TS-1及HZSM-5分子筛对典型气相分子的光催化降解与选择性氧化
收稿日期: 2013-05-06
网络出版日期: 2013-08-11
基金资助
项目受国家973前期研究专项(973, No. 2011CB612314), 国家自然科学基金(No. 21077023)及福建省自然科学基金(Nos. 2010J01035, JA10008及JK2011001)资助.
Photocatalytic Degradation and Selective Oxidation of Typical Gas Phase Molecules with TS-1 and HZSM-5 Zeolites
Received date: 2013-05-06
Online published: 2013-08-11
Supported by
Project supported by the National Basic Research Program of China (973 Program, No. 2011CB612314), the National Natural Science Foundation of China (No. 21077023) and Natural Science Foundation of Fujian Province (Nos. 2010J01035, JA10008, and JK2011001).
以典型气态探针分子及骨架含高分散非毗邻过渡金属(Ti, Fe)的沸石分子筛材料(TS-1, HZSM-5)、半导体二氧化钛(P25)为考察对象, 拟通过沸石分子筛对不同探针分子所表现的迥异光催化行为揭示催化材料本征物化结构、吸附特性、活性位类型对光催化行为的影响规律. 催化材料表征及所获得的气相光催化反应结果表明: 沸石分子筛(TS-1, HZSM-5)上的光催化氧化-还原反应主要通过表面金属-氧结构单元的电荷转移激发态实现; 源于独特MFI拓扑孔道结构的优异吸附能力、特殊表面活性位分布环境及不同的光生电子-空穴分离机制, 使得具规整分子级孔窗的TS-1及HZSM-5对三氯甲烷的光催化降解效率与活性稳定性远高于传统二氧化钛光催化剂; 对单碳分子甲醇及含仲碳醇羟基异丙醇的光催化反应中, 上述沸石分子筛则表现异常突出的选择性氧化特征, 对终端产物甲醛及丙酮均具较高的转化效率和选择性. 本文的反应设计路径及选择性氧化结果, 可为高分散过渡金属修饰沸石分子筛在有机小分子的光催化转化上提供思路借鉴.
员汝胜 , 范少龙 , 周华希 , 许珍 , 林晨 , 费恩虎 , 吴棱 , 王绪绪 . TS-1及HZSM-5分子筛对典型气相分子的光催化降解与选择性氧化[J]. 化学学报, 2013 , 71(10) : 1404 -1410 . DOI: 10.6023/A13050479
In this study, we selected zeolite molecular sieves (TS-1 and HZSM-5) with highly dispersed transition metal (Ti or Fe) in their frameworks and TiO2 P25 as photocatalysts and typical gas as probe molecules. The structure and crystallization, specific surface area, pore size distribution, light absorption and active radical species were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller surface area (BET), diffuse reflectance spectroscopy (DRS) and electron spin resonance spectroscopy (ESR). The influences of the intrinsic structure, adsorption property and the kind of active sites of the catalytic materials on their photocatalytic behaviors of different molecules were investigated. The emphases were placed on the photocatalytic conversion of hydrophobic halohydrocarbons and hydrophilic lower alcohol over zeolite molecular sieves. The photocatalytic reactions were performed in a tubular vessel microreactor operating in a continuous-flow mode under UV irradiation. Analysis of the reactor effluent was conducted by a gas chromatograph (HP6890). The concentrations of gas molecules and carbon dioxide were determined by using the flame ionization detector (FID) and thermal conductivity detector (TCD), respectively. Under UV irradiation, the excited state between the isolated and highly dispersed Fe3+/Ti4+and bridging oxygen atom can activate the molecular oxygen into superoxide radical via the surface electron transfer, which can participate in the subsequent selective oxidation reactions. Due to zeolites with excellent adsorption relative to their unique MFI pore structure, active sites environment and the separation mechanism of photogenerated holes and electrons, these resulted that TS-1 and HZSM-5 zeolites with regular pore structure of molecular dimensions showed good degradation rate of chloroform (about 80%) for 16 h, obviously higher than that of TiO2. Also, they exhibited excellent selectivity for photocatalytic oxidation of methanol and isopropanol into formaldehyde and acetone, respectively. This is different from TiO2 as a typical representative of conventional semiconductor photocatalysts, in which the hydroxyl radicals with strong oxidation were produced as main active species and can mineralize the organic compounds into inorganic small molecules completely. This study provides ideas for the photocatalytic transformation of small organic molecules over molecular sieves with highly dispersed transition metal.
Key words： photocatalysis; zeolite; gas; degradation; selective oxidation
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