Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

Metal-organic frameworks (MOFs) have attracted much attention as adsorbents for the separation of CO₂ from flue gas or natural gas. Here, a typical metal-organic framework HKUST-1(also named Cu-BTC or MOF-199) was chemically reduced by doping it with alkali metals (Li, Na and K) and they were further used to investigate their CO₂ adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction (XRD), thermo-gravimetric analysis (TGA) and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO₂ storage capacity of HKUST-1 doped with moderate quantities of Li⁺, Na⁺ and K⁺, individually, was greater than that of unmodified HKUST-1. The highest CO₂ adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST-1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO₂ than those of N₂. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO₂ after 10 cycles.     

Fast recovery of Au (III) and Ag(I) via amine-modified zeolitic imidazolate framework-8

In this paper, zeolitic imidazolate framework-8 modified by the ethanediamine (NH₂-ZIF-8) was employed for adsorbing Au (III) and Ag(I) from aqueous solutions. The adsorption capacities of NH₂-ZIF-8 towards Au (III) and Ag(I) were found to be significantly affected by the pH values of the solution. The adsorption kinetics studies show that NH₂-ZIF-8 presents a fast adsorption property towards metals, attaining 93% of adsorption equilibrium uptake for Au (III) within the first 30 min. This phenomenon can be ascribed to the coordination interaction between the amino group and Au (III). The thermodynamic data suggest that the adsorption of NH₂-ZIF-8 towards Au (III) is endothermic process, while that for Ag(I) is exothermic. The maximum adsorption capacities of NH₂-ZIF-8 toward Au (III) and Ag(I) can be achieved to 357 mg·g⁻¹ and 222.25 mg·g⁻¹, respectively. The metal ions interference results show that Cu (II) and Ni (II) hardly have no interference on Au (III) adsorption in e-waste containing 1500 mg·l⁻¹ Cu (II),100 mg·l⁻¹ Ni (II) and 10 mg·l⁻¹ Au (III); while for Ag(I), Cd (II) and Zn (II) have little interference on Ag(I) adsorption in the hybrid solutions containing Ag(I), Ni (II), Cd (II) and Zn (II) with equal concentration (50 mg·l⁻¹), but Ni (II) interference most. The XPS study shows that partial Au (III) was reduced to Au(I), and that Ag(I) was completely reduced to Ag(0) during the adsorption process. The abundant of active sites of NH₂-ZIF-8 containing C=N, N-H, and Zn-OH groups play a key role in the adsorption of Au (III) and Ag(I). In addition, electrostatic interaction can be responsible for the adsorption of Au (III) by NH₂-ZIF-8. The regeneration experiments results show that the adsorption capacities of NH₂-ZIF-8 towards Au (III) and Ag(I) can maintain after three cycles. This work provides a reliable method to improve the adsorption kinetics for metal ions.     

Equilibrium isotherms and isosteric heat for CO<Subscript>2</Subscript> adsorption on nanoporous carbons from polymers

Four nanoporous carbons obtained from different polymers: polypyrrole, polyvinylidene fluoride, sulfonated styrene–divinylbenzene resin, and phenol–formaldehyde resin, were investigated as potential adsorbents for carbon dioxide. CO₂ adsorption isotherms measured at eight temperatures between 0 and 60 °C were used to study adsorption properties of these polymer-derived carbons, especially CO₂ uptakes at ambient pressure and different temperatures, working capacity, and isosteric heat of adsorption. The specific surface areas and the volumes of micropores and ultramicropores estimated for these materials by using the density functional theory-based software for pore size analysis ranged from 840 to 1990 m² g^?1, from 0.22 to 1.47 cm³ g^?1, and from 0.18 to 0.64 cm³ g^?1, respectively. The observed differences in the nanoporosity of these carbons had a pronounced effect on the CO₂ adsorption properties. The highest CO₂ uptakes, 6.92 mmol g^?1 (0 °C, 1 atm) and 1.89 mmol g^?1 (60 °C, 1 atm), were obtained for the polypyrrole-derived activated carbon prepared through a single carbonization-KOH activation step. The working capacity for this adsorbent was estimated to be 3.70 mmol g^?1. Depending on the adsorbent, the CO₂ isosteric heats of adsorption varied from 32.9 to 16.3 kJ mol^?1 in 0–2.5 mmol g^?1 range. Overall, the carbons studied showed well-developed microporosity and exceptional CO₂ adsorption, which make them viable candidates for CO₂ capture, and for other adsorption and environmental-related applications.     

