Mesoporous carbon adsorbents from melamine-formaldehyde resin using nanocasting technique for CO2 adsorption

Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine–formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), thermogravimetric analysis(TGA), elemental(CHN) analysis, Fourier transform infrared(FTIR) spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO_2 capture.The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO_2 adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO_2 adsorption capacity among the synthesized adsorbents. Breakthrough time and CO_2 equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent–CO_2 system was found to be reversible with stable adsorption capacity over four consecutive adsorption–desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.     

Mesoporous carbon adsorbents from melamine–formaldehyde resin using nanocasting technique for CO2 adsorption

Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine–formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), elemental (CHN) analysis, Fourier transform infrared (FTIR) spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO₂ capture. The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO₂ adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO₂ adsorption capacity among the synthesized adsorbents. Breakthrough time and CO₂ equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent–CO₂ system was found to be reversible with stable adsorption capacity over four consecutive adsorption–desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.     

Application of magnetic particles modified with amino groups to adsorb copper ions in aqueous solution

A magnetic adsorbent can be easily recovered from treated water by magnetic force,without requiring further downstream treatment.In this research,amine-functionalized silica magnetite has been synthesized using N-[3-(trimethoxysilyl)propyl]-ethylenediamine(TPED) as a surface modification agent.The synthesized magnetic amine adsorbents were used to adsorb copper ions in an aqueous solution in a batch system,and the maximum adsorption was found to occur at pH 5.5 ± 0.1.The adsorption equilibrium data fitted t...     

Enhancement of formaldehyde degradation by amine functionalized silica/titania films

Doping amine functional groups into SiO2/TiO2 films for enhancing the decomposition of formaldehyde has been investigated using the modified sol-gel method to prepare organic-inorganic hybrid photocatalysts via the co-condensation reaction of methyltrimethoxysilane (MTMOS) and amine functional groups. n-(2-Aminoethyl)-3-aminopropyl-trimethoxysilane (AEAPTMS) and 3-aminopropyl-trimethoxysilane (APTMS) were selected to study the e ect of amine functional groups on the enhancement of formaldehyde adsorption and degradation under a UV irradiation process. Physicochemical properties of prepared photocatalysts were characterized with nitrogen adsorption-desorption isotherms measurement, X-ray di raction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. The results indicated that the APTMS/SiO2/TiO2 film demonstrated a degradation e ciency of 79% superior to those of SiO2/TiO2 and AEAPTMS/SiO2/TiO2 films due to the synergetic e ect of adsorption and photocatalytic properties. The APTMS/SiO2/TiO2 film can be recycled with about 7% decreasing of degradation e ciency after seven cycles.     

Insight into the adsorption of tetracycline onto amino and amino–Fe functionalized mesoporous silica: Effect of functionalized groups

In order to study the influences of functionalized groups onto the adsorption of tetracycline (TC), we prepared a series of amino and amino–Fe^3 + complex mesoporous silica adsorbents with diverse content of amino and Fe^3 + groups (named N,N-SBA15 and Fe-N,N-SBA15). The resulting mesoporous silica adsorbents were fully characterized by X-ray powder diffraction, Fourier transform infrared spectrometer and N₂ adsorption/desorption isotherms. Furthermore, the effects of functionalized groups on the removal of TC were investigated. The results showed that the periodic ordered structure of SBA-15 was maintained after modification of amino/Fe^3 + groups. The functionalized amino groups decreased the adsorption capacity while the coordinated Fe^3 + increased the adsorption capacity. The adsorption kinetics of TC fitted pseudo-second-order model well and the equilibrium was achieved quickly. The adsorption isotherms fitted the Langmuir model well and with the Fe^3 + content increased from 3.93% to 8.26%, the Q_max of the adsorbents increased from 102 to 188 mmol/kg. The solution pH affected the adsorption of TC onto amino complex adsorbents slightly while influenced the adsorption onto Fe-amine complex adsorbents greatly. The adsorption of TC on SBA15 and N,N-SBA15 may be related to the formation of outer-sphere surface complexes, while the adsorption of TC onto Fe-N,N-SBA15 was mainly attributed to the inner-sphere surface complexes. This study could offer potential materials that have excellent adsorption behavior for environmental remediation and suggested useful information for the preparing other adsorbents in environmental applications.     

