核—壳结构的TiO_2/ZnO纳米材料的制备及性能研究
摘要
TiO2是一种重要的无机功能材料,因其具有湿敏、气敏、光电转换、介电效应、光致变色及优越的光催化等性能,使其在传感器、介电材料、光电材料、自洁材料和催化剂及载体等领域具有广泛的应用前景。
TiO2纳米管是TiO2的又一种存在形式,由于纳米管具有大的比表面积,因而具有较高的吸附能力,可望提高TiO2的光催化性能,特别是如果能在管中装入更小的无机、有机、金属或磁性纳米粒子组装成复合纳米材料,将会大大改善TiO2的光电、电磁及催化性能。
纳米TiO2存在太阳能利用率低,光生电子和光生空穴极易复合导致的光催化效率不高这两个主要缺点,极大地限制了TiO2的实际应用。氧化锌为直接带隙半导体,二氧化钛为间接带隙半导体,两者的禁带宽度非常接近,导带底和价带顶能量相差不多,将两者耦合能对其光学性能产生重要影响。
有研究表明氧化锌的引入可以抑制二氧化钛晶型转变过程和粒子生长,使ZnO-TiO2复合半导体在紫外光、自然光、太阳光照射下的光催化效率都较单一ZnO和TiO2高,且吸收光谱发生红移。
本文主要研究了ZnO纳米棒、TiO2纳米管、TiO2／ZnO纳米复合材料的制备及相关性能,为上述纳米材料更好和更为广泛的应用提供了理论依据和实验基础。具体内容如下：
(1)以不同原料和反应条件制得不同形貌、具有六角纤锌矿单晶结构的ZnO纳米棒,且这类ZnO纳米棒分布均匀、无明显团聚现象。
讨论了原料组成、反应温度、反应时间、醇水比、表面活性剂等因素对ZnO微晶形成的影响,并初步分析了其形成机理。以0.04M的Zn(NO3)·6H20和0.05M的(NH4)2CO3,在以SDS为表面活性剂辅助下,于体积比2：1的醇／水体系中200℃水热反应10小时制得的ZnO微晶形貌最佳,其平均直径约59nm,长径比达40。采用XRD分析确定所制得的ZnO微晶具有六角纤锌矿结构,尺寸小晶型良好,且XRD数据与TEM结果一致。
(2)采用电化学阳极氧化法,在F-存在下制得形貌规整、有序、排列紧密的中空Ti02纳米管。
通过调整制备工艺条件,可知TiO2纳米管的制备受阳极氧化电压、时间、反应液pH值影响。经实验优化得在阳极氧化电压60V、反应液pH值为6、反应9小时的条件下制得的TiO2纳米管的形貌最好。由SEM结果分析知所制得TiO2纳米管管径约100nm,具有高长径比。由XRD分析确定所得TiO2纳米管的晶型良好,且与SEM结果一致。
(3)采用二步法成功地制备了形貌规整、清晰的核-壳结构的TiO2／ZnO纳米复合材料,由EDS分析确定其元素组成为钛、锌、氧。
实验证明表面活性剂、锌含量对TiO2／ZnO纳米复合材料的形貌具有较大影响。表面活性剂影响纳米复合材料中氧化锌的尺寸,可能是由表面活性剂的极性导致而成,采用SDS做表面活性剂得到的尺寸比CTAB小一半；锌含量对复合纳米材料表面形貌影响较大,锌含量在0.0002M时制得的TiO2／ZnO纳米复合材料形貌最佳,过多的锌会使钛管被堵塞而见不到孔洞状。
TiO2／ZnO纳米复合材料的形成是在TiO2纳米管形成的基础上异相成核,最终形成TiO2／ZnO纳米复合材料。
(4)以甲基橙为目标降解物,自然光为光源,研究TiO2／ZnO纳米光催化剂的光催化活性,结果表明,TiO2／ZnO复合光催化剂能提高对太阳光的利用率,发现在降解液pH值为3,太阳光催化降解5小时,催化剂的降解效果最好,达到90%以上。
TiO2 is an important inorganic functional materials.Because of its humidity, gas, photoelectric conversion, dielectric effects, photochromic and excellent photocatalytic performance. TiO2 has a wide range of application in many fields such as sensor, dielectric materials, optical materials, self-cleaning materials, catalysts and carriers and so on.