Theoretical Investigations on MIL-100(M) (M=Cr,Sc, Fe) with High Adsorption Selectivity for Nitrogen and Carbon Dioxide over Methane

The removal of impurity gases (N₂, CO₂) in natural gas is critical to the efficient use of natural gas. In this work, the selective adsorption for N₂ and CO₂ over CH₄ on MIL-100 (M) (M=⁴Cr, ¹⁰Cr, ⁶Fe, ¹In, ¹Sc, ³V) is studied by density functional theory (DFT) calculations. The calculated adsorption energy of the large-size cluster model (LC) of MIL-100 (M) shows that the ⁴MIL-100 (⁴Cr) is the best at the refinement of natural gas due to the lower adsorption energy of CH₄ (−2.58 kJ/mol) in comparison with that of N₂ (−21.49 kJ/mol) and CO₂ (−23.82 kJ/mol). ¹MIL-100 (¹Sc) and ¹MIL-100 (⁶Fe) can also achieve selective adsorption and follows the order ⁴MIL-100 (⁴Cr)>¹MIL-100 (¹Sc)>¹MIL-100 (⁶Fe). In the research of the selective adsorption mechanism of MIL-100 (M) (M=⁴Cr, ¹Sc, ⁶Fe), the independent gradient model (IGM) indicates that these outstanding adsorbents interact with CO₂ and N₂ mainly through the electrostatic attractive interaction, while the van der Walls interaction dominates in the interaction with CH_4. The atomic Projected Density of State (PDOS) further confirms that CH₄ contributes least to the intermolecular interaction than that of CO₂ and N₂. Through the scrutiny of molecular orbitals, it is found that electrons transfer from the gas molecule to the metal site in the adsorption of CO₂ and N₂. Not only does the type of the metallic orbitals, but also the delocalization of the involved orbitals determines the selective adsorption performance of MIL-100. Both Cr and Sc share their orbitals with the gases, making ¹MIL-100 (¹Sc) another potential effective separator for CH₄. Additionally, the comparison of adsorption energy and PDOS shows that the introduction of ligands such as benzene impedes the electron donation from gas molecules (CO₂, N₂) to the metal site, indicating electron-withdrawing ligands will further favor the adsorption.     

粉煤灰磁性吸附剂的制备及磷吸附机理

通过化学沉淀法制备了CMS@La_2O_3磁性磷吸附剂。结构及磁性表征显示,氧化镧较均匀的包覆在粉煤灰磁珠表面;样品的比磁化强度达20.35 emu·g~(-1),可实现高效磁分离。利用钼酸铵分光光度法对所得磁性吸附剂的磷吸附性能进行了试验研究。研究表明,其最高磷比饱和吸附量可达19.50 mg·g~(-1),吸附时间、pH值、共存阴离子等因素对磷吸附效果均具有显著影响。吸附动力学拟合表明,CMS@La_2O_3对含磷离子的吸附符合准二级动力学方程,以化学吸附为主,磁性吸附剂对含磷离子的吸附反应过程可由La_2O_3表面羟基化-离子交换模型解释。吸附磷后的CMS@La_2O_3吸附剂经处理后可多次循环使用。     

Effective removal of 2,4,6‐trinitrophenol over hexagonal metal–organic framework NH2‐MIL‐88B(Fe)

A nanostructured organic–inorganic framework, hexagonal NH₂‐MIL‐88B, has been prepared through a facile one‐pot reflux reaction and then it was characterized using various techniques. The as‐prepared sample with high specific surface area (414 m² g^?1) showed excellent adsorption for 2,4,6‐trinitrophenol (TNP) in the liquid phase. Detailed studies of the adsorption kinetics, adsorption mechanism, adsorption isotherm, activation energy and various thermodynamic parameters were conducted. The adsorption mechanism of NH₂‐MIL‐88B for TNP may be ascribed to hydrogen bond interaction, and the complexation between ─OH in TNP and unsaturated Fe(III) on the surface of NH₂‐MIL‐88B. The maximum adsorption capacity of NH₂‐MIL‐88B for TNP based on the Langmuir isotherm was 163.66 mg g^?1. The as‐prepared NH₂‐MIL‐88B adsorbent seems to be a promising material in practice for TNP removal from aqueous solution.     

