负载型TiO_2光催化剂的制备及其降解有害挥发物性能的研究
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摘要
半导体光催化是一项环境友好的技术,在环境净化领域,特别是在治理室内空气污染方面有着很好的应用前景。制备负载型纳米TiO_2光催化剂,获得很好的光催化活性,用于降解空气中的易挥发性有机物。并可将活性组分和载体的各种功能进行组合,设计出更理想的光催化反应。
本文利用泡沫镍网做载体,负载具有大比表面积的SiO_2中孔材料中间层,以增大泡沫镍载体比表面积,提高复合光催化剂的活性和稳定性。再负载纳米TiO_2,制得光催化效率高的泡沫镍基纳米TiO_2-SiO_2复合光催化剂。在该复合光催化剂上通过热还原法沉积贵金属Pt,进一步提高其光催化反应活性。对制得的各种复合光催化剂光催化降解乙醛和甲醛的光催化活性进行静态和动态的测试及评价。主要研究内容包括:
1.用溶胶-凝胶法在已经过预处理的泡沫镍基上负载二氧化硅中间层,再负载二氧化钛,制得泡沫镍基TiO_2-SiO_2复合光催化剂。对该光催化剂进行静态测评,结果表明:泡沫镍基TiO_2-SiO_2复合光催化剂在主波长为253.7nm的紫外光源下,调节催化剂表面光强为400μW/cm2,乙醛初始浓度为100ppm,光照1.5小时以内,对乙醛的降解率可达100%。连续7次实验后,降解率下降约40%。将经过反复实验而部分失活的复合光催化剂在马弗炉中于空气气氛下在300℃加热1小时,或者用大量去离子水冲洗,再100℃烘干,其光催化活性均能完全恢复。
2.为了在实际生产中便于操作,采用热还原法在泡沫镍基TiO_2-SiO_2复合光催化剂上沉积贵金属Pt,以Pt:TiO_2为1wt%的比例,制得泡沫镍基Pt/TiO_2-SiO_2光催化剂。实验结果显示负载Pt的复合光催化剂比没负载时的光催化活性提高了两倍。同时对日本某株式会社生产的蓝色泡沫网状光催化剂和某液态喷涂型光催化剂在本实验条件下进行测试,结果表明,这些光催化剂无法达到满意的降解效果。故将采用泡沫镍基Pt/TiO_2-SiO_2光催化剂进行动态测试及评价。
3.对泡沫镍基TiO_2-SiO_2复合光催化剂进行静态条件下的乙醛降解实验,考察不同光照强度和不同波长光源对光催化效率的影响,对其中机理进行分析,并确定出实际应用中各个反应条件的参数。根据实验结果,在实际的光催化空气净化机中将采用主波长为253.7nm的紫外灯管,并确保其照射到光催化剂表面的光强不低于400μW/cm2。
4.将泡沫镍基Pt/TiO_2-SiO_2光催化剂在本实验室自行开发设计的风洞和测试仓中进行动态测试。结果表明,在风洞实验中,该光催化剂对甲醛的光催化降解效率平均约为15%;在测试仓实验中,其光催化降解效率约为每小时降解0.1ppm的目标气体。
本文中的泡沫镍基TiO_2-SiO_2复合光催化剂具备较高的光催化活性。通过进一步改性,该复合光催化剂将有望应用到实际的空气净化机中,投入市场,带来一定的社会和经济效益。
Photocatalysis as an environment friendly technology has attracted much attention and showed great potential in environmental protect applications, especially in the purification of indoor air pollution. Combined with the charactaristcs of the photocatalysts and the supports, the immobilization of nano-size TiO_2 is an ideal material to photocatalytic degredate the VOCs.
In this study, foam nickel was chosen as the support for TiO_2 photocatalysts. First, SiO_2 layers, the mesoporous transition layers with large specific surface area, were coated on foam nickel substrate. Then the nano-size TiO_2 layers were coated on. The composite nano-size TiO_2-SiO_2 photocatalysts loaded on foam nickel substrate have high photocatalytic ability. For higher photocatalytic ability, Pt was loading on the composite photocatalysts. All of the composite photocatalysts were tested in static system and dynamic real-time system. The main content and innovation of this work are presented as follow:
1. TiO_2 photocatalysts and SiO_2 layers loaded on pre-oxidized foam nickel substrate prepared by sol-gel processes. The composite TiO_2-SiO_2 photocatalysts were tested in static system. Results showed that when the .wavelength was 253.7nm, the light intensity was 400μW/cm2, and the initial concentration of acetaldehyde was 100ppm, the removal ratio of acetaldehyde by composite photocatalysts was 100% after 1.5 hours under the UV light irradiation. After 7 consecutive runs, the photocatalytic activity of composite photocatalysts reduced almost 40%. The composite photocatalysts can be regenerated easily by two methods: 1) Heating at 300℃in muffle 2) washing under pure water followed by dring at 100℃.