氨三乙酸酐改性纤维素对Cd~(2+)的吸附性能

本实验采用氨三乙酸酐改性玉米秸秆纤维素和苎麻纤维素,制备了两种改性纤维素吸附剂NTAA-CS及NTAA-RF,并研究了这两种吸附剂对水中Cd2+的吸附性能.通过元素分析、FTIR及SEM分析发现,纤维材料表面成功引入了氨三乙酸分子中的酯键和氨基基团.在改性纤维素吸附剂投加量为2 g·L-1,Cd2+的初始浓度为200 mg·L-1,p H值为4.0时,NTAA-CS和NTAA-RF对Cd2+的去除率分别为82.6%和90.2%.吸附实验结果表明:改性纤维素吸附剂对Cd2+的吸附是一个快速过程,吸附的最佳p H范围为4.0~7.0.吸附等温线用Langmuir方程的拟合效果优于Freundlich方程.经过5次吸附再生,吸附剂仍可以保持较大的吸附容量.这些结果表明,NTAA-CS和NTAA-RF在去除重金属废水中有较大的应用前景.     

改性颗粒活性炭吸附低浓度甲醛的试验研究

通过试验研究了表面改性方法、焙烧气氛和气相水分对颗粒活性炭(GAC)吸附低浓度甲醛性能的影响。结果表明:3%HNO3浸泡改性可增加GAC表面的含氧官能团,显著改善GAC对甲醛的吸附性能,并延长吸附穿透时间;O2气氛下焙烧所得GAC的吸附效果优于N2气氛下焙烧的GAC;反应气体含水1.5%时,GAC对甲醛的吸附性能明显降低。另外,分别采用低温N2吸附法和傅立叶红外光谱法表征了3%NHO3浸泡改性前、后GAC的孔结构和孔表面化学性质的差别,从而揭示了GAC的吸附性能与孔结构、孔表面化学性质之间的关系。     

Comparison of dynamic adsorption/desorption characteristics of toluene on different porous materials

Four different types of adsorbents, SBA-15, MCM-41, NaY and SiO₂, were used to study the dynamic adsorption/desorption of toluene. To further investigate the influence of pore structure on its adsorption performance, two SBA-15 samples with different microspores were also selected. It is shown that microporous material NaY has the largest adsorption capacity of 0.2873 mL/g, and the amorphous SiO₂ exhibits the least capacity of 0.1003 mL/g. MCM-41 also shows a lower break through capacity in spite of the relatively small pore diameter, because it can not provide the necessary small geometric confinement for the tiny adsorbates. However, the mesoporous SBA-15 silica with certain micropore volume shows relatively higher adsorption capacity than that of MCM-41 silica. The presence of micropores directly leads to an increase in the dynamic adsorption capacity of toluene. Although NaY has the highest adsorption capacity for toluene, its complete desorption temperature for toluene is high (>350℃), which limits its wide application. On the contrary, mesoporous silica materials exhibits a good desorption performance for volatile organic compounds at lower temperatures. Among these materials mesoporous SBA-15 samples, with a larger amount micropores and a lower desorption temperature, are a potentially interesting adsorbent for the removal of volatile organic compounds. This behavior should been related with the best synergetic effect of mesopores and micropores.     

nZVI@mesoSiO2的可控合成及应用性能研究

采用改进的两步法在原位基础上合成了以纳米零价铁(nano Zero Valent Iron,nZVI)为核芯的核壳型介孔二氧化硅(nZVI@mesoSiO_2).同时,通过简单地调控铁源用量得到具有单一nZVI核芯和不同壳层厚度的核壳型纳米复合材料.结果发现,铁源用量的增加会导致核芯尺寸减小、壳层厚度增加及颗粒比表面积下降.当铁源用量为2.78 g时,得到的nZVI@mesoSiO_2不仅具有较高的比表面积和单一且均匀的孔径分布,而且对2,4,6-三氯苯酚(2,4,6-Trichlorophenol, 2,4,6-TCP)的去除表现出很高的性能.影响因素实验表明,材料的最佳投加量为1.0 g·L~(-1),体系适宜初始pH为5.0,污染物初始浓度升高会导致去除效果下降,并且反应体系内乙二胺四乙酸(EDTA)的存在可以提高2,4,6-TCP的去除率.材料的重复利用实验结果表明,经过多次循环反应后会导致材料nZVI核芯的失活和孔道的堵塞.本研究不仅为制备可控壳层厚度的核壳型介孔材料提供了理论指导,而且为进一步改性合成对2,4,6-TP具有高选择性的复合材料提供了依据.     