磁性壳聚糖复合微球的制备及其Cu2+吸附性能

以球磨后的粉煤灰磁珠（MS）颗粒为磁核,通过溶胶凝胶法和反相微乳液法依次包覆SiO₂和壳聚糖（CS）,制备了MS@SiO₂@CS磁性微球。利用扫描电镜及能量色散谱仪、热重分析仪、红外光谱仪、X射线衍射仪、振动样品磁强计对所得样品的结构和磁性进行了系统表征。结果表明,磁珠颗粒表面实现了逐层包覆,较均匀的分散于壳聚糖基体中,MS@SiO₂@CS微球的比饱和磁化强度可达7.04 emu·g^-1。Cu²⁺离子吸附实验表明,所得磁性壳聚糖微球对Cu²⁺具有良好的吸附能力,最大吸附量可达11.08 mg·g^-1;而且可通过磁选法高效固液分离。吸附动力学研究表明,MS@SiO₂@CS微球对Cu²⁺离子的吸附符合准二级动力学模型,以化学吸附为主。     

Carbon dioxide and nitrogen adsorption on porous copolymers of divinylbenzene and acrylic acid

Porous copolymers of divinylbenzene (DVB) and acrylic acid (AA) having DVB:AA ratios of 6:4, 8:2 and 9:1 were prepared following a distillation-precipitation method, using toluene as the porogenic agent. The materials thus obtained, which showed specific surface area in the range of 380–600 m² g^?1 and pore volume in the range of 0.14–0.18 cm³ g^?1, were investigated as possible adsorbents for CO₂ capture from the flue gas of coal-fired power stations. For that purpose, the isosteric heat of adsorption (and CO₂ adsorption capacity) was analysed from N₂ and CO₂ adsorption equilibrium isotherms obtained over a temperature range. For CO₂, q _st resulted to be in the range of 27–31 kJ mol^?1 (the highest value corresponding to the 6:4 sample), while for N₂ a value of q _st ≈ 12 kJ mol^?1 was obtained. Equilibrium adsorption capacity for CO₂ (at ambient temperature and pressure) showed the value of about 1.35 mmol g^?1. These results are discussed in the broader context of corresponding literature data for CO₂ capture using protonic zeolites.     

Investigations for Modification of Polyacrylamide-Bentonite by Phytic Acid and its Usability in Fe3+, Zn2+ and UO2 2+ Adsorption

Composite of polyacrylamide-bentonite (PAA-B) was prepared by direct polymerisation of PAA in a suspension of bentonite (B). Adsorption and thermodynamic features of phytic acid (Phy) adsorption onto B, PAA and PAA-B, and those of Fe³⁺, Zn²⁺, UO₂ ²⁺ adsorption onto PAA-B and its modification by Phy (PAA-B-Phy) have been investigated. The reusability, storagability, ion selectivity and recoverability of sorbed ions with 1 M HCl have also been considered.The chemical and physical structure of adsorbents has been characterised by means of FT-IR and XRD. All adsorption isotherms for Phy and the ions were L-type of the Giles classification except, the one which is S type for adsorption of Phy onto PAA. The maximum adsorption capacities for the ions adsorbed were in order of UO₂ ²⁺ > Fe³⁺ > Zn²⁺ for PAA-B and Zn²⁺ > Fe³⁺ > UO₂ ²⁺ for PAA-B-Phy. Langmuir equilibrium constants for the adsorption of ions onto PAA-B-Phy were significantly higher than those found for PAA-B; the magnitude of increase for UO₂ ²⁺ was about 100. The thermodynamic parameters indicated that adsorption reactions are spontaneous in terms of adsorption free enthalpy.The chemical structure of PAA-B-Phy was not changed at the end of the studies of reusability and storagability. The composite was selective for UO₂ ²⁺ of the ions of interest.The composite of PAA-B and its modification by Phy have been used for the first time in this investigation. It is proposed that the composites can be practically used in the investigations and applications of adsorption.     

