Fabrication of layered double hydroxide spheres through urea hydrolysis and mechanisms involved in the formation

The goal of this study is to prepare hydrotalcite pellets and validate their potential utility in catalysts and catalysts support. Hydrotalcite pellets were synthesized by urea hydrolysis. Urea hydrolysis can provide both carbonate as the intercalated anion and hydroxyl anions to form Mg–Al layered double hydroxide (LDH) with carbonate intercalation. Urea hydrolysis was also used to generate NH₃ which plays a critical role in the process of synthesis hydrotalcite pellets. Mechanism of the formation hydrotalcite pellets was also discussed. The as-prepared samples were well characterized by X-ray diffraction, scanning electron microscopy, transmission electronic microscope, N₂ adsorption/desorption, and Fourier transform infrared spectroscopy, respectively. The results revealed that the hydrotalcite pellets were well-crystallized and formed by self-assembly of hexagonal platelets LDHs. The present work suggests that it is possible to grow hydrotalcite pellets directly through one-step aqueous solution-phase chemical route under controlled conditions.     

介孔Al2O3分离富集-火焰原子吸收法测定麻黄和马钱子中的铅

研究了介孔Al2O3分离富集-火焰原子吸收法测定麻黄和马钱子中的铅的新方法.探讨了溶液pH、吸附温度、洗脱条件及共存离子对铅分离富集的影响.在最佳实验条件下,介孔Al2O3能定量、快速吸附试液中的痕量pb2+,其静态饱和吸附容量为8.53 mg/g.吸附在介孔Al2O3上的pb2可用0.2 mol/LEDTA完全洗脱....     

离子交换树脂的选择及柠檬酸溶液循环使用研究

用离子交换树脂法吸附柠檬酸溶液中的金属离子,苯乙烯系阳离子交换树脂的吸附性能较好,它对镍、铝离子的吸附容量均较大,且吸附前后柠檬酸溶液的浓度变化较小.静态条件下树脂对镍的吸附容量为16.83mg Ni/g干树脂,对铝为21.36mg Al/g干树脂;动态条件下树脂对镍的吸附容量为6.78mg Ni/g干树脂,对铝为31.8mgAl/g干树脂,吸附液流速为1m/h～3m/h.吸附后的柠檬酸溶液可循环使用.当用1mol/L硫酸解吸时,树脂对镍铝的解吸率可达90%以上.当硫酸中Ni2 为1.70mmol/L,Al3 为7.40mmol/L时,树脂的解吸率仍可达80%以上.     

Potential of boronic acid functionalized magnetic particles in the adsorption of human antibodies under mammalian cell culture conditions

In this work, we systematically evaluated the potential of using boronic acid functionalized magnetic particles in the capturing of human immunoglobulin G under typical mammalian cell culture conditions. For comparison, Protein A coated magnetic particles were also used. The binding pH was found to significantly influence the adsorption isotherms of boronic acid particles with the higher capacities (0.216 g IgG/g support) being observed at pH 7.4. Comparatively, this value was 0.109 g IgG/g support, for Protein A particles under the same conditions. Both particles revealed very fast adsorption kinetics with more than 70% of the maximum binding capacity being achieved in a few seconds. The effect of glucose and lactate, which are known to interact with boronic acid, was evaluated. For glucose, the binding capacity was significantly influenced by the pH and decreased as pH increased. At pH 9.5, a 70% lower binding capacity was observed for glucose concentrations as low as 0.5 g/l. The effect of lactate was less pronounced and almost pH independent reaching at most 20% decrease in binding capacity. Nevertheless, the effect of both molecules was always lower at pH 7.4. The optimization of the elution conditions enabled complete recovery of bound IgG from boronic acid particles using 50mM Tris-HCl, 200 mM sorbitol, 200 mM NaCl at pH 8.5.     

