Development of regenerative dye impregnated mesoporous silica materials for assessing exposure to ammonia

The mesostructured materials MCM-41 and SBA-15 were studied as possible supports of bromocresol green (BG) dye impregnation for the ammonia gas detection because of their large surface area, high regenerative property, and high thermal stability. X-ray diffraction, transmission electron microscopy, scanning electron microscope, and N₂ adsorption analysis were used to characterize the prepared materials. These materials could sense ammonia via visible color change from yellowish-orange to blue color. The color change process of the nanostructured materials was fully reversible during 10 cyclic tests. The results indicated that the ammonia absorption responses of the two nanostructured materials were both very sensitive, and high linear correlation and high precision were achieved. As the gaseous ammonia concentrations were 50 and 5 ppmv, the response times for the SBA-15/BG were only 1 and 5 min, respectively. Moreover, the BG dye-impregnated SBA-15 was less affected by the variation in the relative humidity. It also had faster response for the detection of NH₃, as well as lower manufacturing price as compared to that of the dye-impregnated MCM-41. Such feature enables SBA-15/BG to be a very promising material for the detection of ammonia gas.

Implications: The detector tube is a convenient ambient ammonia detection device. However, almost all the commercial detector tubes can be used once only, which not only increases the purchase cost but also produces lots of waste. In this study, we developed two sensing materials that are sensitive for repeated usage. The two mesoporous silica-based materials, MCM-41 and SBA-15, are impregnated by an organic dye of bromocresol green to induce color change behavior that can be easily observed by the naked eye, and it is concluded that dye-impregnated SBA-15/BG is a very promising material for the detection of ammonia gas.     

Development of regenerative dye impregnated mesoporous silica materials for assessing exposure to ammonia

The mesostructured materials MCM-41 and SBA-15 were studied as possible supports of bromocresol green (BG) dye impregnation for the ammonia gas detection because of their large surface area, high regenerative property, and high thermal stability. X-ray diffraction, transmission electron microscopy, scanning electron microscope, and N2 adsorption analysis were used to characterize the prepared materials. These materials could sense ammonia via visible color change from yellowish-orange to blue color. The color change process of the nanostructured materials was fully reversible during 10 cyclic tests. The results indicated that the ammonia absorption responses of the two nanostructured materials were both very sensitive, and high linear correlation and high precision were achieved. As the gaseous ammonia concentrations were 50 and 5 ppmv, the response times for the SBA-15/BG were only 1 and 5 min, respectively. Moreover the BG dye-impregnated SBA-15 was less affected by the variation in the relative humidity. It also had faster response for the detection of NH3, as well as lower manufacturing price as compared to that of the dye-impregnated MCM-41. Such feature enables SBA-15/BG to be a very promising material for the detection of ammonia gas.     

Adsorption of mesitylene via mesoporous adsorbents

Mesitylene (or 1,3,5-trimethylbenzene) is a volatile organic compound emitted from various industrial processes, e.g., spray coating. Its emissions have become a critical issue because mesitylene is toxic and cannot be removed using traditional adsorbents, e.g., zeolite (H-ZSM-5; the diameter of mesitylene molecules is greater than the pore size of H-ZSM-5). Hence, an adsorbent with a large pore size, MCM-41, is used in this study to investigate its adsorption capacity for mesitylene and compare with that of H-ZSM-5. Experimental results reveal that MCM-41 without Al₂O₃ exhibits a good adsorption capacity (184 mg/g) for the gas stream containing 100 ppm of mesitylene at a relative humidity of 10%. The adsorption kinetics is well described by the Freundlich isotherm. Furthermore, experimental results reveal that MCM-41 is effective for the adsorption of low concentrations (10 ppm) of mesitylene. In addition, adsorption–desorption tests revealed that the sample MCM-41-AS is stable to sustain the adsorption capacity after 10 adsorption–desorption cycles. After 10 adsorption–desorption cycles, MCM-41-AS retains 92.4% of its initial adsorption capacity (170 vs. 184 mg/g). Finally, MCM-41 and H-ZSM-5 in series are effective for the simultaneous removal of mesitylene and toluene in the gas stream.

Implications: This study aims to improve the performance of adsorbent for mesitylene, which is typically applied in the spray-coating industry. The zeolite MCM-41-AS is selected as a candidate for the investigation. Experimental results reveal that MCM-41-AS exhibits a good adsorption capacity for mesitylene and that it can be integrated with H-ZSM-5-25 for the simultaneous adsorption of mesitylene and toluene.     

