二氧化钛基空心球的制备及光催化性能
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摘要
开发高比表、高活性、可见光响应的高效光催化材料是光催化领域的研究热点,人们对TiO_2光催化剂的掺杂、贵金属沉积、负载等改性方法进行了广泛研究。多孔空心球材料、核壳结构材料和大孔材料具有稳定性好、密度低、比表面积大等特性,在催化反应、光电子器件、环境保护等领域应用前景广阔。
本论文结合水热、溶胶-凝胶、模板等合成技术,合成了以TiO_2为主的一系列半导体金属氧化物的多孔空心球、核壳和大孔结构光催化剂。研究了不同催化剂的的形貌、结构、组成及光催化性能,采用扫描电镜、透射电镜、X射线衍射、红外、热重-同步热差和紫外-可见吸收光谱等技术手段进行了表征。在紫外光照射条件下以亚甲基蓝溶液的光催化降解为探针反应,考察了产品的光催化活性。
主要结果如下:
1.设计了一种小巧智能型悬浮式光催化反应装置,具有光照强度均匀、光利用率高、传质速率快、反应时间自动控制、取样快捷方便和安全可靠等优点,能够较为科学准确地研究光催化剂的活性和光催化反应的影响因素。
2.用葡萄糖为原料,水热合成了富含活性官能团的炭微球模板,利用沉积-表面反应法制备了锐钛矿型TiO_2、WO_3和W掺杂TiO_2空心球,考察了W掺杂量和煅烧温度对W-TiO_2空心球的光催化活性的影响;溶胶-凝胶法制备了TiO_2多孔光催化剂,研究了炭微球用量对其光催化活性的影响。
3.用葡萄糖和AgNO_3为原料,水热合成了富含活性官能团的Ag@C核-壳微球模板,沉积-表面反应法制备了Ag/TiO_2、Ag/AgCl/TiO_2和Ag/WO_3空心球催化剂,溶胶-凝胶法制备了Ag/NiO、Ag/SnO_2和Ag/WO_3具有大孔结构的材料。
4.利用分散聚合法制备出单分散PS微球,用浓硫酸改性得到磺化PS微球。以其为模板,在水热条件下合成了Fe-TiO_2-PS、Fe-TiO_2、α-FeO(OH)-PS和α-Fe_2O_3空心球催化剂,研究了Fe掺杂量对Fe-TiO_2空心球光催化活性的影响;结合模板法和溶胶凝胶法,制备了大孔TiO_2光催化剂,考察了煅烧温度其光催化活性的影响。
5.用溶胶-凝胶法制备了SiO_2粒子和纳米Ag粒子修饰的Ag/SiO_2复合粒子,以葡萄糖为炭源通过水热反应对Ag/SiO_2进行炭包覆,得到表面富含活性官能团的Ag/SiO_2@C核壳结构粒子,以其为模板制备出了Ag/SiO_2@TiO_2核壳结构催化剂,并对其光催化活性进行了研究。
Nowadays,the creation of effective photocatalytic materials with large specific surface area,high catalytic activity,visible-light-respond,become a hot topic in photo-catalytic research.The modifications of TiO_2 photocatalyst is studied widely,such as metallic or non-metallic doping,noble metal depositing as well as supported TiO_2.Porous hollow sphere materials,core-shell structure materials and macroporous materials with good stability,low density,large specific surface area and other characteristics,have promising applications in the catalytic reaction,optoelectronic devices,and environmental protection.
In this paper,combined hydrothermal with so-gel and template methods,a series of TiO_2-based photocatalysts were successfully synthesized,including porous hollow spheres, core-shell structure and macroporous materials.The structures,morphologies and compositions of the samples were characterized by SEM,TEM,X-ray diffraction, TGA-SDTA,FT-IR spectrometer and UV-Vis spectrophotometer.The photo-catalytic activities of the products were evaluated via the photo-catalytic degradation of methyl blue under UV-light irradiation.