介孔炭干凝胶对孔雀石绿的吸附性能研究

以间苯二酚和甲醛为原料,采用溶胶-凝胶法,通过调整碱性催化剂碳酸钠用量,制备了一系列介孔丰富的炭干凝胶吸附剂.主要考察了介孔炭干凝胶对染料孔雀石绿的吸附性能,并进行了孔结构、表面形貌和官能团的分析.结果表明,催化剂用量不同的介孔炭干凝胶具有不同的粒径和孔径,当间苯二酚与碳酸钠的物质的量比为1000∶1时,制得的吸附剂比表面积和介孔最丰富,且其对孔雀石绿的吸附量最大.同时,介孔炭干凝胶的用量、吸附时间和温度对吸附容量均有一定的影响,吸附过程符合伪二阶动力学模型和Langmuir等温模型,最大吸附量为208.33 mg·g~(-1);吸附过程是自发的吸热反应.介孔炭干凝胶对孔雀石绿的主要吸附机理是染料分子与羟基和羧基等官能团之间存在静电作用、氢键作用及范德华力作用.     

Adsorption of benzene,cyclohexane and hexane on ordered mesoporous carbon

Ordered mesoporous carbon (OMC) with high specific surface area and large pore volume was synthesized and tested for use as an adsorbent for volatile organic compound (VOC) disposal. Benzene, cyclohexane and hexane were selected as typical adsorbates due to their different molecular sizes and extensive utilization in industrial processes. In spite of their structural differences, high adsorption amounts were achieved for all three adsorbates, as the pore size of OMC is large enough for the access of these VOCs. In addition, the unusual bimodal-like pore size distribution gives the adsorbates a higher diffusion rate compared with conventional adsorbents such as activated carbon and carbon molecular sieve. Kinetic analysis suggests that the adsorption barriers mainly originated from the difficulty of VOC vapor molecules entering the pore channels of adsorbents. Therefore, its superior adsorption ability toward VOCs, together with a high diffusion rate, makes the ordered mesoporous carbon a promising potential adsorbent for VOC disposal.     

Adsorption of benzene, cyclohexane and hexane on ordered mesoporous carbon

Ordered mesoporous carbon(OMC) with high specific surface area and large pore volume was synthesized and tested for use as an adsorbent for volatile organic compound(VOC)disposal. Benzene, cyclohexane and hexane were selected as typical adsorbates due to their different molecular sizes and extensive utilization in industrial processes. In spite of their structural differences, high adsorption amounts were achieved for all three adsorbates, as the pore size of OMC is large enough for the access of these VOCs. In addition, the unusual bimodal-like pore size distribution gives the adsorbates a higher diffusion rate compared with conventional adsorbents such as activated carbon and carbon molecular sieve. Kinetic analysis suggests that the adsorption barriers mainly originated from the difficulty of VOC vapor molecules entering the pore channels of adsorbents. Therefore, its superior adsorption ability toward VOCs, together with a high diffusion rate, makes the ordered mesoporous carbon a promising potential adsorbent for VOC disposal.     

生物炭孔径结构-氮缺陷与四环素降解的相关性

制备了具有不同孔径结构和氮缺陷的生物炭材料,通过吸附、过硫酸盐高级氧化(催化)两种反应体系获得的动力学数据,结合氮气吸脱附测试、X射线光电子能谱、拉曼光谱、电子顺磁共振测试等表征手段,系统并深入分析了孔径结构-氮缺陷与典型抗生素污染物(盐酸四环素)降解的相关性.结果表明,孔径结构中与降解过程线性相关性最大的是介孔面积,相关系数(R²)高达0.9804,其次是总比表面积.而元素中与降解过程线性相关性最大的为氮元素,特别是石墨氮(R²为0.9766)及吡啶氮(R²为0.9596).此外,吸附、催化两个反应体系中孔径结构的相关性规律基本一致,但氮元素,尤其是石墨氮和吡啶氮,在催化体系中的R²大于吸附.通过淬灭实验、电子顺磁共振测试、线性扫描伏安法及拉曼测试等分析发现,该催化过程主要是以单线态氧为主的非自由路径.本研究为过硫酸盐高级氧化系统中生物炭基催化材料的制备明确了思路:对于盐酸四环素这类抗生素的降解可制备具有高介孔面积、高比表面积及富氮元素,特别是石墨氮及吡啶氮的生物炭材料.     

