Adsorption studies and release of selected dyes from functionalized mesoporous MCM-41 silica

Functionalized mesoporous MCM-41 silica was subjected to adsorption and release studies of encapsulated guest molecules of three chosen dyes. These mesoporous systems were composed of three different capping reagents introduced by grafting method on the silica surface to control the release of dye molecules at two different pH values. The amounts of dyes adsorbed on the silica surface were measured using ultraviolet-visible (UV-VIS) spectrophotometry. The efficiency of grafting was calculated on the basis of differential thermal analysis (TG) results and elemental analysis. The release profiles were determined for all obtained systems using USP Dissolution Apparatus 2. Adsorption of the two azo dyes used was the most efficient after the positively charged functionalization and lower after functionalization with neutral and negatively charged capping reagents, while the phthalocyanine dye adsorption was almost functionalization-independent. Grafting efficiency was the highest for neutral capping reagent and much lower for electrically charged molecules of other reagents. Release studies showed clearly that desorption was pH-dependent for azo dyes and pH independent for Alcian Blue. The adsorption and release seem to be connected with the electrical charge of all constituents of these systems. Results obtained can be used for further analysis of different electrically charged molecules.      

NMR study of the adsorption-desorption kinetics of dissolved tetraalanine in MCM-41 mesoporous material

In this study we show how deuterium magic-angle spinning NMR spectroscopy can be used to investigate the adsorption-desorption kinetics of molecules in solution at surface-liquid interfaces. An aqueous solution of deuterium-labeled tetraalanine is inserted in the pores of MCM-41 mesoporous material, and its 2H MAS NMR spectrum is measured as a function of temperature and fraction of filling of the pores. Prior to this study, the different types of water in MCM-41 are characterized as a function of water loading of the pores. Analysis of 2H MAS sideband line shapes enabled the determination of the adsorption and desorption rates and the activation energies of desorption.     

Adsorption of methylene blue onto jute fiber carbon: kinetics and equilibrium studies

Jute fiber obtained from the stem of a plant was used to prepare activated carbon using phosphoric acid. Feasibility of employing this jute fiber activated carbon (JFC) for the removal of Methylene blue (MB) from aqueous solution was investigated. The adsorption of MB on JFC has found to dependent on contact time, MB concentration and pH. Experimental result follows Langmuir isotherm model and the capacity was found to be 225.64 mg/g. The optimum pH for the MB removal was found to be 5-10. The kinetic data obtained at different concentrations have been analyzed using a pseudo-first-order, pseudo-second-order equation, intraparticle diffusion and Elovich equation. Among the kinetic models studied, the intraparticle diffusion was the best applicable model to describe the adsorption of MB onto JFC.     

壳聚糖对酸性艳橙GS的吸附平衡与动力学研究

研究了壳聚糖(CS)对水溶液中的酸性艳橙GS(ABO)染料的吸附性能,考察了温度、pH值、壳聚糖分子量对吸附性能的影响.不同温度下的动力学数据分别采用拟一级、拟二级、内扩散方程进行关联;不同温度下壳聚糖对酸性艳橙GS的吸附平衡数据分别用1angmuir、Freundlich、Tempkin模型拟合.结果表明:该吸附过程...     

Photoluminescence study of mesoporous MCM-41 and Ti-grafted MCM-41

Photoluminescence combined with diffuse reflectance UV—Vis spectroscopy was used to characterise both the pure siliceous MCM-41 and Ti-MCM-41 containing tetrahedral Ti(IV) species anchored onto the inner walls of the siliceous MCM-41. Both Ti-MCM-41 and MCM-41 showed complex photoemission signals and this study allows, for the first time, the distinction of the emission signals of tetrahedral Ti9IV) ions from those due to silica surface centres.     

Adsorption of diazinon and fenitothion on MCM-41 and MCM-48 mesoporous silicas from non-polar solvent

The adsorption of two common organophosphorus pesticides, diethoxy-[(2-isopropyl-6-methyl-4-pyrimidinyl)oxy]-thioxophosphorane (diazinon) and dimethoxy-(3-methyl-4-nitrophenoxy)-thioxophosphorane (fenitrothion), by MCM-41 and MCM-48 mesoporous silicas at room temperature was investigated. UVvis and IR spectroscopy, small-angle X-ray diffraction, and the specific surface area analysis (S _BET) were used to study the adsorption behavior of diazinon and fenitrothion. The results show that the MCM-41 and MCM-48 mesoporous silicas adsorb diazinon more efficiently than fenitrothion. The extraction of adsorbed materials from the adsorbents with polar solvents and subsequent analysis by ³¹P NMR showed that the adsorption of diazinon and fenitrothion on mesoporous silicas is destructive and non-destructive, respectively. Nitrogen adsorption measurements showed that the specific surface area of both silicas decreases after the adsorption of pesticides, and the larger effect is observed for diazinon. The article is published in the original.     

