VUV/β-Ga_2O_3光催化降解室内VOCs研究
摘要
随着人类对室内环境的依存度逐渐提高,室内空气品质(IAQ)愈发引起人们的重视和关注。光催化氧化作为一种新型高级氧化技术,在室内空气治理领域有巨大的应用潜力。本文从解决光催化技术存在的光生载流子易于复合、光催化效率低的问题入手,采用简便、温和、低成本的水热法,通过优化材料生长条件,调控制备出具有特殊结构的高效β-Ga_2O_3光催化剂,并研究了其结构形貌、光学特性与光催化性能之间的关系。
利用低温水热法成功制备出具有特殊形貌结构的β-Ga_2O_3光催化剂,优化了水热反应条件,表明在水热温度140℃,水热时间6h,初始反应物硝酸镓和尿素摩尔比为1:10时,所得催化剂具有最高的光催化活性,这与催化剂在不同生长条件下的晶型结构、晶粒大小和比表面积密切相关。
在水热体系中考察了PEG浓度和分子量对材料光催化性能的影响机制。证明了PEG分子量为200,用量为20mL时所得β-Ga_2O_3具有最高的催化活性。这是因为适宜的PEG浓度和分子量可以优化催化剂形貌,增加催化剂的比表面积,并产生丰富的氧空位及镓氧空位对,对提高气固传质反应速率和抑制光生载流子的复合率起到了积极的作用。
利用PTR-MS和GC-MS对VUV光解室内低浓度甲苯和萘过程的中间产物进行了在线检测和定性分析,发现了一些醛、酮等毒性较大的中间产物。空气下光解萘过程还发现了2种碳原子数大于10的光生聚合体,聚合体的形成可能与臭氧氧化作用相关。
联合VUV/β-Ga_2O_3光催化降解技术净化单一和复合污染物,与普通UV/β-Ga_2O_3和VUV/TiO_2光催化进行了效果对比,表明VUV/β-Ga_2O_3技术具有更强的污染物去除能力,连续流中单一甲苯污染物去除率可达92.2%。在VUV下β-Ga_2O_3因其更大的禁带宽度,也表现出了较TiO_2更优越的光催化性能。
As increasing of dependence on indoor environment, people has paid more andmore attention to the indoor air quality (IAQ). Photocatalytic oxidation (PCO), as anadvanced oxidation technology, has potential values for application in indoorpollutants treatment. In this dissertation, a simple, mild and low-cost hydrothermalmethod was used to prepared high efficientβ-Ga_2O_3 with special microstructure byoptimizing the material growth conditions, to solve main photocatalytic bottlenecks,including high photoinduced hole-eletron recombination rate and low photocatalyticefficiency. Also, the relationships between morphology, crystallization, opticalproperties with photocatalytic activities were investigated.
High efficientβ-Ga_2O_3 photocatalyst was successfully synthesized via alow-temperature hydrothermal method. It is indicated that when the hydrothermaltemperature is 140℃, hydrothermal time is 6h, the initial reactant molar ratio ofgallium nitrate and urea is 1:10, the obtained sample has highest photocatalyticactivity, which is closely concerned with the crystallization, grain size and surfacearea under different grow conditions.
The factors of PEG concentration and molecular weight on the photocatalyticproperties ofβ-Ga_2O_3 were investigated in the hydrothermal system and the impactmechanism was deduced. The experimental data showed that when PEG molecularweight was 200, volume dosage was 20mL, the synthesized catalyst exhibited highestphotocatalytic activity. It is proved that suitable PEG concentration and molecularweight can optimize the catalysts morphology, increase the catalysts surface area,produce more oxygen vacancies and gallium-oxygen vacancies, which played anactive role in improving the gas-solid mass transfer rates and suppressing therecombination of photogenerated holes-electrons.
The reaction process of VUV photodegradation of toluene and naphthalene byPTR-MS and GC-MS were investigated. A lot of by-products were determinedqualitatively. Some more toxic intermediates such as aldehydes and ketones weredetected. Two kinds of photo-polymer species were discovered in photodegradationnaphthalene at moist air, which were related to the ozone. The possible mechanismsof VUV photodegradation pollutants in different conditions were also proposed.