The main results are summarized as follows:
1.A smart and compact floating-type photocatalytic reactor was designed,with the advantages of uniform light intensity,high light utilization and high mass transfer rate,reaction time automatic controlling,sampling convenience,safety and reliability.It can be used to investigate photo-catalyst activities and photocatalytic reaction factors scientifically and accurately.
2.Carbonaceous micro-sphere templates with rich oxygen-containing groups on their surface were synthesized under hydrothermal condition using glucose as starting materials. TiO_2,WO_3 and W doped TiO_2 porous hollow spheres were prepared through template-deposition-surface reaction method.The influence of W contents and calcination temperatures on the catalytic activites of W doped TiO_2 porous hollow spheres was systematically examined.TiO_2 macroporous catalyst was prepared by so-gel method,and the relationship between its photocatalytic activity and the amount of carbon microspheres used was also investigated.
3.Ag@C core-shell micro-spheres with rich oxygen-containing groups on their surface were synthesized under hydrothermal condition using glucose and AgNO_3 as starting materials.With Ag@C as templates,deposition-surface reaction was used to prepare Ag/TiO_2, Ag/AgCl/TiO_2 and Ag/WO_3 porous hollow spheres,while so-gel method was used to prepare Ag/NiO,Ag/SnO_2 and Ag/WO_3 macroporous materials.
4.Monodisperse polystyrene(PS) microspheres were synthesized through dispersion polymerization method,and their surface was modified by concentrated sulfuric acid.With the sulfonated PS microspheres as templates,Fe-TiO_2-PS,Fe-TiO_2,α-FeO(OH)-PS andα-Fe_2O_3 porous hollow microspheres were successfully prepared under hydrothermal condition.The influence of Fe-doped amount on the photocatalytic activity of Fe-TiO_2 porous hollow microspheres was also examined.
5.Monodisperse SiO_2 microspheres were prepared by Stober method,then Ag nanoparticles were deposited on their surface by Ag~+ reduction in aqueous solution, carbonaceous materials was sequentially encapsulated on Ag/SiO_2 microspheres with glucose as the carbon precursor during hydrothermal process to form Ag/SiO_2@C microspheres.With Ag/SiO_2@C microsphere as templates,Ag/SiO_2@TiO_2 composites were successfully fabricated with template-deposition-surface reaction method.The photo-catalytic activity of the obtained Ag/SiO_2@TiO_2 was investigated.
本论文结合水热、溶胶-凝胶、模板等合成技术,合成了以TiO_2为主的一系列半导体金属氧化物的多孔空心球、核壳和大孔结构光催化剂。研究了不同催化剂的的形貌、结构、组成及光催化性能,采用扫描电镜、透射电镜、X射线衍射、红外、热重-同步热差和紫外-可见吸收光谱等技术手段进行了表征。在紫外光照射条件下以亚甲基蓝溶液的光催化降解为探针反应,考察了产品的光催化活性。
主要结果如下:
1.设计了一种小巧智能型悬浮式光催化反应装置,具有光照强度均匀、光利用率高、传质速率快、反应时间自动控制、取样快捷方便和安全可靠等优点,能够较为科学准确地研究光催化剂的活性和光催化反应的影响因素。
2.用葡萄糖为原料,水热合成了富含活性官能团的炭微球模板,利用沉积-表面反应法制备了锐钛矿型TiO_2、WO_3和W掺杂TiO_2空心球,考察了W掺杂量和煅烧温度对W-TiO_2空心球的光催化活性的影响;溶胶-凝胶法制备了TiO_2多孔光催化剂,研究了炭微球用量对其光催化活性的影响。
3.用葡萄糖和AgNO_3为原料,水热合成了富含活性官能团的Ag@C核-壳微球模板,沉积-表面反应法制备了Ag/TiO_2、Ag/AgCl/TiO_2和Ag/WO_3空心球催化剂,溶胶-凝胶法制备了Ag/NiO、Ag/SnO_2和Ag/WO_3具有大孔结构的材料。
4.利用分散聚合法制备出单分散PS微球,用浓硫酸改性得到磺化PS微球。以其为模板,在水热条件下合成了Fe-TiO_2-PS、Fe-TiO_2、α-FeO(OH)-PS和α-Fe_2O_3空心球催化剂,研究了Fe掺杂量对Fe-TiO_2空心球光催化活性的影响;结合模板法和溶胶凝胶法,制备了大孔TiO_2光催化剂,考察了煅烧温度其光催化活性的影响。
5.用溶胶-凝胶法制备了SiO_2粒子和纳米Ag粒子修饰的Ag/SiO_2复合粒子,以葡萄糖为炭源通过水热反应对Ag/SiO_2进行炭包覆,得到表面富含活性官能团的Ag/SiO_2@C核壳结构粒子,以其为模板制备出了Ag/SiO_2@TiO_2核壳结构催化剂,并对其光催化活性进行了研究。
Nowadays,the creation of effective photocatalytic materials with large specific surface area,high catalytic activity,visible-light-respond,become a hot topic in photo-catalytic research.The modifications of TiO_2 photocatalyst is studied widely,such as metallic or non-metallic doping,noble metal depositing as well as supported TiO_2.Porous hollow sphere materials,core-shell structure materials and macroporous materials with good stability,low density,large specific surface area and other characteristics,have promising applications in the catalytic reaction,optoelectronic devices,and environmental protection.
