有序介孔炭的合成及液相有机大分子吸附性能研究

分别采用有序介孔氧化硅SBA-15和NaY分子筛为硬模板合成了系列有序介孔炭OMC和微孔炭CFY. N₂静态吸附测试表明, 所合成的介孔炭具有丰富的介孔结构和集中的介孔分布. 以亚甲基蓝为探针分子, 研究其在有序介孔炭OMC和微孔炭CFY上的吸附行为. 研究结果表明, 有序介孔炭中大于3.5 nm的大介孔孔容是决定亚甲基蓝吸附容量和吸附速率的关键因素. 吸附动力学理论研究表明, 准二级动力学方程可以很好地描述亚甲基蓝分子在介孔炭上吸附动力学行为.     

NPE在有序介孔炭上的吸附行为研究

采用有序介孔硅为硬模板制备了具有不同孔径的有序介孔炭(OMCs). 氮气吸附测试表明, 有序介孔炭具有丰富的介孔表面和集中的介孔分布. 以壬基酚聚氧乙烯醚(NPE)为探针分子, 研究了大分子酚类在有序介孔炭上的吸附行为. 吸附研究表明, NPE在有序介孔炭上的吸附满足Langmuir吸附模型. 孔结构分析表明, 大于1.5 nm的孔的表面积是决定NPE吸附量的关键因素, 而有序介孔炭的最可几孔径决定吸附速率的大小. 与吸附量相比, 吸附速率更容易受环境温度的影响. 动力学研究表明, NPE在有序介孔炭上的吸附满足准二级动力学方程.     

NPE在有序介孔炭上的吸附行为研究

采用有序介孔硅为硬模板制备了具有不同孔径的有序介孔炭(OMCs). 氮气吸附测试表明, 有序介孔炭具有丰富的介孔表面和集中的介孔分布. 以壬基酚聚氧乙烯醚(NPE)为探针分子, 研究了大分子酚类在有序介孔炭上的吸附行为. 吸附研究表明, NPE在有序介孔炭上的吸附满足Langmuir吸附模型. 孔结构分析表明, 大于1.5 nm的孔的表面积是决定NPE吸附量的关键因素, 而有序介孔炭的最可几孔径决定吸附速率的大小. 与吸附量相比, 吸附速率更容易受环境温度的影响. 动力学研究表明, NPE在有序介孔炭上的吸附满足准二级动力学方程.     

中分子毒素在碳纳米管上的吸附

研究了两种不同形态的碳纳米管(随机生长多壁碳纳米管(MWCNTs)及定向生长多壁碳纳米管(ACNTs))对典型中分子毒素的吸附性能. 并与两种现有商用血液灌流吸附材料(活性炭(AC)及大孔吸附树脂(MR))进行了对比. 结果显示, 碳纳米管(CNTs)具有优异的中分子吸附能力, 其中MWCNTs对典型中分子毒素的吸附量可达47.18 mg·g-1, 为活性炭的10.8倍, 为大孔吸附树脂的5.5倍. 此外, 碳纳米管的吸附非常迅速, 中分子毒素在MWCNTs及ACNTs达到吸附平衡的时间仅为10 min和15 min, 而活性炭及大孔吸附树脂则分别需要60 min及120 min. 碳纳米管优异的吸附性能得益于其独特的微观结构所形成的发达的中孔. 因此, 碳纳米管可望成为高效的吸附材料, 应用于血液灌流中.     

碳纳米管/活性炭复合微球的制备及其对VB12的吸附应用

采用反相乳液法制备碳纳米管/壳聚糖复合微球(CNTs/CTS), 并对其进一步炭化、活化制得碳纳米管/活性炭复合微球(CNTs/AC). 以此复合微球为吸附材料, 探索了其对中分子代表物质VB12的吸附. 研究结果表明, 碳纳米管含量70%(w)的复合微球经水蒸气适当活化后球形度好、吸附性能优异, 其对VB12的吸附量达23.59 mg·g-1, 分别是活性炭和大孔吸附树脂的5.4和2.7倍. 分析表明这是由于碳纳米管/活性炭复合微球具有发达的中孔结构.     