2. The noble metal Pt was loaded on the composite TiO_2-SiO_2 photocatalysts. Considering the production in factory, the noble metal Pt nano-particles were deposited on TiO_2-SiO_2 surface by heating reduction method (MTiO_2: MPt=1%). Results showed that the photocatalytic activity was enhanced greatly by Pt deposition; the acetaldehyde removal ratio by Pt/TiO_2-SiO_2 composite photocatalysts was two times higher than that of TiO_2-SiO_2. Test of other photocatalysts under the same work conditions were also made, such as the blue foam photocatalyst produced in Japan and the liquid photocatalyst. Results showed the acetaldehyde removal ratios were much lower than Pt/TiO_2-SiO_2 composite photocatalysts. So the Pt/TiO_2-SiO_2 composite photocatalysts will be tested in dynamic real-time system.
3. The composite TiO_2-SiO_2 photocatalysts were tested in static system. The influences of different intensity and wavelength on the degradation activity were investigated. It was found that the bactericidal lamp withλ=253.7nm, and the light intensity between 400-450μW/cm2 has the best degradation activity. Therefore, the ultraviolet lamp used in the nano-photocatalytic air purification equipment has the rationg voltage of 15W, the wavelength of 253.7nm and the light sensitivity more than 400μW/cm2.
4. Pt/TiO_2-SiO_2 composite photocatalysts were tested in dynamic real-time experimentation equipments. Results showed the rate of degradation formaldehyde is almost 15% in the wind tunnel. In the test house, the photocatalysts can degrade formaldehyde almost 0.1ppm per hour.
The TiO_2-SiO_2 composite photocatalysts loaded on foam nickel substrates showed a good degradation activity. The modified composite photocatalysts will be used in the nano-photocatalytic air purification equipment to create more social and economic profits.
本文利用泡沫镍网做载体,负载具有大比表面积的SiO_2中孔材料中间层,以增大泡沫镍载体比表面积,提高复合光催化剂的活性和稳定性。再负载纳米TiO_2,制得光催化效率高的泡沫镍基纳米TiO_2-SiO_2复合光催化剂。在该复合光催化剂上通过热还原法沉积贵金属Pt,进一步提高其光催化反应活性。对制得的各种复合光催化剂光催化降解乙醛和甲醛的光催化活性进行静态和动态的测试及评价。主要研究内容包括:
1.用溶胶-凝胶法在已经过预处理的泡沫镍基上负载二氧化硅中间层,再负载二氧化钛,制得泡沫镍基TiO_2-SiO_2复合光催化剂。对该光催化剂进行静态测评,结果表明:泡沫镍基TiO_2-SiO_2复合光催化剂在主波长为253.7nm的紫外光源下,调节催化剂表面光强为400μW/cm2,乙醛初始浓度为100ppm,光照1.5小时以内,对乙醛的降解率可达100%。连续7次实验后,降解率下降约40%。将经过反复实验而部分失活的复合光催化剂在马弗炉中于空气气氛下在300℃加热1小时,或者用大量去离子水冲洗,再100℃烘干,其光催化活性均能完全恢复。
2.为了在实际生产中便于操作,采用热还原法在泡沫镍基TiO_2-SiO_2复合光催化剂上沉积贵金属Pt,以Pt:TiO_2为1wt%的比例,制得泡沫镍基Pt/TiO_2-SiO_2光催化剂。实验结果显示负载Pt的复合光催化剂比没负载时的光催化活性提高了两倍。同时对日本某株式会社生产的蓝色泡沫网状光催化剂和某液态喷涂型光催化剂在本实验条件下进行测试,结果表明,这些光催化剂无法达到满意的降解效果。故将采用泡沫镍基Pt/TiO_2-SiO_2光催化剂进行动态测试及评价。
3.对泡沫镍基TiO_2-SiO_2复合光催化剂进行静态条件下的乙醛降解实验,考察不同光照强度和不同波长光源对光催化效率的影响,对其中机理进行分析,并确定出实际应用中各个反应条件的参数。根据实验结果,在实际的光催化空气净化机中将采用主波长为253.7nm的紫外灯管,并确保其照射到光催化剂表面的光强不低于400μW/cm2。
4.将泡沫镍基Pt/TiO_2-SiO_2光催化剂在本实验室自行开发设计的风洞和测试仓中进行动态测试。结果表明,在风洞实验中,该光催化剂对甲醛的光催化降解效率平均约为15%;在测试仓实验中,其光催化降解效率约为每小时降解0.1ppm的目标气体。
本文中的泡沫镍基TiO_2-SiO_2复合光催化剂具备较高的光催化活性。通过进一步改性,该复合光催化剂将有望应用到实际的空气净化机中,投入市场,带来一定的社会和经济效益。
Photocatalysis as an environment friendly technology has attracted much attention and showed great potential in environmental protect applications, especially in the purification of indoor air pollution. Combined with the charactaristcs of the photocatalysts and the supports, the immobilization of nano-size TiO_2 is an ideal material to photocatalytic degredate the VOCs.