碱式碳酸镁为新结合相的薄膜梯度扩散技术原位富集测定富营养水体中的磷

薄膜扩散梯度技术(Diffusive gradients in thin films technique, DGT)是近年来应用于自然水体、沉积物和土壤中活性磷原位测定的一种新技术。利用含碱式碳酸镁的聚丙烯酰胺凝胶膜为 DGT 新结合相,探讨了初始浓度、放置时间、pH 值及离子强度对组装后 DGT 吸附性能的影响。用10 mL 0.25 mol/ L H2 SO4对结合相进行洗脱,洗脱率为85%±5%。组装后 DGT 对磷的测定不受溶液 pH 值(4.10~9.15)和离子强度(0.001~0.05 mol/ L)的影响。在温度25℃,pH 7.00,磷初始浓度为2 mg/ L 时, DGT 对磷的最大吸附容量为20.4μg。初始磷浓度为0.001~20 mg/ L 时,新 DGT 测定值与磷钼蓝比色法测定值一致。本方法对磷的检出限为102.4 ng/ L。将碱式碳酸镁-DGT 和商品化的 Ferrihydrite-DGT 应用于合成海水、厦门近岸海水、易海、巢湖水和南淝河中的对比检测,结果表明,碱式碳酸镁-DGT 能更准确测定不同水体中磷浓度。     

Nitrate absorption through hydrotalcite reformation

Thermally activated hydrotalcite based upon a Zn/Al hydrotalcite with carbonate in the interlayer has been used to remove nitrate anions from an aqueous solution resulting in the reformation of a hydrotalcite with a mixture of nitrate and carbonate in the interlayer. X-ray diffraction of the reformed hydrotalcites with a d(003) spacing of 7.60 A shows that the nitrate anion is removed within a 30 min period. Raman spectroscopy shows that two types of nitrate anions exist in the reformed hydrotalcite (a) nitrate bonded to the 'brucite-like' hydrotalcite surface and (b) aquated nitrate anion in the interlayer. Kinetically the nitrate is replaced by the carbonate anion over a 21 h period. Two types of carbonate anions are observed. This research shows that the reformation of a thermally activated hydrotalcite can be used to remove anions such as nitrate from aqueous systems.     

Formation of high-capacity protein-adsorbing membranes through simple adsorption of poly(acrylic acid)-containing films at low pH

Layer-by-layer polyelectrolyte adsorption is a simple, convenient method for introducing ion-exchange sites in porous membranes. This study demonstrates that adsorption of poly(acrylic acid) (PAA)-containing films at pH 3 rather than pH 5 increases the protein-binding capacity of such polyelectrolyte-modified membranes 3-6-fold. The low adsorption pH generates a high density of -COOH groups that function as either ion-exchange sites or points for covalent immobilization of metal-ion complexes that selectively bind tagged proteins. When functionalized with nitrilotriacetate (NTA)-Ni(2+) complexes, membranes containing PAA/polyethylenimine (PEI)/PAA films bind 93 mg of histidine(6)-tagged (His-tagged) ubiquitin per cm(3) of membrane. Additionally these membranes isolate His-tagged COP9 signalosome complex subunit 8 from cell extracts and show >90% recovery of His-tagged ubiquitin. Although modification with polyelectrolyte films occurs by simply passing polyelectrolyte solutions through the membrane for as little as 5 min, with low-pH deposition the protein binding capacities of such membranes are as high as for membranes modified with polymer brushes and 2-3-fold higher than for commercially available immobilized metal affinity chromatography (IMAC) resins. Moreover, the buffer permeabilities of polyelectrolyte-modified membranes that bind His-tagged protein are ~30% of the corresponding permeabilities of unmodified membranes, so protein capture can occur rapidly with low-pressure drops. Even at a solution linear velocity of 570 cm/h, membranes modified with PAA/PEI/PAA exhibit a lysozyme dynamic binding capacity (capacity at 10% breakthrough) of ~40 mg/cm(3). Preliminary studies suggest that these membranes are stable under depyrogenation conditions (1 M NaOH).     

Comparison of adsorption performances of metal–chelated polyamide hollow fibre membranes in lysozyme separation

Commercially available microporous polyamide hollow fibres are modified by acid hydrolysis to activate the reactive groups and subsequently binding of the ligand, i.e. Cibacron Blue F3GA. Then the Cibacron Blue F3GA-derived hollow fibres were loaded with different metal ions (i.e. Zn(II), Cu(II), Ni(II)) to form the metal chelate. The internal polymer matrix was characterised by scanning electron microscopy. The effects of pH, initial concentration of lysozyme, metal type and temperature on the adsorption of lysozyme to the metal–chelated hollow fibres were examined in a batch reactor. The non-specific adsorption of lysozyme onto the polyamide hollow fibres was 1.8 mg/g. Cibacron Blue F3GA immobilisation increased the lysozyme adsorption up to 62.3 mg/g. Metal–chelated hollow fibres showed a significant increase of the adsorption efficiency. Lysozyme adsorption capacities of Zn(II), Cu(II) and Ni(II)-chelated hollow fibres were different. The maximum capacities of Zn(II), Cu(II) or Ni(II)-chelated hollow fibres were 144.2, 75.2 and 68.6 mg/g, respectively. Significant amount of the adsorbed lysozyme (up to 97%) was eluted in 1 h in the elution medium containing 1.0 M NaSCN at pH 8.0 and 25 mM EDTA at pH 4.9. Repeated adsorption–desorption process showed that this novel metal–chelated polyamide hollow fibres are suitable for lysozyme adsorption.     