污泥基活性炭吸附空气中甲醛的研究

以城市污水处理厂脱水污泥为原料,氯化锌为活化剂制备污泥基活性炭,采用BET比表面积测试、扫描电镜(SEM)、傅里叶红外光谱(FTIR)等方法研究其理化性能,利用动态吸附实验系统和蒸馏装置,将污泥基活性炭与选定的商业活性炭进行了甲醛吸附性能对比,并利用热重分析法研究了甲醛在各活性炭上的脱附情况.结果表明,污泥基活性炭对空气中浓度分别为498,0.41mg/m3的甲醛均有很好的吸附效果,吸附量分别可达74.27,7.62mg/g,最大去除率分别为83.72%和89.56%,其吸附性能与选定的商业活性炭相当,特别是在处理浓度为0.41mg/m3甲醛时超过选定的商业活性炭.该污泥基活性炭BET比表面积为509.88m2/g,氮吸附等温线属于BDDT分类中的I-B型,表明其具有大量的超微孔和极微孔,更适用于低浓度甲醛的吸附.FTIR分析表明其表面含有各种含氮基团,特别是-NH2的存在,可能形成化学吸附中心,但从吸附甲醛后各活性炭的微商热重分析(DTG)曲线可以看出,各甲醛在活性炭上的吸附主要为物理吸附.     

Adsorption of single and mixed haloacetonitriles on silica-based porous materials: Mechanisms and effects of porous structures

Adsorption mechanisms and the role of different porous and crystalline structures on the removal of five haloacetonitriles (HANs) over hexagonal mesoporous silica (HMS), titanium substituted mesoporous silica (Ti-HMS), rod-shaped SBA-15 and microporous zeolite NaY were investigated. In addition, the effect of pH on adsorption mechanism and selective adsorption of five HANs individually and in an equimolar mixed solution were evaluated. The results indicated that the intraparticle diffusion rate constants of the mesoporous adsorbents were higher than that of the microporous NaY. In single solute, the order of adsorption preference (highest to lowest) was mono-HANs?>?di-HANs?>?tri-HAN. However, in mixed solute, the large molecular weight of the tri-HAN and di-HANs are more easily adsorbed than the smaller molecular weight mono-HANs. Except for SBA-15, the order of adsorption capacities in mixed HANs solute was not different compared to that observed for the single HAN solute, which might be caused by the higher accessibility to the active sites due to larger pore size. The ion-dipole electrostatic interaction was likely to be the main adsorption mechanism, and was favored at high pH values due to the high negative surface charge density of the adsorbent. The molecular structure of the HANs and hydrophilic/hydrophobic nature affected the adsorption capacities and their selective adsorption from mixed solutes.     

介孔磁性微球的制备表征及其在环境中的应用

文章在Fe3O4(magnetite)纳米粒子的表面包覆一层SiO2(silica),再以十六烷基三甲基溴化铵(CTAB)表面活性剂作为结构导向剂,包覆一层介孔SiO2,形成一种核壳式介孔磁性二氧化硅材料(MS),然后在其表面引进巯基(mercapto)从而成为一种新型巯基修饰的磁性二氧化硅载体(MMS).这种材料是介...     

高效去除Cd2+介孔硅酸钙的制备优化及表征

为了进一步研制高效、廉价的Cd²⁺吸附剂,从介孔硅酸钙（CSH）的制备与优化出发,选择钙硅比（Ca/Si）、表面活性剂种类及其用量为因素,采用正交试验探讨CSH的最优制备条件,并结合扫描电镜（SEM）、红外光谱（FTIR）、比表面积测试（BET）、X-射线衍射分析（XRD）,对CSH的结构形貌、材料性能进行评价.结果表明,各因素对合成材料吸附性能的影响顺序为：表面活性剂种类 > 表面活性剂用量 > Ca/Si;最优制备条件为：Ca/Si=1：1,以聚乙二醇（PEG）为表面活性剂,表面活性剂添加量为2%;表面活性剂的添加能显著提高材料的吸附性能,最优条件下制备的介孔硅酸钙对Cd²⁺的饱和吸附容量高达687.71 mg·g^-1,吸附等温线符合Langmiur模型;合成的水化硅酸钙为介孔结构,为狭缝孔,呈纳米花状,比表面积为333.47 m²·g^-1,BJH孔径为10.9 nm,孔隙度为2.199 cm³·g^-1;巨大的比表面积、高孔隙度、表面丰富的活性—OH及材料富含可交换态Ca²⁺,以及能与Cd²⁺发生吸附沉淀、表面络合和离子交换,致使其具有优异的吸附性能,有望为Cd²⁺污染水体治理和土壤修复提供潜在优势新材料.     

