N、F共掺杂可见光响应介孔TiO2光催化剂:纤维素模板剂合成及活性

以纤维素为模板剂,TiCl4为钛源,采用液相水解-沉淀法制备了浅黄色的N、F共掺杂可见光响应介孔TiO2催化剂(TiONF)。以苯酚为模型物,考察了TiONF在紫外光区、可见光区及太阳光下催化活性;采用X射线光电子能谱(XPS)、傅里叶变换红外(FTIR)、紫外-可见漫反射光谱(UV-Vis DRS)、X射线衍射(XRD)、热重/量热扫描(TG/DSC)、透射电镜(TEM)及低温N2物理吸附-脱附等技术对TiONF催化剂的结构进行了表征。结果表明,以纤维素为模板剂合成适量N、F共掺杂的TiONF催化剂在紫外光区、可见光区及太阳光下均表现出较高的活性,且高于无模板剂合成的TiONF催化剂的活性。N、F共掺杂提高了TiO2表面羟基数量和锐钛矿相TiO2向金红石相转变的温度;N掺杂形成新的能级结构,诱发TiO2可见光催化活性;F掺杂促进TiO2粒子表面氧空穴产生,致使TiO2粒子表面酸度和Ti3+增加。另外,纤维素的加入可减小TiONF颗粒平均尺寸,改善催化剂分散性,提高催化剂比表面积。     

N、F共掺杂TiO2可见光响应光催化剂的酸催化水解法制备及表征

采用酸催化水解法由TiCl4、NH4F混合液合成N、F共掺杂可见光响应TiO2光催化剂(TONF). 以苯酚为模型物, 考察了催化剂在可见光区、紫外光区的催化活性. 采用X射线光电子能谱(XPS)、紫外-可见漫反射光谱(DRS)、X射线衍射(XRD)、扫描电子显微镜(SEM)及低温氮物理吸附对光催化剂的晶相结构、光谱特征和表面结构等进行表征. 结果表明, 适量的N、F共掺杂TONF催化剂表现出较高的可见光催化活性. N、F共掺杂可显著提高TiO2分散性能, 促进锐钛矿相的形成, 抑制其向金红石相转变, 提高相转变温度. N掺杂可提高TiO2在可见光区的吸收; F掺杂可使TiO2能隙变窄.     

N、F共掺杂TiO2可见光响应光催化剂的酸催化水解法制备及表征

采用酸催化水解法由TiCl4、NH4F混合液合成N、F共掺杂可见光响应TiO2光催化剂(TONF).以苯酚为模型物,考察了催化剂在可见光区、紫外光区的催化活性.采用X射线光电子能谱(XPS)、紫外.可见漫反射光谱(DRS)、X射线衍射(XRD)、打描电子显微镜(SEM)及低温氮物理吸附对光催化剂的晶相结构、光谱特征和表面结构等进行表征.结果表明,适量的N、F共掺杂TONF催化剂表现出较高的可见光催化活性.N、F共掺杂可显著提高TiO2分散性能,促进锐钛矿相的形成,抑制其向金红石相转变,提高相转变温度.N掺杂可提高TiO2在可见光区的吸收;F掺杂可使TiO2能隙变窄.     

酸催化水解法制备可见光响应N掺杂纳米TiO2催化剂

 以TiCl4为钛源,采用酸催化水解法合成了TiO2前驱体,在NH3/N2气氛中经程序升温处理制得不同N掺杂量的TiO2可见光响应催化剂. 以苯酚为模型物,考察了催化剂在可见光及紫外光区的催化活性. 采用X射线衍射、紫外-可见漫反射光谱、傅里叶变换红外光谱、扫描电镜和低温氮物理吸附对光催化剂的晶相结构、光谱特征和表面结构进行了表征. 结果表明,掺杂N后锐钛矿TiO2的可见光催化活性显著提高,在500 ℃焙烧5 h制得的催化剂在可见光区及紫外光区均表现出最高的光催化活性. N掺杂对TiO2的晶粒大小、比表面积和晶相结构影响不大. 适量N掺杂可在TiO2表面形成Ti-O-N键,形成了新的能级结构,使催化剂的吸收带边红移至490～550 nm; 同时该结构也可有效提高TiO2的紫外光催化活性.     

