Fluoride removal using lanthanum incorporated chitosan beads

Highly selective material based on naturally occurring biomaterial namely chitosan has been designed for the defluoridation of water. Lanthanum incorporated chitosan beads (LCB) were prepared using precipitation method. The synthesis was optimized by varying different synthesis parameters namely lanthanum loading, complexation and precipitation time, strength of ammonia solution used for precipitation, drying time, etc. Lanthanum incorporated chitosan beads were characterized using SEM, FTIR, XRD and EDX. Surface area of LCB was observed to be 2.76 m² g⁻¹. The equilibrium adsorption data fitted well to Langmuir adsorption isotherm and showing maximum fluoride adsorption capacity of 4.7 mg g⁻¹ with negligible lanthanum release. Kinetic study reveals that adsorption of fluoride is fast and follows pseudo-first-order kinetics. The effect of pH was also studied and the best efficiency was observed at pH 5. Presence of sulphate, nitrate and chloride marginally affected the removal efficiency, however drastic reduction in fluoride uptake was observed in the presence of carbonate and bicarbonate. Negative value of change in free energy (ΔG°) and positive value of change in entropy (ΔS°) suggest the adsorption of fluoride by LCB is feasible and spontaneous process. Positive value of change in enthalpy (ΔH°) suggests the process of fluoride adsorption is endothermic in nature. Regeneration study reveals that 1 M ammonium chloride solution appears to be the promising regeneration media showing 81.22% regeneration. The adsorption capacity of LCB was similar in fluoride-contaminated ground water collected from Dhar district of Madhya Pradesh, India, as compared to simulated water.     

Surface tension and adsorption behavior of mixtures of diacyl glycerol arginine-based surfactants with DPPC and DMPC phospholipids

The binary surface interactions of some novel cationic diacyl glycerol arginine-based surfactants with model phospholipids, which are often used as model membrane components, are studied at 25 °C in aqueous solutions of 0.1 M sodium chloride. The surfactants are 1,2-dimyristoyl-rac-glycero-3-O-(N^α-acetyl-l-arginine) hydrochloride (1414RAc) and 1,2-dilauroyl-rac-glycero-3-O-(N^α-acetyl-l-arginine) hydrochloride (1212RAc), and they are important as potential antimicrobial agents which are biodegradable and with less toxicity than other cationic surfactants. The phospholipids are 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) and 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC). The equilibrium and dynamic surface tension of each surfactant, each phospholipid, and some of their binary mixtures are studied using the bubble surfactometry method at constant area or pulsating area conditions. In addition, the surface densities of pure and mixed monolayers of these compounds at the air/water interface are probed with infrared reflection–absorption spectroscopy (IRRAS). Steady state and dynamic surface tension synergism, or antisynergism in one case, and synergistic adsorption effects are detected for the mixed dispersions studied. The enhanced adsorption detected with IRRAS, and the enhanced dynamic and steady state surface tension lowering indicate strong miscibility and net attractive interactions between the compounds in the adsorbed mixed monolayers.     

Synthesis, structure and adsorption properties of nanoporous SBA-15 materials with framework and surface functionalities

Highly ordered SBA-15 nanoporous silica containing ethylene, phenylene bridges or/and amine, thiol, vinyl and phenyl surface groups were synthesized by using amphiphilic block copolymer as the structure-directing agent. The XRD data shows high degree of the order of the final structures. Obtained materials have well-developed porous structure—values of specific surface area are in the range 700–1050 m²/g and the sizes of cylindrical mesopores are in the range 6.5–9.5 nm. It was determined that size of the mesopores strongly depends even on small amounts of co-monomers co-condensing with TEOS. A new technique to introduce some amount of pendant amine groups by co-condensation of proper monomers has been proposed. Tetragonal structure was obtained when small amount of vinyl groups was introduced to the system. A new approach of determining pore size based only on the XRD measurements was compared with KJS method, confirming full usefulness of the former for calculation of the size of mesopores in SBA-15 materials. Dedicated to Professor Mietek Jaroniec on the occasion of his 60th birthday.     