Removal of carbonyl sulfide from CO2 stream using AgNO3-modified NaZSM-5

Removal of carbonyl sulfide (COS) from CO₂ stream is significant for the production and utilization of food grade CO₂. This study investigates the adsorption performance of Ag/NaZSM-5 as adsorbent prepared by incipient wetness impregnation for the removal of COS from a CO₂ stream in a fixed-bed adsorption apparatus. Effects of various conditions on the preparation of adsorbent, adsorption and desorption were intensively examined. The results revealed that COS can be removed to below 1×10^?9 from a CO₂ stream (1000 ppm COS/CO₂) using Ag/NaZSM-5 (10 wt% AgNO₃) with an adsorption capacity of 12.86 mg-g^?1. The adsorbent can be fully regenerated using hot air at 450 °C. The adsorption ability remained stable even after eight cycles of regeneration.     

Study of CO2 adsorption in functionalized carbon

We evaluated the ability of CO₂ adsorption in functionalized activated carbons granular and monolithic type, obtained by chemical activation of African palm stone with H₃PO₄ and CaCl₂. We made a comparison between two methods of incorporation of nitrogen groups: the impregnation method with NH₄OH solution and NH₃ gasification. The materials were texturally characterized by N₂ adsorption at 77 K, the isotherms shows obtaining microporous materials with surface areas between 545–1425 m²?g^?1 and pore volumes between 0.22 to 0.53 cm³?g^?1. It was established that with the methodologies used for functionalization is increased content of nitrogen groups, was achieved a higher proportion of such groups when carrying out the process in liquid phase with NH₄OH. The incorporation of nitrogen groups in the material generates an increase of up to 65 % in the CO₂ adsorption capacity of the MCa2 (Monolith prepared with CaCl₂ solution at 2 %) sample. Was reached a maximum adsorption capacity of 344 mgCO²?g^?1 in the MCa2FAL (sample MCa2 functionalized with NH₄OH solution) sample.     

Calorimetric study of the CO2 adsorption on carbon materials

Given the great interest in the CO₂ removal and decreasing their impact on the environment, in this work, a calorimetric study of CO₂ adsorption on different activated carbons was performed. For this purpose, we used two methodologies for the determination heat of CO₂ adsorption: determination of CO₂ isotherms at different temperatures and adsorption calorimetry. The heats determined by these two techniques were compared. In this regard, carbonaceous materials of granular and monolithic types were prepared, characterized, and functionalized for carbon dioxide adsorption. As precursor material, African palm stones that were activated with H₃PO₄ and CaCl₂ at different concentrations was used. The obtained materials were functionalized in gas phase with NH₃ and liquid phase with NH₄OH, with the intention to incorporate the surface basic groups (amines or nitrogen groups) and subsequently were studied for CO₂ adsorption at 273 K and atmospheric pressure. For characterization of these materials, the following techniques are used: N₂ adsorption at 77 K and immersion calorimetry in different solvents. The experimental results show the obtaining of micropores and mesoporous (moderately) materials, with surface area between 430 and 1,425 m² g^?1 and pore volumes between 0.17 and 0.53 cm³ g^?1. It was determined that there is a difference between the heats of CO₂ adsorption obtained by the techniques employed. This deviation between the values corresponds to the methodological difference between the two experiments. In this work, we obtained a maximum adsorption capacity of CO₂, which is greater than 334 mg CO₂ g^?1 at 273 K and 1 bar in carbon materials with moderate surface area and pores volume.     