SiO2负载氮掺杂TiO2可见光响应光催化剂的制备及性能

以四氯化钛为钛源,尿素为氮源,采用液相水解-沉淀法制得SiO2负载N掺杂TiO2可见光响应TiO2-xNy/SiO2光催化剂(TSN)。以苯酚为模型物,考察了TSN在可见光区、紫外光区及太阳光下的光催化活性,以及催化剂的使用寿命、分离性能。采用XPS、FTIR、UV-Vis DRS、XRD、TEM和低温氮物理吸附等对催化剂的结构进行表征。结果表明,N以阴离子形式进入TiO2体相并置换晶格中的O,适量N掺杂的TSN在紫外光区、可见光区及太阳光下均表现出较高的活性。SiO2与TiO2界面间有Ti-O-Si键形成,结合牢固。N掺杂在TiO2表面生成Ti-O-N键,形成新的能级结构,使催化剂的吸收红移至450~500 nm,诱发TiO2可见光催化活性。SiO2负载可减小TiO2颗粒平均尺寸,增加催化剂比表面积;同时SiO2负载还可改善催化剂的分离性能,提高催化剂使用寿命。     

S掺杂S-TiO_2/SiO_2可见光响应光催化剂的制备及性能

以四氯化钛为钛源,硫脲为硫源,采用液相水解-沉淀法制备了S掺杂的TiO2/SiO2(S-TiO2/SiO2)催化剂,并以苯酚为模型物,考察了催化剂在可见光区、紫外光区和太阳光下的光催化活性,以及催化剂的使用寿命和分离性能.采用X射线光电子能谱、傅里叶变换红外光谱、紫外-可见漫反射光谱、X射线衍射、透射电镜及N2吸附-脱附等技术对催化剂进行了表征.结果表明,S以+6价形式进入TiO2体相并置换晶格中的Ti4+,适量S掺杂的S-TiO2/SiO2在紫外光区、可见光区和太阳光下均表现出较高的光催化活性.SiO2与TiO2界面间有Ti-O-Si键形成,结合牢固.S掺杂在TiO2表面生成Ti-O-S键,形成新的能级结构,使光催化剂在450～550nm产生吸收,诱发TiO2可见光催化活性;同时提高了TiO2表面羟基数量.SiO2的加入可减小TiO2颗粒的平均尺寸,增大催化剂的比表面积,改善催化剂的分离性能,提高催化剂的使用寿命.     

S掺杂宽光域响应Ti1-xSyO2光催化剂的制备及表征

以TiCl4和硫脲为主要原料, 采用酸催化水解法制得浅黄色S掺杂Ti1-xSyO2光催化剂. 以苯酚为模型物, 考察了Ti1-xSyO2在可见光区、紫外光区及太阳光下的催化活性. 采用XPS、DRS、XRD、FT-IR、SEM、低温氮物理吸附对光催化剂进行表征. 结果表明, 掺杂S以S6+形式置换TiO2晶格中的Ti4+, 适量S 掺杂的Ti1-xSyO2在可见光区、紫外光区及太阳光下均表现出较高的光催化活性.掺杂S 在TiO2表面形成新的能级结构, 使催化剂吸收红移至450-550 nm, 诱发可见光催化活性;紫外光照射下, 新形成的能级结构与体相TiO2形成复合半导体结构, 捕获光生空穴, 提高光生电子鄄空穴分离效率.同时, S掺杂可以改善TiO2的分散性, 增加其比表面积SBET并提高相转变温度.     

硼硫共掺杂TiO2的光催化性能及掺杂机理

采用水热法制备了硼硫共掺杂的TiO2光催化剂(TiO2-B-S),并用其光催化降解甲基橙.结果表明,在240℃下水热反应12h时制得的TiO2-B-S具有较高的催化活性,紫外光照射50min和太阳光照射230min时对甲基橙的降解率分别达99.8%和81%.X射线粉末衍射、紫外-可见漫反射光谱和X射线光电子能谱等研究表明,TiO2-B-S为锐钛矿晶型,硫硼掺杂能抑制TiO2粒径的生长;TiO2-B-S同时具有较高的紫外光和可见光活性的原因可能是掺杂的硼以B3 进入晶格中,导致TiO2晶格畸变,带隙变窄.掺杂的硼和硫还提高了TiO2的表面酸度和对可见光的吸收.     

