Mg-Al 类水滑石/二氧化钛异质复合纳米晶光催化氧化苯的性能

 采用过饱和沉淀法合成 n(Mg)/n(Al) = 2 的 Mg-Al 类水滑石化合物 (Mg-Al-HT), 再用水热法将它与钛胶复合, 制得 Mg-Al-HT/TiO2 异质复合光催化剂. 采用 X 射线粉末衍射、透射电子显微镜、场发射扫描电子显微镜、低温 N2 吸附-脱附、紫外-可见漫反射光谱和热重等技术对催化剂结构、成分和性质进行了表征. 结果表明, 在波长 365 nm 的紫外光照射降解苯的反应中, Mg-Al-HT/TiO2 异质复合光催化剂表现出优于单一的 TiO2 或 Mg-Al-HT 催化剂的光催化活性, 且稳定性更高; 同时讨论了该复合催化剂性能优异的原因. 另外, 运用电子顺磁共振技术检测到体系中存在羟基自由基等活性物种, 并据此提出了 Mg-Al-HT/TiO2 异质复合纳米晶催化剂光催化降解苯的反应机理.     

Adsorption and separation of proteins by a synthetic hydrotalcite

In this study, the potential use of a synthetic Mg/Al hydrotalcite (layered double hydroxide) as a novel chromatography material for protein purification was investigated. The hydrotalcite is present in its carbonate form and is characterized by an Al/Mg-ratio of 1.85. Zetapotential measurements confirm a positive surface potential up to pH 10 suggesting applicability as anion exchanger. The binding of model proteins covering a broad range of isoelectric points and molecular weights was performed at different pH-values under batch conditions to evaluate the binding behaviour of the hydrotalcite. Furthermore, static binding capacities were exemplarily determined for hemoglobin and human serum albumin. Additionally, the adsorption and elution of hemoglobin was studied under dynamic conditions. The binding behaviour of the hydrotalcite was compared to commercially available anion exchangers and was found to be a function of pH, depending on the model protein. Variant adsorption behaviour is explained by further interactions like hydrogen bonds and by an unequal charge distribution over the protein surfaces. The hydrotalcite reveals high adsorption capacities under static (260 mg/g) as well as under dynamic conditions (88 mg/g at 34 cm/h; 61 mg/g at 340 cm/h). With appropriate buffers like 500 mM carbonate (pH 10) the adsorbed proteins can be nearly completely desorbed making regeneration possible. Due to the binding and elution properties it is concluded, that the hydrotalcite can serve anion exchange material for chromatographic protein separations.     

Mn-Mg-Al-O催化剂上NOx的氧化 储存性能

采用共沉淀法制备系列Mn-Mg-Al-O水滑石前驱体,经500℃焙烧制成复合氧化物Mn-Mg-Al-O催化剂,并用XRD方法进行了表征。恒温储存实验研究了催化剂氧化NO和储存NO_x的性能,NO_x-TPD考察了储存的NO_x脱附情况。结果表明,Mn在前驱体中高度分散;焙烧后,Mg₂MnO₄是主要的活性组分,Mn能够催化NO的氧化反应,且有一定的NO_x储存能力,Mg是主要的储存组分,将NO_x以硝酸盐的形式储存起来;硝酸盐在氮气气氛中300℃～600℃下分解,释放出NO_x。不同含量的SO₂均使催化剂NO_x储存能力降低。     

High temperature adsorption of carbon dioxide on Cu–Al hydrotalcite-derived mixed oxides: kinetics and equilibria by thermogravimetry

The effect of Cu/Al molar ratio on the high-temperature adsorption characteristics of CO₂ on the mixed oxides of Cu–Al hydrotalcite skeletal structure has been studied by thermogravimetry. The Cu/Al molar ratio of the hydrotalcites synthesized was varied between 1.0 and 3.0, and the adsorption temperature ranged from ambient to 600 °C. The hydrotalcite with Cu/Al molar ratio of 2.0 was found to be the most suitable adsorbent for high-temperature CO₂ adsorption, in both the capacity and the rate of adsorption. The activation energy values suggested that the physical adsorption dominates at low temperatures (<400 °C) and the chemisorption dominates at high temperatures (>400 °C).     

Enthalpies of sorption of linear hydrocarbons (C2–C8) and chloroderivatives of methane and ethylene on the surface of hydrotalcite

Differential molar adsorption enthalpies (DMAE) were determined by gas chromatographic measurements of specific retention volume of vapors on the surface of two forms of Mg–Al hydrotalcite. A linear dependence of the DMAE on the number of the carbon atoms in hydrocarbons was observed for both form of hydrotalcite. The dependence of the differential molar adsorption enthalpies on the number of chlorine atoms in organic molecules is discussed. A linear dependence of DMAE on the molecular weight of chloroderivatives of methane and ethylene on the basic form in an order monochloromethane < dichloromethane < trichloromethane or vinylidene chloride < 1,1-dichloroethylene < trichloroethylene was found.     