Adsorption study for removal of Congo red anionic dye using organo-attapulgite

The organo-attapulgite was prepared using hexadecyltrimethylammonium bromide (HTMAB) with equation equivalent ratio of HTMAB to CEC of attapulgite added and then used as adsorbent for the removal of Congo red (CR) anionic dye from aqueous solution. Adsorbent characterizations were investigated using infrared spectroscopy and X-ray diffraction. The effects of contact time, temperature, pH and initial dye concentration on organo-attapulgite adsorption for CR were investigated. The results show that the amount adsorbed of CR on the organo-attapulgite increase with increasing dye concentration, temperature, and by decreasing pH. The adsorption kinetics was studied with the pseudo-first-order, pseudo-second-order and intraparticle diffusion models, and the rate constants were evaluated. It was found that the adsorption mechanisms in the dye/organo-attapulgite system follow pseudo-second-order kinetics with a significant contribution of film diffusion. Equilibrium data fitted perfectly with Langmuir isotherm model compared to Freundlich isotherm model, and the maximum adsorption capacity was 189.39 mg g⁻¹ for the adsorbent. Kinetic and desorption studies both suggest that chemisorption should be the major mode of CR removal by the organo-attapulgite. The results indicate that HTMAB-modified attapulgite could be employed as low-cost material for the removal of Congo red anionic dye from wastewater.     

Boron substituted graphene: energy landscape for hydrogen adsorption

We have analyzed the modifications of interaction energy between a molecule of hydrogen and graphene layers partially substituted by boron. We show that the presence of boron modifies the symmetry of the energy landscape. It is due to both the larger boron size (with respect to carbon) and its stronger interaction with hydrogen molecules. The changes of energy surface are not confined to the neighborhood of substituted sites but extend over several graphene carbon sites, making the surface more heterogeneous. We show that the average increase of adsorption energy could meet DOE targets for hydrogen storage if a partial charge transfer between boron and hydrogen occurs during adsorption.     

Adsorption of xylene isomers on ordered hexagonal mesoporous FDU-15 polymer and carbon materials

The oil industry has been facing the challenges of separation of xylene isomers, o-xylene, m-xylene and p-xylene or removing them from the environment. In our present work, we investigated the adsorption of the three isomers on two mesoporous materials, FDU-15-350 polymer and FDU-15-900 carbon materials. The isomer adsorption capacities are well correlated with their physical pore properties. It is found that the micropores are very crucial for the adsorption of these three isomers. The more micropore volume the adsorbent has, the better the adsorption capacity is. Henry’s constants were also calculated for the three isomers on the two adsorbents. Both on FDU-15-350 polymer and FDU-15-900, the Henry’s constants for the three isomers show the same trend o>m>p xylene which is coincidently in accordance with their polarity trend, indicating more polar adsorbate is preferred for adsorption on the two adsorbents. The isosteric heats of adsorption are correlated with the microporosity and the size of the adsorbate molecule. More microporosity and smaller molecules give higher heats of adsorption. Extracted information on pore properties of adsorbents by using the three isomers has very similar results as that resolved from nitrogen adsorption, indicating the feasibility of using the three isomers as adsorbates to extract pore information. This work is devoted to commemorating the 60th birthday of Professor Mieczyslaw (Mietek) Jaroniec.     

