Effect of F, V and Mn co-doping on the catalytic performance of TiO2-pillared bentonite in the photocatalytic denitration
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摘要: 采用溶胶-凝胶法制备氟钒锰共掺改性的TiO2柱撑膨润土，使用XRD、氮吸附、UV-vis光谱和SEM等手段对其进行了表征测试，并对其室温下的可见光催化脱硝性能进行了评价研究。结果表明，对于NO质量浓度为661 μg/m3的气体，F-V-Mn共掺TiO2柱撑膨润土的光催化脱除效率近似达到100%，而NO质量浓度提升至1657 μg/m3时，光催化效率为81.9%，与未柱撑的F-V-Mn共掺TiO2相比提高了33.8%。F-V-Mn共掺TiO2柱撑膨润土上光催化脱反应速率常数最大，是V-Mn共掺TiO2柱撑膨润土的2倍，且前者的抗水和抗SO2中毒能力也更强。TiO2柱撑不仅保留了膨润土的片状晶体结构，而且使膨润土层间距由0.667 nm增大至0.710 nm，吸附能力增强；同时，掺杂元素能抑制TiO2金红石相生长，降低TiO2禁带宽度，提高可见光响应，延长使用寿命，拓宽应用范围。Abstract: F, V and Mn co-doped TiO2-pillared bentonite was prepared by the sol-gel method and characterized by XRD, nitrogen sorption, UV-vis spectroscopy, SEM, etc.; its performance in the photocatalytic denitration of NO was investigated under visible light irradiation at room temperature. The results indicate that the photocatalytic denitration efficiency of F-V-Mn co-doped TiO2-pillared bentonite for NO at a concentration of 661 μg/m3 is approximately 100%; when the concentration of NO increases to 1657 μg/m3, the photocatalytic efficiency decreases to 81.9%, which is however 33.8% higher than that over the unpillared F-V-Mn co-doped TiO2. The reaction rate constant over the F-V-Mn co-doped TiO2-pillared bentonite is twice as high as that over the V-Mn co-doped TiO2 pillared bentonite; moreover, the F-V-Mn co-doped TiO2-pillared bentonite also displays improved resistance against water and SO2 poisoning. TiO2 pillars can not only retain the flaky crystal structure of bentonite, but also increase the distance between bentonite layers from 0.667 to 0.710 nm and enhance the adsorption capacity. Meanwhile, the doping elements can inhibit the growth of TiO2 rutile and reduce the band gap of TiO2, which is effective in improving the response to visible light, prolonging the service life, and broadening the application range of TiO2 for the photocatalytic denitration.
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Key words:
- Co-doped TiO2 /
- pillared bentonite /
- NO /
- photocatalysis /
- denitration
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图 2 TiO2的XRD谱图
Figure 2 XRD patterns of TiO2 modified with different elements
A and R represent anatase and rutile phases, respectively
图 3 紫外-可见漫反射光谱谱图
Figure 3 UV-visible diffuse reflection spectra of TiO2 modified with different elements
图 4 样品N2吸-脱附等温线及孔径分布
Figure 4 Nitrogen adsorption-desorption isotherms (a) and pore size distribution (b) of F, V and Mn doped TiO2-pillared bentonite
图 6 膨润土与F-V-Mn/TiO2/PILC的SEM照片
Figure 6 SEM images of bentonite (a), F-V-Mn/TiO2/PILC (b) and F-V-Mn/TiO2/PILC, magnified (c)
图 7 掺杂元素对TiO2可见光催化性能影响
Figure 7 Effect of doping element on the photocatalytic denitration performance of TiO2 at room temperature under visible light in the simulated flue gas with a NO concentration of 696 μg/m3
图 8 不同改性催化剂光催化NO效率
Figure 8 Photocatalytic denitration efficiency of different modified catalysts
表 1 TiO2晶粒粒径及晶型比例
Table 1 Grain size and anatase fraction of TiO2 modified with different elements
Sample Crystal Grain size /nm A ratio/% TiO2 anatase + rutile 29.8 80.8 V-Mn/TiO2 anatase + rutile 15.9 93.2 F-V-Mn/TiO2 anatase 12.7 100.0 
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表 2 样品表面结构数据
Table 2 Textural properties of F, V and Mn doped TiO2-pillared bentonite
Sample Surface area S/(m2·g-1) Average aperture r/nm Adsorption capacity vm/(cm3·g-1 STP) Pore volume vp/(cm3·g-1) F-V-Mn/TiO2/PILC 85.6 3.7 19.7 0.080 V-Mn/TiO2/PILC 26.1 3.9 6.0 0.025 TiO2/PILC 3.4 9.6 0.8 0.008 S-specific surface area; r-average aperture; vm-adsorption capacity; vp-pore volume
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表 3 不同条件下F-V-Mn/TiO2/PILC光催化NO效果
Table 3 Effect of the initial NO concentration and light source power on the photocatalytic denitration activity of F-V-Mn/TiO2/PILC
NO concentration /(μg·m-3) Denitration efficiency /% Light source power /W Denitration efficiency /% 661 99.2 65 69.5 1657 81.9 89 81.9 2267 57.9 115 83.4
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表 4 光催化反应速率
Table 4 Kinetic analysis for the photocatalytic reaction
Sample CNO/(μg·m-3) k/min-1 F-V-Mn/TiO2/PILC 661 0.0280 F-V-Mn/TiO2/PILC 1657 0.0050 F-V-Mn/TiO2/PILC 2267 0.0032 V-Mn/TiO2/PILC 1657 0.0024
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表 5 TiO2柱撑膨润土光催化脱硝的连续使用次数
Table 5 Photocatalytic denitration efficiency of TiO2 pillared bentonite after repetitive utilization
Times Denitration efficiency /% F-V-Mn/TiO2/PILC V-Mn/TiO2/PILC 1 81.9 62.0 2 78.8 56.8 3 75.5 53.4 4 70.1 51.6 5 61.8 46.4 6 60.1 7 55.1 8 45.1
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