Removal of Phenol by Using Montmorillonite,Clinoptilolite and Hydrotalcite

This work is to study the removal of phenol from aqueous solutions by adsorption using three different adsorbents, clinoptilolite, montmorillonite, and hydrotalcite (HT). Except for montmorillonite, the other adsorbents were treated. Clinoptilolite was modified using cetyltrimethylammonium bromide (CTAB) and hydrotalcite was calcined by heating to 550C. Adsorption isotherms of phenol on all of the mentioned adsorbents was determined by using the batch equilibration technique and indicated that, the adsorption behavior could be modelled by using the Modified Freundlich equation. The differences observed in the isotherms were explained by the variations in adsorbent-adsorbate interactions under the effects of the different surface structures of adsorbents and the pH dependent ionization behavior of phenol. Calcined hydrotalcite (HTC) was found to be the best among the studied adsorbents since it can adsorb 52% of phenol from a solution containing initially 1 g/L phenol for the 1/100 adsorbent solution ratio while the others can adsorb only 8% of phenol for the same concentration and adsorbent solution ratio.     

Reversible Adsorption of NOx on ZrO2-supported CeO2 Prepared in Water-in-oil Microemulsion

Nitric oxides (NOx) storage catalyst^[1] provides an alternative route for abatement of NO in presence of oxygen by first adsorbing NOx and then desorbing it by temperature swing or pressure swing. YBa₂Cu₃Oy^[2] and Mn-Zr mixed oxides^[3] were reported to have large NOx adsorption capacity, but the former suffered from a great amount of coexisting CO₂ gases. The author previously reported that high NOx adsorption capacity could be obtained on Ce modified TiO₂-pillared montmorillonite without deactivation by CO₂^[1]. Microemulsion method was reported to be effective to control particle sizes and microstructures of the metal oxides^[4]. In this paper, a thermal stable ZrO₂ with high surface area was prepared in water-in-oil microemulsion, and NOx adsorption capacity was tested on the above ZrO₂ sample after impregnating with manganese nitrate and cerium nitrate.     

NOx分子在[Ag]-AlMOR分子筛中的吸附

采用Dmol3程序中密度泛函理论(DFT)的广义梯度方法GGA/BLYP和DND基组研究了银离子交换的丝光沸石([Ag]-AlMOR)结构及其对NOx分子吸附性能的影响, 获得吸附复合物的平衡几何结构参数、吸附能以及红外振动频率等数据. 结果表明, NOx分子与丝光沸石间的主要作用力为NOx分子中的氮(或氧)原子上的孤对电子和Ag+间的静电作用力. 吸附能数据表明, NOx分子以η1-N模式吸附在[Ag]-AlMOR分子筛中的结构更稳定; 在η1-N模式中, NOx分子吸附作用强度的次序为NO>NO2>N2O. 红外振动频率结果表明, 吸附态NOx分子中N—O和N—N键伸缩振动频率的位移趋势与N—O和N—N 键变化规律基本相一致. 另外, 对[Ag]-AlMOR分子筛的抗硫、抗水及抗氧化性能也进行了研究和分析.     

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.     

水滑石的插层及其选择性红外吸收性能

离子交换;水滑石的插层及其选择性红外吸收性能     

Adsorption/desorption studies of NOx on well-mixed oxides derived from Co-Mg/Al Hydrotalcite-like compounds

CoxMg3-x/Al hydrotalcite-like compounds (where x=0.0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0) were synthesized by the coprecipitation method and characterized by the XRD and TGA techniques. Incorporation of Co for x=0.0-3.0 gradually decreased the transformation temperature of the hydrotalcites to the corresponding oxides from 444 to 246 degrees C and also decreased the surface area from 162.7 to 21.6 m2/g upon calcination at 800 degrees C for 4 h in air. The resultant oxide was generally composed of a poor MgO phase and a spinel phase, with more spinel phase at higher Co incorporation. The derived oxides were tested as the storage/reduction catalysts for NOx adsorption/desorption. The storage capacity for NOx was highly dependent on the catalyst composition and storage temperature. In general, more NOx was stored at lower temperature (100 degrees C) than that at higher temperature (300 degrees C), and tertiary catalysts (x=0.5-2.5) stored more NOx than binary catalyst (x=0.0 or 3.0). The catalytic conversion of NO to NO2 and the catalytic decomposition of NOx were observed on the tertiary catalysts during NOx adsorption at 300 degrees C, which was highly related to the loading of cobalt. The reducibility of catalysts was determined by TPR experiments, and the reduction of cobalt cations started at 150-200 degrees C in H2. In situ IR spectra of catalysts adsorbing NOx revealed that the major NOx species formed on the catalysts were various kinds of nitrites and nitrates, together with some forms of dimers, such as N2O2(2-) and N2O4 (or NO+NO3-). The storage/reduction mechanism and the function of Co in the mixed oxides are proposed and discussed on the basis of these observations.     