Adsorption of chlorhexidine onto cellulosic fibers

Comparative investigations of adsorption properties of chlorhexidine (CHX) on two cellulose fibers, bleached cotton and viscose, were studied in order to obtain dry gauzes covered with known amount of this antiseptic. Adsorption isotherm results carried out at 293 and 323 K can be described by Langmuir isotherm model, nevertheless, at high concentration correlation is better to Freundlich isotherm. Electrokinetic potential evolution with CHX concentration, shows that initial negative zeta potential of cotton and viscose diminish its absolute value as the concentration of the treatment increases; both fibers present an isoelectric point at high concentration of CHX that is 0.3 mM for viscose and 0.8 mM for cotton. Electrostatic interactions between cationic groups of CHX and carboxylic acid groups of the fibers could explain adsorption at low concentration, but when it is higher than these values, possible hydrogen bonding between the amine groups of CHX and hydroxyl groups of cellulose could explain increasing adsorption when it is hindered by electrostatic repulsion as it is predicted by Freundlich model, that describes heterogeneous surface and multilayer adsorption. Adsorption kinetics isotherms reveal that the process is quick with t _1/2 values of 5.4 min for cotton and 2.8 min for viscose. Differences in adsorption behaviour between the two fibers could be attributed to structural differences as we have observed from estimation of CI index based on FTIR spectra. Values obtained 1.6 for viscose and 2.2 for cotton could explain that the amount of CHX adsorbed on viscose is higher than it is on cotton. Finally desorption experiments performed with 0.01 M of NaCl solution at room temperature and pH 6 reveals the possibility of therapeutical application of these fibers although further investigations must be done to optimize the process.     

一种后交联大孔吸附树脂的合成及其对苯酚和维生素B_(12)吸附性能研究

工业二乙烯苯悬浮聚合制备的大孔树脂,在二氯乙烷溶剂中以无水三氯化铁为催化剂进行悬挂双键后交联反应,得到的后交联树脂的比表面积和孔容都有显著增加.低温氮气吸附/脱附等温线得到的孔径分布曲线证明初始共聚物PDT-55(polydivinylbenzene,toluene as porogen)和PDH-55(polydivinylbenzene,heptane andtoluene as porogen)经后交联反应,所形成的新孔以微孔为主.树脂对水溶液中苯酚和维生素B12(VB12)的静态吸附研究发现树脂经后交联后,对苯酚的吸附量有显著提高,但对VB12的吸附量增加不大,原因是分子尺寸较大的VB12无法进入由悬挂双键后交联反应所形成的微孔.树脂PDT-55pc对苯酚的吸附量大于商品树脂XAD-4;后交联前后树脂PDT-55、PDT-55pc(post-crosslinking of PDT-55)、PDH-55、PDH-55pc(post-crosslinking ofPDH-55)对VB12的吸附量均大于树脂XAD-4.在本研究的实验条件下,Langmiur和Freundlich吸附等温线方程能很好地拟合树脂对水溶液中苯酚和VB12的吸附,相关系数在0.99以上.静态吸附动力学实验结果表明后交联前后树脂对苯酚的吸附较VB12更容易达到吸附平衡.吸附动力学数据的拟合结果显示,McKay二级吸附动力学模型符合树脂对苯酚的吸附,而对VB12的吸附更符合Lagergren一级吸附动力学模型.     

光敏季铵盐Gemini表面活性剂a4-6-m在气/液界面的吸附

合成了3种不对称结构的季铵盐Gemini表面活性剂a4-6-m, 分子的一根疏水链是偶氮苯为端基的4个亚甲基链, 另一根是不同长度的脂肪链(m=12, 14, 16). 研究结果表明, 反式偶氮苯封端的a4-6-m在气/液界面上以直立方式排列, 偶氮苯端基间的π-π相互作用导致吸附分子较为紧密地排列, 但吸附层外表面含有偶氮苯成分使临界胶束浓度(cmc)时的表面张力(γcmc)较大. 紫外光激发使反式结构偶氮苯变为顺式结构, 这些极性较强的顺式偶氮苯夹杂在直立的烷烃链间, 增强的偶极-偶极相互作用促进了分子紧密排列, 使分子占据面积(Amin)略微减小. 增长脂肪链长度有助于降低临界胶团浓度和C20(使水的表面张力降低20 mN·m-1时所需的表面活性剂浓度), 但对γcmc影响不大.