不同孔径的介孔碳分子筛对VB12的吸附性质研究

摘要利用SBA-15为模板, 在不同温度下合成了孔径大小在3.7(CMK-3-100)和6-3 nm(CMK-3-150)之间的介孔碳， 以其作为吸附剂, 研究了它们在水溶液中对VB12的吸附作用. 结果表明, CMK-3-130与CMK-3-100和CMK-3-150相比， 表现出对VB12最大的吸附能力(吸附能力为412.5 mg/g), 这是因为它有比较高的有序结构和比较大的孔容.     

Kinetics and Thermodynamics of Adsorption of VB12 onto Mesoporous Carbon Coated with PMMA

Ordered mesoporous carbons CMK-3, CMK-1 coated with poly(methyl methacrylate)(PMMA)(CMK-3- PMMA and CMK-1-PMMA) and pristine mesoporous carbons CMK-3, CMK-1 were employed to adsorb vitamin B12(VB12) from water solution. Adsorption isotherm and kinetics of adsorption were investigated via batch experi- ments. It was found that the adsorption capacity of VB12 at 30, 40 and 50 °C can reach 688.2, 572.4 and 428.7 mg/g, respectively. The adsorption isotherm can be described by Langmuir model. The pseudo first- and second-order kinetic models were employed to fit the dynamic adsorption. It was found that the dynamic adsorption follows the pseudo second-order model. The thermodynamic equilibrium coefficients obtained at different temperatures were used to evaluate the thermodynamic constants ΔG0, ΔH0 and ΔS0. The negative value of Gibbs free energy, ΔG0 indicates that the adsorption occurred via a spontaneous process. The increase in the value of –ΔG0 with increasing temperature indicates that higher temperatures were favourable to the sorption process. The enthalpy values of ΔH040 kJ/mol(66.36 kJ/mol and 56.43 kJ/mol) for CMK-3-PMMA and CMK-1-PMMA confirm that chemisorption were involved in the adsorption process. This is consistent with the IR spectra and is another evidence for the formation of hydrogen bond between PMMA in the pore of CMK-3 and VB12.     

Sorption study of uranium from aqueous solution on ordered mesoporous carbon CMK-3

The ability of ordered mesoporous carbon CMK-3 has been explored for the removal and recovery of uraium from aqueous solutions. The textural properties of CMK-3 were characterized using small-angle X-ray diffraction and N₂ adsorption–desorption, and the BET specific surface area, pore volume and the pore size were 1143.7 m²/g, 1.10 cm³/g and 3.4 nm. The influences of different experimental parameters such as solution pH, initial concentration, contact time, ionic strength and temperature on adsorption were investigated. The CMK-3 showed the highest uranium sorption capacity at initial pH of 6.0 and contact time of 35 min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir and Freundlich isotherm. The thermodynamic parameters, ?G°(298 K), ?H° and ?S° were determined to be ?7.7, 21.5 k J mol^?1 and 98.2 J mol^?1 K^?1, respectively, which demonstrated the sorption process of CMK-3 towards U(VI) was feasible, spontaneous and endothermic in nature. The adsorbed CMK-3 could be effectively regenerated by 0.05 mol/L HCl solution for the removal and recovery of U(VI). Complete removal (99.9 %) of U(VI) from 1.0 L industry wastewater containing 15.0 mg U(VI) ions was possible with 2.0 g CMK-3.     

介孔碳CMK-3对苯酚的吸附动力学和热力学研究

研究了介孔碳CMK-3对苯酚的吸附性能, 与传统商用活性碳(CAC)进行了比较, 结果表明, CMK-3比CAC的吸附量大、吸附速率快、达到平衡时间短, 是一种较好的吸附剂. 同时探讨了介孔碳CMK-3对苯酚的吸附热力学和动力学特征. CMK-3对苯酚的吸附行为可用Langmuir和Freundlich等温式进行描述, 相关性都较好, 但更符合Freundlich经验公式. 分别采用模拟一阶反应和二阶反应模型考察了吸附动力学, 并计算了这些动力学模型的速率常数. 模拟二级反应模型和实验数据之间有较好的相关性. 分别计算了热力学参数ΔG0, ΔS0和ΔH0, 结果表明, CMK-3对苯酚的吸附过程是吸热和自发的.     

