碳纳米管负载氧化铝材料的制备及其吸附水中氟离子的研究

采用碳纳米管和硝酸铝制备了碳纳米管负载氧化铝新型除氟材料.X射线衍射检测发现,当焙烧温度低于850℃时,氧化铝为无定形态,当焙烧温度为1050℃时,氧化铝为α形态,扫描电子显微镜观察到碳纳米管与氧化铝均匀掺杂.同时用碳纳米管负载氧化铝复合材料进行水中氟离子的吸附研究,结果表明,该复合材料具有优良的除氟效能.氧化铝负载量为30%、焙烧温度为450℃条件下制备的碳纳米管负载氧化铝复合材料的吸附除氟能力是γ-氧化铝的2.0～3.5倍,与IRA-410聚合树脂的吸附除氟能力相当,适宜pH范围为5.0～9.0,吸附等温线符合Freundlich方程.     

功能化碳纳米管的电化学性质及在6-巯基嘌呤分析检测中的应用

采用修饰单壁碳纳米管(SWNT、SWNT-COOH或SWNT-OH)及多壁碳纳米管(MWNT、MWNT-COOH或MWNT-OH)的石墨电极研究配位阴离子[Fe(CN)6]3-和配位阳离子[Co(phen)3]3+的电化学行为与吸附性能,借助[Co(phen)3]3+在碳纳米管(CNT)的强吸附特性制备[Co(phen)3]3+/CNT/C修饰电极,以其应用于6-MP的分析检测.结果表明:1)在CNT修饰电极上[Fe(CN)6]3-/4-呈现很好的氧化还原可逆性,而[Co(phen)3]3+则显示明显的吸附控制特征.2)[Co(phen)3]3+在多壁碳纳米管修饰电极上的吸附量较单壁碳纳米管大,但经羧基化或羟基化后,吸附量减小,而且在羧基化表面的吸附量较羟基化的大.3)[Co(phen)3]3+与6-MP间存在明显的相互作用,其配位产物的还原峰电流与6-MP浓度呈线性关系.     

Adsorption of fluoride from water by amorphous alumina supported on carbon nanotubes

A new candidate for fluoride adsorption from water, amorphous Al₂O₃ supported on carbon nanotubes (Al₂O₃/CNTs), is reported in this Letter. The adsorption isotherms show that the best fluoride adsorption of Al₂O₃/CNTs occurs at a pH range of 5.0–9.0. The adsorption capacity for Al₂O₃/CNTs is about 13.5 times higher than that of AC-300 carbon, 4 times higher than that of γ-Al₂O₃ at equilibrium fluoride concentration of 12 mg/l. The broad range of the pH values and high adsorption capacity of Al₂O₃/CNTs make it very suitable for potential applications in fluoride removal from water.     

Theoretical study of CO adsorption on gold/alumina substrates

Aiming to understand the role of the substrate in the adsorption of carbon monoxide on gold clusters supported on metal-oxides, we have started a study of that process on two different alumina substrates: an amorphous-like fully relaxed stoichiometric (Al2O3)20 cluster and the Al terminated (0001) surface of alpha-(Al2O3) crystal. In this paper, we present first principles calculations for the adsorption of one Au atom on both alumina substrate and the adsorption of Au8 on (Al2O3)20. Then, we study the CO adsorption on the minimum energy structure of these three different gold/alumina systems. A single Au adsorbs preferably on top of an Al atom with low coordination, the binding energy being higher in the case of Au/(Al2O3)20. CO absorbs preferably on top of the Au atom, but in the case of Au/(Al2O3)20, Au forms a bridge with the Al and O substrate atoms after CO adsorption. We find other stable sites for CO adsorption on the cluster but not on the surface. This result suggests that the Au activity toward CO may be larger for the amorphous cluster than for the crystal surface substrate. For the most stable Au8/(Al2O3)20 configuration, two Au atoms bind to Al and a O atoms respectively and CO adsorbs on top of the Au which binds to the Al atom. We find other CO adsorption sites on supported Au8 which are not stable for the free Au8 cluster.     