H3PW12O40/CNTs吸附-分解NOx及微波作用效果

将碳纳米管(CNTs)载体分别经混酸与硝酸蒸气预处理并在不同温度下煅烧, 然后分别采用浸渍法及机械研磨法负载磷钨酸(HPW), 制备出HPW/CNTs催化剂, 对比考察了上述催化剂对NOx的吸附与分解效果. 在空速为10000 h-1、 吸附温度为200℃的条件下, 用0.5 g催化剂对1696 mg/m3的NOx进行吸附实验, 结果表明, 以硝酸蒸气预处理且经300℃煅烧后的CNTs为载体, 采用机械研磨负载法制备的催化剂HPW/CNTs对NOx的吸附率与吸附能力最高, 分别为54%与16.6 mg NOx/(g\5h). 对吸附NOx后的催化剂体系进行了催化分解NOx的程序升温脱附-质谱(TPD-MS)研究, 结果表明, 所吸附的NOx在快速升温过程中发生分解, 在此过程中有氧产生, 分解产物包括N2, O2及N2O. 采用电阻炉快速加热与微波辐射2种方式分别对吸附的NOx进行催化分解, 结果表明, 微波功率为700 W时, NOx分解为N2的收率为33.3%, 高于电阻炉以150℃/min快速升温的N2收率. 使用过的催化剂通水蒸气后可实现再生, 对再生后的催化剂进行循环使用研究, 结果表明, 再生后的催化剂吸附与催化分解NOx的性能未有明显下降.     

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.     

载体性质对Pt催化剂H2选择催化还原NOx活性和选择性的影响

研究了Pt/MgO, Pt/γ-Al2O3, Pt/ZrO2和Pt/HZSM-5催化剂上H2选择催化还原消除NOx(H2-SCR)反应。结果发现, H2-SCR活性和N2生成选择性受催化剂中Pt的金属性以及载体的氮氧化物吸附能力影响很大。 HZSM-5的表面酸性使载体对NOx吸附能力较小,使担载Pt以较高的金属性存在,从而导致Pt/HZSM-5催化剂的高活性和高选择性。相反, Pt/MgO和Pt/γ-Al2O3催化剂较差的活性和选择性可归因于其载体的碱性表面、催化剂中Pt较低的金属性以及载体对氮氧化物较大的吸附能力。结合反应的原位红外光谱结果可以认为,在Pt/载体界面处亚硝酸根/硝酸根物种被还原为N2或N2O,取决于该处参与反应的活性H与这些含氮物种的相对数目。     

Sorption of 2,4-dichlorophenol on modified hydrotalcites

The adsorption of anionic surfactants (sodium dodecyl sulfate (SDS) and sodium bis[2-ethylhexil]sulfosuccinate (AOT)) on hydrotalcite (HT) and the adsorption of 2,4-dichlorophenol (DCP) on HT and its modified forms from aqueous solutions was studied. The modification was carried out by calcinations (heat treatment) and hydrophobization using different anionic surfactants. The anionic surfactant isotherms were of the H-type. It was assumed that first the ion exchange mechanism takes place until approximately the anion exchange capacity of HT is reached and hereafter, the hydrophobic mechanism occurs forming surfactant bilayers. While the DCP adsorption was very poor on HT, significant uptake of DCP took place on calcined HT which was attributed to the simultaneously occurring rehydration and adsorption during the reconstruction of the layered structure. On anionic surfactant-HT complexes (“organo-hydrotalcites”) DCP was considerably adsolubilized in the anionic surfactant layers intercalated in HT. The AOT–HT complex appeared the more effective adsorbents for DCP.     

Memory effect of activated Mg-Al hydrotalcite: in situ XRD studies during decomposition and gas-phase reconstruction

The thermal decomposition of Mg-Al hydrotalcite and the subsequent reconstruction of the decomposed products in the presence of water vapor (2 vol. % H(2)O in N(2)) have been investigated by in situ XRD. Thermographic analysis and temperature-programmed desorption MS results complemented the diffraction data. Valuable mechanistic and kinetic insights into these processes, which are of prime importance for optimal activation of this type of material for catalytic applications, were obtained. Hydrotalcite decomposition to the mixed oxide proceeds via formation at 423-473 K of an intermediate phase, consisting of a highly disordered, dehydrated, layered structure. The latter evolves by removal of interlayer water on heating, causing a shrinking of the interlayer space (it is up to 45 % smaller than in the as-synthesized hydrotalcite). Above 623 K, Mg(Al)O(x) oxide with the periclase structure is formed. Reversion of the intermediate dehydrated structure to hydrotalcite upon contact with water vapor is complete and very fast at room temperature. Recovery of hydrotalcite from the oxide calcined at 723 K is two orders of magnitude slower than rehydration of the intermediate layered structure and one order of magnitude slower than the typically practiced liquid-phase reconstruction. In contrast to the decomposition, the reconstruction mechanism does not involve an intermediate phase. The gas-phase rehydration and reconstruction was interrupted above 303 K. This is attributed to the poor wetting of the surface of the decomposed materials induced by hampered H(2)O adsorption above room temperature at the water vapor pressure applied. The Avrami-Erofe'ev model describes the reconstruction kinetics well.     