多阶有序多孔炭的软模板法合成与结构控制

多阶有序多孔炭材料综合了多种多孔炭材料的结构优点,在催化、吸附、储能、电化学等方面具有潜在的重要应用。多阶有序多孔炭材料的合成方法很多,到目前为止,模板法是控制孔结构和调节尺寸的最有效方法。在模板法中,软模板法因为其工艺简单、省时、成本低、环境污染小等优势,近些年来广泛被人们采用。用软模板法合成的多阶有序多孔炭包括:大孔-介孔炭,介孔-微孔炭,介孔-介孔炭,大孔-介孔-微孔炭等。本文对多阶有序多孔炭的软模板法合成与结构控制进行了综述。总结了软模板法在实现上述材料孔结构控制中的影响因素。     

三维有序大孔炭的设计构筑、性能及应用研究

多孔炭材料具有高的比表面积、发达的孔结构、耐热、耐腐蚀、无毒无害、价廉、易操作等特点,以其为研究核心,在学术界和工业界均具有广阔的应用前景。通过胶晶模板法合成孔径在亚微米范围内的三维有序大孔炭,其高度规整的孔道结构,在吸附分离、催化和电极等领域已展现出巨大的应用潜能。利用双模板法将介孔结构融汇于三维有序大孔炭的孔壁中,设计构筑出三维有序大孔-介孔炭,势必会显著增强其应用价值。本文主要阐述了以胶晶为主体模板制备三维有序大孔炭的各种路径;采用双模板法将介孔引入大孔通道内获取三维有序大孔-介孔炭;探索影响孔结构参数的主要因素,并与各种功能材料复合增强其性能;着重对三维有序大孔炭及大孔-介孔炭在环境净化和新型能源转化与储备领域的应用进行概述。     

氨基功能化SBA-15的直接合成及其对CO_2的吸附性能研究

通过直接法合成了氨基功能化SBA-15介孔材料。使用X-射线粉末衍射法(XRD),N2吸-脱附,透射电子显微(TEM)等技术对氨基功能化材料进行了表征。实验结果表明:当反应原料中nAPTES/(nAPTES+nTEOS)≤0.20时,APTES功能化的材料都具有典型的介孔SBA-15结构;但当nAPTES/(nAPTES+nTEOS)≥0.225时,由于氨基对SBA-15结构的副作用导致SBA-15介孔结构坍塌。在氟离子辅助合成下可以获得高含量氨基(反应原料中nAPTES/(nAPTES+nTEOS)的比值为0.25)功能化的SBA-15材料,且此材料中的介孔孔径和BET比表面积都较大。CO2吸附结果表明,随着反应原料中APTES含量提高,所合成的材料对CO2的吸附量相应增加,同时在101kPa和25℃下,通过氟离子辅助合成的材料对CO2的吸附量远远优于无氟离子辅助合成材料的。本研究还对后嫁接法和直接合成法获得氨基功能化SBA-15介孔材料的优缺点进行了讨论。     

炭材料对铀的吸附

铀既是核燃料的主要成分又是乏燃料后处理的关键核素。将铀从乏燃料后处理流程中的高放射性料液或者其他含铀废水中分离出来既可以将此宝贵的核燃料回收使用,又有利于降低乏燃料处理后期的处置费用,以及减少铀对环境的污染。而从海水、盐湖水、尾矿废水等贫铀水体中提取铀则可能是解决将来铀资源匮乏的主要方法。炭质材料具有较大的比表面积、较高的孔隙率,耐高温,抗辐射,对各种酸碱环境有很高稳定性,而且本身无毒,环境友好,有望作为吸附剂或固相萃取材料用于从水体中吸附分离铀。本文介绍了活性炭、介孔炭、碳纳米管等材料对铀的吸附研究进展。表面功能化可以提高炭材料对铀酰离子的吸附容量与选择性,对炭材料功能化的方法主要有表面氧化、浸渍、负载和接枝等手段。由于化学稳定性高,采用化学方法在炭材料表面接枝功能分子是具有应用前景的研究方向。采用碳纤维作电极,电吸附铀的方法可以大量地从水溶液中将铀吸附到电极表面,再通过电脱附回收铀,具有工业化应用前景。     

介孔碳材料CMK-3的合成及其吸附性能研究——介绍一个综合化学实验

介绍一个集物理化学、分析化学和无机化学为一体的综合实验——介孔碳材料CMK-3的合成及其吸附性能研究。实验通过合成具有高比表面积的介孔碳材料CMK-3,运用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和氮气吸附/脱附技术表征材料的形貌和多孔结构;考察了介孔碳材料CMK-3对水溶液中次甲基蓝染料分子的吸附性能。     

磺化碳纳米管/活性炭复合微球的制备及其对低密度脂蛋白的吸附性能

采用悬浮聚合、炭化、活化制得碳纳米管/活性炭复合微球; 而后利用重氮盐偶合法将对氨基苯磺酸接枝到此复合微球上, 得到磺化碳纳米管/活性炭复合微球; 将其用于吸附血清中的低密度脂蛋白(LDL). 结果表明: 所制备的磺化碳纳米管/活性炭复合微球球形度好, 表面光洁, 中孔发达, 并且接枝有对氨基苯磺酸. 此复合微球对LDL的吸附量随着碳纳米管加入量的增加而逐渐增大; 当碳纳米管加入量为45% (w)时, LDL吸附量达6.564 mg·g^-1, 是未添加碳纳米管的3.3倍. 此复合微球在作为血液灌流LDL吸附剂方面有较好的应用前景.     