Adsorption of acid blue on synthesized polymeric nanocomposites,PPy/MCM-41 and PAni/MCM-41: Isotherm,thermodynamic and kinetic studies

In the this research, removal of acid blue 62 from aqueous solution using mesoporous crystalline material-41 (MCM-41) loaded by polypyrrole (PPy) and polyaniline (PAni) was investigated. Synthesized composites were characterized by SEM, TEM, FTIR, XRD and BET analysis. Langmuir adsorption isotherm showed the best compatibility with the experimental data in comparison with other isotherm models (q_m = 55.55 mg/L). Kinetic studies proved that the adsorption process is compatible with the pseudo-second-order kinetic model. Thermodynamic parameters such as Gibbs free energy changes (ΔG^o), Enthalpy changes (ΔH^o) and Entropy changes (ΔS^o) were calculated. Negative value of ΔG^o and positive value of ΔH^o show that adsorption of Acid blue 62 on PPy/MCM-41 nanocomposite is a spontaneous process also endothermic.     

Adsorption equilibrium and kinetics of copper ions and phenol onto modified adsorbents

The adsorption equilibrium and kinetics of single and binary component copper ions and phenol onto powdered activated carbon (PAC), alginate beads and alginate-activated carbon beads (AAC) were studied. Adsorption equilibrium data for single component copper ions and phenol onto the adsorbents could be represented by the Langmuir equation. Multicomponent equilibrium data were correlated by the extended Langmuir and ideal adsorbed solution theory (IAST). The IAST gave the best fit to our data. The amount of copper ions adsorbed onto the AAC beads in the binary component was greater than that of phenol. The internal diffusion coefficients were determined by comparing the experimental concentration curves with those predicted from surface diffusion and pore diffusion model.     

Hybrid mesoporous MCM-41 type material containing 1,4-diazobutadiene chelate ligand in the walls

A new organic–inorganic hybrid mesoporous MCM-41 type material has been synthesised by co-condensation of tetraethyl orthosilicate (TEOS) and 1,4-diazobutadiene (DAB) ligand RNC(Ph)–C(Ph)NR where R = (CH₂)₃Si(OEt)₃, in the presence of cetyltrimethylammonium bromide as the structure-directing agent. Surfactant extraction using acidified methanol leaves a hybrid mesoporous material with periodical hexagonal channels, large pore volume and high specific surface area. The material was characterised by powder X-ray diffraction, transmission electron microscopy, nitrogen gas adsorption, ¹³C and ²⁹Si solid-state NMR, FTIR, elemental and thermogravimetry. The ordered structure and the integrity of the ligand structure are preserved after the extraction step.     

Novel coassembly route to Cu-SiO2 MCM-41-like mesoporous materials

A series of mesostructured Cu-SiO2 composites have been synthesized with sodium metasilicate (Na2SiO3) and cuprammonia nitrate (Cu(NH3)4(NO3)2) respectively used as Si and Cu sources. The synthetic procedures were conducted at room temperature, and cetyltrimethylammonia bromide was used as a template. Under our experimental conditions, ordered mesoporous Cu-SiO2 composites could be obtained with a copper content up to 16.8 wt %. Average pore diameters (2.80-3.15 nm), wall thickness (1.30-2.20 nm), and specific surface area (1020-690 m2/g) are found to vary linearly with copper content (0-16.8 wt %). Results of thermal gravimetry-differential thermal analysis reveal the collapse temperature of the order structure starts at approximately 1250 K for mesoporous Cu-SiO2 with 16.8 wt % copper content. As indicated by the outcomes of inductively coupled plasma and X-ray photoelectron spectroscopy studies, copper is mainly incorporated inside the pore wall rather than embedded on the wall surface. Copper species strongly interact with silica, and calcination at high temperatures cannot cause phase separation between silica and copper oxide. Cu status in mesoporous Cu-SiO2 composites is similar to that in copper silicate in neighboring structures. Based on the results, a S+ I- I+ I- mechanism is proposed in which copper entities are surrounded by silicon species during synthesis of the mesostructured composite.     