In this study, foam nickel was chosen as the support for TiO_2 photocatalysts. First, SiO_2 layers, the mesoporous transition layers with large specific surface area, were coated on foam nickel substrate. Then the nano-size TiO_2 layers were coated on. The composite nano-size TiO_2-SiO_2 photocatalysts loaded on foam nickel substrate have high photocatalytic ability. For higher photocatalytic ability, Pt was loading on the composite photocatalysts. All of the composite photocatalysts were tested in static system and dynamic real-time system. The main content and innovation of this work are presented as follow:
1. TiO_2 photocatalysts and SiO_2 layers loaded on pre-oxidized foam nickel substrate prepared by sol-gel processes. The composite TiO_2-SiO_2 photocatalysts were tested in static system. Results showed that when the .wavelength was 253.7nm, the light intensity was 400μW/cm2, and the initial concentration of acetaldehyde was 100ppm, the removal ratio of acetaldehyde by composite photocatalysts was 100% after 1.5 hours under the UV light irradiation. After 7 consecutive runs, the photocatalytic activity of composite photocatalysts reduced almost 40%. The composite photocatalysts can be regenerated easily by two methods: 1) Heating at 300℃in muffle 2) washing under pure water followed by dring at 100℃.
2. The noble metal Pt was loaded on the composite TiO_2-SiO_2 photocatalysts. Considering the production in factory, the noble metal Pt nano-particles were deposited on TiO_2-SiO_2 surface by heating reduction method (MTiO_2: MPt=1%). Results showed that the photocatalytic activity was enhanced greatly by Pt deposition; the acetaldehyde removal ratio by Pt/TiO_2-SiO_2 composite photocatalysts was two times higher than that of TiO_2-SiO_2. Test of other photocatalysts under the same work conditions were also made, such as the blue foam photocatalyst produced in Japan and the liquid photocatalyst. Results showed the acetaldehyde removal ratios were much lower than Pt/TiO_2-SiO_2 composite photocatalysts. So the Pt/TiO_2-SiO_2 composite photocatalysts will be tested in dynamic real-time system.
3. The composite TiO_2-SiO_2 photocatalysts were tested in static system. The influences of different intensity and wavelength on the degradation activity were investigated. It was found that the bactericidal lamp withλ=253.7nm, and the light intensity between 400-450μW/cm2 has the best degradation activity. Therefore, the ultraviolet lamp used in the nano-photocatalytic air purification equipment has the rationg voltage of 15W, the wavelength of 253.7nm and the light sensitivity more than 400μW/cm2.
4. Pt/TiO_2-SiO_2 composite photocatalysts were tested in dynamic real-time experimentation equipments. Results showed the rate of degradation formaldehyde is almost 15% in the wind tunnel. In the test house, the photocatalysts can degrade formaldehyde almost 0.1ppm per hour.
The TiO_2-SiO_2 composite photocatalysts loaded on foam nickel substrates showed a good degradation activity. The modified composite photocatalysts will be used in the nano-photocatalytic air purification equipment to create more social and economic profits.
引文
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