浓度梯度分布的镍和氮共掺杂TiO2光催化剂的制备和表征

以TiCl4为钛前驱体, 氨水和氯化镍为掺杂离子给体, 采用沉淀和层层浸渍相结合的方法制备了氮、镍共掺杂TiO2光催化剂. 采用X射线衍射(XRD)、氮气吸附-脱附、X射线光电子能谱(XPS)、紫外-可见漫反射吸收光谱(UV-Vis)等现代表征方法对催化剂的晶体结构、微结构、掺杂基团和光谱性质进行了表征. XRD和氮吸附-脱附分析结果表明, 氮、镍共掺杂TiO2为单一锐钛矿相, 具有介孔结构. XPS谱证实掺杂的氮和镍分别以NOx和Ni2O3及NiO的形式存在, 且镍在共掺杂表面的浓度高于体相中的浓度, 在扩散方向上存在浓度梯度分布. 4-氯酚的降解实验结果表明, 浓度梯度分布镍和氮共掺杂TiO2的紫外光-可见光催化活性均高于均相共掺杂TiO2、单掺杂和未掺杂TiO2的催化活性. 其原因是掺杂的氮以NOx形式存在, 使催化剂的感光范围拓展至可见光区; 而掺杂的镍维持了半导体体系的电荷平衡, 有效抑制了Ti3+的产生. 同时掺杂的镍在催化剂中存在浓度梯度分布, 减少了光生电子和空穴的复合几率, 提高了催化剂的光催化活性.     

铬和硫共掺杂二氧化钛催化剂的制备及其可见光催化性能

以钛酸四丁酯为前驱体,硝酸铬和硫脲为掺杂离子给体,通过溶胶-凝胶法成功制备了纯TiO2、不同浓度的铬掺杂和铬/硫共掺杂TiO2光催化剂.以靛红为目标污染物,进行了可见光催化降解活性测试实验.结果表明,共掺杂催化剂的活性高于未掺杂和单掺杂催化剂.当共掺杂催化剂含0.60%(原子比)的铬,1.2%(原子比)的硫,焙烧温度为500℃时具有最高的光催化降解活性.X射线衍射、N2吸附、X射线光电子能谱和紫外-可见漫反射吸收光谱表征结果显示,共掺杂催化剂为锐钛矿型,具有较高的比表面积,对可见光有较强的吸收能力.共掺杂TiO2具备较高可见光催化活性的原因可能是铬掺杂降低了TiO2的禁带宽度,拓展了可见光吸收区域,而硫掺杂能够维持体系的电荷平衡,增强催化剂对可见光的吸收.     

离子液体-水混合溶剂中制备纳米晶TiO2的结构特性及其光催化活性

以钛酸四丁酯为原料, 离子液体1-乙基-3-甲基咪唑醋酸盐([EMIM]+AcO-)-水为混合溶剂, 通过低温水热法制备了锐钛矿相TiO2纳米晶. 用XRD、N2吸附-脱附、XPS及UV-Vis漫反射等技术对产物的晶相、比表面积、表面性质及光吸收性进行表征, 并以甲基橙水溶液为研究对象, 考察了产物的光催化活性及催化剂用量、溶液酸碱度对其的影响. 结果表明, 离子液体鄄水混合溶剂中反应24 h 所得到的TiO2具有较高光催化活性, 并明显优于Degussa P25, 这一结果可归因于其具有较高的锐钛矿含量和较大的比表面积.     

Enhanced photo-catalytic activity of TiO2 nanostructured thin films under solar light by Sn and Nb co-doping

In this study, preparation of Sn and Nb co-doped TiO₂ dip-coated thin films on glazed porcelain substrates via sol–gel process have been investigated. The effects of co-doping content on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD), field emission SEM (FE-SEM), high resolution transmission electron microscopy (HR-TEM), and UV–Vis absorption spectroscopy. Surface chemical state of thin films was examined by atomic X-ray photoelectron spectroscopy (XPS). XRD results suggest that adding impurities has a great effect on the crystallinity and particle size of TiO₂. Titania Rutile phase formation in thin film was promoted by Sn⁴⁺ addition but was inhibited by Nb⁵⁺ doping. The prepared co-doped TiO₂ photo-catalyst films showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of methylene blue (MB) solution under solar irradiation. Comparison with undoped and Sn or Nb-doped TiO₂, codoped TiO₂ shows an obviously higher catalytic activity under solar irradiation.     

Pd/N共掺杂TiO_2的制备及其光催化活性

将纳米管TiO2浸入含尿素和硝酸钯的乙醇溶液中,将乙醇超声挥发后所得样品先在空气中600℃下煅烧,再在H2气氛中400℃中热还原,得到Pd/N共掺杂TiO2.分别采用DRS、X射线衍射仪及X射线光电子能谱仪分析了掺杂TiO2样品的光吸收能力、晶体结构及表面化学组成;并评价了其对紫外光和可见光照下丙烯降解反应的催化活性.结果表明,共掺杂TiO2样品的活性优于单一Pd或N掺杂TiO2.其原因在于,Pd和N共掺杂具有协同作用,从而共同提高了TiO2的光催化活性.     