Pd/PdO在MCM-41介孔材料孔表面的溶液移植

利用PdCl~2溶液与介孔结构硅酸铝合成原粉反应,把Pd/PdO多用途催化剂移植到MCM-41材料孔表面。产物用XRD,热分析(TG/DTA),TEM,N~2吸附及FT-IR光谱等手段进行表征。结果表明,钯经由Si-O-Pd键负载在硅酸铝骨架及孔表面上。在有序介孔材料外表面沿着孔道方向粘附着直径为10-30nm的Pd/PdO晶粒。研究表明,采用这种液相移植的方法可以有效负载金属催化剂,并防止孔道堵塞。     

Kinetic and equilibrium studies of urea adsorption onto activated carbon: Adsorption mechanism

We found that activated carbon effectively removed urea from solution and that urea adsorption onto activated carbon followed a pseudo-second-order kinetic model. We classified the urea adsorption on activated carbon as physical adsorption and found that it was best described by the Halsey adsorption isotherm, suggesting that the multilayer adsorption of urea molecules on the adsorption sites of activated carbon best characterized the adsorption system. The mechanism of adsorption of urea by activated carbon involved two steps. First, an amino (–NH₂) group of urea interacted with a carbonyl (–C?O) group and a hydroxyl (?OH) group on the surface of activated carbon via dipole–dipole interactions. Next, the –C?O group of the urea molecule adsorbed to the activated carbon interacted with another –NH₂ group from a second urea molecule, leading to multilayer adsorption.     

Gas adsorption in mesoporous micelle-templated silicas: MCM-41, MCM-48, and SBA-15

This paper reports a molecular simulation and experimental study on the adsorption and condensation of simple fluids in mesoporous micelle-templated silicas MCM-41, MCM-48, and SBA-15. MCM-41 is described as a regular cylindrical silica nanopore, while SBA-15 is assumed to be made up of cylindrical nanopores that are connected through lateral channels. The 3D-connected topology of MCM-48 is described using a gyroid periodic minimal surface. Argon adsorption at 77 K is calculated for the three materials using Grand Canonical Monte Carlo simulations. Qualitative comparison with experiments for nitrogen adsorption in mesoporous micelle-templated silicas is made. The adsorption isotherm for SBA-15 resembles that for MCM-41. In particular, capillary condensation and evaporation are not affected by the presence of the connecting lateral channels. In contrast, the argon adsorption isotherm for MCM-48 departs from that for MCM-41 having the same pore size. While condensation in MCM-41 is a one-step process, filling of MCM-48 involves two successive jumps in the adsorbed amounts which correspond to condensation in different domains of the porosity. The condensation pressure for MCM-48 is larger than that for MCM-41. We attribute this result to the morphology of the MCM-48 surface (made up of both concave and convex regions) that differs from that for MCM-41 (concave only). Our results suggest that the pore connectivity affects pore filling when the size of the connections is comparable to that of the nanopores.     

氮气在MCM－41分子筛中的吸附：实验和分子模拟

用美国Micromeritics公司生产的ASAP2010物理吸附仪测定了低温（77 K） N_2在MCM-41分子筛中的吸附等温线，获得了表征MCM-41特征的BET比表面、BJH孔 容和平均孔径。同时用巨正则Monte Carlo（GCMC）模拟方法考究了N_2在MCM-41中 的吸附，得到了N_2在MCM-41中的模拟吸附等温线，分析了流体在MCM-41分子筛中 的微观结构。GCMC模拟中MCM-41介孔材料模型化为圆柱孔，N_2模型化为Lennard- Jones（LJ）球。N_2和MCM-41介孔墙壁间的相互作用采用Tjatjopoulos-Feke- Mann（TFM）势能模型进行表征。通过使模拟和实验结果有一个好的吻合，确定了 一组有效的MCM-41分子筛的势能参数（σ_(ww) = 0.265 nm，∈_(ww)/k = 190 K ）。这为以后其他吸附质在MCM-41中吸附的预测奠定了基础、提供了依据。     