镁铝类水滑石在Cr(Ⅵ)和对甲基苯酚复合污染中的吸附

以Cr(Ⅵ)、对甲基苯酚为代表污染物,用实验室模拟法研究了镁铝类水滑石（Mg-Al HTlc）对Cr(Ⅵ)的吸附行为。 结果表明,在Mg-Al HTlc/Cr(Ⅵ)/对甲基苯酚体系中,吸附动力学和热力学分别符合准二级动力学方程和Langmuir吸附等温式;溶液中共存的对甲基苯酚会延缓Mg-Al HTlc对Cr(Ⅵ)的吸附速率,但会增加其对Cr(Ⅵ)的吸附量。 一方面,Cr(Ⅵ)与对甲基苯酚产生竞争吸附,竞争作用的大小和溶液中对甲基苯酚与Cr(Ⅵ)的浓度比有关;另一方面,Mg-Al HTlc对对甲基苯酚的吸附可降低体系pH值,增加Cr(Ⅵ)的吸附量,随Cr(Ⅵ)初始浓度的增加,酚离子的竞争能力相对减弱,当Cr(Ⅵ)与对甲基苯酚的质量浓度比大于3时,Cr(Ⅵ)的吸附量增加显著,去除率增强。体系温度升高使Cr(Ⅵ)的吸附量降低。     

低温等离子体处理对NiO/A12O3吸附NOx的促进作用

采用共沉淀法制备了不同NiO负载量的NiO/A12O3催化剂,并用于NOx储存还原技术去除NOx反应中.结果表明,当Ni/Al摩尔比为0.3时,NiO/A12O3样品的NOx吸附量最大;随着Ni含量的增加,NiAl2O4晶相减少.沉淀物在高温煅烧前利用低温等离子体处理后,所得催化剂吸附NOx的能力明显增强,当Ni/Al...     

Thiocyanate removal from aqueous solution by a synthetic hydrotalcite sol

The use of a chloride-containing synthetic hydrotalcite sol (LDHC) as adsorbent to remove thiocyanate from aqueous solution was investigated. LDHC was prepared by coprecipitation and was characterized by HRTEM, particle size, XRD, and FTIR. The experiments showed that LDHC was particularly effective in removing thiocyanate due to its small particle size and high zeta potential. The adsorption of thiocyanate on LDHC was favored when the initial solution pH was in the range 3-10, though the most effective pH range was between 4.0 and 8.0. The adsorption reached equilibrium within 150 min. The interaction between the surface sites of LDHC and thiocyanate ions may be a combination of both anion exchange and surface complexation. The pseudo-second-order model best described the adsorption kinetics of thiocyanate onto LDHC. The equilibrium isotherm showed that the adsorption of thiocyanate on LDHC was consistent with the Langmuir equation and the saturated adsorption capacity of LDHC for thiocyanate was 98.3 mg/g at 20°C. The regenerated LDHC in FeCl(3) solution can be used repeatedly in adsorption-regeneration cycles. The results showed that LDHC can be used as a new adsorbent for thiocyanate removal from aqueous solution because of its high adsorption capacity and rapid adsorption rate.     

Adsorption of phosphate from wastewater by a ZnO-ZnAl hydrotalcite

ABSTRACT

A ZnO-ZnAl hydrotalcite (ZZA) was prepared by a new centrifugal method, and its micromorphology was characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) analyses. The adsorption by ZZA of phosphate in a simulated wastewater was studied in detail. The effects of a variety of factors, including pH, coexisting ions, adsorption time, ZZA dosage, and adsorption temperature, on the phosphate adsorption were evaluated. The reaction of ZZA adsorbing phosphate in the simulated wastewater may be an endothermic reaction. The adsorption process is more in line with the Langmuir model equation, indicating that it may be homogeneous surface monolayer chemisorption. By studying the thermodynamic index of ZZA adsorbing phosphate in simulated wastewater, it was suggested that the adsorption is a spontaneous, endothermic, and entropy-increasing process. For moderate and low level of phosphate amount wastewater, the emission requirements can be met.