二氧化硅气凝胶对挥发性有机污染物的吸附性能研究（英文）

以TEOS为前驱体、乙醇为溶剂、氢氟酸为催化剂,一步法合成了常规二氧化硅气凝胶。经乙醇超临界干燥后,通过SEM、FTIR和N_2吸脱附分析仪等仪器对二氧化硅气凝胶样品进行表征,以更好地了解吸附机理与样品性质的关系。结果表明,样品的比表面积高达519m~2/g,孔体积为1.9cm~3/g,平均孔径为15.15nm,是一种优良的吸附材料。考察了样品对甲苯、对二甲苯和苯的吸附效果。结果表明,二氧化硅气凝胶对三种污染物都具有很高的吸附量,其高吸附能力归因于气凝胶的三维纳米网络结构。综上所述,二氧化硅气凝胶具有优异的吸附性能,是一种很有前景的处理挥发性有机化合物的吸附剂。     

疏水二氧化硅气凝胶对甲苯蒸气吸附性能研究

吸附法是控制挥发性有机物(VOCs)的重要方法,对吸附材料的研究有着重要的意义。为了开发出吸附量高、稳定性好的吸附材料,利用溶胶-凝胶法制备出疏水二氧化硅气凝胶,并对其进行了低温氮气吸附、傅里叶变换红外光谱和热重分析,同时对疏水二氧化硅气凝胶进行了甲苯蒸气的静态、动态和循环吸附实验,研究其对甲苯蒸气的吸附性能。结果表明,所制疏水二氧化硅气凝胶为比表面积达732m~2/g的介孔吸附材料,其表面具有疏水性甲基基团,吸附容量高达1.6g/g,吸附稳定性强,动态吸附温升最高达12℃,用Logistic模型拟合吸附穿透曲线相似度高。     

疏水性二氧化硅气凝胶吸附水中微量苯酚和甲醛的研究

气凝胶是一种新型纳米多孔非晶材料,其密度低、比表面积大、孔隙率高,可以作为吸附剂.本文研究了稻壳灰为硅源制成的合甲基的疏水性二氧化硅气凝胶对水中微量苯酚和甲醛的吸附性能.结果表明,疏水性气凝胶对水中微量苯酚和甲醛具有一定的吸附能力,实验中对苯酚的吸附容量是1.93mg/g,要大于对甲醛的吸附容量0.92mg/g;增大气凝胶的疏水化程度可以增加其对水中微量苯酚和甲醛的平衡吸附容量;苯酚的吸附平衡等温曲线符合Langmuir和Freundlich方程,甲醛的吸附平衡等温曲线符合Freundlich方程.     

热解析-气相色谱法测定印刷品中总挥发性有机化合物释放量

建立用气袋法收集整册印刷品释放的挥发性有机化合物,热解析-气相色谱法检测总挥发性有机化合物(TVOC)的方法。将印刷品样品置入充满高纯氮气的密封PVF采样袋中,在35℃下放置12 h后,用采样器串联Tenax-TA采样管和采样袋,让袋内气体通过采样管,样品释放出的有机化合物被吸附到采样管的吸附剂上。用热解析-气相色谱法测试采样管中挥发性有机化合物的含量,其中苯、甲苯、邻二甲苯、间二甲苯、对二甲苯、乙苯、乙酸丁酯、苯乙烯和正十一烷按外标法定量,其它物质按甲苯标准曲线定量。该方法的加标回收率为74.4%~91.1%,测定结果的相对标准偏差不大于10%(n=9)。该方法的样品采集更贴近印刷品的实际生活场景,可以为评价印刷品挥发性有机物释放对人体健康的影响提供数据基础,为相关评价提供新思路。     

