胶原纤维为模板TiO_2、La_x/TiO_2纳米纤维的制备、表征及光催化活性研究

以胶原纤维为模板分别负载钛(Ti4+)或钛(Ti4+)和镧(La3+),经高温煅烧制得介孔TiO2和La x/TiO2纳米纤维。通过场发射扫描电镜(FESEM)、N2吸附-脱附等温线、X射线衍射(XRD)、分子荧光光谱(PL)和紫外-可见吸收光谱(UV-Vis)等对这2类纳米纤维的结构和物理性能进行了表征。结果表明胶原纤维的纤维状结构能被较好地保留在TiO2和La x/TiO2纳米纤维中。TiO2和La x/TiO2纳米纤维的N2吸附-脱附等温线属于典型的Ⅳ型,表明其具有介孔结构。XRD分析表明,La3+的掺杂减小了TiO2的晶粒尺寸。与Degussa P25相比,介孔TiO2和La x/TiO2(x≤0.02)纳米纤维的紫外-可见吸收光谱红移,分子荧光光谱强度明显减弱。以孔雀石绿的光催化降解为模型反应,在可见光和紫外光激发下,介孔TiO2和La x/TiO2纳米纤维的光催化活性均高于Degussa P25。此外,La x/TiO2在可见光激发下的光催化活性高于未掺杂的TiO2纳米纤维。     

La3+掺杂TiO2纳米纤维的制备、表征与光催化性能

结合溶胶-凝胶法、静电纺丝技术和高温煅烧制备了La3+掺杂TiO2纳米纤维.采用扫描电子显微镜、X射线能谱仪、比表面积及孔隙分析仪、X射线衍射仪和紫外分光光度计对纳米纤维的形貌、晶型、表面和孔隙结构以及光催化性能进行了表征和测试.结果表明,La3+掺杂TiO2纳米纤维表面为多孔的纤维状结构.La3+掺杂明显改善了TiO2纳米纤维的表面孔隙结构,对TiO2纳米纤维的粒子生长有一定的抑制作用.光催化降解性能测试结果表明,当La3+掺杂量为0.04%(质量分数)时,TiO2纳米纤维的光催化性能最佳.     

纳米La-TiO2光催化降解甲基橙废水的研究

采用溶胶-凝胶法制备了纯TiO2和La掺杂TiO2复合纳米粉体,通过XRD,UV-Vis等测试手段分析了在紫外光照射下,以降解甲基橙为探针反应研究其可见光催化性能。结果显示样品均为锐钛矿相纳米TiO2,稀土元素镧掺杂后纳米TiO2特征衍射峰宽化,强度降低;掺入的La主要以La2O3的形式存在,同时有一部分形成Ti-O-La键;La掺杂可减小TiO2晶粒尺寸及增大催化剂比表面积;与未掺杂的二氧化钛相比较,适当含量的镧掺杂可有效促进TiO2表面光生载流子的分离,从而显著提高其光催化活性。当La/Ti的摩尔比为0.010时,可见光催化性能最好。     

La3+掺杂对纳米TiO2微观结构及光催化性能的影响

以钛酸丁酯和氯化镧为原料,采用溶胶-凝胶法制备了La3+掺杂TiO2纳米粉体,讨论了不同掺杂浓度、不同热处理温度的样品催化降解刚果红染料实验中的光催化活性,并通过X射线衍射(XRD)、透射电镜(TEM)分析了La3+掺杂TiO2样品的相组成、晶胞参数和晶粒大小对光催化活性的影响.结果表明:La3+掺杂能够显著提高TiO2粒子的光催化活性,最佳掺杂浓度为100∶3 0,最佳热处理温度为600℃;La3+掺杂的TiO2的相组成是影响光催化活性的决定性因素;晶格膨胀程度及晶粒大小对光催化活性的影响,主要是在相组成相同或相近时才体现得比较明显.     

磁性La3+掺杂TiO2的制备及性能

利用溶胶-凝胶法,在室温条件下,以钛酸四丁酯、硝酸镧为主要原料,无水乙醇为溶剂,冰醋酸为抑制剂,浓硝酸为催化剂制得稳定的掺La3+TiO2溶胶,陈化后的凝胶经不同温度煅烧3h后制得不同掺La3+量的TiO2。通过XRD对不同煅烧温度及不同掺La3+量的TiO2进行了表征;以紫外光为光源,研究了掺La3+-TiO2对甲基橙溶液的光降解效果。用化学共沉淀法制备了具有强磁性的Fe3O4水基磁流体,再与La3+掺杂TiO2进行复合,制备了Fe3O4负载量不同的磁性La3+掺杂TiO2,研究了Fe3O4负载量不同的La3+掺杂TiO2对甲基橙的光催化降解效果、磁分离回收率的影响。结果表明,掺La3+量及煅烧温度对TiO2的晶型、各晶型TiO2的相对含量及对甲基橙的光降解效果均有影响。La3+掺杂TiO2比纯TiO2显示出更强的光催化性能,掺La3+量2%,热处理温度450℃的La3+掺杂TiO2光催化活性最高。Fe3O4负载量为10%的Fe3O4/La3+-TiO2对甲基橙的降解率8h时为99.4%;磁分离回收率达97.39%。     

