal treatment and modified by three kinds of amines,namely ethylenediamine,polyetherimide and tetraethylenepentamine （TEPA）,to study their CO2 adsorption properties from gas streams.The resultant samples were characterized by X-ray diffraction,transmission electron microscopy,and infrared spectroscopy,as well as low temperature N 2 adsorption.CO2 capture was investigated in a dynamic packed column at 30℃.TEPA-modified TiO2 nanotubes showed the highest adsorption capacity of 167.64 mg/g because it had the highest amino-group content among the three amines.CO2 fixation on TiNT impregnated by TEPA was investigated at 30,50,and 70℃,and the adsorption capacity increased slightly with temperature.Following the adsorption step,the sorbents were regenerated by temperature programmed desorption,and the TiNT-TEPA sample,as CO2 sorbent,was found to be readily regenerated and energy-efficient.The cycle test also revealed that the TiNT-TEPA adsorbent is fairly stable,with only a 5% drop in the adsorption capacity after 10 adsorption/desorption cycles.In addition,the CO2 adsorption behavior was investigated with the deactivation model,and which showed an excellent prediction for the TiNT-TEPA breakthrough curves.

Enhanced carbon dioxide adsorption performance and kinetic study of K and Al co-doped Li4SiO4

Herein, we report the effects of doped K and Al on the carbon dioxide （CO2） adsorption performance of the Li4SiO4-based adsorbents. The CO2 adsorption capacity of 0.8 wt% K and 1.5 wt% AI doped Li4SiO4 is ～2.2 times and ～1.3 times higher than that of the pristine Li4SiO4 at 500 and 600℃, respectively. The kinetic study further indicated that the reaction rates of the lithium diffusion process is greatly improved by K and AI doping, and the lithium diffusion rate of 0.8 wt% K and 1.5 wt% AI doped Li4SiO4 is ～2 times higher than that of the pristine Li4SiO4 at 575-650 ℃. K and AI doping increases the adsorption capacity of Li4SiO4-based adsorbents, and widens its effective adsorption temperature range

CO_2 adsorption using TiO_2 composite polymeric membranes:A kinetic study

CO2is the main greenhouse gas which causes global climatic changes on larger scale. Many techniques have been utilised to capture CO2. Membrane gas separation is a fast growing CO2 capture technique, particularly gas separation by composite membranes. The separation of CO2 by a membrane is not just a process to physically sieve out of CO2 through the controlled membrane pore size. It mainly depends upon diffusion and solubility of gases, particularly for composite dense membranes. The blended components in composite membranes have a high capability to adsorb CO2. The adsorption kinetics of the gases may directly affect diffusion and solubility. In this study, we have investigated the adsorption behaviour of CO2 in pure and composite membranes to explore the complete understanding of diffusion and solubility of CO2 through membranes. Pure cellulose acetate（CA） and cellulose acetatetitania nanoparticle（CA-TiO2） composite membranes were fabricated and characterised using SEM and FTIR analysis. The results indicated that the blended CA-TiO2 membrane adsorbed more quantity of CO2 gas as compared to pure CA membrane. The high CO2 adsorption capacity may enhance the diffusion and solubility of CO2 in the CA-TiO2 composite membrane, which results in a better CO2 separation. The experimental data was modelled by Pseudo first-order, pseudo second order and intra particle diffusion models.According to correlation factor R2, the Pseudo second order model was fitted well with experimental data. The intra particle diffusion model revealed that adsorption in dense membranes was not solely consisting of intra particle diffusion.

Microporous Hypercross-linked Conjugated Quinonoid Chromophores of Anthracene: Novel Polymers for CO_2 Adsorption

Microporous hypercross-linked conjugated quinonoid chromophores represent a novel class of amorphous polymers, synthesized by the reaction of anthracene with dimethoxy methane in the presence of FeCl3 catalyst. Their N2 adsorption isotherms confirm their microporous nature. Diffuse reflectance UV-Visible（DRS UV-Vis） spectroscopy confirms their matrix built with the conjugated quinonoids by their broad light absorption characteristics extending from 1000 nm to 200 nm with the absorbance maximum close to 400 nm. The catalyst cross-linked anthracene with ―CH2― bridges and subsequently dehydrogenating them to form quinonoids. Their Fourier transform infrared（FTIR） spectra showed their characteristic quinonoid vibrations between 1600 and 1700 cm-1. The synthesis of polymers was carried out at 30, 40, 50, 60, 70 and 80 ℃, but the quinonoid content of the polymer obtained at 80 ℃ was higher than that of the others. Their scanning electron microscopy（SEM） images showed microspheres of 1 to 5 μm size built with tiny particles. Their surfaces were not smooth. The polymer synthesized at 80 ℃ showed 5.1 wt% CO2 sorption at 25 ℃ and 0.1 MPa, but when it was recross-linked, the CO2 sorption increased to 8 wt%. Hence, hypercross-linked conjugated quinonoid chromophores of anthracene are good for sorption of CO2.