MCM-41介孔分子筛的合成及其对铜离子的吸附性能

以微硅粉为硅源，CTAB和PEG-6000为模板剂，合成MCM-41介孔分子筛。采用XRD、N2吸附-脱附曲线、FT—IR以及TEM表征了其结构、比表面积、孔径分布及晶体形貌，并且以该样品为吸附剂，对含Cu2＋的溶液进行了静态吸附实验。结果表明，以微硅粉为硅源成功合成了具有典型六方排列孔道结构的MCM-41，其比表面积为869．5m。／g，孔容为0．97cm3／g，平均孔径为3．3nm；溶液pH为5—6时，MCM-41对Cu2＋的去除效果最好；MCM-41对Cu3＋的最大吸附吸附容量36．3mg／g；MCM-41对Cu2＋的吸附性能符合Langmuir吸附方程的特征。动力学研究表明，该过程符合准二级动力学模型。     

Adsorption of basic dyes onto MCM-41

The adsorption of two basic dyes, Basic Green 5 (BG5) and Basic Violet 10 (BV10), onto MCM-41 was studied to examine the possible effect of interactions between large adsorbates and MCM-41 on the pore structure stability of MCM-41 and the potential of MCM-41 for the removal of basic dyes from wastewater. The revolutions of surface characteristics and pore structure of MCM-41 induced by dyes adsorption were characterized based on the analyses of the nitrogen isotherms, the XRD patterns, and the FTIR spectra. It was experimentally concluded that when the effect of interactions between large dyes (such as BV10) and MCM-41 on the pore structure stability of MCM-41 was insignificant, MCM-41 might be a good adsorbent for the removal of basic dyes from wastewater. The adsorption of BV10 on MCM-41 with respect to contact time, pH, and temperature was then measured to provide more information about the adsorption characteristics of MCM-41. Both Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the pseudo-second-order kinetic model was used to describe the kinetic data, from which some adsorption thermodynamic parameters were also evaluated.     

MCM-41介孔分子筛的合成及其对铜离子的吸附性能简

以微硅粉为硅源，CTAB和PEG-6000为模板剂，合成MCM-41介孔分子筛。采用XRD、N₂吸附-脱附曲线、FTIR以及TEM表征了其结构、比表面积、孔径分布及晶体形貌，并且以该样品为吸附剂，对含Cu²⁺的溶液进行了静态吸附实验。结果表明，以微硅粉为硅源成功合成了具有典型六方排列孔道结构的MCM-41，其比表面积为869.5 m²/g，孔容为0.97 cm³/g，平均孔径为3.3 nm；溶液pH为5~6时，MCM-41对Cu²⁺的去除效果最好；MCM-41对Cu²⁺的最大吸附吸附容量36.3 mg/g；MCM-41对Cu²⁺的吸附性能符合Langmuir吸附方程的特征。动力学研究表明，该过程符合准二级动力学模型。     

Catalytic reduction of NO on copper/MCM-41 studied by in situ EXAFS and XANES

Speciation of copper in the channels of MCM-41 during reduction of NO with CO at 473-773 K was studied by in situ extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies in the present work. The component fitted (in situ) XANES spectra of the catalyst showed that about 72% of metallic copper (Cu(0)) in MCM-41 was oxidized to higher oxidation state coppers (Cu(II) (46%) and Cu(I) (26%)) during the NO reduction process (at 473 K). By EXAFS, we also found that in the NO reduction process, oxygen was inserted into the metallic copper matrix and led to a formation of the copper oxide species with a Cu-O bond distance of 1.93 A which was greater than that of the model compound Cu(2)O (typically 1.86 A). At 573-673 K, mainly Cu(II) was found in the channels of MCM-41. Nevertheless, at a higher temperature (e.g., 773 K), about 61% Cu(I), 31% Cu(II), and 8% Cu(O) with averaged Cu-Cu and Cu-O bond distances of 3.04 and 1.88 A, respectively were observed, that might account for the high selectivity-to-decomposition (S/D) ratios for yields of N(2) and CO(2) in the catalytic reduction of NO with CO.     