顶空–气相色谱/质谱法测定餐垫纸中16种挥发性有机物残留

采用顶空–气相色谱/质谱法同时测定餐垫纸中16种挥发性有机化合物(无水乙醇、异丙醇、正丁醇、丙酮、丁酮、己醛乙酸乙酯、乙酸异丙酯、乙酸丁酯、丙二醇甲醚、乙酸正丙酯、苯、甲苯、间二甲苯、对二甲苯、邻二甲苯)的含量。采用恒流模式,流速设定为2.5 mL/min,程序升温,16种挥发性有机化合物可以很好地分离。各成分工作曲线的相关系数r2均大于0.999 5,加标回收率在86.6%~104.8%之间,测定结果的相对标准偏差均不大于6.9%(n=6);各成分的检出限均低于0.01 mg/m2。该法具有进样简单,分离效果好,精密度高等特点,能够满足餐垫纸中挥发性有机物检测要求。     

吸附/一级热解吸/气相色谱联用测定室内空气中的挥发性有机物

本文以高聚物TenaxTA动态吸附,一级热解吸/毛细管气相色谱法联用测定室内空气中的挥发性有机物。优化了热解吸温度和热解吸时间,建立了苯、甲苯、乙酸正丁酯、乙苯、对二甲苯、苯乙烯、邻二甲苯、正十一烷等8种典型有机污染物的外标定量曲线,各化合物线性范围为103,相关系数R为0.9983～0.9999,最低检出浓度可达2×10-4mg/m3;考察了方法的重复性、热解吸率和残留率,并分析了实际空气样品。     

汽车内部装饰材料挥发性苯系物的热脱附/气相色谱-质谱法测定

建立了热脱附/气相色谱-质谱测定汽车内部装饰材料中苯、甲苯、邻二甲苯、间二甲苯、对二甲苯、乙苯、苯乙烯等挥发性苯系物的方法.将样品密封于采样袋中,充入5 L纯氮气,置于80 ℃恒温烘箱中加热2 h后,用采样泵抽取1 L气体经过Tenax-TA吸附管,通过热脱附/气相色谱-质谱联用仪对吸附管中苯系物的种类及含量进行测试.研究了样品处理的温度、时间对测试结果的影响.方法检出限0.9 ～1.2 ng/L,测量线性范围0.01 ～3.00 μg,回收率52% ～74%,相对标准偏差4% ～5%.     

地下水检测典型挥发性有机物标准样品研究

依据我国地下水污染现状,研究制备了地下水中典型挥发性有机物(VOCs)质量控制模拟标准样品,包含4种卤代烃和6种苯系物,经过气相色谱/质谱分析检测,均匀性和稳定性良好。组织行业内9家实验室,探索开展水中挥发性有机物检测的协作定值研究。开展不确定度来源分析和量值评定,标准样品的标准值和扩展不确定度(k=2)为:三氯甲烷(60.6±5.4)μg/L、四氯化碳(60.2±7.4)μg/L、三氯乙烯(60.4±5.8)μg/L、四氯乙烯(60.6±7.6)μg/L、苯(60.9±4.2)μg/L、甲苯(60.4±4.8)μg/L、乙苯(60.7±5.0)μg/L、邻二甲苯(60.5±6.2)μg/L、间二甲苯(60.4±6.2)μg/L、对二甲苯(60.4±6.2)μg/L。本标准样品主要用于地下水、地表水和饮用水环境监测工作中质量控制、分析方法验证、仪器性能的核查以及技术人员能力考核等。     

顶空进样-气相色谱/质谱联用法同时测定食品接触用润滑油中11种苯系物

建立了顶空自动进样-气相色谱/质谱联用(HS-GC/MS)同时测定食品接触用润滑油中11种痕量苯系物(苯、甲苯、乙苯、对二甲苯、间二甲苯、邻二甲苯、氯苯、1,3,5-三甲苯、1,2,4-三甲苯、苯乙烯、α-甲基苯乙烯)的方法。在优化的检测条件下,11种苯系物在10～100μg/kg范围内具有良好的线性,检出限为2～5μg/kg,加标回收率为73.8%～100%,RSD为3.3%～9.9%。方法满足食品接触用润滑油中苯系物高通量及痕量检测的要求。     