Support effects on the chemical property and catalytic activity of Co-Mo HDS catalyst in sulfur recovery

Effects of carbon nanotubes (CNT) and alumina (γ-Al2O3) supports on the catalytic activities of hydrodesulfurization (HDS) process over CoMo catalyst have been studied. XRD results indicated that the main active phases in CNT and γ-Al2O3 supported Co-Mo catalysts are MoO2 and MoO3, respectively. The TPR results reveal that the reduction peak temperatures of the active species on CNT supported Co-Mo catalyst is lower than those on alumina supported Co-Mo catalyst, indicating that the CNT supports favor the r...     

Conducting polymer/alumina composites as viable adsorbents for the removal of fluoride ions from aqueous solution

The polyaniline/alumina (PANi-AlO) and polypyrrole/alumina (PPy-AlO) composites were prepared and characterized by FT-IR, SEM and X-ray diffraction studies and were employed as adsorbents for the removal of fluoride ions from aqueous solution by the batch sorption method. The amount of fluoride ions adsorbed per unit mass of the adsorbents was observed to be higher than that by the individual constituents. The maximal amount of adsorption is 6.6 mg/g for PANi-AlO and for PPy-AlO it is 8 mg/g. The Langmuir and Freundlich isotherms were used to describe adsorption equilibrium. The kinetics of the adsorption process was investigated using Natarajan-Khalaf equation and intraparticle diffusion model. FT-IR and XRD pattern of the adsorbent, before and after the adsorption is recorded to get better insight into the mechanism of the adsorption process. The results of equilibrium and spectral investigations revealed that the mechanism of fluoride ion removal by these composites involve both the formation of aluminium-fluoro complexes on the alumina surface and doping/dopant-exchange of fluoride ions in the polymer.     

活性氧化铝及其再生氧化铝对水中氟离子的吸附

Fluoride contamination of water is a problem worldwide and has caused great concern. Our study focused on the removal of fluorides from aqueous solutions using newly prepared and regenerated activated alumina. To obtain a suitable adsorbent, industrial boehmite was calcined from 573 K to 1473 K and the sample was characterized. The X-ray diffraction patterns showed that the sample was transformed to γ-alumina (activated alumina) at temperatures from 773 K to 1173 K, and the BET dates showed that the specific surface area of the sample decreased gradually from the temperature of 773 K to 1173 K. In our study, the activated alumina calcined from 773 K to 973 K was selected as the defluoridation adsorbent, and dynamic adsorption was employed for the removal of fluorides from aqueous solutions. The breakthrough curves demonstrated that the adsorption capacity of the adsorbent decreased with increasing calcination temperature. To investigate the effect of initial fluoride concentration on the adsorption capacity, 15 mg·L^-1, 20 mg·L^-1, and 25 mg·L^-1 fluoride solutions were selected as the initial aqueous fluoride solution. As a result, the capacity of the adsorbent increased gradually with the increase in the initial fluoride concentration. In order to improve the capacity, we also studied the regeneration process in our experiment. When the activated alumina was saturated by the fluorides, it was regenerated with a NaOH solution (pH = 13.0, 13.3, 13.5) and activated with a HCl solution (0.1 mol·L^-1). By a comparison of the five desorption and Al³⁺ dissolution rates during the regeneration process, it was determined that the NaOH solution with pH 13.0 was the most suitable desorption agent. An analysis of the nitrogen adsorption-desorption isotherm showed that its sharpness was almost unchanged after regeneration, which indicated that the pore structure of the adsorbent was not destroyed during this process. The change in the specific surface area and isoelectric point for the five-times regenerated adsorbent were important impact factors for fluoride adsorption. The specific surface area of the regenerated adsorbent increased, and the study of the zeta potential demonstrated that the isoelectric point also increased after regeneration. To observe the adsorption effect of regenerated activated alumina, we performed an adsorption experiment after each regeneration. The breakthrough curves demonstrated that the regenerated activated alumina exhibited faster saturation and increased adsorption capacity compared to fresh activated alumina. To elucidate the adsorption mechanism, IR spectroscopy was employed to characterize the O―H band of the adsorbent. The change in the Al―O―H content of the activated alumina during regeneration was the main factor impacting the fluoride adsorption capacity of the activated alumina.     