Ba/TiO2/MCM-41光催化降解对硝基苯甲酸

以钛酸丁酯为钛源、MCM-41分子筛为载体,采用溶胶-凝胶法制备了掺杂与负载相结合的光催化剂Ba/TiO2/MCM-41。结果表明:Ba/TiO2/MCM-41是一种比表面积高达341.2 m2/g的介孔材料,主要晶相为锐钛矿相,比P25有更强的紫外光吸收。将Ba/TiO2/MCM-41用于光催化氧化水中的对硝基苯甲酸,当催化剂投加量为0.5 g/L,对硝基苯甲酸初始pH为4、浓度为2×10-4mol/L时,紫外光照30 min后,对硝基苯甲酸降解率达到96.0%。用紫外光谱、红外光谱和高效液相色谱分析对硝基苯甲酸降解前后的变化,发现随着光照时间延长,苯环上的硝基、羧基吸收峰逐渐减弱;对硝基苯甲酸首先被降解为一些中间小分子产物,随着反应进行,小分子物质也逐渐被降解。     

Study on the indoor volatile organic compound treatment and performance assessment with TiO2/MCM-41 and TiO2/quartz photoreactor under ultraviolet irradiation

Volatile organic compounds (VOCs) are the cause of indoor air pollution and are readily emitted from furniture and cleaning agents. In Taiwan, the concentrations of indoor VOCs range roughly from 1 to 10 ppm. It is important to effectively reduce indoor VOC emissions and establish the implementation of long-term, low-cost, controlled techniques such as those found in the ultraviolet/titanium dioxide (UV/TiO2) control systems. This study evaluates the performance of a photoreactor activated by visible irradiation and packed with TiO2/quartz or TiO2/mobile catalytic material number 41 (MCM-41). The photocatalysts tested include commercial TiO2 (Degussa P-25) and synthesized TiO2 with a modified sol-gel process. The UV light had a wavelength of 365 nm and contained an 8-W, low-pressure mercury lamp. Reactants and products were analyzed quantitatively by using gas chromatography with a flame-ionization detector. It is important to understand the influence of such operational parameters, such as concentration of pollutant, temperature, and retention time of processing. The indoor concentrations of VOCs varied from 2 to 10 ppm. Additionally, the temperatures ranged from 15 to 35 degrees C and the retention time tested from 2 to 8.2 sec. The results show that quartz with TiO2 had a better photoreductive efficiency than quartz with MCM-41. The toluene degradation efficiency of 77.4% with UV/TiO2/quartz was larger than that of 54.4% with the UV/TiO2/MCM-41 system under 10-min reaction time. The degradation efficiency of the UV/TiO2 system decreased with the increasing concentrations of indoor VOCs. The toluene degradation efficiency at 2 ppm was approximately 5 times greater than that at 10 ppm. The photoreduction rate of the VOCs was also evaluated with the Langmuir-Hinshewood model and was shown to be pseudo-first-order kinetics.     

Evaluation of new surfactant expanded zirconium and titanium phosphates for polycyclic aromatic hydrocarbons extraction from waters

A newly synthesized family of materials prepared with surfactant as organic template were tested for the extraction of polycyclic aromatic hydrocarbons (PAHs) from water, using pyrene (Pyr) and benzo[a]pyrene (B[a]P) as PAHs representatives. Particular attention was paid to the evaluation of the recovery factors with dichloromethane as eluent in order to estimate their potential as adsorbing solid phases for PAH remediation or analysis. Eleven lamellar MCM-50 type materials incorporating n-alkyl- (n = 12, 16, 18) trimethylammonium bromide molecules with different concentrations and chain lengths and two hexagonal MCM-41 type materials incorporating octadecyl-trimethyl ammonium bromide were tested. Best results were obtained by preparing lamellar MCM-50 zirconium and titanium phosphates in the presence of n-dodecyl-trimethylammonium at a relative molar concentration (surfactant/phosphate) of 1.     

过渡金属离子改性MCM-41对乙烯吸附的影响

为了提高吸附剂对乙烯气体的吸附量，对常见的MCM-41分子筛进行了过渡金属离子改性研究。通过镍离子交换实验，确定了改性条件，改性后的样品对乙烯的吸附行为发生改变。使用镍离子改性后的MCM-41在常温常压下对乙烯的最大吸附量为可达416cm3／g，约为商用颗粒活性炭的6倍，远高于其他文献的报道。吸附质的检测结果说明乙烯在其吸附过程中发生多聚反应，高碳数的直链烯烃为最终产物。CO原位红外吸附的引人证实经过热处理后，一价镍能在镍离子改性后的MCM-41样品中形成并成为乙烯聚合反应的活性中心。     