自生纳米纤维增强SiO_2气凝胶的制备及性能研究

采用溶胶-凝胶法和乙醇超临界干燥工艺制备ZrOX/SiO2复合气凝胶,再经1 200℃高温热处理得到自生纳米纤维增强SiO2复合气凝胶。利用扫描电子显微镜、透射电子显微镜、X射线衍射、热重和氮气吸附等手段对气凝胶的结构和性能进行了分析,并且测试了样品的压缩强度及真密度。实验结果表明:自生纳米纤维增强SiO2复合气凝胶具有均匀的多孔网络结构,锆氧纳米纤维是以化学键连接复合的方式无序穿插在气凝胶中,对复合气凝胶的机械强度和隔热性能有明显的改善。经1 200℃热处理后的ZrOX/SiO2复合气凝胶比表面积为827.22 m2·g-1,压缩强度为9.68 MPa,真密度为0.23 g·cm-3。     

Application of hydrophobic silica based aerogels and xerogels for removal of toxic organic compounds from aqueous solutions

This work is devoted to the application of hydrophobic silica based aerogels and xerogels for the removal of three toxic organic compounds from aqueous solutions. These materials were tested and characterized regarding their morphology, particle size distribution, surface area and porous structure. The equilibrium tests were carried out at different adsorbate concentrations and the experimental data were correlated by means of Langmuir and Freundlich isotherms. The equilibrium data were well described by Langmuir and Freundlich in most cases. The maximum adsorption capacity by Langmuir model was observed for the adsorption of benzene onto aerogel (192.31 mg/g), though the most promising results were obtained for toluene adsorption due to the greater adsorption energy involved. Comparing these results with other reported results, the hydrophobic silica based aerogels/xerogels were found to exhibit a remarkable performance for the removal of benzene and toluene. In addition, the regeneration of previously saturated aerogel/toluene was also investigated by using an ozonation process. The adsorption/regeneration tests with ozone oxidation showed that the aerogel might be regenerated, nevertheless the materials lost their hydrophobicity and thus different methods should be evaluated in forthcoming investigations.     

Preparation and characterization of nanocomposite,silica aerogel,activated carbon and its adsorption properties for Cd (II) ions from aqueous solution

A novel composite adsorbent, silica aerogel activated carbon was synthesized by sol-gel process at ambient pressure drying method. The composite was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and Nitrogen adsorption/desorption isotherms (BET).In the present study, the mentioned adsorbent was used moderately for the removal of cadmium ions from aqueous solutions and was compared with two other adsorbents of cadmium, activated carbon and silica aerogel. The experiments of Cd adsorption by adsorbents were performed at different initial ion concentrations, pH of the solution, adsorption temperature, adsorbent dosage and contact time. Moreover, the optimum pH for the adsorption was found to be 6.0 with the corresponding adsorbent dosage level of 0.1 g at 60 °C temperature. Subsequently, the equilibrium was achieved for Cd with 120 min of contact time.Consequently, the results show that using this composite adsorbent could remove more than 60% of Cd under optimum experimental conditions. Langmuir and Freundlich isotherm model was applied to analyze the data, in which the adsorption equilibrium data were correlated well with the Freundlich isotherm model and the equilibrium adsorption capacity (q_e) was found to be 0.384 mg/g in the 3 mg/L solution of cadmium.     

氧化硅-石墨烯气凝胶介孔复合材料的合成及其对苯的吸附性能

采用水热法快速合成了一种新型介孔氧化硅-石墨烯气凝胶复合吸附材料(MSGA)。通过X射线衍射、扫描电镜等方法对MSGA进行表征。结果表明,经过水热反应和冻干处理后的MSGA材料的介孔结构保持完好,介孔氧化硅在MSGA中的分散具有高度均一性。当介孔氧化硅的含量达到88.2(wt)%时,MSGA的比表面积可达395.5m~2/g。MSGA材料对苯蒸汽的常温常压吸附量为10.77mL/g,是石墨烯气凝胶的13倍,吸附穿透时间达到石墨烯气凝胶的34.4倍。在0.8%的环境湿度下,由于材料表面羟基的亲和性,进一步提升了对苯的吸附。得益于超低密度和丰富的内部孔隙结构,MSGA能够适应高达500mL/min的气流量。上述结果表明,该复合材料在VOCs消除领域具有广阔的应用前景。     