二氧化碳/甲烷/氮气二元混合物在有序介孔碳材料CMK-3 中的吸附和分离

采用分子模拟与吸附理论研究了天然气成分在有序介孔碳材料CMK-3上的吸附和分离.巨正则系综蒙特卡罗(GCMC)模拟表明,CH4和CO2气体的较优存储条件分别为208 K、4 MPa和298 K、6 MPa,其最大超额吸附量分别为10.07和14.85 mmol· g-1.基于双位Langmuir-Freundlich (DSLF)模型,使用理想吸附溶液理论(IAST)预测了不同二元混合物在CMK-3中的分离行为,发现吸附选择性Sco2/CH4与ScH4/N2比较接近,在298 K和4 MPa下约等于3,而N2-CO2体系中的CO2吸附选择性较高,可达到7.5,说明CMK-3是一种适合吸附和分离天然气组分的碳材料.     

Adsorption of U(VI) from aqueous solution by sulfonated ordered mesoporous carbon

The sulfonated mesoporous carbon (CMK-3-SO₃H) prepared by functionalizing mesoporous carbon (CMK-3) via vapor transfer method has been explored for the removal and recovery of uranium from aqueous solutions. The influences of different experimental parameters such as solution pH, initial concentration, contact time and temperature on adsorption were investigated. The results showed that CMK-3-SO₃H has the highest uranium sorption capacity at initial pH of 5.0 and contact time of 120 min, and the adsorption process could be better described by the pseudo-second-order model and Langmuir isotherm. Selective adsorption studies showed that the CMK-3-SO₃H could selectively remove of U(VI), and the selectivity coefficients of mesoporous carbon in the presence of co-existing ions, Mg(II), Zn(II), Mn(II), Cu(II), Ni(II), Sr(II) and Hg(II) improved after functionalization.     

Adsorption studies of arsenic on Mn-substituted iron oxyhydroxide

Mn-substituted iron oxyhydroxide (Mn(0.13)Fe(0.87)OOH) was prepared by the oxidation of ferrous carbonate precipitated from ferrous sulfate and sodium carbonate solutions. X-ray diffraction analysis led to the conclusion that the sample was basically iron manganese hydroxide with bixbyite structure. The sample exhibited a surface area of 101 m2 g(-1) and a pore volume of 0.35 cm3 g(-1). Batch experiments were conducted to study the adsorption of arsenite and arsenate species onto Mn-substituted iron oxyhydroxide (MIOH) and adsorption equilibrium time was evaluated. The temperature of adsorption was varied from 30 to 60 degrees C. The maximum uptake of arsenite and arsenate was found to be 4.58 and 5.72 mg g(-1), respectively. Zeta potential measurements and FT-IR spectral studies were also conducted to study the nature of adsorption. In both cases, adsorption was best described by Langmuir isotherm and activation energies as calculated from a model-free isoconversional method were found to be on the order of 15-24 and 45-67 kJ mol(-1) for arsenate and arsenite, respectively.     

Removal of thorium from aqueous solution by ordered mesoporous carbon CMK-3

The ability of ordered mesoporous carbon CMK-3 has been explored for the removal and recovery of thorium from aqueous solutions. The textural properties of CMK-3 were characterized using small-angle X-ray diffraction and N₂ adsorption–desorption, and the BET specific surface area, pore volume and the pore size were 1143.7 m²/g, 1.10 cm³/g and 3.4 nm. The influences of different experimental parameters such as solution pH, initial concentration, contact time, ionic strength and temperature on adsorption were investigated. The CMK-3 showed the highest thorium sorption capacity at initial pH of 3.0 and contact time of 175 min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, △G°(298 K), △H° and △S° were determined to be -0.74 kJ·mol^?1, 9.17 kJ·mol^?1 and 33.24 J·mol^?1·K^?1, respectively, which demonstrated the sorption process of CMK-3 towards Th(IV) was feasible, spontaneous and endothermic in nature. The adsorbed CMK-3 could be effectively regenerated by 0.02 mol/L HCl solution for the removal and recovery of Th(IV).     

Dye affinity hollow fibers for albumin purification

Reactive Green HE 4BD was immobilized on polyamide (PA) hollow fibers for human serum albumin (HSA) adsorption from both aqueous solutions and human plasma. Different amounts of Reactive Green HE 4BD were incorporated on the PA hollow fibers by changing the dye attachment conditions, i.e. the initial dye concentration and the addition of sodium carbonate and sodium chloride. The maximum amount of dye attachment was obtained as 39.4 micromol x g(-1) when the hollow fibers were treated with 3 M HCl for 30 min before performing the dye attachment. HSA adsorption onto unmodified and dye-attached hollow fibers was investigated batchwise. The non-specific adsorption of HSA was low (6.0 mg/g hollow fiber). Dye attachment onto the hollow fibers significantly increased the HSA adsorption (86.7 mg/g). The maximum HSA adsorption was observed at pH 5.0. Higher HSA adsorption was observed from human plasma (198 mg HSA/g). The desorptions were performed by adding 0.1 M Tris/HCl buffer containing 0.5 M NaSCN or 1.0 M NaCl to the HSA solutions in which adsorption equilibria had been reached. The desorption results demonstrated that the adsorption of HSA to the adsorbent was reversible. Chemical structure of Reactive Green HE-4BD.     