Ba/TiO_2/MCM-41光催化降解对硝基苯甲酸

以钛酸丁酯为钛源、MCM-41分子筛为载体,采用溶胶-凝胶法制备了掺杂与负载相结合的光催化剂Ba/TiO2/MCM-41。结果表明：Ba/TiO2/MCM-41是一种比表面积高达341.2 m2/g的介孔材料,主要晶相为锐钛矿相,比P25有更强的紫外光吸收。将Ba/TiO2/MCM-41用于光催化氧化水中的对硝基苯甲酸,当催化剂投加量为0.5 g/L,对硝基苯甲酸初始pH为4、浓度为2×10-4mol/L时,紫外光照30 min后,对硝基苯甲酸降解率达到96.0%。用紫外光谱、红外光谱和高效液相色谱分析对硝基苯甲酸降解前后的变化,发现随着光照时间延长,苯环上的硝基、羧基吸收峰逐渐减弱;对硝基苯甲酸首先被降解为一些中间小分子产物,随着反应进行,小分子物质也逐渐被降解。     

Physical and chemical regeneration of zeolitic adsorbents for dye removal in wastewater treatment

Natural zeolite and synthetic zeolite, MCM-22, were employed as effective adsorbents for a basic dye, methylene blue, removal from wastewater. Two methods, Fenton oxidation and high temperature combustion, have been used for regeneration of used materials. It is found that MCM-22 exhibits equilibrium adsorption at 1.7 x 10(-4) mol g(-1), much higher than the adsorption of natural zeolite (5 x 10(-5) mol g(-1)) at initial dye concentration of 2.7 x 10(-5)M and 30 degrees C. Solution pH will affect the adsorption behaviour of MCM-22. Higher solution pH results in higher adsorption capacity. The regenerated adsorbents show different capacity depending on regeneration technique. Physical regeneration by high temperature combustion will be better than chemical regeneration using Fenton oxidation in producing effective adsorbents. Regeneration of MCM-22 by high temperature treatment can make the adsorbent exhibit comparable or superior adsorption capacity as compared to the fresh sample depending on the temperature and time. The optimal temperature and time will be 540 degrees C and 1h. The Fenton oxidation will recover 60% adsorption capacity. For natural zeolite, regeneration can not fully recover the adsorption capacity with the two techniques and the regenerated natural zeolites by the two techniques are similar, showing 60% adsorption capacity of fresh sample. Kinetic studies indicate that the adsorption follows pseudo-second-order kinetics.     

Modified SBA-15 mesoporous silica for heavy metal ions remediation

N-Propylsalicylaldimino-functionalized SBA-15 mesoporous silica was prepared, characterized and used as an adsorbent for heavy metal ions. The organic-inorganic hybrid material was obtained using successive grafting procedures of SBA-15 silica with 3-aminopropyl-triethoxysilane and salicylaldehyde, respectively. For comparison an amorphous silica gel was functionalized using the same procedure. The structure and physicochemical properties of the materials were characterized by means of elemental analysis, X-ray diffraction (XRD), nitrogen adsorption-desorption, thermogravimetric analysis and FTIR spectroscopy. The organic functional groups were successfully grafted on the SBA-15 surfaces and the ordering of the support was not affected by the chemical modification. The behavior of the grafted solids for the adsorption of heavy metals ions from aqueous solutions was investigated. The hybrid materials showed high adsorption capacity and high selectivity for copper ions. Other ions, such as nickel, zinc, and cobalt were adsorbed by the modified SBA-15 material. The adsorbent can be regenerated by acid treatment without altering its properties.     

Eco-friendly synthesis of nanostructured mesoporous materials from natural source rice husk silica for environmental applications

Environmental Science and Pollution Research - Nanostructured mesoporous materials of MCM-41 type were synthesized using a natural, non-toxic, and cheap source of silica from rice husk. Then, this...     

Cartographic modelling of aerotechnogenic pollution in snow cover in the landscapes of the Kola Peninsula

The goal of this work was to develop computational techniques for sulphates, nickel and copper accumulation in the snow in the local pollution zone. The main task was to reveal the peculiarities of formation and pollution of snow cover on the region with complex cross-relief. A digital cartographic model of aerotechnogenic pollution of snow cover in the landscapes of the local zone has been developed, based on five-year experimental data. Data regarding annual emissions from the industrial complex, information about distribution of wind and the sum of precipitation from meteostation "Nikel" for the winter period, allowed the model to ensure: * material presentation in the form of maps of water capacity and accumulation of sulphates, nickel and copper in the snow over any winter period in retrospective; * calculation of water capacity and accumulation of pollutants for watersheds and other natural-territorial complexes; * solution of the opposite problem about the determination of the emissions of sulphates, nickel and copper from the enterprise by measuring snow pollution in datum points. The model can be used in other northern regions of the Russian Federation with similar physical-geographical and climatic conditions. The relationships between the sum of precipitation and water capacity in the landscapes of the same type and also the relationships between pollution content in snow and relief, pollution content in snow and distance from the source of emissions, were used as the basis for the model.     