Eu3+和Sm3+共掺杂TiO2光催化剂的协同效应

采用溶胶-凝胶法制备了纯TiO2和Eu3+/Sm3+共掺杂TiO2复合粉体,采用XRD,DRS和SEM等技术进行表征,以亚甲基蓝(methylene blue,MB)的光催化降解为目标反应,评价了其光催化活性,探讨了Eu3+/Sm3+共掺杂对TiO2粉体光催化的影响机制.结果表明,Eu3+/Sm3+共掺杂可以显著提高TiO2粉体光催化活性,Eu3+/Sm3+共掺杂在TiO2粉体中产生协同作用,可以抑制TiO2由锐钛矿相向金红石相转变,使TiO2的粒径减小.Eu3+/Sm3+共掺杂增大了TiO2粉体的晶格畸变,使TiO2粉体吸收带边蓝移.当Eu3+/Sm3+的掺杂量分别为0.05%和0.1%,TiO2光催化活性最高,光催化降解率达到84.8%.     

电气石/La/TiO2光催化材料的合成与表征

以硝酸镧、天然电气石(Tourmaline,简称T)和钛酸丁酯为原料,采用溶胶-凝胶法制备掺杂电气石和稀土La的TiO2复合光催化薄膜样品。用正交试验方法对影响该薄膜样品光催化性能的制备工艺进行优化,并通过紫外可见光谱对复合薄膜样品的吸收光谱进行分析。结果表明,掺杂稀土元素La可使TiO2的光吸收范围发生红移,掺杂电气石将增强La/TiO2光吸收强度,T/La/TiO2复合光催化薄膜最佳制备工艺为:La3+掺杂量为1.2%(wt,下同)、电气石掺杂量为0.8%、焙烧温度为500℃、焙烧时间为1.5h、负载次数2次,样品的的甲醛降解率可达82.5%。     

Sm3+和Gd3+共掺杂TiO2粉体的制备和性能表征

采用溶胶-凝胶法制备了纯TiO2,1%Sm3+或2%Gd3+单掺杂和1%Sm3+/2%Gd3+共掺杂TiO2复合粉体,采用XRD和SEM/EDAX等技术进行表征。以对亚甲基蓝的光催化降解为目标反应,评价了TiO2复合粉体的光催化活性,探讨了Sm3+/Gd3+共掺杂、亚甲基蓝初始浓度和粉体投加量对TiO2粉体光催化活性的影响机制。结果表明,Sm3+/Gd3+共掺杂可以显著提高TiO2粉体的光催化活性;Sm3+/Gd3+共掺杂在TiO2粉体中产生协同作用,抑制了TiO2由锐钛矿相向金红石相转变,使TiO2粒径尺寸减小,增大了TiO2的晶格畸变。当亚甲基蓝初始浓度为4mg/L和粉体投加量为2g/L时,TiO2复合粉体的光催化活性最高,对亚甲基蓝光催化降解率达99.71%;降解亚甲基蓝反应符合Langmuir-Hinshelwood动力学方程。     

La、Fe共掺杂TiO_2/活性炭纤维的制备及其光催化性能

采用溶胶-凝胶法,以硝酸镧和钛酸丁酯为原料,选取活性炭纤维作为载体,制备了La、Fe共掺杂TiO2/ACF复合材料,通过紫外灯照射,对甲醛气体进行光催化降解,考察材料的光催化活性。结果表明,适宜的La、Fe掺杂量能够提高TiO2/活性炭纤维的光催化活性。当La的掺杂量为0.5%(摩尔分数),Fe的掺杂量为0.5%(摩尔分数),焙烧温度为350℃时,La、Fe共掺杂TiO2/ACF光催化性能最佳,反应2h甲醛降解率达到98.9%。     

模板法制备介孔TiO2及其光催化性能研究

以十六烷基三甲基溴化铵(CTAB)作为模板剂,钛酸正四丁酯(TBOT)为钛源,异丙醇为溶剂,通过溶胶-凝胶过程合成出介孔TiO2前驱体凝胶后,经老化、焙烧得到了TiO2介孔材料.利用XRD、HR-TEM、TGA、N2的吸附-脱附、BET等方法对材料的结构、形貌、比表面积、孔径分布进行表征.以亚甲基蓝的降解为模型反应,对其催化性能进行评价并与商品DegussaP-25进行比较.实验结果表明,比表面积为137.5m2/g、孔径为8.62nm的锐钛型介孔TiO2具有很高的催化活性.     