Equilibrium and kinetic studies on the adsorption of VB_(12) onto CMK-3

The adsorption of VB12 onto CMK-3 was studied as a function of temperature and initial VB12 concentration. The highest VB12 adsorption capacity was determined as 353.4 mg/g at 40℃. Adsorption data were well described by the Langmuir model, although they could be modelled by the Freundlich equation. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The pseudo-second-oider kinetic model provided the best correlation of the experimental data compared to the pseudo-nrsi-order model.     

Kinetic modeling of adsorption of di-2-pyridylketone salicyloylhydrazone on silica gel

The kinetics of DPKSH (di-2-pyridylketone salicyloylhydrazone) adsorption onto silica gel has been investigated at (25+/-1) degrees C and pH 1 and 4.7. The kinetics of adsorption of DPKSH is discussed using three kinetic models, the first-order Lagergren model, the pseudo-second-order model, and the intraparticle diffusion model. The adsorption of DPKSH, at pH 1 and 4.7, onto silica gel proceeds according to the pseudo-second-order model and the correlation coefficients were very close to 1. The intraparticle diffusion of DPKSH molecules within the silica gel particles was identified as the rate-limiting step. The parameters of the pseudo-second-order model are q(max,calc)=1.02 x 10(-4) and 1.5 x 10(-4) g DPKSH/g silica; k(2)=3.01 x 10(4) and 9.67 x 10(4) h(-1)g silica/g DPKSH, respectively, for pH 1 and 4.7.     

Biomaterial immobilization in nanoporous carbon molecular sieves: influence of solution pH, pore volume, and pore diameter

The adsorption of lysozyme (Lz) onto nanoporous carbon molecular sieves with various pore diameters has been studied at different solution pH values. All the adsorption isotherms have successfully been correlated by the Langmuir equation. The amount of adsorbed Lz depends on the solution pH as well as on the specific pore volume and pore diameter of the adsorbents. The maximum adsorption was observed near the isoelectric point of the Lz (pI approximately 11), suggesting that suppression of electric repulsion between the enzymes plays an important role in the adsorption process. Moreover, the amount adsorbed depends on the pore size and pore volume of the nanoporous carbon adsorbents, indicating that the Lz molecules are adsorbed inside the mesopores. CMK-3-150 shows a larger amount of Lz adsorption as compared to CMK-3. The increased Lz adsorption capacity of CMK-3-150 may be due to the larger pore volume and pore diameter as compared to that of CMK-3. The unaltered structural order of the nanoporous adsorbents after the adsorption has been confirmed by the physicochemical characterization techniques such as XRD and N(2) adsorption. In addition, FT-IR spectroscopic studies confirm that the Lz used in this study is stable even after the adsorption on the nanoporous carbon. These results indicate that nanoporous carbon has superior water stability and thus is a more appropriate adsorbent for biomaterials than nanoporous silica.     

Mucin Adsorption to Hydrophobic Surfaces

The adsorption isotherm of bovine submaxillary gland mucin (BSM) onto a hydrophobic polystyrene surface was determined by using the solution depletion method, in which mucin concentrations were analyzed by amino acid analysis. Adsorption and desorption kinetics of BSM onto hydrophobic polystyrene surfaces were also studied by the solution depletion method, in which mucin solution concentrations were determined by measuring UV absorbance at a wavelength of 280 nm and by a BCA colorimetric assay with final calibration by amino acid analysis. From the adsorption isotherm, we found that the saturated surface concentration (Gamma(max)) was 2.3 mg/m(2), and the adsorption constant (K) was calculated as 0.099 (ml/mg). By using a Langmuir adsorption model and nonlinear fitting, kinetics parameters, k(on) and k(off), were found to be 8.13x10(-3) cm(3) mg(-1) s(-1) and 5.67x10(-4) s(-1), respectively. The coating was found to be very stable with very limited desorption (less than 2%) from a long-term observation (28 h). The mucin coating layer thickness was investigated by several analytical techniques: flow field-flow-fractionation, photon correlation spectroscopy, scanning electron microscopy, and atomic force microscopy. The thickness was measured as 4-5 nm, from which a monolayer coating was concluded. Finally, the weight average molecular weight of purified bovine submaxillary gland mucin (BSM) was determined as 1.6x10(6) Da by using static light scattering. Copyright 2000 Academic Press.     