Preparation of Ce-TiO2 catalysts by controlled hydrolysis of titanium alkoxide based on esterification reaction and study on its photocatalytic activity

The Ce-TiO2 catalysts were prepared by controlled hydrolysis of Ti(OC(4)H(9))(4) with water generated "in situ" via an esterification reaction between acetic acid and ethanol, followed by hydrothermal treatment. The samples were characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), atomic absorption flame emission spectroscopy (AAS), and nitrogen adsorption-desorption methods. Both of undoped TiO2 and Ce-TiO2 samples exclusively consist of primary anatase crystallites, which further form spherical aggregates with diameters ranging from 100 to 500 nm. The photocatalytic activity of Ce-TiO2 was investigated for the photocatalytic degradation of Rhodamine B (RB) aqueous solution both under UV and visible light irradiation. Doping of Ce(4+) effectively improves the photocatalytic activity under both UV light irradiation and visible light irradiation with an optimal doping concentration of 0.2 and 0.4%, respectively. The photocatalytic mechanisms of Ce-TiO2 catalysts were tentatively discussed.     

Characterization of Visible Light Response N-F Codoped TiO2 Photocatalyst Prepared by Acid Catalyzed Hydrolysis

N-F codoped TiO₂ (TONF) photocatalysts were prepared using acid catalyzed hydrolysis method from mixed aqueous solution of TiCl₄ and NH₄F. The photocatalytic activity of the TONF was evaluated through the degradation of phenol under both visible and UV light irradiation. X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), scanning electron microscope (SEM), and N₂ adsorption isotherm were used to characterize the obtained powders. The results showed that N-F codoped TiO₂ exhibited significant improvement of visible light catalytic activity. N-F codoping could improve dispersion of TiO₂, inhibit particle size agglomeration, and retard phase transformation. Doped N could extend the light response of TiO₂ to visible light region. In addition, narrower band gap formed by F-doping was beneficial to the high visible light photocatalytic activity.     

碳掺杂的二氧化钛纳米管的制备及其可见光催化性能

以尿素作为碳元素前驱体对TiO2纳米管进行掺杂,采用比表面积测定、X射线衍射、透射电子显微镜、能量色散X射线荧光光谱、X射线光电子能谱、固体漫反射紫外-可见吸收光谱和荧光光谱对产物进行了表征。 结果表明,以尿素作为前驱体可制备C掺杂的TiO2纳米管,C掺杂后,TiO2纳米管的可见光催化活性明显提高。 此外,研究了C掺杂量、煅烧温度、催化剂用量和pH值对TiO2纳米管光催化降解活性的影响,发现当C的掺杂量为5.3%、催化剂用量为1.5 g/L、溶液的pH值为5时,在其催化作用下,可见光光照3 h后罗丹明B的降解率可达到91%。     

铁和铈共掺杂二氧化钛中的协同效应

The co-doping of iron and cerium into TiO2 was studied by means of X-ray diffraction, Raman spectroscopy, UV-Vis diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. when separately doping via the sol-gel method, iron was introduced in the framework of anatase TiO2 whereas cerium was not; interestingly, both iron and cerium were introduced in the framework when co-doping by the sol-gel method. The co-doped TiO2 behaves much more intense surface hydroxyl concentration than the separately-doped and pure TiO2. This observation demonstrates for the first time a cooperative effect in the co-doping of transitional metals in the framework of TiO2.     

Characterization and mechanism analysis of Mo-N-co-doped TiO2 nano-photocatalyst and its enhanced visible activity

In this study, Mo-N-co-doped TiO(2) nano-photocatalysts have been synthesized through hydrolysis-precipitation method, combined with sonication posttreatment. The resulting materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). XRD showed that co-doping with Mo and N favored the formation of anatase and retarded the growth of crystallite size. XPS revealed that N was incorporated into the lattice of TiO(2) through substituting oxygen atoms and coexisted in the forms of β-N and γ-N in co-doped TiO(2). Meanwhile, Mo was also incorporated into the lattice of TiO(2) through substituting titanium atoms and existed in the form of Mo(6+). DRS indicated that the light absorbance in visible region was improved by co-doping with Mo and N, leading to a narrower band gap and higher visible light photocatalytic activity for the degradation of phenol than that of pure and N-doped TiO(2). The enhanced visible light photocatalytic activity of Mo-N-co-doped TiO(2) nano-photocatalyst was attributed to the small crystallite size, narrow band gap and intense light absorbance in visible region. This study provides a new method to synthesize visible light active TiO(2)-based photocatalyst.