Temperature effect on the zeta potential and fluoride adsorption at the alpha-Al2O3/aqueous solution interface

The effect of temperature and pH on the zeta potential of alpha-Al2O3 and adsorption of fluoride ions at the alpha-Al2O3/aqueous solution interface has been investigated through electrophoretic mobility measurements and adsorption studies, to delineate mechanisms involved in the removal of fluoride ions from water using alumina as adsorbent. When the temperature increases from 10 to 40 degrees C, the pH of the point of zero charge (pH(pzc)) shifts to smaller values, indicating proton desorption from the alumina surface. The pH(pzc) increases linearly with 1/T, which allowed estimation of the standard enthalpy change for the surface-deprotonation process. Fluoride ion adsorption follows a Langmuir-type adsorption isotherm and is affected by the electric charge at the alpha-Al2O3/aqueous solution interface and the surface density of hydroxyl groups. Such adsorption occurs through an exchange between fluoride ions and surface-hydroxyl groups and it depends on temperature, pH, and initial fluoride ion concentration. At 25 and 40 degrees C, maximum fluoride adsorption density takes place between pH 5 and 6. Increasing the temperature from 25 to 40 degrees C lowers the adsorption density of fluoride.     

Synthesis of La-incorporated chitosan beads for fluoride removal from water

In this study, lanthanum incorporated chitosan beads (LCB) were synthesized using precipitation method and tested for fluoride removal from drinking water. The effect of various parameters like complexation and precipitation time, lanthanum loading and ammonia strength on fluoride removal have been studied. It is observed that the parameters for the synthesis of LCB have significant influence on development of LCB and in turn on fluoride removal capacity. The optimal condition for synthesis of LCB includes lanthanum loading: 10 wt%, complexation time: 60 min, precipitation time: 60 min, drying temperature: 75 °C for 72 h. The maximum fluoride adsorption capacity of LCB was found to be 4.7 mg/g and negligible release of lanthanum ion was observed. XRD analysis shows the presence of lanthanum hydroxide and amorphous nature of LCB. SEM of LCB shows the presence of oval lanthanum hydroxide particles spread over the chitosan matrix. Fluoride adsorption capacity has been calculated by applying Langmuir and Freundlich isotherms. The comparative study suggests that LCB shows four times greater fluoride adsorption capacity than the commercially used activated alumina.     

磷酸铝吸附除水中氟的研究

采用静态吸附法研究了比表面为308m2/g的无定形磷酸铝吸附除氟性能,研究了接触时间、pH值、吸附剂量等对吸附的影响。结果表明,磷酸铝吸附除氟高效、迅速,30min内可以接近最大吸附量。对含氟50mg/g的溶液,优化条件下的最大除氟率约93%。研究了吸附与溶液pH的关系,得到了优化pH值并解释了吸附机理。吸附的最佳pH值约为5.5。用拟二级动力学方程描述了吸附速率并计算了速率常数。用Langmuir方程拟合了吸附等温线,计算的饱和吸附量为53.5mg/g。吸附剂量对分配系数的影响表明吸附剂表面是不均匀的。     

Fluoride wastewater treatment by adsorption onto metallurgical grade alumina

The adsorption of fluoride onto metallurgical grade alumina (to produce Al) was investigated under different conditions: pH, contact time and adsorbent concentration. Data were evaluated with the aim of developing an alternative treatment technology for washing wastewater arising from an Aluminum can production plant. Kinetics and adsorption isotherms data have been also produced Sorption is greatly affected by pH and the best condition for fluoride removal are obtained at pH 5-6 and alkalinity competes successfully with fluoride ions for the exchange sites. Experiments with fixed beds indicate that fluoride is removed from wastewater by metallurgical-grade alumina with a capacity of 12.21 mg of F per gram and adsorption increases of about 25% at appropriate pH. The Mass Transfer Zone at 5% of the breakthrough occupies 70.6% of the total column length. The optimization of aluminum precipitation by pH adjustment and with different precipitant agents has been done.     