Ordered mesoporous carbon as an efficient and reversible adsorbent for the adsorption of fullerenes

An ordered mesoporous carbon, CMK-3, was synthesized using a mesoporous siliceous material, SBA-15, as the template. CMK-3 was characterized and used for the adsorption of fullerenes C60 and C70. It was found that the adsorption capacity of CMK-3 is 4 times higher than that of activated carbon. The adsorption equilibrium isotherms of C60 and C70 on CMK-3 were studied for both single and binary systems. The reversibility of fullerene adsorption on CMK-3 was also explored. The results showed that CMK-3 is an effective and reversible adsorbent for the separation of fullerenes by adsorption.     

Diethylenetriamine-grafted poly(glycidyl methacrylate) adsorbent for effective copper ion adsorption

Amine-functionalized adsorbents have attracted increasing interest in recent years for heavy metal removal. In this study, diethylenetriamine (DETA) was successfully grafted (through a relatively simple solution reaction) onto poly(glycidyl methacrylate) (PGMA) microgranules to obtain an adsorbent (PGMA-DETA) with a very high content of amine groups and the PGMA-DETA adsorbent was examined for copper ion removal in a series of batch adsorption experiments. It was found that the PGMA-DETA adsorbent achieved excellent adsorption performance in copper ion removal and the adsorption was most effective at pH>3 in the pH range of 1-5 examined. X-ray photoelectron spectroscopy (XPS) revealed that there were different types of amine sites on the surfaces of the PGMA-DETA adsorbent but copper ion adsorption was mainly through forming surface complexes with the neutral amine groups on the adsorbent, resulting in better adsorption performance at a higher solution pH value. The adsorption isotherm data best obeyed the Langmuir-Freundlich model and the adsorption capacity reached 1.5 mmol/g in the case of pH 5 studied. The adsorption process was fast (with adsorption equilibrium time less than 1-4 h) and closely followed the pseudo-second-order kinetic model. Desorption of copper ions from the PGMA-DETA adsorbent was most effectively achieved in a 0.1 M dilute nitric acid solution, with 80% of the desorption being completed within the first 1 min. Consecutive adsorption-desorption experiments showed that the PGMA-DETA adsorbent can be reused almost without any loss in the adsorption capacity.     

Adsorption of acridine yellow G from aqueous solutions using functionalized graphene nanoplatelets/modified polybutadiene hybrid composite

This paper presents an analysis of adsorption of acridine yellow G (AYG) from aqueous solutions through the use of functionalized grapheme nanoplatelets/modified polybutadiene hybrid composite (FGNPs/MPB). The adsorption of AYG onto FGNPs/MPB was investigated based on the AYG concentration, pH, contact time, temperature, and adsorbent dose. A maximum adsorption capacity was obtained at a pH of 7 (23.7 mg/g), an adsorbent dose of 1.0 g/L (20.8 mg/g), and an initial AYG concentration of 28.5 mg/L (16.9 mg/g). The value of q_e of FGNPs/MPB increases with an increase in temperature from 293 to 323 K. Equilibrium isotherm data were analyzed using the Langmuir and Freundlich isotherm models. The Langmuir model best describes the adsorption processes of AYG, which showed that the monolayer adsorption capacity of FGNPs/MBP is 22.9 mg/g. The pseudofirst-order, pseudosecond-order, and intraparticle diffusion models were used to study the kinetics of the AYG adsorption onto FGNPs/MPB. The pseudosecond-order model better described kinetic data for the adsorption of AYG onto FGNPs/MPB. Thermodynamic parameters, such as the Gibbs free energy, enthalpy, and entropy, indicated that the AYG adsorption onto FGNPs/MPB was spontaneous feasible, and endothermic.     

Characterization of a peptide affinity support that binds selectively to staphylococcal enterotoxin B

The influences of mass transfer and adsorption-desorption kinetics on the binding of staphylococcal enterotoxin B (SEB) to an affinity resin with the peptide ligand, Tyr-Tyr-Trp-Leu-His-His (YYWLHH) have been studied. The bed and particle porosities, the axial dispersion coefficient and the pore diffusivity were measured using pulse experiments under unretained conditions. Adsorption isotherms for SEB on YYWLHH resins with peptide densities in the range from 6 to 220 micromol/g were measured and fitted to a bi-Langmuir equation. At peptide densities below 9 micromol/g and above 50 micromol/g, dissociation constants were lower (2 x 10(-3) to 7 x 10(-3) mol/m3), and binding capacities were larger (43-47 mg SEB/g). In the range from 9 to 50 micromol/g dissociation constants were larger (13 x 10(-3) to 24 x 10(-3) mol/m3) and capacities were lower (33-37 mg SEB/g). These observations are consistent with a transition from single point attachment of the protein to the ligand at low peptide densities to multipoint attachment at high peptide densities. The general rate (GR) model of chromatography was used to fit experimental breakthrough curves under retained conditions to determine the intrinsic rate constants for adsorption, which varied from 0.13 to 0.50 m3 mol(-1) s(-1), and exhibited no clear trend with increasing peptide density. An analysis of the number of transfer units for the various mass transfer steps in the column indicated that film mass transfer, pore diffusion (POR) and the kinetics of adsorption can all play an important role in the overall rate of adsorption, with the intrinsic adsorption step apparently being the rate determining step at peptide densities below 50 micromol/g.     