The Adsorption of NOx on Magnesium Aluminium Hydrotalcite

Magnesium aluminium hydrotalcite (Mg-Al-HT) with molar ratio of Mg-to-Al of 3 to 1 was prepared and characterized by X-ray diffraction (XRD) and infrared spectra (IR). The performances of Mg-Al-HT for the adsorption and desorption of NOx were studied. The results indicated that the adsorption capacity of the hydrotalcite for NOx was 1398.2mg/g, and it was higher than the acticarbon‘s. The adsorption capacities depended on adsorption time and temperature.Mg-Al-HT could be regenerated by thermal decomposition, and the adsorption efficiency had not changed markedly after three cycles.     

Adsorption of phenol from water by N-butylimidazolium functionalized strongly basic anion exchange resin

N-butylimidazolium functionalized strongly basic anion exchange resin with Cl(-) anion (MCl) was prepared by anchoring N-butylimidazole onto chloromethylated macroporous styrene-divinylbenzene (St-DVB) copolymer. The adsorption performances of phenol on MCl were studied using the batch technique at acidic and alkaline pH. The studies showed that phenol can be effectively removed at both acidic and alkaline pH. The maximum adsorption was achieved at about pH 11. The maximum adsorption capacities of phenol on MCl at pH 6.6 and 11.2 were 80.2 and 92.9 mg/g, respectively. The adsorption mechanism was mainly molecular adsorption at acidic pH and anion exchange at alkaline pH. The adsorption of phenol was hindered by the presence of Cl(-) and SO(4)(2-) at alkaline pH due to the competitive anion exchange reaction. The adsorption of molecular phenol species on MCl at acidic pH was exothermic, and the anion exchange of phenolate species by MCl at alkaline pH was endothermic. Desorption of phenol from loaded adsorbent was achieved by using 0.5 mol/L NaOH and 0.5 mol/L NaCl mixed solution. MCl can simultaneously remove phenol and Cr(VI) from their mixtures, which would be of practical value in actual industrial wastewater treatment.     

Adsorption mechanism of synthetic reactive dye wastewater by chitosan

Chitosan was able to remove the color from synthetic reactive dye wastewater (SRDW) under acidic and caustic conditions. The effect of the initial pH on SRDW indicated that electrostatic interaction occurred between the effective functional groups (amino groups) and the dye under acidic conditions. Moreover, SRDW adsorption under caustic conditions was also affected by the covalent bonding of dye and hydroxyl groups of chitosan. In addition, elution tests confirmed that chemical adsorption occurred under acidic conditions, while both physical and chemical adsorption appeared under caustic conditions. The spectra of attenuated total reflectance Fourier transform infrared spectrometry confirmed the functional groups of chitosan that affected the SRDW adsorption. However, the maximum adsorption capacities of chitosan increased when the temperature increased. The maximum adsorption capacity of chitosan obtained from the Langmuir model was 68, 110, and 156 mg g(-1) under a system pH of 11.0 at 20, 40, and 60 degrees C, respectively. The negative values of enthalpy change (DeltaH), free energy change (DeltaG), and entropy change (DeltaS) indicated an exothermic, spontaneous process and decreasing disorder of the system, respectively. Therefore, the mechanism of SRDW adsorption by chitosan was probably by chemical adsorption for a wide range of pH's and at high temperatures.     

