以Ce(NO3)3?6H2O和Cu(NO3)2?3H2O为改性剂制备Ce–Cu/TiO2空心微球，通过均匀设计与BP神经网络模型优化Ce–Cu/TiO2空心微球的制备工艺参数。用激光粒度分析仪对Ce–Cu/TiO2空心微球的粒度分布进行测试，用SEM和TEM对Ce–Cu/TiO2空心微球的微观形貌进行表征，用比表面积及孔径测定仪对Ce–Cu/TiO2空心微球的孔结构进行测试，采用等温吸放湿法对粒度均匀分布的Ce–Cu/TiO2空心微球的湿性能进行测试，用紫外–可见分光光度计测试其光性能。结果表明，粒度均匀分布的Ce–Cu/TiO2空心微球制备工艺参数为：磁力搅拌速度VMS=910 r/min、溶液B加入溶液A的速度VAB=1.32 mL/min、溶液D加入溶液C的速度VCD=0.86 mL/min、煅烧升温速度VTC=2.47℃/min和煅烧温度TC=485℃，所制空心微球d10=103.74 nm，d50=141.46 nm和d90=188.84 nm，粒径分布区间d90–d10为85.10 nm，空心微球具有良好的光–湿性能，1~6 h对甲醛气体的降解率为21.6%~53.9%，相对湿度32.28%~84.34%的平衡含湿量为0.0364~0.2746 g/g。
Cerous nitrate Ce(NO3)3?6H2O and cupric nitrate Cu(NO3)2?3H2O were used as modifier to make Ce–Cu/TiO2 hollow microspheres. The preparation scheme of Ce–Cu/TiO2 hollow microspheres with uniform particle size distribution was optimized by conducting uniform design and building BP neural network model. Particle size distribution of Ce–Cu/TiO2 hollow microspheres was tested and characterized by laser particle size analyzer (LPSA), the microstructure was characterized by SEM and TEM, the pore structure was tested by brunauer–emmett–teller surface areas analyzer (BET). Humidity performance of Ce–Cu/TiO2 hollow microspheres with uniform particle size distribution was tested by isothermal absorption–desorption, the photocatalysis performance was tested by ultraviolet–visible spectrophotometer (UV–Vis). Finally, optimal technology parameters of Ce–Cu/TiO2 hollow microspheres were obtained. The results showed that the magnetic stirring rate (VMS), dropping rate of solution B added to solution A (VAB), dropping rate of solution D added to solution C (VCD), calcination heating rate (VTC), and calcination temperature (TC) were 910 r/min, 1.32 mL/min, 0.86 mL/min, 2.47℃/min and 485℃, respectively. Besides, for Ce–Cu/TiO2 hollow microspheres with uniform particle size distribution, other sizes were shown as follows: d10 =103.74 nm, d50=141.46 nm and d90 =188.84 nm. Particle size distribution interval of d90–d10 was 85.10 nm. It was also proved that Ce–Cu/TiO2 hollow microspheres with uniform particle size distribution had good photocatalysis and humidity control performance. Specifically, degradation rate of formaldehyde gas was 21.6%~53.9% after 1~6 h, and equilibrium moisture content under the relative humidity of 32.28%~84.34% reached 0.0364~0.2746 g/g accordingly. The above research provided certain theoretical basis and technical support for further systematic research on particle size distribution of Ce–Cu/TiO2 hollow microspheres and photocatalysis–humidity control performance.
[1] Fujishima A, Hondo K. Electrochemical Photolysis of Water at a Semiconductor Electrode [J]. Nature. 1972, 37:238?245.
[2] Jing L Q, Xin B F, Yuan F L, et al. Effects of Surface Oxygen Vacancies on Photophysical and Photochemical Processes of Zn-Doped TiO2 Nanoparticles and Their Relationships [J]. The Journal of Physical Chemistry B. 2006, 110(36):17860?17865.
[3] Zhao H M, Chen Y, Quan X, et al. Preparation of Zn-Doped TiO2 Nanotubes Electrode and Its Application in Pentachlorophenol Photoelectrocatalytic Degradation [J]. Chinese Science Bull. 2007, 52(11): 1456?1461.