TiO2 nanotubes are another form of TiO2 materials. As nanotubes with a large surface area and has a high adsorption capacity, is expected to enhance the photocatalytic properties of TiO2, especially if a smaller inorganic, organic, metallic or magnetic nanoparticles assembled into TiO2 nanotubes, to assemble composite nanomaterials. It will greatly improve the photovoltaic, electromagnetic and catalytic properties of TiO2.
Titanium dioxide exist two main shortcomings that is low solar energy utilization, photo-electronic and photo-generated hole can easily composite. The two main shortcomings greatly limits the practical application of TiO2 due to its low photocatalytic efficiency. Zinc oxide is a direct band-gap semiconductors, titanium dioxide is the indirect band-gap semiconductors. The band gap between the two materials is very close. Energy from the end of the conduction band to the top of valence band is very similar. To couple the two can have a major impact on their optical properties.
Studies have shown that the introduction of zinc oxide can inhibit the process of crystalline transformation of titanium dioxide and particle growth. As a result ZnO-TiO2 semiconductor showed higher photocatalysis efficiency compared with single ZnO and TiO2 under ultraviolet, natural light and sunlight. What's more the absorption spectrum red shift occurs.
This paper mainly studies the preparation and related properties of ZnO nanorods, TiO2 nanotubes, TiO2/ZnO nano-composites. In this paper we provide theoretical basis and experimental foundation for the nano-materials above-mentioned to expand more extensive applications. Details are as follows:
(1) ZnO nanorods with different morphologies are obtained with different raw materials and reaction conditions. These ZnO nanorods have hexagonal wurtzite crystal structure, dispersed uniform and obvious agglomeration unobserved.
Discussed the effect of raw materials composition, reaction temperature, reaction time, alcohol-water ratio, surfactant on the formation of ZnO. Preliminary analyze the formation mechanism of ZnO. ZnO crystallite obtained the best morphology With 0.04M of Zn(NO3)·6H2O, and 0.05M of (NH4) 2CO3, used SDS as assisted surfactant, at 2:1 volume ratio of alcohol/water system, at 200℃hydrothermal reaction 10 hours. The ZnO nanorods with an average diameter of about 59nm and aspect ratio up to 40. We make use of XRD to identify obtained ZnO crystallite with a hexagonal wurtzite structure, small size, well crystalline, and the results are in accordance with TEM.
(2)Electrochemical anodic oxidation method is adopted. In the presence of F-, TiO2 nanotubes with orderly, tightly arranged hollow tubes are obtained.
By adjusting the process of preparation conditions, we can see the TiO2 nanotubes are influenced by anodization voltage, reaction time, pH value. We optimized The technology on the preparation of TiO2 nanotubes. We obtained the best anode voltage of 60V, pH value of 6, and reaction time of 9 hours. The results from SEM analysis we observed the average diameter of TiO2 nanotubes are about 100nm with a high aspect ratio. Confirmed by XRD analysis we identified the crystalline structure of TiO2 nanotubes.They have well crystalline structure and the results are consistent with the SEM.
(3) Using a two-step method successfully prepared TiO2/ZnO nano-composite with regular and clear core- shell structure. Using EDS analysis to certificate the elemental composition ofthecomposites, which are made up of titanium, zinc, and oxygen.
Experiments prove that the surfactant, zinc content have great impact on morphology of TiO2/ZnO nanocomposite. Surfactant affects the size of zinc oxide in nanocomposite materials, which may be caused by the polarity of surfactant. Using SDS as surfactant can get nearly a half smaller size than CTAB. Zinc content concluded in nanocomposites has effect on surface morphology of composite. We obtained the best morphology of TiO2/ZnO nanocomposites when the zinc content in the composites is up to 0.00002M. Too much zinc conten will block titanium tubes and cover titanium tube-shaped holes.
TiO2/ZnO nano-composite materials formed on the basis of the formation of TiO2 nanotubes. By heterogeneous nucleation, TiO2/ZnO nanocomposites formed.
(4) Using methyl orange as the goal of degradation, natural light as the light source to study the activity of TiO2/ZnO nano-photocatalytic. Results showed that, TiO2/ZnO composite photocatalyst can improve the utilization of the sunlight. It is found that the best degradation of catalytic is observed to reach 90% when the solution pH value equals 3, in sunlight degradation 5 hours.