Adsorbent-adsorbate interactions in the adsorption of organic and?inorganic species on ozonized activated carbons: a?short?review

This objective of this work was to summarize the main results obtained in previous papers related to the adsorbent-adsorbate interactions involved in the adsorption of naphthalenesulphonic acids and heavy metals (Cd(II) or Hg(II)) by modified activated carbons. The adsorption of organic compounds (1-naphthalenesulphonic acid, 1,5-naphthalenedisulphonic acid and 1,3,6-naphthalenetrisulphonic acid) and inorganic species (Cd(II) and Hg(II)) was studied on a series of ozonized activated carbon in aqueous phase. Commercial activated carbon (Filtrasorb 400) was treated with different ozone doses to study the effect of ozone treatment on its surface properties and investigate the behavior of the treated carbon samples in the above adsorption processes. After ozonation, carbonyl- and carboxyl-type groups were generated on the carbon surface. The action of ozone also affected the textural characteristics of the carbon; thus, the surface area diminished due both to the ozone attack and to the increase in oxygenated groups, which prevented the diffusion of nitrogen by obstructing micropore entrances. The capacity of activated carbon to adsorb naphthalenesulphonic acids sharply decreased with a greater number of sulphonic groups in the aromatic rings of these acids. As the concentration of oxygenated electron-withdrawing groups on the carbon surface increased, a significant reduction in adsorption capacity was observed. In all cases, the adsorption uptake decreased with higher solution pH. The adsorption of metallic ions, Cd(II) and Hg(II), by this series of ozonized activated carbons was also studied. In the case of Cd(II), the adsorption capacity and affinity of the adsorbents increased with a higher concentration of acid oxygenated groups on the activated carbon surface. In the case of Hg(II), the adsorption diminished with an increase in the degree of oxidation of the activated carbon. The adsorption of 1,3,6-naphthalenetrisulphonic acid on the ozonized carbons was also studied in the presence of Cd(II) and Hg(II). The presence of Cd(II)) in the medium enhanced the sulphonic acid uptake, mainly for the most ozonized activated carbon sample, whereas the presence of Hg(II) had no significant effect on the adsorption.     

Inhibition of nitrobenzene adsorption by water cluster formation at acidic oxygen functional groups on activated carbon

The inhibition effect of nitrobenzene adsorption by water clusters formed at the acidic groups on activated carbon was examined in aqueous and n-hexane solution. The activated carbon was oxidized with nitric acid to introduce CO complexes and then outgassed in helium flow at 1273 K to remove them completely without changing the structural properties of the carbon as a reference adsorbent. The amounts of acidic functional groups were determined by applying Boehm titration. A relative humidity of 95% was used to adsorb water onto the carbon surface. Strong adsorption of water onto the oxidized carbon can be observed by thermogravimetric analysis. The adsorption kinetic rate was estimated to be controlled by diffusion from the kinetic analysis. Significant decline in both capacity and kinetic rate for nitrobenzene adsorption onto the oxidized carbon was also observed in n-hexane solution by preadsorption of water to the carbon surface, whereas it was not detected for the outgassed carbons. These results might reveal that water molecules forming clusters at the CO complexes inhibited the entrance of nitrobenzene into the interparticles of the carbon.     

载铜活性炭吸附一氧化碳的密度泛函理论计算

应用密度泛函理论和相对论有效核势方法, 用C₁₆H₁₀, C₁₃H₉, C₁₂H₁₂原子簇模型模拟活性炭表面, 计算得到了CO在载铜活性炭上的吸附位、吸附构型和吸附能. 研究表明: 载铜活性炭吸附CO的过程, 本质上是Cu(I)通过σ-π配键与CO络合, 形成Cu—C键的过程. 载铜活性炭对CO的络合吸附能在50～60 kJ/mol之间, 远大于活性炭对CO的物理吸附能(9.15 kJ/mol), 因而络合吸附更稳定, 选择性也更高. Cu(I)选择吸附在活性炭表面的顶位和桥位, 一个Cu(I)至多可以吸附一个到两个CO分子, 但吸附一个CO比吸附两个CO稳定.     