[4] Tojo S, Tachikawa T, Fujtsuka M, et al. Iodine-Doped TiO2 Photocatalysts: Correlation Between Band Structure and Mechanism [J]. The Journal of Physical Chemistry C. 2008, 112(38): 14948?14954.
[5] Zhao D, Peng T Y, Liu M, et al. Fabrication, Characterization and Photocatalytic Activity of Gd3+-Doped Titania Nanoparticles with Mesostructure [J]. Microporous and Mesoporous Materials. 2008, 114: 166?174.
[6] Hamal D B, Klabunde K J. Synthesis, Characterization, and Visible Light Activity of New Nanoparticle Photocatalysis Based on Silver, Carbon and Sulfur-Doped TiO2 [J]. Journal of Colloid and Interface Science. 2007, 311: 514?522.
[7] Yu J G, Zhang L J, Bei C. Hydrothermal Preparation and Photocatalytic Activity of Hierarchically Sponge-Like Macro-/Mesoporous Titania [J]. The Journal of Physical Chemistry C. 2007, 111(28):10582?10589.
[8] Syoufian A, Nakashima K. Degradation of Methylene Blue in Aqueous Dispersion of Hollow Titania Photocatalyst: Optimization of Reaction by Peroxydisulfate Electron Scavenger [J]. Journal of Colloid and Interface Science. 2007, 313(1): 213?218.
[9] 刘阳龙, 郑玉婴, 尚鹏博. 铕掺杂的TiO2的制备及光催化性能[J]. 无机材料学报. 2015, 30(7): 699?705.
Liu Y L, Zheng Y Y, Shang P B. Preparation, Characterization and Photocatalytic Property of Eu-Doped TiO2 Hollow Microspheres [J]. Journal of Inorganic Material. 2015, 30(7): 699?705.
[10] 尚鹏博, 郑玉婴, 冀峰, 等. 锌离子掺杂的二氧化钛介孔空心微球的制备及光催化性能 [J]. 无机化学学报. 2014, 30(10): 2323?2331.
Shang P B, Zheng Y Y, Yi F, et al. Zinc Doped TiO2 Mesoporous Hollow Miscrospheres: Preparation and Photocatalytic Activity [J]. Chinese Journal of Inorgainc Chemistry. 2014, 30(10): 2323?2331.
[11] 尚建丽，宗志芳. 基于湿效应Ce-La/TiO2空心微球制备及光-湿效应 [J]. 浙江大学学报(工学版), 2017, 51(2): 304?311
Shang J L, Zong Z F. Preparation of Ce-La/TiO2 Hollow Microspheres and Its photocatalysis and humidity control performance based on humidity absorption and desorption [J]. Journal of Zhejiang University (Engineering Science), 2017, 51(2): 304?311
[12] 尚建丽，张浩，熊磊，等. 基于均匀设计优化制备癸酸-棕榈酸/SiO2复合相变材料 [J]. 材料工程, 2015, 43(9): 94?102
Shang J L, Zhang H, Xiong L, et al. Optimized Preparation of Decanoic-palmitic Acid/SiO2 Composite Phase Change Metarials Based on Uniform Design [J]. Journal of Materials Engineering, 2015, 43(9): 94?102
[13] 张浩. 基于RBF网络优化制备均匀粒度分布的微米级SiO2基相变调湿复合材料 [J]. 材料工程, 2017, 45(8): 24?29
Zhang H. Optimizing Preparation of Micron SiO2-based Phase Change and Humidity Controlling Composites with Uniform Particle Size Distribution Based on RBF Neural Network [J]. Journal of Materials Engineering, 2017, 45(8): 24?29
[14] 张浩. 基于光催化性能的Cu-Ce/TiO2湿性能 [J].材料工程, 2018, 46(1): 114?118
Zhang H. Cu-Ce/TiO2 Moisture Performance Based on Photocatalytic Performance. Journal of Materials Engineering, 2018, 46(1): 114?118
[15] 张浩，黄新杰，宗志芳，等. 基于吸附性能的生物质基多孔活性炭制备方案的响应面法优化 [J]. 材料工程, 2017, 45(6): 67?72
Zhang H, Huang X J, Zong Z F, et al. Optimizatiom of Preparation Program for Biomass Based Porous Active Carbon by Response Surface Methodology Based on Adsorptive Property [J]. Journal of Materials Engineering, 2017, 45(6): 67?72