TiO2纳米管是TiO2的又一种存在形式,由于纳米管具有大的比表面积,因而具有较高的吸附能力,可望提高TiO2的光催化性能,特别是如果能在管中装入更小的无机、有机、金属或磁性纳米粒子组装成复合纳米材料,将会大大改善TiO2的光电、电磁及催化性能。
纳米TiO2存在太阳能利用率低,光生电子和光生空穴极易复合导致的光催化效率不高这两个主要缺点,极大地限制了TiO2的实际应用。氧化锌为直接带隙半导体,二氧化钛为间接带隙半导体,两者的禁带宽度非常接近,导带底和价带顶能量相差不多,将两者耦合能对其光学性能产生重要影响。
有研究表明氧化锌的引入可以抑制二氧化钛晶型转变过程和粒子生长,使ZnO-TiO2复合半导体在紫外光、自然光、太阳光照射下的光催化效率都较单一ZnO和TiO2高,且吸收光谱发生红移。
本文主要研究了ZnO纳米棒、TiO2纳米管、TiO2／ZnO纳米复合材料的制备及相关性能,为上述纳米材料更好和更为广泛的应用提供了理论依据和实验基础。具体内容如下：
(1)以不同原料和反应条件制得不同形貌、具有六角纤锌矿单晶结构的ZnO纳米棒,且这类ZnO纳米棒分布均匀、无明显团聚现象。
讨论了原料组成、反应温度、反应时间、醇水比、表面活性剂等因素对ZnO微晶形成的影响,并初步分析了其形成机理。以0.04M的Zn(NO3)·6H20和0.05M的(NH4)2CO3,在以SDS为表面活性剂辅助下,于体积比2：1的醇／水体系中200℃水热反应10小时制得的ZnO微晶形貌最佳,其平均直径约59nm,长径比达40。采用XRD分析确定所制得的ZnO微晶具有六角纤锌矿结构,尺寸小晶型良好,且XRD数据与TEM结果一致。
(2)采用电化学阳极氧化法,在F-存在下制得形貌规整、有序、排列紧密的中空Ti02纳米管。
通过调整制备工艺条件,可知TiO2纳米管的制备受阳极氧化电压、时间、反应液pH值影响。经实验优化得在阳极氧化电压60V、反应液pH值为6、反应9小时的条件下制得的TiO2纳米管的形貌最好。由SEM结果分析知所制得TiO2纳米管管径约100nm,具有高长径比。由XRD分析确定所得TiO2纳米管的晶型良好,且与SEM结果一致。
(3)采用二步法成功地制备了形貌规整、清晰的核-壳结构的TiO2／ZnO纳米复合材料,由EDS分析确定其元素组成为钛、锌、氧。
实验证明表面活性剂、锌含量对TiO2／ZnO纳米复合材料的形貌具有较大影响。表面活性剂影响纳米复合材料中氧化锌的尺寸,可能是由表面活性剂的极性导致而成,采用SDS做表面活性剂得到的尺寸比CTAB小一半；锌含量对复合纳米材料表面形貌影响较大,锌含量在0.0002M时制得的TiO2／ZnO纳米复合材料形貌最佳,过多的锌会使钛管被堵塞而见不到孔洞状。
TiO2／ZnO纳米复合材料的形成是在TiO2纳米管形成的基础上异相成核,最终形成TiO2／ZnO纳米复合材料。
(4)以甲基橙为目标降解物,自然光为光源,研究TiO2／ZnO纳米光催化剂的光催化活性,结果表明,TiO2／ZnO复合光催化剂能提高对太阳光的利用率,发现在降解液pH值为3,太阳光催化降解5小时,催化剂的降解效果最好,达到90%以上。
TiO2 is an important inorganic functional materials.Because of its humidity, gas, photoelectric conversion, dielectric effects, photochromic and excellent photocatalytic performance. TiO2 has a wide range of application in many fields such as sensor, dielectric materials, optical materials, self-cleaning materials, catalysts and carriers and so on.