Preparation of activated carbon from organic fraction of municipal solid wastes by ZnCl2 activation method and use it for elimination of chromium(VI) from aqueous solutions

In this study, the use of the organic fraction of municipal solid waste as an abundant and low-cost raw material for producing activated carbon was investigated. For this purpose, ZnCl₂ was used as a chemical activation agent and the carbonization process took place at 800 °C in N₂ atmosphere. Seven sorbents were prepared by chemical activation (pyrolysis under N₂ atmosphere at temperature of 800 °C after impregnation with ZnCl₂) with different ratios of ZnCl₂. The optimum ratio of organic fraction of municipal solid waste to ZnCl₂ was inspected via methylene blue number and iodine number (ASTM Designation: D4607–94). The results showed that the adsorbent with 60 % ZnCl₂/raw material was the most appropriate one with a satisfactory adsorption capacity, 112.4 mg g^?1 for methylene blue and 134.0 mg g^?1 for iodine. In addition, the structural analysis of this sorbent was performed using FT-IR, BET surface area, SEM–EDX and thermal analysis. Application of this sorbent to remove Cr(VI) from wastewater was studied to find an adsorption capacity of 66.7 mg g^?1. The experimental adsorption equilibrium data were fitted to Langmuir adsorption model with an acceptable adsorption capacity of 66.7 mg g^?1.     

Evaluation of CO2 adsorption capacity of solid sorbents

The CO₂ adsorption capacity of the low-cost solid sorbents of waste tire char (TC) and chicken waste char (CW) was compared with commercial active carbon (AC) and 5 ? zeolite (ZA) using thermogravimetric analysis (TG), pressurized TG, and differential scanning calorimetry (DSC). The sorbents were degassed in a TG up to 150 °C to release all gases on the surface of the sample, then cooled down to the designed temperature for adsorption. TG results indicated that the CO₂ adsorption capacity of TC was higher than that of CW, but lower than those of AC and ZA. The maximum adsorption rate of TC at 50 °C was 0.61% min⁻¹, lower than that of AC, but higher than that of CW, 0.44% min⁻¹. The maximum adsorption rate of ZA at 50 °C was 3.1% min⁻¹. When the pressure was over 4 bar, the adsorption rate of ZA was lower than that of TC and AC. At 30 bar, the total CO₂ uptake of TC was 20 wt%, higher than that of CW and ZA but lower than that of AC. The temperature, nitrogen concentration, and water content also influenced the CO₂ adsorption capacity of sorbents to some extent. DSC results showed that adsorption was an exothermic process. The heat of CO₂ adsorption per mole of CO₂ of TC at 50 °C was 24 kJ mol⁻¹ while the ZA had the largest heat of adsorption at 38 kJ mol⁻¹. Comparing the characteristics of TC and CW, TC may be a promising sorbent for removal of CO₂.     

Optimizing Adsorption of 17α-Ethinylestradiol from Water by Magnetic MXene Using Response Surface Methodology and Adsorption Kinetics,Isotherm, and Thermodynamics Studies

Magnetic MXene composite Fe₃O₄@Ti₃C₂ was successfully prepared and employed as 17α-ethinylestradiol (EE2) adsorbent from water solution. The response surface methodology was employed to investigate the interactive effects of adsorption parameters (adsorption time, pH of the solution, initial concentration, and the adsorbent dose) and optimize these parameters for obtaining maximum adsorption efficiency of EE2. The significance of independent variables and their interactions were tested by the analysis of variance (ANOVA) and t-test statistics. Optimization of the process variables for maximum adsorption of EE2 by Fe₃O₄@Ti₃C₂ was performed using the quadratic model. The model predicted maximum adsorption of 97.08% under the optimum conditions of the independent variables (adsorption time 6.7 h, pH of the solution 6.4, initial EE2 concentration 0.98 mg L⁻¹, and the adsorbent dose 88.9 mg L⁻¹) was very close to the experimental value (95.34%). pH showed the highest level of significance with the percent contribution (63.86%) as compared to other factors. The interactive influences of pH and initial concentration on EE2 adsorption efficiency were significant (p < 0.05). The goodness of fit of the model was checked by the coefficient of determination (R²) between the experimental and predicted values of the response variable. The response surface methodology successfully reflects the impact of various factors and optimized the process variables for EE2 adsorption. The kinetic adsorption data for EE2 fitted well with a pseudo-second-order model, while the equilibrium data followed Langmuir isotherms. Thermodynamic analysis indicated that the adsorption was a spontaneous and endothermic process. Therefore, Fe₃O₄@Ti₃C₂ composite present the outstanding capacity to be employed in the remediation of EE2 contaminated wastewaters.     

