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黏土-TiO₂纳米复合材料对一种典型疏水性空气污染物的光催化消除效率

Efficiency of clay--TiO2 nanocomposites on the photocatalytic elimination of a model hydrophobic air pollutant.

作者信息

Kibanova Daria, Cervini-Silva Javiera, Destaillats Hugo

机构信息

Facultad de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, Coyoacán, C.P. 04150, México City, México.

出版信息

Environ Sci Technol. 2009 Mar 1;43(5):1500-6. doi: 10.1021/es803032t.

Abstract

Clay-supported TiO2 photocatalysts can potentially improve the performance of air treatment technologies via enhanced adsorption and reactivity of target volatile organic compounds (VOCs). In this study, a benchtop photocatalytic flow reactor was used to evaluate the efficiency of hectorite-TiO2 and kaolinite-TiO2, two novel composite materials synthesized in our laboratory. Toluene, a model hydrophobic VOC and a common indoor air pollutant, was introduced in the air stream at realistic concentrations, and reacted under UVA (lamda(max) = 365 nm) or UVC (lamda(max) = 254 nm) irradiation. The UVC lamp generated secondary emission at 185 nm, leading to the formation of ozone and other short-lived reactive species. Performance of clay-Ti02 composites was compared with that of pure TiO2 (Degussa P25), and with UV irradiation in the absence of photocatalyst under identical conditions. Films of clay-TiO2 composites and of P25 were prepared by a dip-coating method on the surface of Raschig rings, which were placed inside the flow reactor. An upstream toluene concentration of approximately 170 ppbv was generated by diluting a constant flow of toluene vapor from a diffusion source with dry air, or with humid air at 10, 33, and 66% relative humidity (RH). Toluene concentrations were determined by collecting Tenax-TA sorbent tubes downstream of the reactor, with subsequent thermal desorption--GC/MS analysis. The fraction of toluene removed, %R, and the reaction rate, Tr, were calculated for each experimental condition from the concentrations measured with and without UV irradiation. Use of UVC light (UV/TiO2/O3) led to overall higher reactivity, which can be partially attributed to the contribution of gas phase reactions by short-lived radical species. When the reaction rate was normalized to the light irradiance, Tr/Ilamda,the UV/TiO2 reaction under UVA irradiation was more efficient for samples with a higher content of TiO2 (P25 and Hecto-TiO2), but notfor Kao-TiO2. In all cases, reaction rates peaked at 10% RH, with Tr values between 10 and 50% higherthan those measured under dry air. However, a net inhibition was observed as RH increased to 33% and 66%, indicating that water molecules competed effectively with toluene for reactive surface sites and limited the overall photocatalytic conversion. Compared to P25, inhibition by coadsorbed water was less significant for Kao-TiO2 samples, but was more dramatic for Hecto-TiO2 due to the high water uptake capacity of hectorite.

摘要

粘土负载的二氧化钛光催化剂有可能通过增强目标挥发性有机化合物(VOCs)的吸附和反应性来提高空气处理技术的性能。在本研究中,使用台式光催化流动反应器评估了锂蒙脱石 - 二氧化钛和高岭土 - 二氧化钛这两种在我们实验室合成的新型复合材料的效率。甲苯作为一种典型的疏水性VOC和常见的室内空气污染物,以实际浓度引入气流中,并在UVA(λ(max)=365nm)或UVC(λ(max)=254nm)照射下反应。UVC灯在185nm处产生二次发射,导致臭氧和其他短寿命活性物种的形成。将粘土 - TiO₂复合材料的性能与纯TiO₂(德固赛P25)的性能进行了比较,并在相同条件下与无光催化剂时的紫外线照射进行了比较。通过浸涂法在拉西环表面制备了粘土 - TiO₂复合材料和P25的薄膜,拉西环放置在流动反应器内。通过用干燥空气或相对湿度(RH)为10%、33%和66%的潮湿空气稀释来自扩散源的恒定甲苯蒸气流,产生上游甲苯浓度约为170ppbv。通过在反应器下游收集Tenax - TA吸附剂管并随后进行热脱附 - GC/MS分析来测定甲苯浓度。根据有无紫外线照射时测得的浓度,为每个实验条件计算甲苯去除率%R和反应速率Tr。使用UVC光(UV/TiO₂/O₃)导致整体反应性更高,这部分可归因于短寿命自由基物种的气相反应的贡献。当反应速率归一化为光辐照度Tr/Iλ时,对于TiO₂含量较高的样品(P25和锂蒙脱石 - TiO₂),UVA照射下的UV/TiO₂反应更有效,但对于高岭土 - TiO₂则不然。在所有情况下,反应速率在RH为10%时达到峰值,Tr值比在干燥空气中测得的值高10%至50%。然而,当RH增加到33%和66%时观察到净抑制作用,表明水分子与甲苯有效地竞争反应表面位点并限制了整体光催化转化。与P25相比,共吸附水对高岭土 - TiO₂样品的抑制作用较小,但由于锂蒙脱石的高吸水能力,对锂蒙脱石 - TiO₂的抑制作用更为显著。

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