In this paper,combined hydrothermal with so-gel and template methods,a series of TiO_2-based photocatalysts were successfully synthesized,including porous hollow spheres, core-shell structure and macroporous materials.The structures,morphologies and compositions of the samples were characterized by SEM,TEM,X-ray diffraction, TGA-SDTA,FT-IR spectrometer and UV-Vis spectrophotometer.The photo-catalytic activities of the products were evaluated via the photo-catalytic degradation of methyl blue under UV-light irradiation.
The main results are summarized as follows:
1.A smart and compact floating-type photocatalytic reactor was designed,with the advantages of uniform light intensity,high light utilization and high mass transfer rate,reaction time automatic controlling,sampling convenience,safety and reliability.It can be used to investigate photo-catalyst activities and photocatalytic reaction factors scientifically and accurately.
2.Carbonaceous micro-sphere templates with rich oxygen-containing groups on their surface were synthesized under hydrothermal condition using glucose as starting materials. TiO_2,WO_3 and W doped TiO_2 porous hollow spheres were prepared through template-deposition-surface reaction method.The influence of W contents and calcination temperatures on the catalytic activites of W doped TiO_2 porous hollow spheres was systematically examined.TiO_2 macroporous catalyst was prepared by so-gel method,and the relationship between its photocatalytic activity and the amount of carbon microspheres used was also investigated.
3.Ag@C core-shell micro-spheres with rich oxygen-containing groups on their surface were synthesized under hydrothermal condition using glucose and AgNO_3 as starting materials.With Ag@C as templates,deposition-surface reaction was used to prepare Ag/TiO_2, Ag/AgCl/TiO_2 and Ag/WO_3 porous hollow spheres,while so-gel method was used to prepare Ag/NiO,Ag/SnO_2 and Ag/WO_3 macroporous materials.
4.Monodisperse polystyrene(PS) microspheres were synthesized through dispersion polymerization method,and their surface was modified by concentrated sulfuric acid.With the sulfonated PS microspheres as templates,Fe-TiO_2-PS,Fe-TiO_2,α-FeO(OH)-PS andα-Fe_2O_3 porous hollow microspheres were successfully prepared under hydrothermal condition.The influence of Fe-doped amount on the photocatalytic activity of Fe-TiO_2 porous hollow microspheres was also examined.
5.Monodisperse SiO_2 microspheres were prepared by Stober method,then Ag nanoparticles were deposited on their surface by Ag~+ reduction in aqueous solution, carbonaceous materials was sequentially encapsulated on Ag/SiO_2 microspheres with glucose as the carbon precursor during hydrothermal process to form Ag/SiO_2@C microspheres.With Ag/SiO_2@C microsphere as templates,Ag/SiO_2@TiO_2 composites were successfully fabricated with template-deposition-surface reaction method.The photo-catalytic activity of the obtained Ag/SiO_2@TiO_2 was investigated.
引文
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