ZnCl2、KOH和HNO3改性MWCNT对苯酚的吸附行为研究

通过扫描电子显微镜、X射线衍射仪、N₂吸附分析仪及Boehm滴定法获得ZnCl₂、KOH和HNO₃化学处理对高纯多壁碳纳米管的结构和表面含氧官能团的影响,通过批处理实验考察吸附条件（吸附时间、初始浓度、温度）对处理前后的碳纳米管吸附苯酚行为的影响,并采用准一级、准二级、Evolich动力学模型和热力学方程拟合其吸附数据,分析其动力学行为、热力学行为和吸附机理。结果表明,虽然ZnCl₂、KOH和HNO₃化学处理法均未对碳纳米管BET比表面积产生显著影响,但会影响其表面化学性质（即,对于ZnCl₂和KOH化学处理降低表面羧基、内酯基含量和增大碱性官能团量,而对于HNO₃化学处理可以增大表面羧基、内酯基含量,而碱性官能团略有增加）;改性处理影响碳纳米管去除苯酚效率：由于ZnCl₂和KOH改性处理降低碳纳米管表面羧基量,故其提高了苯酚去除率,而HNO₃处理则略减小碳纳米管的苯酚去除率,可能是由于碳纳米管结构和表面化学性质共同影响所致;碳纳米管的苯酚去除率均随苯酚溶液初始浓度的增大而减小;高温不利于吸附;热力学研究发现碳纳米管吸附苯酚过程是自发的和放热的,属于物理吸附;动力学研究表明,吸附过程符合准二级动力学方程。通过ZnCl₂和KOH化学处理,可以显著提高碳纳米管对苯酚的吸附性能。     

Studies on fluoride adsorption capacities of amorphous Fe/Al mixed hydroxides from aqueous solutions

This study evaluated the effectiveness of amorphous iron and aluminum mixed hydroxides in removing fluoride from aqueous solutions. A series of mixed Fe/Al samples were prepared at room temperature by co-precipitating Fe and Al mixed salt solutions at pH 7.5. The compositions (Fe:Al molar ratio) of the oxides were varied as 1:0, 3:1, 2:1, 1:1 and 0:1 and the samples were characterized by XRD, BET surface area and pH_ZPC. The XRD studies indicated the amorphous nature of the samples and Al(III) incorporation on Fe(III) hydroxides. Batch adsorption studies for fluoride removal on these materials showed that the adsorption capacities of the materials were highly influenced by solution pH, temperature and initial fluoride concentration. The rate of adsorption was fast and equilibrium was attained within 2 h. The adsorption followed first-order kinetics with intraparticle diffusion as the rate determining step for all the samples. The experimental data fitted well to both Langmuir and Freundlich adsorption isotherms. All samples exhibited very high Langmuir adsorption capacities; the sample with molar ratio 1 has shown maximum adsorption capacity of 91.7 mg/g. The thermodynamic parameters were determined to study the feasibility of the adsorption process.     

甲烷干重整催化剂Ni/Al2O3表面积炭表征与分析

用蒸发法制备了Ni/Al2O3催化剂及浸渍法制备了Ni/α-Al2O3和Ni/γ-Al2O3催化剂, 并与商品天然气水蒸气重整催化剂Z118Y一起进行了甲烷干重整实验, 考察了各催化剂上表面积炭行为. 通过H2程序升温还原(H2-TPR)、BET(Brunauer-Emmett-Teller)比表面积分析、X射线衍射(XRD)、透射电镜(TEM)、热重-差式扫描量热(TG-DSC)、程序升温氢化(TPH)等表征手段对催化剂表面沉积炭的特性进行了表征. 结果表明, 各催化剂上至少存在三种形式的碳物种: 无定形碳、丝状碳及石墨碳. 由于载体性质不同, 各催化剂上沉积炭的种类及其含量有所差别. Z118Y、Ni/Al2O3及Ni/α-Al2O3催化剂上主要沉积丝状炭, 而Ni/γ-Al2O3催化剂上则主要是石墨碳. Ni/γ-Al2O3催化剂中金属Ni颗粒较小(小于15 nm)、粒径分布范围较窄、分散性较好, 能减少催化剂表面炭的沉积, 有效地抑制丝状碳的生长.     

