优化制备粒度均匀分布的Ce-Cu/TiO_2空心微球及其光-湿性能
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摘要
以Ce(NO_3)_3×6H_2O和Cu(NO_3)_2×3H_2O为改性剂制备Ce-Cu/TiO_2空心微球,通过均匀设计与BP神经网络模型优化Ce-Cu/TiO_2空心微球的制备工艺参数。用激光粒度分析仪对Ce-Cu/TiO_2空心微球的粒度分布进行测试,用SEM和TEM对Ce-Cu/TiO_2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/TiO_2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/TiO_2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/TiO_2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=0.86m L/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=103.74nm,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?6 H2 O and cupric nitrate Cu(NO3)2?3 H2 O 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.
Cerous nitrate Ce(NO3)3?6 H2 O and cupric nitrate Cu(NO3)2?3 H2 O 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.
引文
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[15]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.
[16]张浩.基于RBF网络优化制备粒度均匀分布的微米级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.
[17]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[J].Journal of Materials Engineering,2018,46(1):114-118.
[18]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.
[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].Journal of Physical Chemistry B,2006,110(36):17860-17865.
[3]Chen L,Huang R,Yin S F,et al.Flower-like Bi2O2CO3:facile synthesis and their photocatalytic application in treatment of dye-containing wastewater[J].Chemical Engineering Journal,2012,193/194:123-130.
[4]Tojo S,Tachikawa T,Fujtsuka M,et al.Iodine-doped TiO2photocatalysts:correlation between band structure and mechanism[J].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]Chen L,Huang R,Xiong M,et al.Room-temperature synthesis of flower-like BiOX(X=Cl,Br,I)hierarchical structures and their visible-light photocatalytic activity[J].Inorganic Chemistry,2013,52(19):11118-11125.
[7]Yu J G,Zhang L J,Bei C.Hydrothermal preparation and photocatalytic activity of hierarchically sponge-like macro-/mesoporous titania[J].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,Ji 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]张浩,曹现雷,刘秀玉,等.基于RBF网络优化制备粒度均匀分布的Cu-Ce/TiO2[J].过程工程学报,2016,16(6):1064-1068.Zhang H,Cao X L,Liu X Y,et al.Optimizing preparation of Cu-Ce/TiO2 with uniform particle size distribution based on RBFneural network[J].The Chinese Journal of Process Engineering,2016,16(6):1064-1068.
[13]张浩,刘守城,胡义,等.基于正交设计与BP神经网络优化制备Cu-Ce/TiO2的预测模型[J].稀土,2015,36(2):72-77.Zhang H,Liu S C,Hu Y,et al.Predicition model for optimizing preparation of Cu-Ce/TiO2 based on orthogonal design and backpropagation neural network[J].Chinese Rare Earths,2015,36(2):72-77.
[14]张浩,何兆芳,黄新杰.Cu-Ce/TiO2的制备及其在室内甲醛气体中的光催化性能[J].稀土,2014,35(6):72-78.Zhang H,He Z F,Huang X J.Preparation and indoor formaldehyde photocatalytic property of Cu-Ce/TiO2[J].Chinese Rare Earths,2014,35(6):72-78.
[15]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.
[16]张浩.基于RBF网络优化制备粒度均匀分布的微米级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.
[17]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[J].Journal of Materials Engineering,2018,46(1):114-118.
[18]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.
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