可见光响应温控光催化剂的制备、表征及其光催化活性研究
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摘要
近年来,环境净化中采用的TiO2太阳光催化技术因具有无毒、廉价、活性高等优点而引起人们的关注。其中,具有可见光响应的多壁碳纳米管(MWCNTs)／TiO2复合光催化剂体系,可以使宽带隙TiO2光催化材料的光生电子(e-)-空穴(h+)有效分离,有效抑制光生电子-空穴的复合,使其响应光谱向可见光扩展,大大提高了TiO2光催化反应效率。但是此光催化体系中存在超细TiO2／MWCNTs粉体在溶液中易团聚、分离回收困难、有效组分易流失、以及具有极性表面的TiO2与有机相的界面相容性差等问题,很大程度上限制了MWCNTs／TiO2光催化材料在降解有机污染物中的应用。
聚(NIPAM-co-MAH-β-CD)水凝胶是由可控温敏“开-关”特性的N-异丙基丙烯酰胺(NIPAM)结构单元以及分子包络识别能力的β-环糊精马来酸酐衍生物(MAH-β-CD)结构单元聚合而成,在水中具有良好的溶胀性,温敏性和透明性,且聚合物中含有能与TiO2发生反应形成配位化学键的羟基官能团。本课题制备出了新型的聚(NIPAM-co-MAH-β-CD)负载化的MWCNTs／TiO2复合材料,使此类新型TiO2光催化剂具有温度敏感、分子包络识别、稳定均匀等独特的性质和功能。
本文在文献报道基础上,首先制备了NIPAM,并采用顺丁烯二酸酐(MAH)对β-CD进行改性制得MAH-β-CD,然后以N,N′-亚甲基双丙烯酰胺(BIS)为交联剂,过硫酸钾(KPS)为引发剂,采用无皂乳液聚合法合成了聚(NIPAM-co-MAH-β-CD)水凝胶颗粒。采用元素分析法确定出水凝胶组成,并讨论了不同单体配比、交联剂用量、引发剂用量、聚合温度对水凝胶温敏性能的影响。
在此基础上,制备了聚(NIPAM-co-MAH-β-CD)／MWCNTs／TiO2有机-无机复合光催化剂,运用X-射线粉末衍射(XRD)、透射电子显微镜(TEM)、热重(TG)、紫外-可见吸收(UV-vis)光谱等技术对制备的复合光催化剂进行了表征。用溶胀平衡(ESR)测定法考察了其在水中的温敏性能。最后利用甲基橙为探针分子,研究了单体配比、交联剂用量、不同MWCNTs／TiO2负载量对催化剂催化活性的影响。结果显示,复合物中TiO2为锐钛矿型结构且平均粒径为20～25 nm左右的球形粒子。以水凝胶聚合物为载体解决了MWCNTs／TiO2光催化剂在使用中的容易团聚、流失严重、回收困难等问题。
Recently, environmental purification using TiO2 as a photocatalyst under solar irradiation has attracted a great deal of attention due to its non-toxic, inexpensive and highly reactive nature. Among them, with a visible light response, multi-walled carbon nanotubes(MWCNTs) /TiO2 composite photocatalyst can make photoinduced electrons(e-)-hole(h+) of wide band-gap TiO2 photocatalytic materials effective separation, effectively inhibiting the recombination of photo-generated electron-hole and making their responsive spectrum expand to the visible light, greatly enhancing the TiO2 photocatalytic reaction efficiency. However, in practical applications, ultra-fine MWCNTs/TiO2 powder can be aggregated easily in solution, but hardly separated and recovered. In addition, because of the polar surface of the TiO2, its interface compatibility with organic phase is poor, the application of MWCNTs/TiO2 is limited to a large extent in degradation of organic pollutants.
Poly(NIPAM-co-MAH-β-CD) hydrogel consists of N-isopropyl acrylamide(NIPAM) unit with temperature sensitive "on-off" property and P-cyclodextrin derivatives of maleic anhydride(MAH-β-CD) unit with molecular identification ability, and in water it has good swelling, thermo-sensitive and transparent features. Besides, the polymer contains hydroxyl functional groups which can react with TiO2 to form coordination bond. This subject prepared a new type photocatalyst material of poly(NIPAM-co-MAH-β-CD) load-oriented MWCNTs/TiO2 with temperature-sensition, molecular identification, stability, uniformity properties and functions.
In this paper, based on the reported literatures, NIPAM, MAH-β-CD, MWCNTs/TiO2 composite material unites first were prepared, and then, temperature responsive microspherical gels of NIPAM and P-cyclodextrin carrying vinyl carboxylic acid functional groups were synthesized by a surfactant-free emulsion polymerization method with N, N'-methylene bisacrylamide(BIS) as crosslinker, potassium peroxydisulfate(KPS) as initiator. The hydrogel's composition was determined by element analysis. Equilibrium swelling ratio(ESR) of hydrogels were tested under different temperature in water, and the effects of ratios of reactants, the amount of cross linker, the amount of initiator and reaction temperature on thermosensitivity of hydrogels were investigated thoroughly.
Then, organic-inorganic composites were prepared with multi-walled carbon nanotubes (MWCNTs)/TiO2 photocatalysts embedded within colloidal particles of a cross-linked, thermally responsive poly(NIPAM-co-MAH-P-CD). The composites were characterized by X-ray diffraction(XRD), transmission electron microscope(TEM), thermo gravimetric analysis (TG) and ultraviolet-visible absorption spectra(UV-vis). Equilibrium swelling ratio(ESR) of composites were tested to show their temperature-sensitive property in water, and the effects of ratios of reactants, the amount of cross linker, the amount of MWCNTs/TiO2 on photocatalytic activity were studied. The results indicate that the prepared samples were sphericity, anatase phase with mean size of 20～25 nm, and the introduction of the hydrogels could make MWCNTs/TiO2 recovered easily, as well as inhibiting it to aggregate and lose seriously in practical process.