Uniformly carbon-covered alumina and its surface characteristics

Uniformly carbon-covered alumina (CCA) was prepared via the carbonization of sucrose highly dispersed on the alumina surface. The CCA samples were characterized by XRD, XPS, DTA-TG, UV Raman, nitrogen adsorption experiments at 77 K, and rhodamine B (RB) adsorption in aqueous media. UV Raman spectra indicated that the carbon species formed were probably conjugated olefinic or polycyclic aromatic hydrocarbons, which can be considered molecular subunits of a graphitic plane. The N(2) adsorption isotherms, pore size distributions, and XPS results indicated that carbon was uniformly dispersed on the alumina surface in the as-prepared CCA. The carbon coverage and number of carbon layers in CCA could be controlled by the tuning of the sucrose content in the precursor and impregnation times. RB adsorption isotherms suggested that the monolayer adsorption capacity of RB on alumina increased drastically for the sample with uniformly dispersed carbon. The as-prepared CCA possessed the texture of alumina and the surface properties of carbon or both carbon and alumina depending on the carbon coverage.     

Influence of mesoporosity on the sorption of 2,4-dichlorophenoxyacetic acid onto alumina and silica

Two SiO2 and three Al2O3 adsorbents with varying degrees of mesoporosity (pore diameter 2-50 nm) were reacted with 2,4-dichlorophenoxyacetic acid (2,4-D) at pH 6 to investigate the effects of intraparticle mesopores on adsorption/desorption. Anionic 2,4-D did not adsorb onto either SiO2 solid, presumably because of electrostatic repulsion, but it did adsorb onto positively charged Al2O3 adsorbents, resulting in concave isotherms. The Al2O3 adsorbent of highest mesoporosity consistently adsorbed more 2,4-D per unit surface area than did the nonporous and less mesoporous Al2O3 adsorbents over a range of initial 2,4-D solution concentrations (0.025-2.5 mM) and reaction times (30 min-55 d). Differences in adsorption efficiency were observed despite equivalent surface site densities on the three Al2O3 adsorbents. Hysteresis between the adsorption/desorption isotherms was not observed, indicating that adsorption is reversible. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy studies confirm that 2,4-D adsorption does not occur via ligand exchange, but rather via electrostatic interaction. The results indicate that adsorbent intraparticle mesopores can result in consistently greater 2,4-D adsorption, but the amount adsorbed is dependent upon surface charge and the presence of adsorbent mesoporosity. The data also suggest that when mineral pores are significantly larger than the adsorbate, they do not contribute to diffusion-limited adsorption/desorption hysteresis. Adsorbent transformations through time are discussed.     

Performance and Mechanisms of Fluoride Removal from Groundwater by Lanthanum-aluminum-loaded Hydrothermal Palygorskite Composite

Lanthanum-aluminum loaded hydrothermal palygorskite(La-Al-HP) composite was prepared and selected as adsorbent for the fluoride removal from simulated groundwater. The adsorbent was characterized by scanning electron microscopy(SEM), Brunauer-Emmet-Teller(BET) analysis, X-ray diffraction(XRD) analysis and X-ray photoelectron spectroscopy(XPS). SEM visualization shows that the dense surface structure of raw HP appeared loose and presented micro canals after modification. The BET analysis also proved the specific surface area of La-Al-HP composite(95.58 m²/g) was higher than that of the raw HP(34.31 m²/g). Subsequently, the adsorption capacity of La-Al-HP composite was demonstrated in adsorption experiments. The kinetics of fluoride ion adsorption into La-Al-HP composite followed the pseudo-second order with a correlation coefficient of 0.997. The isotherm data was well fitted with the Langmuir model. The monolayer adsorption capacity of La-Al-HP composite was 1.30 mg/g. The XRD and XPS results reveal that the La³⁺ and Al³⁺ ions were loaded on the surface of modified HP and the fluoride ion was adsorbed onto the La-Al-HP composite. A large amount of La-Al-O composite oxide existing on the surface of La-Al-HP composite might be the immanent cause for the excellent adsorption capacity of fluoride ions.     