Characterization of methylated nanoscale MCM-41 material

In this study, nanoscale MCM-41 molecular sieve was prepared under a basic condition by a hydrothermal method using cetyltrimethylammonium bromide as a template and tetraethyl orthosilicate as a silica source. Methylated nanoscale MCM-41 molecular sieve was prepared from the nanoscale MCM-41 by post-synthesis method using trimethylchlorosilane (TMCS) as coupling agent. The product was characterized by means of element analysis, powder X-ray diffraction, Fourier transform infrared (FT-IR) spectroscopy, low-temperature nitrogen adsorption-desorption technique at 77 K, scanning electron microscopic (SEM), thermogravimetry-differential thermal analysis (TG-DTA). Powder XRD showed that the framework of the molecular sieve was well retained and the degree of ordering of the methylated MCM-41 decreases. IR spectra and the low-temperature nitrogen adsorption-desorption technique suggested that methyl was successfully grafted to the inner surface of the methylated MCM-41 and the mesoporous channels of the methylated MCM-41 were still maintained. Scanning electron microscopic results showed that the average size of the methylated MCM-41 prepared was 112 nm. Differential thermal analysis showed that the prepared material has preferable thermal stability and the methylated MCM-41 can be stable at 903 °C.     

Hydrogenation of naphthalene on noble-metal-containing mesoporous MCM-41 aluminosilicates

Aromatic saturation of oil fractions is a key process in the refining industry due to increasing demand for cleanest distillates with superior performances. In this study, the behavior of different catalysts containing 1 wt.% of noble-metal inside a mesoporous MCM-41 (Si:Al=20) framework was investigated in the hydrogenation of naphthalene, as preliminary step to investigate bimetallic catalysts. While at atmospheric pressure only Rh and Pd showed a low hydrogenation activity, in the tests performed at 6.0 MPa the catalytic activity grew, exhibiting the following order: Pt>RhPd>>>Ru≈Ir. However, all the catalysts required a large H₂ excess, to avoid a decrease in hydrogenation and ring-opening activity, and gave rise to the best performance for a contact time of 6.8 s, favouring at lower values the partial hydrogenation to tetralin and at higher values cracking reactions. Finally, all the catalysts showed low thio-tolerance, with significant deactivation already feeding 100 ppm wt. of dibenzothiophene (DBT), with a partial reversibility only for the Pt-containing catalyst (CAT 3).     

Epoxidation of cyclohexene on modified Ti-containing mesoporous MCM-41

Ti-MCM-41, B-Ti-MCM-41 and Ti-grafted MCM-41 were synthesized, characterized and studied in the epoxidation of cyclohexene. The synthetic methods and the effect of water in the oxidant are discussed.     

Adsorption dynamics and equilibrium studies of Zn (II) onto chitosan

Batch equilibration studies are conducted to determine the nature of adsorption of zinc (II) over chitosan. The factors affecting the adsorption process like particle size, contact time, dosage, pH, effects of chloride and nitrate are identified. The influence of temperature and co-ions on the adsorption process is verified. The fraction of adsorption,Y _t and the intraparticle diffusion rate constant,k _p are calculated at different environments and the results are discussed. The nature of adsorption of the zinc (II)-chitosan system is explained using Freundlich, Langmuir isotherms and thermodynamic parameters     

Thermal and FTIR spectroscopic analysis of the interactions of aniline adsorbed on to MCM-41 mesoporous material

The adsorption of aniline on Na-AlMCM-41 synthesized by us has been characterized by infrared spectroscopy, temperature programmed desorption (TPD), and differential thermal analysis methods. Aniline would be mostly bound to the mesostructure through weak pi interactions. On the mesostructure containing adsorbed water, the co-adsorption of aniline could occur by weak hydrogen bonding through surface water molecules. For water, two possible modes of adsorption have been identified. Different associations between aniline and hydrated and nonhydrated mesostructures have been evaluated in order to favor the posterior in situ polymerization of adsorbed aniline.     

Sulfonic acid functionalized mesoporous MCM-41 silica as a convenient catalyst for Bisphenol-A synthesis

Sulfonic acid groups anchored to the surface of mesoporous MCM-41 silica have been identified with S K-edge XANES spectra and the material is an efficient catalyst for the liquid phase condensation of phenol with acetone to form Bisphenol-A with high selectivity.