Tuning of Microenvironment in Covalent Organic Framework via Fluorination Strategy promotes Selective CO2 Capture

Herein, we have designed and synthesized two heteroatom (N, O) rich covalent organic frameworks (COF), PD-COF and TF-COF , respectively, to demonstrate their relative effect on CO₂ adsorption capacity and also CO₂/N₂ selectivity. Compared to the non-fluorinated PD-COF (BET surface area 805 m² g⁻¹, total pore volume 0.3647 ccg⁻¹), a decrease in BET surface area and also pore volume have been observed for fluorinated TF-COF due to the incorporation of fluorine to the porous framework (BET surface area 451 m² g⁻¹, total pore volume 0.2978 ccg⁻¹). This fact leads to an enormous decrease in the CO₂ adsorption capacity and CO₂/N₂ selectivity of TF-COF , though it shows stronger affinity towards CO₂ with a Qst of 37.76 KJ/mol. The more CO₂ adsorption capacity by PD-COF can be attributed to the large specific surface area with considerable amount of micropore volume compared to the TF-COF . Further, PD-COF exhibited CO₂/N₂ selectivity of 16.8, higher than that of TF-COF (CO₂/N₂ selectivity 13.4).     

Lead ion adsorption from aqueous solutions in modified Algerian montmorillonites

The adsorption of lead (II) ions on three Algerian montmorillonites (sodium, non-sodium, and acidic-activated) was studied. Transmission electron microscopy coupled with energy dispersive X-ray analysis, X-ray fluorescence and physical adsorption of gases were used to characterize the clays. This characterization has shown than the activation with acid increases the surface area as a consequence of the rupture of the laminar structure. The effect of the pH in the lead adsorption capacity was analyzed. The results show that adsorption is strongly depended on the pH. At low pH values, the mechanism that governs the adsorption behavior of clays is the competition of the metal ions with protons. Between pH 2 and 6, the main mechanism is an ion exchange process. The kinetics of the adsorption is tested with respect to pseudo-first-order and second-order models. The adsorption process, gives a better fit with the Langmuir isotherm, being the monolayer capacity ranging between 18.2 and 24.4?mg?g^?1. The adsorption of lead decreased in the order Acidic-M₂?>?M₂?>?M₁. Thermodynamic parameters such as ??H, ??S, and ??G were calculated. The adsorption process was found to be endothermic and spontaneous. The enthalpy change for Pb(II) by M₁ adsorption has been estimated as 60?kJ?mol^?1, indicating that the adsorption of Pb(II) by all montmorillonites used corresponds to a physical reaction. The adsorption capacity of washed Acidic-M₂ was very high compared to M₂ and M₁.     

连续在线原位ATR-FTIR技术测定介孔CuAl2O4对黄药的吸附

以丁胺和正十二醇为混合模板剂, 采用共沉淀法制备了介孔纳米CuAl₂O₄. 用X射线粉末衍射(XRD)、傅里叶变换红外(FTIR)光谱、N₂吸附-脱附对产物的结构进行了表征. 采用连续在线原位衰减全反射傅里叶变换红外(ATR-FTIR)光谱技术研究了水溶液中丁基和辛基黄药在介孔CuAl₂O₄表面的吸附. 随着吸附时间的延长,1200 和1040 cm^-1两处黄药特征峰的高度逐渐增加, 根据1200 cm^-1处C-O-C伸缩振动峰的变化来评价黄药在CuAl₂O₄表面的吸附动力学过程. 结果表明, 介孔纳米CuAl₂O₄对黄药有很强的吸附能力, 在100 min 的时间内, CuAl₂O₄样品对丁基和辛基黄药的吸附量分别达到了236 和300 mg·g^-1, 且属于化学吸附. 对实验数据进行理论模拟, 发现吸附过程更接近于拟二级吸附动力学方程.