Carbon dioxide adsorption on amine-impregnated mesoporous materials prepared from spent quartz sand

Mesoporous MCM-41 was synthesized using cetyltrimethyl ammonium bromide (CTAB) as a cationic surfactant and spent quartz sand as the silica source. Modification of the mesoporous structure to create an absorbent was then completed using 3-aminopropyltrimethoxysilane. Amine-Quartz-MCM (The A-Q-MCM) adsorbents were then characterized by N₂ adsorption/desorption, elemental analysis (EA), X-ray fluorescence (XRF), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), as well as the carbon dioxide (CO₂) adsorption/desorption performance. In this study, spent quartz sand was utilized to synthesize Quartz-MCM (Q-MCM) and the amine functionalized material, A-Q-MCM, which exhibited a higher uptake of CO₂ at room temperature compared with the nongrafted material. The results showed that Q-MCM is similar to MCM-41 synthesized using commercial methods. The surface area, pore volume, and pore diameter were found to be as high as 1028 m²/g, 0.907 cm³/g, and 3.04 nm, respectively. Under the condition of CO₂ concentration of 5000 ppm, retention time of 50 cc/min, and the dosage of 1 g/cm³, the mean adsorption capacity of CO₂ onto A-Q-MCM was about 89 mg/g, and the nitrogen content of A-Q-MCM was 2.74%. The adsorption equilibrium was modeled well using a Freundlich isotherm.

Implications:In this study, spent quartz sand was utilized to synthesize Q-MCM. The amine functionalized material exhibited a higher uptake of CO₂ at room temperature compared with the nongrafted material. The results showed that Q-MCM is similar to MCM-41 synthesized using commercial methods. The adsorption equilibrium was modeled well using a Freundlich isotherm.     

Investigating the potential of functionalized MCM-41 on adsorption of Remazol Red dye

The modification of MCM-41 was performed with 3-aminopropropyltrimethoxysilane. The structural order and textural properties of the synthesized materials were studied by X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry/differential thermogravimetry, nitrogen adsorption, and desorption analysis. The adsorption capacity of NH₂-MCM-41 was studied with Remazol Red dye. The following parameters were studied in the adsorption process: pH, temperature, adsorbent dosage, and initial concentration. The desorption process was studied in different concentrations of NaOH solutions. The Freundlich isotherm model was found to be fit with the equilibrium isotherm data. Kinetics of adsorption follows the modified Avrami rate equation. The maximum adsorption capacity was estimated to be 45.9 mg?g^?1, with removal of the dye of 99.1 %. The NH₂-MCM-41 material exhibited high desorption capacity with 98.1 %.     

The Effect of Grain Size and Element Concentration in Identifying Contaminant Sources

The distribution of metal contaminants between different size fractions of marine sediments is well known. However, the use of size normalization techniques may alter the ability or usefulness in identifying potential sources in complex environments. In a reassessment of metal data from the shelf area of Sydney, Australia, the mud and sand fractions were investigated separately by PCA and PLS methodologies. The analyses were able to produce clear distinctions between industrial/urban sources when based on a suite of metals rather than individual (single-element) concentrations. Signature analysis by PLS with copper, lead, zinc, manganese, chromium, cobalt, nickel, and cadmium demonstrated the dispersion of the fine-grained contaminated material to the south in the East Australian Current. However, due to the commonality between many of the metals, a subset of four metals was used to define the signature. This significantly improved separation, showing clear plumes extending ～30 km from the source rivers.     

Biosorption characteristics of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions by Chara sp. and Cladophora sp.

The aim of this research was to expose individual removals of copper, chromium, nickel, and lead from aqueous solutions via biosorption using nonliving algae species, Chara sp. and Cladophora sp. Optimum pH values for biosorption of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions were determined to be 6, 7, 7, and 3 for Cladophora sp. and 5, 3, 5, and 4 for Chara sp. respectively. Maximum adsorption capacities of Chara sp. [10.54 for chromium (III) and 61.72 for lead (II)] and Cladophora sp. [6.59 for chromium (III) and 16.75 and 23.25 for lead (II)] for chromium (III) and lead (II) are similar. On the other hand, copper (II) and nickel (II) biosorption capacity of Cladophora sp. [14.28 for copper (II) and 16.75 for nickel (II)] is greater than Chara sp. [6.506 for copper (II) and 11.76 for nickel (II)]. Significantly high correlation coefficients indicated for the Langmuir adsorption isotherm models can be used to describe the equilibrium behavior of copper, chromium, nickel, and lead adsorption onto Cladophora sp. and Chara sp.