钙蒙脱土吸附镧的影响因素及其应用

以钙基蒙脱土(Ca-MMT)为载体,研究其对镧(La)的吸附。 采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和元素mapping分析、傅里叶红外光谱(FT-IR)、BET、X射线荧光光谱分析(XRF)对其晶型结构、表面形态、比表面积、化学结构进行表征,考察了La的初始浓度、pH值、温度对Ca-MMT吸附镧性能的影响,考察了载镧钙基蒙脱土(Ca-MMT@La)的除磷效果。 结果表明:Ca-MMT投入量为10 g/L时,Ca-MMT的平衡吸附量随镧的初始浓度增加而增大,最大吸附量为49.62 mg/g;随着pH值增大,吸附能力增强,pH=6时为最佳pH吸附镧条件,吸附量为38.36 mg/g;随温度的升高,其吸附量先下降再上升,20 ℃吸附能力最大,吸附量为41.23 mg/g。 Langmuir等温吸附方程推断其吸附属于单分子层吸附。 Ca-MMT不具有吸附磷效果,而Ca-MMT@La对磷酸根有很强的吸附能力,吸附量为7.24 mg/g,除磷率为72.41%,其除磷率随含镧量增大而增大。     

NPE在有序介孔炭上的吸附行为研究

采用有序介孔硅为硬模板制备了具有不同孔径的有序介孔炭(OMCs). 氮气吸附测试表明, 有序介孔炭具有丰富的介孔表面和集中的介孔分布. 以壬基酚聚氧乙烯醚(NPE)为探针分子, 研究了大分子酚类在有序介孔炭上的吸附行为. 吸附研究表明, NPE在有序介孔炭上的吸附满足Langmuir吸附模型. 孔结构分析表明, 大于1.5 nm的孔的表面积是决定NPE吸附量的关键因素, 而有序介孔炭的最可几孔径决定吸附速率的大小. 与吸附量相比, 吸附速率更容易受环境温度的影响. 动力学研究表明, NPE在有序介孔炭上的吸附满足准二级动力学方程.     

Highly efficient removal of diazinon pesticide from aqueous solutions by using coconut shell-modified biochar

This study evaluates the adsorption of diazinon from aqueous solutions onto coconut shell-modified biochar using a batch system. The amount of dosage and initial pH are the main parameters being studied to obtain maximum adsorption capacity of the probe molecules. The carbonized coconut shell biochar (BC1), activated coconut shell biochar (BC2), chemically modified phosphoric acid (BC3) and sodium hydroxide coconut shell biochar (BC4) were prepared and tested as variables in the adsorption experiment. The characteristic of biochar via SEM, EDX and BET analysis revealed the large porous of surface morphology and slight changes in the composition with high surface area (405.97 – 508.07 m²/g) by following the sequence of BC3 > BC2 > BC4. Diazinon removal percentage as high as 98.96% was achieved at pH 7 with BC3 as adsorbent dosing at 5.0 g/L. The high coefficient of determination, R² with a small value of ERRSQ and χ² error analysis present the BC1 (0.9971) and BC2 (0.9999) are best fitted with Freundlich isotherm indicates multilayer sorption onto heterogeneous surface whereby the Langmuir isotherm model is the best fitting is described of monolayer adsorption process onto the homogenous surface of BC3 and BC4. The results indicated the maximum adsorption capacity (q_m) was achieved by BC3 with 10.33 mg/g, followed by BC2 (9.65 mg/g) in accordance to the Langmuir isotherm while Freundlich isotherm showed the highest adsorption capacity (k_F) with 1.73 mg/g (L/mg)^1/n followed by BC4 with 0.63 mg/g (L/mg)^1/n at favorable adsorption isotherm (1 ≤ n ≤ 10). Thus, the results obtained depicted that BC2 and BC3 are highly efficient adsorbents and both exhibit great potential in removing diazinon from aqueous solutions.