高活性纳米TiO_2光催化剂的制备、表征及应用
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摘要
实验分别以Ti(SO_4)_2溶液和加入H_2SO_4的Ti(SO_4)_2溶液作为原料采用水解法制备了系列纳米TiO_2光催化剂，考察了Ti(SO_4)_2溶液浓度、氨水浓度、水解时间、焙烧温度等因素对产品的粒径及晶型的影响，用HRTEM、TEM、BET、FS、XRD及激光粒子分布和孔分布等检测手段对产品进行了表征。结果表明：本实验制备的系列纳米TiO_2光催化剂的一次粒径范围是7～25nm，以团聚体形式存在，二次粒径范围是0.1～2μm，焙烧温度在300～700℃范围内，粒子的晶型为锐钛矿型。
实验以降解二甲酚橙溶液、甲基橙溶液为探针反应，对制备的系列纳米TiO_2光催化剂的催化活能进行了研究，并考察了降解过程中染料浓度、溶液pH、降解时间等因素对降解效率的影响。以加入H_2SO_4的Ti(SO_4)_2溶液为原料制得的经300℃焙烧的纳米TiO_2光催化剂，在紫外光(365nm)和太阳光的照射下，对二甲酚橙溶液有较好的降解效果；以Ti(SO_4)_2溶液为原料制得的经300～700℃焙烧的纳米TiO_2光催化剂对甲基橙溶液均有降解能力，经400℃、600℃焙烧的催化剂降解能力较强。将经400℃焙烧的催化剂用于降解甲基橙溶液，分别在紫外光(254nm)照射20min，在太阳光照射90min，对甲基橙溶液的脱色率均达到为100％；用于降解实际花系染料废水，分别在紫外光(254nm)照射40min，在太阳光照射210min，废水COD的去除率达到92.9％和91.2％。
本实验利用紫外—可见分光光度计和高效液相色谱—质谱联用仪对甲基橙溶液的降解过程进行分析。还考察了催化剂重新使用的情况，分析了催化剂的荧光强度和催化剂的催化性能的关系，建立了甲基橙溶液在太阳光下降解反应的一级动力学方程。
A series of nanometer TiO_2 photocatalysts were prepared from the solution of Ti(SO_4)_2 and Ti(SO_4)_2 with H_2SO_4 by hydrolyzation respectively. The effects of the concentration of Ti(SO_4)_2 and NH_3·H_2O solution, the time of hydrolyzation, the calcination temperature on the crystallographic form and the size of nano TiO_2 photocatalyst were studied. Nanometer TiO_2 was characterized by HRTEM, TEM, FS, XRD and determination of N_2 adsorption analysis and pore distribution. The particles existed in the form of aggregate with the size of 0.1-2μm which was made up of uniform original grains with the size of 7-25 nm. The products were anatase when the calcination temperature was between 300-700℃.The photocatalytic activity of the series nanometer TiO_2 photocatalyst was evaluated by the degradation of Xylenol Orange and Methyl Orange used as probe reaction respectively. The factors such as the initial concentration and pH value of the perylene dye solution, the irradiation time affecting photocatalytic oxidation were discussed in detail. The nanometer TiO_2 photocatalyst prepared by the solution of Ti(SO_4)_2 with H_2SO_4 and calcinated at 300℃exhibited good photocatalytic activity to degrade Xylenol Orange. The nanometer TiO_2 photocatalyst prepared with the solution of Ti(SO_4)_2 and calcinated at 300-700℃demonstrated good photocatalytic activity to degrade Methyl Orange. The catalyst calcinated at 400℃and 600℃respectively had better photocatalytic activity. When the photocatalyst calcinated at 400℃was used to degrade Methyl Orange, the decoloring rate reached 100% under UV(254nm) radiation for 20 min and sunlight for 90min respectively. When it was used to degrade the perylene dye solution, the removal rate of COD was up to 92.9% under UV (254nm) radiation for 40 min and 91.2% under sunlight for 210min respectively.