聚(NIPAM-co-MAH-β-CD)水凝胶是由可控温敏“开-关”特性的N-异丙基丙烯酰胺(NIPAM)结构单元以及分子包络识别能力的β-环糊精马来酸酐衍生物(MAH-β-CD)结构单元聚合而成,在水中具有良好的溶胀性,温敏性和透明性,且聚合物中含有能与TiO2发生反应形成配位化学键的羟基官能团。本课题制备出了新型的聚(NIPAM-co-MAH-β-CD)负载化的MWCNTs／TiO2复合材料,使此类新型TiO2光催化剂具有温度敏感、分子包络识别、稳定均匀等独特的性质和功能。
本文在文献报道基础上,首先制备了NIPAM,并采用顺丁烯二酸酐(MAH)对β-CD进行改性制得MAH-β-CD,然后以N,N′-亚甲基双丙烯酰胺(BIS)为交联剂,过硫酸钾(KPS)为引发剂,采用无皂乳液聚合法合成了聚(NIPAM-co-MAH-β-CD)水凝胶颗粒。采用元素分析法确定出水凝胶组成,并讨论了不同单体配比、交联剂用量、引发剂用量、聚合温度对水凝胶温敏性能的影响。
在此基础上,制备了聚(NIPAM-co-MAH-β-CD)／MWCNTs／TiO2有机-无机复合光催化剂,运用X-射线粉末衍射(XRD)、透射电子显微镜(TEM)、热重(TG)、紫外-可见吸收(UV-vis)光谱等技术对制备的复合光催化剂进行了表征。用溶胀平衡(ESR)测定法考察了其在水中的温敏性能。最后利用甲基橙为探针分子,研究了单体配比、交联剂用量、不同MWCNTs／TiO2负载量对催化剂催化活性的影响。结果显示,复合物中TiO2为锐钛矿型结构且平均粒径为20～25 nm左右的球形粒子。以水凝胶聚合物为载体解决了MWCNTs／TiO2光催化剂在使用中的容易团聚、流失严重、回收困难等问题。
Recently, environmental purification using TiO2 as a photocatalyst under solar irradiation has attracted a great deal of attention due to its non-toxic, inexpensive and highly reactive nature. Among them, with a visible light response, multi-walled carbon nanotubes(MWCNTs) /TiO2 composite photocatalyst can make photoinduced electrons(e-)-hole(h+) of wide band-gap TiO2 photocatalytic materials effective separation, effectively inhibiting the recombination of photo-generated electron-hole and making their responsive spectrum expand to the visible light, greatly enhancing the TiO2 photocatalytic reaction efficiency. However, in practical applications, ultra-fine MWCNTs/TiO2 powder can be aggregated easily in solution, but hardly separated and recovered. In addition, because of the polar surface of the TiO2, its interface compatibility with organic phase is poor, the application of MWCNTs/TiO2 is limited to a large extent in degradation of organic pollutants.
Poly(NIPAM-co-MAH-β-CD) hydrogel consists of N-isopropyl acrylamide(NIPAM) unit with temperature sensitive "on-off" property and P-cyclodextrin derivatives of maleic anhydride(MAH-β-CD) unit with molecular identification ability, and in water it has good swelling, thermo-sensitive and transparent features. Besides, the polymer contains hydroxyl functional groups which can react with TiO2 to form coordination bond. This subject prepared a new type photocatalyst material of poly(NIPAM-co-MAH-β-CD) load-oriented MWCNTs/TiO2 with temperature-sensition, molecular identification, stability, uniformity properties and functions.
In this paper, based on the reported literatures, NIPAM, MAH-β-CD, MWCNTs/TiO2 composite material unites first were prepared, and then, temperature responsive microspherical gels of NIPAM and P-cyclodextrin carrying vinyl carboxylic acid functional groups were synthesized by a surfactant-free emulsion polymerization method with N, N'-methylene bisacrylamide(BIS) as crosslinker, potassium peroxydisulfate(KPS) as initiator. The hydrogel's composition was determined by element analysis. Equilibrium swelling ratio(ESR) of hydrogels were tested under different temperature in water, and the effects of ratios of reactants, the amount of cross linker, the amount of initiator and reaction temperature on thermosensitivity of hydrogels were investigated thoroughly.
Then, organic-inorganic composites were prepared with multi-walled carbon nanotubes (MWCNTs)/TiO2 photocatalysts embedded within colloidal particles of a cross-linked, thermally responsive poly(NIPAM-co-MAH-P-CD). The composites were characterized by X-ray diffraction(XRD), transmission electron microscope(TEM), thermo gravimetric analysis (TG) and ultraviolet-visible absorption spectra(UV-vis). Equilibrium swelling ratio(ESR) of composites were tested to show their temperature-sensitive property in water, and the effects of ratios of reactants, the amount of cross linker, the amount of MWCNTs/TiO2 on photocatalytic activity were studied. The results indicate that the prepared samples were sphericity, anatase phase with mean size of 20～25 nm, and the introduction of the hydrogels could make MWCNTs/TiO2 recovered easily, as well as inhibiting it to aggregate and lose seriously in practical process.
引文
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