Amino functionalised Silica-Aerogels for CO2-adsorption at low partial pressure

Effective adsorption of CO₂ at low partial pressures is required for many technical processes, such as gas purification or CO₂ removal in closed loop environmental control systems. Since the concentration of CO₂ in such applications is rather low, a high adsorption capacity is a required property for the adsorbent. Silica aerogels possessing an open pore structure, a high porosity and a high surface area, have a great potential for utilisation as CO₂ adsorbents. Nonetheless in order to reach high adsorption capacities, silica aerogels should be functionalised, for instance by amino functionalisation. In this work, two different functionalisation methods were applied for the generation of amino functionalised aerogels: co-condensation during the sol-gel process and post-treatment of the gel. The co-condensation functionalisation allows the introduction of up to 1.44 wt.% nitrogen into the aerogel structure with minor reductions in surface area, leading however only to minor increases in the adsorption capacity at low partial pressures. The post functionalisation of the gel causes a greater loss in surface area, but the CO₂ adsorption capacity increases, due to the introduction of higher amounts of amino groups into the aerogel structure (up to 5.2 wt.% nitrogen). Respectively, 0.523 mmol CO₂/g aerogel could be adsorbed at 250 Pa. This value is comparable with the adsorption capacity at this pressure of a standard commercially available adsorbent, Zeolite 13X.     

Effect of pore structure in mesoporous silicas on VOC dynamic adsorption/desorption performance

The dynamic adsorption/desorption behavior of volatile organic compounds (VOCs) such as toluene (C7H8) and benzene (C6H6) was evaluated for three kinds of mesoporous silicas of SBA-15, all having almost the same mesopore size of ca. 5.7 nm, and a MCM-41 silica with a smaller pore size of 2.1 nm using a continuous three-step test. The fiberlike SBA-15 silica exhibited exceptionally good breakthrough behavior, a higher VOC capacity, and easier desorption. The fiberlike silica was composed through the catenation of rodlike particles. The rodlike silicas, by comparison, were proven to be less useful in dynamic adsorption processes because of lower dynamic VOC capacities despite having comparative porous parameters with the fiberlike silica. The large dynamic VOC capacity of the fiberlike silica was attributed to the presence of a bimodal pore system consisting of longer, one-dimensional mesopore channels connected by complementary micropores.     

Adsorption of Volatile Organic Compounds (VOCs) on Oxygen-rich Porous Carbon Materials Obtained from Glucose/Potassium Oxalate

To investigate the effects of oxygen-containing functional groups on the adsorption of volatile organic compounds (VOCs) with different polarity, oxygen-rich porous carbon materials (OPCs) were synthesized by heat treatment of glucose/potassium oxalate material. The carbon material had a large specific surface area (1697 m² g⁻¹) and a high oxygen content (18.95 at.%). OPC exhibited high adsorption capacity of toluene (309 mg g⁻¹) and methanol (447 mg g⁻¹). The specific surface area and total pore volume determined the adsorption capacity of toluene and methanol at the high-pressure range, while the oxygen-containing groups became the main factor affecting the methanol adsorption at the low-pressure range due to the hydrogen bond interaction through the density functional theory (DFT) calculations. This study provides an important hint for developing a novel O-doped adsorbent for the VOCs adsorption applications and analyzing the role of oxygen-containing groups in the VOCs adsorption under the low-pressure range.     