The photocatalytic process of the degradation of Xylenol Orange solution was examined by ultraviolet-visible photometer and HPLC-MS. The regeneration of the catalyst and the relationship of the fluorescence intensity of the TiO_2 with the photocatalytic activity were studied as well. The first order kinetic equation to describe the procedure of photocatalytic degradation of Methyl Orange solution under the sunlight was set up.
实验以降解二甲酚橙溶液、甲基橙溶液为探针反应，对制备的系列纳米TiO_2光催化剂的催化活能进行了研究，并考察了降解过程中染料浓度、溶液pH、降解时间等因素对降解效率的影响。以加入H_2SO_4的Ti(SO_4)_2溶液为原料制得的经300℃焙烧的纳米TiO_2光催化剂，在紫外光(365nm)和太阳光的照射下，对二甲酚橙溶液有较好的降解效果；以Ti(SO_4)_2溶液为原料制得的经300～700℃焙烧的纳米TiO_2光催化剂对甲基橙溶液均有降解能力，经400℃、600℃焙烧的催化剂降解能力较强。将经400℃焙烧的催化剂用于降解甲基橙溶液，分别在紫外光(254nm)照射20min，在太阳光照射90min，对甲基橙溶液的脱色率均达到为100％；用于降解实际花系染料废水，分别在紫外光(254nm)照射40min，在太阳光照射210min，废水COD的去除率达到92.9％和91.2％。
本实验利用紫外—可见分光光度计和高效液相色谱—质谱联用仪对甲基橙溶液的降解过程进行分析。还考察了催化剂重新使用的情况，分析了催化剂的荧光强度和催化剂的催化性能的关系，建立了甲基橙溶液在太阳光下降解反应的一级动力学方程。
A series of nanometer TiO_2 photocatalysts were prepared from the solution of Ti(SO_4)_2 and Ti(SO_4)_2 with H_2SO_4 by hydrolyzation respectively. The effects of the concentration of Ti(SO_4)_2 and NH_3·H_2O solution, the time of hydrolyzation, the calcination temperature on the crystallographic form and the size of nano TiO_2 photocatalyst were studied. Nanometer TiO_2 was characterized by HRTEM, TEM, FS, XRD and determination of N_2 adsorption analysis and pore distribution. The particles existed in the form of aggregate with the size of 0.1-2μm which was made up of uniform original grains with the size of 7-25 nm. The products were anatase when the calcination temperature was between 300-700℃.The photocatalytic activity of the series nanometer TiO_2 photocatalyst was evaluated by the degradation of Xylenol Orange and Methyl Orange used as probe reaction respectively. The factors such as the initial concentration and pH value of the perylene dye solution, the irradiation time affecting photocatalytic oxidation were discussed in detail. The nanometer TiO_2 photocatalyst prepared by the solution of Ti(SO_4)_2 with H_2SO_4 and calcinated at 300℃exhibited good photocatalytic activity to degrade Xylenol Orange. The nanometer TiO_2 photocatalyst prepared with the solution of Ti(SO_4)_2 and calcinated at 300-700℃demonstrated good photocatalytic activity to degrade Methyl Orange. The catalyst calcinated at 400℃and 600℃respectively had better photocatalytic activity. When the photocatalyst calcinated at 400℃was used to degrade Methyl Orange, the decoloring rate reached 100% under UV(254nm) radiation for 20 min and sunlight for 90min respectively. When it was used to degrade the perylene dye solution, the removal rate of COD was up to 92.9% under UV (254nm) radiation for 40 min and 91.2% under sunlight for 210min respectively.
The photocatalytic process of the degradation of Xylenol Orange solution was examined by ultraviolet-visible photometer and HPLC-MS. The regeneration of the catalyst and the relationship of the fluorescence intensity of the TiO_2 with the photocatalytic activity were studied as well. The first order kinetic equation to describe the procedure of photocatalytic degradation of Methyl Orange solution under the sunlight was set up.
引文
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