Étude de l’élimination du Cr(VI) par l’oxyde mixte obtenu par calcination de l’hydroxyde double lamellaire MgAl

A magnesium aluminium hydrotalcite-like compound (HT) containing carbonate anions in the interlayer space and with a final Mg/Al ratio of 2 was synthesized by the co-precipitation method. The obtained material was characterized by powder X-ray diffraction (XRD), Fourier-Transform–Infrared spectroscopy (FT–IR), thermal analysis (ATG/ATD), and surface area measurements (BET). The interaction of the clay with Cr(VI) has been studied by ultraviolet–visible (UV–vis) spectroscopy. The calcined hydrotalcite (HT-C) showed the highest capacity of removal of chromium ions, and their sorption capacities for Cr(VI) are 4.85 mmol/g. The effect of various parameters on the preparation conditions for the removal of chromium, such as the contact time, the amount of sorbent, the initial concentration of Cr(VI), and the pH values of aqueous solution were also investigated to identify their influence on Cr(VI) sorption. The characterization of the calcined hydrotalcite (HT-C) after interaction with Cr(VI) ions by FT–IR spectroscopy showed that Cr(VI) was adsorbed and intercalated by the solid.     

改性纳米二氧化钛对Pb(Ⅱ)的吸附行为研究

利用浸渍法对纳米二氧化钛进行表面改性, 制备出改性纳米二氧化钛, 用扫描电镜(SEM)对其进行了表征, 并以其为吸附剂, 以火焰原子吸收光谱法(FAAS)为分析手段, 探讨了改性纳米二氧化钛在静态吸附条件下对Pb(Ⅱ)的吸附性能, 考察了影响其吸附和解脱的主要因素及优化条件下Pb(Ⅱ)的吸附容量, 考察了常见共存离子的影响. 结果表明: 在pH 5.0下, 改性纳米二氧化钛能定量吸附Pb(Ⅱ); 1.0 mol/L HNO3作为解脱剂可使Pb(Ⅱ)定量解脱; 优化条件下Pb(Ⅱ)的静态饱和吸附容量为32.88 mg/g.     

Adsorption behavior of noble metal ions (Au, Ag, Pd) on nanometer-size titanium dioxide with ICP-AES.

The adsorption behavior of gold (Au), silver (Ag) and palladium (Pd) on nanometer-size titanium dioxide (NSTD) at low concentrations was studied using inductively coupled plasma atomic emission spectrometry (ICP-AES). A preconcentration procedure of the analytes was carried out using NSTD as a solid-phase extractant before their determination by ICP-AES. The optimum conditions for adsorption were studied in detail, and under the condition that Au, Ag and Pd ions could be adsorbed and recovered quantitatively. The static adsorption capacities of Au, Ag and Pd on NSTD were 22.63, 14.06 and 11.82 mg/g, respectively. For the elution of gold, silver and palladium, a mixture of 5% thiourea solution and 3 mol L(-1) HNO3 was used. The parameters tested included: pH conditions, contact time of the analytes with NSTD, flow rate, adsorption capacity and sorption kinetics. According to the definition of IUPAC, the detection limits (3sigma) of this method for Au, Ag and Pd with an enrichment factor of 50 were (0.016), (0.006) and (0.012) microg mL(-1), respectively, the relative standard deviations (RSD) were 8.7%, 4.5% and 7.4%, respectively (n = 6). Some geological samples were determined with satisfactory results.     

Preparation of Keggin‐type phosphomolybdate by a one‐step solid‐state reaction at room temperature and its application in protein adsorption

Keggin‐type phosphomolybdate ((C₁₉H₄₂N)₃PMo₁₂O₄₀) is prepared by a one‐step solid‐state reaction at room temperature and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, and elemental analysis. The as‐prepared phosphomolybdate is demonstrated to be an efficient adsorbent for proteins. In this particular case, the selective adsorption of neutral protein hemoglobin is achieved. While under the same conditions virtually no adsorption of acidic and basic proteins, represented by bovine serum albumin and cytochrome c, are observed. A solid‐phase extraction procedure is developed for the selective isolation of hemoglobin. At pH 6, a sorption efficiency of 91.4% is achieved for 100 μg/mL hemoglobin in 1.0 mL solution by using 5.0 mg of the phosphomolybdate. The adsorption behavior of hemoglobin fits well with a Langmuir adsorption model, corresponding to a theoretical adsorption capacity of 55.86 mg/g. The retained hemoglobin could be readily recovered by using a 60 mmol/L imidazole solution at pH 7, giving rise to a recovery of 64.7%. The practical application of phosphomolybdate for protein adsorption is demonstrated by the selective isolation of hemoglobin from human whole blood followed by a sodium dodecyl sulfate polyacrylamide gel electrophoresis assay.     