介孔硅材料及其负载型催化剂去除挥发性有机物的最新进展

介孔硅材料由于具有大的比表面积,均一的孔结构和大的孔径,常被用于分离、吸附和催化等领域.本文综述了近年来国内外介孔硅材料及其负载型催化剂去除各类挥发性有机物(VOCs)的研究进展,主要包括烃类、甲醇、甲醛、丙酮、苯、甲苯、萘、乙酸乙酯等.讨论了介孔硅材料的结构对VOCs吸附过程的影响;介绍了不同催化剂消除各类VOCs的催化性能及反应机理,并重点评述了甲苯在不同催化剂上的研究进展.分析结果表明,介孔硅材料的表面环境、孔道结构以及宏观形貌是影响VOCs分子在介孔硅材料上吸附的主要因素;贵金属催化剂的应用需要提高其抗中毒性以及降低成本;过渡金属的研究应着重于研发高活性的负载型过渡金属复合氧化物催化剂.最后对国内外介孔硅材料及其负载型催化剂的发展进行了展望,今后催化剂的设计可以从“氧化硅载体”和“介孔孔道”两个方面展开,这将为设计合适的催化剂处理各类VOCs污染物提供一定参考.     

基于L-谷氨酸的手性硅胶球的制备及其应用

无机介孔硅球因其具有足够的机械强度、热稳定性,以及适应多种流动相的优点,成为高效液相色谱(HPLC)柱填料中使用最广泛和最重要的材料。但在此研究领域中,并未见球形的全无机手性硅胶用作HPLC手性固定相。该文以无机球形介孔硅胶作为研究对象,通过堆砌硅珠法,以硅溶胶为原料,L-谷氨酸(L-Glu)为手性源,在手性环境中制造出脲醛树脂与胶体二氧化硅混合的小球,在550 ℃高温下煅烧除去树脂部分,制备基于L-Glu的无机介孔硅胶球。通过元素分析、红外光谱、扫描电镜、透射电镜和氮气吸附等表征证明这是一种具有规则球形的手性硅胶球,其手性来源于硅胶球自身的骨架和孔结构。将L-Glu手性硅胶球作为固定相制备了HPLC色谱柱,以正己烷-异丙醇(9∶1, v/v)作为流动相,流速为0.1 mL/min,考察了该手性柱对一系列外消旋化合物的拆分性能。实验表明,该手性柱拆分了15种外消旋化合物,其中特罗格尔碱、吡喹酮、3-苄氧基-1,2-丙二醇、1,2-环氧己烷、3-羟基-2-丁酮、2-甲基四氢呋喃-3-酮、异丙基缩水甘油醚达到基线分离;还分离了10种苯系位置异构体,o,m,p-氨基苯酚、o,p-氯苯酚、o,m,p-碘苯胺、o,m,p-甲苯胺、o,m,p-二硝基苯、o,m,p-氯苯胺、o,m,p-硝基苯酚、o,m,p-溴苯胺达到基线分离。实验表明,L-Glu手性硅胶球在手性分离方面具有良好的可行性,与普通硅胶相比不需要进一步修饰就可以有较好的手性分离效果,是一种低成本、制备便捷的手性无机硅胶固定相。     

苯基键合高比表面积活性炭的制备及其对挥发性有机化合物的吸附性能研究

以核桃壳为原料,经过碳化、KOH活化, 制备了高比表面积活性炭,通过三甲基氧基苯基硅烷对活性炭表面进行改性,制得苯基键合高比表面积活性炭吸附材料.通过氮气吸附法测定了苯基键合活性炭的比表面积及孔径分布;采用红外光谱、X射线光电子能谱、X射线粉末衍射技术对苯基键合活性炭的有机官能团、表面元素的化学环境及晶体结构进行了表征.将该吸附材料制成采样管,吸附空气中的挥发性有机物,二硫化碳解吸后使用气相色谱进行分析.考察了苯基键合活性炭对乙醇、丙酮、正己烷、乙酸乙酯、四氢呋喃、1,2-二氯乙烷和苯共7种挥发性有机化合物(VOCs)的吸附性能,饱和吸附量在129~216 mg/g之间;在0.05~ 2.50 mg/mL范围内,7种组分的峰高与浓度呈良好的线性关系,检出限在0.92~3.60 mg/m3之间.