Preparation of Corn Stalk-Walnut Shell Mix-based Activated Carbon and Its Adsorption of Malachite Green

The mix-based activated carbon derived from corn stalk and walnut shell was prepared by chemical activation method using phosphoric acid as the activator. The optimized conditions for preparation were obtained by the orthogonal experiment, the characterizations of the activated carbon were performed by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy(FTIR), Boehm's titration method and nitrogen adsorption. For the prepared mix-based activated carbon, the highest iodine number, methylene blue number and BET surface area are 720.5 mg/g, 195.0 mg/g and 1187 m²/g, respectively, and the pores are mainly mesopores. The mix-based activated carbon shows the higher adsorption capacity for malachite green than the raw materials, the activated carbons prepared only from corn stalk or walnut shell and the commercial activated carbon. The kinetics and thermodynamics of the adsorption can be satisfactorily described by the pseudo-second-order kinetic model and the Langmuir isotherm model, separately.     

Activated Carbon Adsorption of Some Phenolic Compounds Present in Agroindustrial Wastewater

Single solute and simultaneous experimental adsorption isotherms of three phenolic compounds: gallic acid, p-hydroxybenzoic acid and syringic acid, have been investigated at 20, 30 and 40°C, using a bituminous coal based activated carbon. Regardless of temperature, the capacity of the activated carbon used to adsorb these compounds presented the following order: syringic acid > p-hydroxybenzoic acid > gallic acid. The increase of temperature slightly favored the adsorption capacity of the phenolic compounds. In binary and ternary component adsorption, experimental data suggest that interactions between adsorbates improve the adsorption capacity of some of the phenolic acid compounds. On the contrary, at high organic concentrations, adsorbed gallic acid was partially removed from the activated carbon surface because of the presence of the other components.     

杂多酸的固载化研究(II)

研究了以多种方法化学改性的不同活性炭表面化学特性及十二硅钨酸（SiW_(12)）在相应表面的吸附. 首次提出，不同原料来源和改性的活性炭对SiW_(12)的吸附有不同的等温线形式和吸附力. 活性炭表面的羰基有利于SiW_(12)的吸附，而表面的羧基则是不利的．     

碳纳米管复合微球修饰L-色氨酸及其对LDL的吸附性能

本文以多孔碳纳米管/活性炭复合微球为载体, 以L-色氨酸为配基, 采用环氧氯丙烷偶联法, 制得修饰L-色氨酸的碳纳米管/活性炭复合微球(L-CNTs/AC)。采用扫描电镜、氮气吸附、傅立叶红外光谱、热分析、X射线光电子能谱等对复合微球进行表征;通过体外静态吸附法对其低密度脂蛋白(LDL)吸附能力进行初步研究。结果表明:环氧氯丙烷偶联法可接枝上L-色氨酸。复合微球中碳纳米管加入量越多, 对LDL的吸附能力越强;当碳纳米管加入量为45wt%时, 对LDL的吸附量达4.623 mg·g^-1, 是未添加碳纳米管的2.3倍多。这是因为碳纳米管不仅可促进复合微球中20~100 nm孔的形成, 而且还可促进复合微球配基修饰量的增多, 从而大大增强了复合微球对LDL的吸附能力。此复合微球可望开发成一种新型的血液灌流LDL吸附剂。     

Hierarchically porous carbon membranes derived from PAN and their selective adsorption of organic dyes

Porous carbon membranes were favorably fabricated through the pyrolysis of polyacrylonitrile(PAN) precursors, which were prepared with a template-free technique-thermally induced phase separation. These carbon membranes possess hierarchical pores, including cellular macropores across the whole membranes and much small pores in the matrix as well as on the pore walls. Nitrogen adsorption indicates micropores(1.47 and 1.84 nm) and mesopores(2.21 nm) exist inside the carbon membranes, resulting in their specific surface area as large as 1062 m2/g. The carbon membranes were used to adsorb organic dyes(methyl orange, Congo red, and rhodamine B) from aqueous solutions based on their advantages of hierarchical pore structures and large specific surface area. It is particularly noteworthy that the membranes present a selective adsorption towards methyl orange, whose molecular size(1.2 nm) is smaller than those of Congo red(2.3 nm) and rhodamine B(1.8 nm). This attractive result can be attributed to the steric structure matching between the molecular size and the pore size, rather than electrostatic attraction. Furthermore, the used carbon membranes can be easily regenerated by hydrochloric acid, and their recovery adsorption ratio maintains above 90% even in the third cycle. This work may provide a new route for carbon-based adsorbents with hierarchical pores via a template-free approach, which could be promisingly applied to selectively remove dye contaminants in aqueous effluents.