The synthesis and spectroscopic characterisation of hydrotalcite formed from aluminate solutions

Raman spectroscopy has been used to characterise nine hydrotalcites prepared from aluminate and magnesium solutions (magnesium chloride and seawater). The aluminate hydrotalcites are proposed to have the following formula Mg(6)Al(2)(OH)(16)(CO(3)(2-))·xH(2)O, Mg(6)Al(2)(OH)(16)(CO(3)(2-),SO(4)(2-))·xH(2)O, and Mg(6)Al(2)(OH)(16)(SO(4)(2-))·xH(2)O. The synthesis of these hydrotalcites using seawater results in the intercalation of sulfate anions into the hydrotalcite interlayer. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structures. The spectra have been conveniently subdivided into spectral features based upon the carbonate anion, the hydroxyl units and water units. This investigation has shown the ideal conditions to form hydrotalcite from aluminate solutions is at pH 14 using a magnesium chloride solution at a volumetric ratio of 1:1. Changes in synthesis conditions resulted in the formation of impurity products aragonite, thenardite, and gypsum.     

Reactivity of Mg–Al hydrotalcites in solid and delaminated forms in ammonium carbonate solutions

Treatment of Mg–Al hydrotalcites (LDHs, layered double hydroxides) in aqueous (NH₄)₂CO₃ at 298 K leads to composites of dawsonite, hydrotalcite, and magnesium ammonium carbonate. The mechanism and kinetics of this transformation, ultimately determining the relative amounts of these components in the composite, depend on the treatment time (from 1 h to 9 days), the Mg/Al ratio in the hydrotalcite (2-4), and on the starting layered double hydroxide (solid or delaminated form). The materials at various stages of the treatment were characterized by inductive coupled plasma-optical emission spectroscopy, X-ray diffraction, transmission electron microscopy, infrared spectroscopy, thermogravimetry, and nitrogen adsorption at 77 K. The progressive transformation of hydrotalcite towards crystalline dawsonite and magnesium ammonium carbonate phases follows a dissolution–precipitation mechanism. A gradual decrease of the Mg/Al ratio in the resulting solids was observed in time due to magnesium leaching in the reacting medium. Dawsonite–hydrotalcite composite formation is favored at high aluminum contents in the starting hydrotalcite, while the formation of magnesium ammonium carbonate is favored at high Mg/Al ratios. The synthetic strategy comprising hydrotalcite delamination in formamide prior to aqueous (NH₄)₂CO₃ treatment is more reactive towards composite formation than starting from the bulk solid hydrotalcite.     

碳酸钾修饰水滑石吸附二氧化碳工艺条件研究

采用共沉淀法合成水滑石,等体积浸渍法将碳酸钾负载于水滑石孔道及层状结构中;在一定空速条件下,考察了吸附温度、碳酸钾添加量、活化温度对碳酸钾修饰水滑石吸附二氧化碳性能的影响;利用SEM、BET等手段对修饰后的水滑石进行了表征。在一定实验条件下,水滑石吸附容量可以达到9.10mol/kg。     

n(Mg)/n(Al)=3的水滑石层板结构及层间距的阴离子调控

利用密度泛函理论(DFT)的B3PW91方法在Lanl2dz水平上研究了镁铝摩尔比为3的水滑石层板分子簇模型[Mg30Al7(OH)72]9+的几何构型, 优化得到的结构参数和采用Reflex模块模拟得到的XRD图谱分别与实验观测结果相符, 由此确定了水滑石层板沿第三维方向的有序堆积, 该结构符合空间群R3m(166), 其晶胞参数a=1.2552 nm, c=2.3400 nm. 进一步构造了具有R3m空间群对称性的Mg-Al-CO32--LDH晶体结构模型, 选取其中的簇模型, 经优化得到了一种稳定构型, 脱除结晶水的水滑石层间距为0.7260 nm, 键参数的变化表明碳酸根离子与层板间存在较强的超分子作用.     

高结晶度镍铝水滑石的制备及其电化学行为研究

水滑石(Hydrotalcite,简称HT)是一类层状结构的阴离子粘土,它具有碱性特征、微孔结构、记忆效应及金属离子的同晶可取代性和层间阴离子的可交换性.此外,由于它具有材料廉价易得,独特的离子交换性能,很好的热和化学稳定性等特点,使其在电分析方面作为安培传感器~([1])、电位传感器~([2])、生物传感器~([3])以及作为超级电容器的电极活性材料~([4-6])刮都有潜在应用价值.