摘要
纳米TiO_2作为纳米材料的一员,由于其具有极大的体积效应、表面效应和颜色效应以及良好的光学特性,故在光、电及催化等方面显示出特殊性质,作为一种新型材料,其应用领域日益广泛。尤其在光催化领域,自从1972年Fujishima等首次发现在单晶TiO_2电极上光催化分解水的现象以来,TiO_2在光解水、氮氧化合物及有机污染物的降解,杀菌,除臭以及表面自洁等方面得到广泛研究与应用。此后,各国学者为阐明TiO_2光催化的基本过程和提高它的光催化效率而对其进行了详尽的研究,以TiO_2为基础的多相光催化过程,有望发展成为直接利用太阳能和空气中的氧降解有毒有害污染物的绿色催化过程,为人类社会的和谐发展做出巨大贡献。本论文旨在研究不同形貌的低维TiO_2纳米材料在可见光降解水中污染物方面的应用,不仅促进了可见光催化剂制备科学的发展,而且加深了光催化反应的基础理论认识。具体研究内容和结果归纳如下:
1.采用水热法合成了具有可见光响应的B掺杂纳米TiO_2,其中B以B-O-Ti的结构存在。用于可见光消除饮用水中硝酸根的反应,发现180℃晶化12 h合成的B含量为2%的样品具有最好的催化效果(5 h转化率96.7%,N_2选择性88%)。用于可见光降解苯酚的反应,发现B掺杂量为2%的催化剂具有最好的可见光降解苯酚活性,且当催化剂用量在0.2 g以上时,5 h的降解率均能达到100%。
2.本论文以高温氮化法合成的N掺杂TiO_2为前躯体和高温氮化钛酸盐纳米管两条路线合成了N掺杂TiO_2纳米管。通过表征可以发现,两种方法合成的N掺杂TiO_2纳米管都具有较强的可见光吸收,N成功的掺杂到纳米管中,其中前一种方法合成的纳米管以钛酸盐结构存在,而后一种方法合成的纳米管则是锐钛型TiO_2的结构;催化活性测试表明,后一种方法合成的N掺杂TiO_2纳米管具有最好的可见光降解甲基橙活性。
3.以溶剂热法合成的金属、N共掺杂TiO_2为前躯体和高温氮化金属掺杂钛酸盐纳米管两条路径分别合成了金属、N共掺杂TiO_2纳米管。研究表明,前一种方法合成纳米管以钛酸盐结构存在,而后一种方法所得样品则是锐钛型TiO_2结构;两种方法合成的金属、N共掺杂纳米管均具有明显的可见光吸收,并具有一定的可见光催化活性。其中,高温氮化法得到的W、N共掺杂TiO_2纳米管具有最好的光催化活性,可见光反应3 h甲基橙降解率达到100%。
4.首次以钛酸盐纳米线为前躯体,不同温度氮化合成了N掺杂TiO_2纳米线。研究发现,在合适的温度下可以实现N掺杂和钛酸盐向TiO_2晶型转化的有机结合并能够同时保持纳米线的形貌。钛酸盐向TiO_2晶型的转化有利于N的掺杂,可以有效提高N含量,并得到比表面积较大的样品。掺杂的N以取代N和间隙N两种状态存在,并导致较强的可见光吸收和吸收边带红移。
5.以金属掺杂纳米TiO_2为前躯体,合成了金属掺杂钛酸盐纳米线,研究表明金属离子的掺杂并没有影响样品的晶型和形貌,得到的样品具有钛酸盐纳米线特有的层状结构,层间距为0.6nm。金属掺杂钛酸盐纳米线在氨气气氛中600℃氮化2 h合成了金属、N共掺杂TiO_2纳米线。将钛酸盐向TiO_2的转化和N的掺杂集中于氮化的过程,减少了实验步骤,有效地实现了TiO_2纳米线的可见光化。一系列表征发现本文合成的金属、N共掺杂TiO_2纳米线具有良好的可见光吸收,并且具有较高的可见光活性。
As an important part of nanomaterials,TiO_2 shows huge volume effect,surface effect,color effect and wonderful optical properties.And it was used widely in more and more fields as a new material,especially in photocatalysis,for its optical, electrical and magnetic characterization.Since 1972,Fujishima et al.found the photo-decompose of water on TiO_2 electrode for the first time,TiO_2 was widely used in photo-decomposion of water,nitride and some organic pollutions and sterilization and deodorization and surface self cleaning,etc.Researchers were engaged in elucidating the process and enhancing the catalytic efficiency of TiO_2,and the friendly heterogeneous catalysis of TiO_2 plays an important part in harmonious development of human society.This thesis mainly focuses on the study of low dimensional TiO_2 with different appearances,summarized as follows:
1.Used hydrothermal method to synthesis B-doped nano-TiO_2 with visible light response,and B atoms existed as B-O-Ti.The as-synthesized B-TiO_2 shows high activity in photo-decompose of nitride and phenol.Samples synthesized at 180℃for 12h shows the highest activity in nitride-decompose(5h,nitride conversion 96.7%,N_2 selectivity 88%) and phenol-decompose(5 h,conversion 100%).
2.N-doped TiO_2 and titanate nanotubes were used as precursor of N-doped TiO_2 nanotubes synyhesis.As characterized,N-doped TiO_2 nanotubes synthesized by both two methods show high visible light response,and N atoms were doped successfully into TiO_2 nanotubes.Structure of nanotubes synthesized from the first method is titanate,but the structure of nanotubes synthesized from the later method is anatase TiO_2;the later one shows the most highest activity in degradation of methyl orange.
3.Using metal,N-codoped TiO_2 or metal-doped titanate nanotubes as precursor, synthesized metal,N-codoped TiO_2 nanotubes.It is confirmed that nanotube synthesized from the first method is composed of titanate and the later one is composed of anatase TiO_2.After the codoping of metal and N,both nanotubes show obvious visible light response and photocatalytic acivity.Among all the nanotubes,W,N-codoped TiO_2 nanotube shows the best photocatalytic activity which synthesized by nitride under NH_3 gas flow.
4.Firstly used titanate nanowire as precursor,nitridated it at different temperatures and obtained N-doped TiO_2 nanowires with layered structure.It is obvious that N doping and transformation of titanate to anatase TiO_2 could be combined in one step under appropriate nitridation temperature.After nitridation at suitable temperature,figure of nanowire reserved,and N was doped successfully.Visible light response and photocatalytic activity were obtained under N-doped TiO_2 nanowire.
5.Firstly synthesized metal-doped titanate nanowire with layered structure using metal doped TiO_2 as precursor,the distance between two layers is about 0.6 nm. After nitridation under NH_3 gas flow for 2 h,titanate turned into anantase TiO_2, and obtained metal,N-codoped TiO_2 nanwire with visible light response and photocatalytic activity.
引文
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