模板剂十二胺对胺改性HMS吸附CO2的影响

以正硅酸乙酯为硅源、十二胺为模板剂制备中孔硅HMS-1,采用焙烧和乙醇萃取的方法去除其模板剂,所得材料分别为HMS-2与HMS-3,并将四乙烯五胺（TEPA）与二乙醇胺（DEA）混合负载于3种材料上,采用X射线衍射（XRD）、傅里叶红外（FTIR）与氮气吸附实验对材料进行表征,研究改性前后的HMS对常压下低浓度CO₂的吸附性能及再生能力.XRD与FTIR结果表明,TEPA与DEA已被成功负载到HMS孔道内.氮气吸附实验表明,保留模板剂和胺基改性后,材料的孔容显著降低.20℃下,初始浓度为10%的CO₂在材料上的吸附量顺序为：MA-HMS-1（3.29mmol/g） > MA-HMS-3（2.7mmol/g） > HMS-1（1.88mmol/g） > MA-HMS-2（1.65mmol/g） > HMS-2（1.33mmol/g）,模板剂的存在,不仅增加了CO₂的吸附位点,还对混合胺改性的HMS吸附CO₂起到了协同作用.在20~75℃范围内,MA-HMS-1与MA-HMS-3受温度影响最明显,65℃时吸附量达最大值;随着温度的升高,HMS-1的吸附量随温度升高持续降低;MA-HMS-2的吸附量基本不变.含胺基的4种材料（HMS-1、MA-HMS-1、MA-HMS-2与MA-HMS-3）在80℃下拥有优良的再生性能,经4次循环再生后,MA-HMS-1的再生率为97.5%,高于MA-HMS-2（83%）和MA-HMS-3（84%）,保留HMS的模板剂对材料的再生性能有明显促进作用.     

高分子树脂与介孔分子筛吸附-脱附VOCs性能对比

采用溶剂热法制备介孔聚二乙烯基苯(PDVB)树脂,并以介孔分子筛MCM-41、SBA-15为参照,从吸附-脱附甲苯、邻二甲苯、均三甲苯性能和高湿度下的疏水性能方面对其进行对比研究.结果表明,PDVB具有最大的比表面积1219.1m2/g,其对低浓度甲苯吸附量约为介孔分子筛的2倍,同时吸附性能几乎不受水汽影响.随着VOCs分子尺寸增加,3种吸附剂对VOCs的饱和吸附量均有所增加,但PDVB的穿透吸附量明显高于分子筛.热重分析表明,在200℃以下3种吸附剂上吸附的有机分子均能脱附完全,具有优良的脱附再生性能.     

磁性高分子复合水凝胶的制备及其对水中铜离子的吸附性能

以海藻酸钠和聚乙烯醇为骨架负载磁性纳米Fe_3O_4颗粒合成了两种磁性高分子复合水凝胶材料:一种是以Ca~(2+)交联制备的磁性海藻酸钙单网络水凝胶(SAPFe),另一种是以海藻酸钙和聚乙烯醇经循环冷冻解冻制成的磁性双网络水凝胶(DAPFe).利用SEM、FTIR、BET对合成的材料进行表征,并研究了SAPFe和DAPFe对Cu~(2+)的吸附性能.结果表明,DAPFe比表面积达89.01 m~2·g~(-1),平均孔径为2.2 nm,DAPFe比SAPFe具有更低的含水率、更高的交联程度、更发达的孔隙结构和更高的比表面积.DAPFe对Cu~(2+)的最大吸附量可达207.01 mg·g~(-1),远大于SAPFe(173.01 mg·g~(-1)).SAPFe和DAPFe对Cu~(2+)的吸附等温线均符合Langmuir模型,吸附动力学符合准二级吸附动力学模型.通过分析SAPFe和DAPFe吸附Cu~(2+)前后官能团的变化,发现磁性高分子复合水凝胶具有丰富的羧基和羟基功能性官能团,并通过与Cu~(2+)产生螯合作用实现去除.