TiO2 nanotubes are another form of TiO2 materials. As nanotubes with a large surface area and has a high adsorption capacity, is expected to enhance the photocatalytic properties of TiO2, especially if a smaller inorganic, organic, metallic or magnetic nanoparticles assembled into TiO2 nanotubes, to assemble composite nanomaterials. It will greatly improve the photovoltaic, electromagnetic and catalytic properties of TiO2.
Titanium dioxide exist two main shortcomings that is low solar energy utilization, photo-electronic and photo-generated hole can easily composite. The two main shortcomings greatly limits the practical application of TiO2 due to its low photocatalytic efficiency. Zinc oxide is a direct band-gap semiconductors, titanium dioxide is the indirect band-gap semiconductors. The band gap between the two materials is very close. Energy from the end of the conduction band to the top of valence band is very similar. To couple the two can have a major impact on their optical properties.
Studies have shown that the introduction of zinc oxide can inhibit the process of crystalline transformation of titanium dioxide and particle growth. As a result ZnO-TiO2 semiconductor showed higher photocatalysis efficiency compared with single ZnO and TiO2 under ultraviolet, natural light and sunlight. What's more the absorption spectrum red shift occurs.
This paper mainly studies the preparation and related properties of ZnO nanorods, TiO2 nanotubes, TiO2/ZnO nano-composites. In this paper we provide theoretical basis and experimental foundation for the nano-materials above-mentioned to expand more extensive applications. Details are as follows:
(1) ZnO nanorods with different morphologies are obtained with different raw materials and reaction conditions. These ZnO nanorods have hexagonal wurtzite crystal structure, dispersed uniform and obvious agglomeration unobserved.
Discussed the effect of raw materials composition, reaction temperature, reaction time, alcohol-water ratio, surfactant on the formation of ZnO. Preliminary analyze the formation mechanism of ZnO. ZnO crystallite obtained the best morphology With 0.04M of Zn(NO3)·6H2O, and 0.05M of (NH4) 2CO3, used SDS as assisted surfactant, at 2:1 volume ratio of alcohol/water system, at 200℃hydrothermal reaction 10 hours. The ZnO nanorods with an average diameter of about 59nm and aspect ratio up to 40. We make use of XRD to identify obtained ZnO crystallite with a hexagonal wurtzite structure, small size, well crystalline, and the results are in accordance with TEM.
(2)Electrochemical anodic oxidation method is adopted. In the presence of F-, TiO2 nanotubes with orderly, tightly arranged hollow tubes are obtained.
By adjusting the process of preparation conditions, we can see the TiO2 nanotubes are influenced by anodization voltage, reaction time, pH value. We optimized The technology on the preparation of TiO2 nanotubes. We obtained the best anode voltage of 60V, pH value of 6, and reaction time of 9 hours. The results from SEM analysis we observed the average diameter of TiO2 nanotubes are about 100nm with a high aspect ratio. Confirmed by XRD analysis we identified the crystalline structure of TiO2 nanotubes.They have well crystalline structure and the results are consistent with the SEM.
(3) Using a two-step method successfully prepared TiO2/ZnO nano-composite with regular and clear core- shell structure. Using EDS analysis to certificate the elemental composition ofthecomposites, which are made up of titanium, zinc, and oxygen.
Experiments prove that the surfactant, zinc content have great impact on morphology of TiO2/ZnO nanocomposite. Surfactant affects the size of zinc oxide in nanocomposite materials, which may be caused by the polarity of surfactant. Using SDS as surfactant can get nearly a half smaller size than CTAB. Zinc content concluded in nanocomposites has effect on surface morphology of composite. We obtained the best morphology of TiO2/ZnO nanocomposites when the zinc content in the composites is up to 0.00002M. Too much zinc conten will block titanium tubes and cover titanium tube-shaped holes.
TiO2/ZnO nano-composite materials formed on the basis of the formation of TiO2 nanotubes. By heterogeneous nucleation, TiO2/ZnO nanocomposites formed.
(4) Using methyl orange as the goal of degradation, natural light as the light source to study the activity of TiO2/ZnO nano-photocatalytic. Results showed that, TiO2/ZnO composite photocatalyst can improve the utilization of the sunlight. It is found that the best degradation of catalytic is observed to reach 90% when the solution pH value equals 3, in sunlight degradation 5 hours.
引文
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