NO在氧化铝负载的Pd催化剂上吸附的TPD-MS研究

消除汽车尾气中的氮氧化物(NOx)对保护大气环境有着重要意义.为了除去NOx,已经进行了许多卓有成效的研究,例如NOx在分子筛上的直接分解和催化还原,在贵金属三效催化剂上的还原等.     

The reactivity of quaternary ammonium- versus potassium-fluorides supported on metal oxides: paving the way to an instantaneous detoxification of chemical warfare agents

The reactions of the chemical warfare agents (CWAs) 2,2'-dichloroethyl sulfide (HD), O-ethyl S-2-(diisopropylamino)-ethyl methylphosphonothioate (VX) and isopropyl methylphosphonofluoridate (GB) with various metal oxide-supported quaternary ammonium fluorides (QAF) and/or potassium fluoride (KF) reagents are described. These active sorbents, which were prepared by a modified procedure, include alumina, silica and titania, enriched with "available" (not bound to the surface) fluoride ions. Alumina-based fluoride reagents were found to be more active than their silica or titania counterparts. QAF/Al(2)O(3) reagents, compared to KF/Al(2)O(3), exhibit an exceptional reactivity toward HD, as demonstrated both in reaction rates and product identity. For example, with TBAF, t(1/2) is 15 min for the formation of the elimination product divinyl sulfide (DVS), while with KF, t(1/2) is 10 h for the formation of the hydrolysis product thiodiglycol (TDG). On the other hand, both sorbents reacted similarly against the nerve agents GB or VX. In order to increase the "available" fluoride content on the solid surface, the mixed active sorbent TBAF/KF/Al(2)O(3) (20/20/60) was developed. On this powder, all three CWAs were degraded instantaneously at the low loading of 1 wt% (t(1/2) < 2 min) and rapidly at the higher loadings of 5-10 wt% (t(1/2) of minutes scale). We assume that the relatively large amount of inorganic fluoride (KF) acts synergistically as a reservoir for the more reactive organic fluorides (TBAF). Moreover, the alumina surface hydroxyl groups may also operate as a water reservoir for the hydrolysis of VX or GB. Therefore, TBAF/KF/Al(2)O(3) might be considered as a promising destructive sorbent for CWAs.     

胶溶法制备镧-钡共稳定氧化铝的性能

以硝酸为胶溶剂, 两种拟薄水铝石为前驱体, 用胶溶法制备了镧-钡共稳定的氧化铝. 采用X 射线衍射(XRD)、表面分析仪(BET)、氨气程序升温脱附(NH3-TPD)和NO2程序升温脱附(NO2-TPD)技术对所制备的镧改性和镧钡共改性氧化铝的结构特性和表面性能进行了表征. XRD结果表明, 改性氧化铝在1273 K焙烧后均以γ-Al2O3相存在. 当BaO添加量达到14%(w)时, 有少量BaCO3生成. BET结果表明, 在1273 K下焙烧5 h后, 5%(w)La2O3稳定的氧化铝(Ba-0)和5%La2O3与8%BaO共同稳定的氧化铝(Ba-8)均具有较大的比表面积, 各种氧化铝的吸附等温线表明它们的孔形状均为狭缝型孔和瓶型孔, 孔径分布曲线表明, 仅有样品Ba-8的孔径分布较宽, 孔径为6-10 nm, 其它三种样品的孔径均集中在10 nm; NH3-TPD结果表明, 随着氧化钡添加量的逐渐增多, 氧化铝表面的酸量、酸强度逐步减少. NO2-TPD结果表明, 添加BaO后载体对NO2的吸附量增多, 随着BaO含量的增多, 体相Ba(NO3)2增多. 由于样品Ba-8同时具有很好的织构性质、适中的表面酸量和酸强度分布及NO2吸附脱附能力, 使得以它为载体的催化剂具有最好的催化性能,丙烷的起燃温度和完全转化温度分别为526 K和593 K.