Treatment of single or complex pollutants were further invested by VUV combined withβ-Ga_2O_3(VUV/β-Ga_2O_3) photocatalytic degradation technology. It isconfirmed that VUV/β-Ga_2O_3 technology is more powerful than VUV/TiO_2 todegradate hamful compounds into less harm intermediates. The removal efficiency oftoluene has reached 92.2% in continuous flow reaction. It is testified that thephotocatalytic properties ofβ-Ga_2O_3 is more superior to P25-TiO_2 due to its largerband gap.
利用低温水热法成功制备出具有特殊形貌结构的β-Ga_2O_3光催化剂,优化了水热反应条件,表明在水热温度140℃,水热时间6h,初始反应物硝酸镓和尿素摩尔比为1:10时,所得催化剂具有最高的光催化活性,这与催化剂在不同生长条件下的晶型结构、晶粒大小和比表面积密切相关。
在水热体系中考察了PEG浓度和分子量对材料光催化性能的影响机制。证明了PEG分子量为200,用量为20mL时所得β-Ga_2O_3具有最高的催化活性。这是因为适宜的PEG浓度和分子量可以优化催化剂形貌,增加催化剂的比表面积,并产生丰富的氧空位及镓氧空位对,对提高气固传质反应速率和抑制光生载流子的复合率起到了积极的作用。
利用PTR-MS和GC-MS对VUV光解室内低浓度甲苯和萘过程的中间产物进行了在线检测和定性分析,发现了一些醛、酮等毒性较大的中间产物。空气下光解萘过程还发现了2种碳原子数大于10的光生聚合体,聚合体的形成可能与臭氧氧化作用相关。
联合VUV/β-Ga_2O_3光催化降解技术净化单一和复合污染物,与普通UV/β-Ga_2O_3和VUV/TiO_2光催化进行了效果对比,表明VUV/β-Ga_2O_3技术具有更强的污染物去除能力,连续流中单一甲苯污染物去除率可达92.2%。在VUV下β-Ga_2O_3因其更大的禁带宽度,也表现出了较TiO_2更优越的光催化性能。
As increasing of dependence on indoor environment, people has paid more andmore attention to the indoor air quality (IAQ). Photocatalytic oxidation (PCO), as anadvanced oxidation technology, has potential values for application in indoorpollutants treatment. In this dissertation, a simple, mild and low-cost hydrothermalmethod was used to prepared high efficientβ-Ga_2O_3 with special microstructure byoptimizing the material growth conditions, to solve main photocatalytic bottlenecks,including high photoinduced hole-eletron recombination rate and low photocatalyticefficiency. Also, the relationships between morphology, crystallization, opticalproperties with photocatalytic activities were investigated.
High efficientβ-Ga_2O_3 photocatalyst was successfully synthesized via alow-temperature hydrothermal method. It is indicated that when the hydrothermaltemperature is 140℃, hydrothermal time is 6h, the initial reactant molar ratio ofgallium nitrate and urea is 1:10, the obtained sample has highest photocatalyticactivity, which is closely concerned with the crystallization, grain size and surfacearea under different grow conditions.
The factors of PEG concentration and molecular weight on the photocatalyticproperties ofβ-Ga_2O_3 were investigated in the hydrothermal system and the impactmechanism was deduced. The experimental data showed that when PEG molecularweight was 200, volume dosage was 20mL, the synthesized catalyst exhibited highestphotocatalytic activity. It is proved that suitable PEG concentration and molecularweight can optimize the catalysts morphology, increase the catalysts surface area,produce more oxygen vacancies and gallium-oxygen vacancies, which played anactive role in improving the gas-solid mass transfer rates and suppressing therecombination of photogenerated holes-electrons.
The reaction process of VUV photodegradation of toluene and naphthalene byPTR-MS and GC-MS were investigated. A lot of by-products were determinedqualitatively. Some more toxic intermediates such as aldehydes and ketones weredetected. Two kinds of photo-polymer species were discovered in photodegradationnaphthalene at moist air, which were related to the ozone. The possible mechanismsof VUV photodegradation pollutants in different conditions were also proposed.
Treatment of single or complex pollutants were further invested by VUV combined withβ-Ga_2O_3(VUV/β-Ga_2O_3) photocatalytic degradation technology. It isconfirmed that VUV/β-Ga_2O_3 technology is more powerful than VUV/TiO_2 todegradate hamful compounds into less harm intermediates. The removal efficiency oftoluene has reached 92.2% in continuous flow reaction. It is testified that thephotocatalytic properties ofβ-Ga_2O_3 is more superior to P25-TiO_2 due to its largerband gap.
引文
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