Synthesis and characterization of Zr4+, La3+ and Ce3+ doped mesoporous TiO2: evaluation of their photocatalytic activity

Sol-gel method was used to synthesize Zr(4+), La(3+) and Ce(3+) doped mesoporous TiO(2) materials with different weight percentage (0.5, 1.0, 2.0 and 3.0 wt%) using triblock copolymer as the structure directing template in ethanol/water medium. Characterization revealed the isomorphic substitution of Zr(4+) ion into the lattice of TiO(2), and surface binding nature of La(3+) and Ce(3+) ions on mesoporous TiO(2). Microscopic examination confirmed the surface adsorption of foreign ion which could alter the particle morphology. The size of the particles was less than 20 nm. Photocatalytic activity of metal ions doped mesoporous TiO(2) was evaluated using aqueous alachlor as a model pollutant. It was found that 1 wt% Ce(3+) doped mesoporous TiO(2) exhibited higher activity than pure and other metal ions doped mesoporous TiO(2). The change of oxidation state of Ce(3+) is suggested to be the cause for enhanced photocatalytic activity.     

合成条件对晶态介孔TiO2结构和性能的影响

采用sol-gel法合成了锐钛矿相介孔氧化钛，利用XRD、BET、TEM和PL对介孔TiO2的结构和光致发光性能进行了表征及分析。结果表明，采用预制TiO2溶胶为钛源，所得介孔氧化钛具有良好的锐钛矿晶型、较大的孔径和比表面积，具有高的光致发光活性。     

Graft copolymer-templated mesoporous TiO(2) films micropatterned with poly(ethylene glycol) hydrogel: novel platform for highly sensitive protein microarrays

In this study, we describe the use of organized mesoporous titanium oxide (TiO(2)) films as three-dimensional templates for protein microarrays with enhanced protein loading capacity and detection sensitivity. Multilayered mesoporous TiO(2) films with high porosity and good connectivity were synthesized using a graft copolymer consisting of a poly(vinyl chloride) (PVC) backbone and poly(oxyethylene methacrylate) (POEM) side chains as a structure-directing template. The average pore size and thickness of the TiO(2) films were 50-70 nm and 1.5 μm, respectively. Proteins were covalently immobilized onto mesoporous TiO(2) film via 3-aminopropyltriethoxysilane (APTES), and protein loading onto TiO(2) films was about four times greater than on planar glass substrates, which consequently improved the protein activity. Micropatterned mesoporous TiO(2) substrates were prepared by fabricating poly(ethylene glycol) (PEG) hydrogel microstructures on TiO(2) films using photolithography. Because of non-adhesiveness of PEG hydrogel towards proteins, proteins were selectively immobilized onto surface-modified mesoporous TiO(2) region, creating protein microarray. Specific binding assay between streptavidin/biotin and between PSA/anti-PSA demonstrated that the mesoporous TiO(2)-based protein microarrays yielded higher fluorescence signals and were more sensitive with lower detection limits than microarrays based on planar glass slides.     

Characteristics of nano-sized (Pb, La)TiO3 powder synthesized at room temperature

We synthesized nano-sized (Pb, La)TiO3 powder using a high energy mechano-chemical technique at room temperature. By the results, nano-sized (Pb, La)TiO3 powder with perovskite structure was successfully synthesized from an oxide mixture using a high energy mechano-chemical technique without any post-annealing. The mechanically-synthesized (Pb, La)TiO3 powder consisted of nanometer sized particles and had very high homogeneity. According to increase of milling time, source phases such as Pb oxides and TiO2 disappeared and the perovskite PLT phase was formed by chemical reaction and the release of OH group.     

Low temperature synthesis and visible light driven photocatalytic activity of highly crystalline mesoporous TiO2 particles

Mesoporous TiO2 powder materials with a high crystallinity have been prepared by evaporation induced self assembly (EISA) process using titanium tetraisopropoxide (TTIP) and pluronic P123 surfactant (EO20PO70EO20) as titanium source and structure-directing reagent, respectively. The prepared materials were characterized by low and wide-angle X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), optical absorption, and N2 adsorption-desorption experiments. The crystallinity of the materials was controlled by varying the calcination temperature. The resulting TiO2 materials showed highly crystalline structure with uniform particle size which increases from 11.8 to 23.8 nm with increasing the calcination temperature from 400 to 600 degrees C, respectively, whereas the specific surface area decreases from 125 to 40 m2/g. TEM and XRD results revealed that the calcination temperature of 600 degrees C is the best condition to obtain highly crystalline mesoporous TiO2. The photocatalytic activity of the TiO2 mesoporous materials with different crystallinity and textural parameters has been studied in the decomposition of methylene blue (MB) dye molecules under visible light irradiation. Among the mesoporous TiO2 materials studied, the material with the highest crystallinity, prepared at 600 degrees C, showed the best photocatalytic performance in the decomposition of MB under visible light in a short time.     

介孔TiO2微球水热法合成及在染料敏化太阳能电池中的应用

以Ti(SO4)2为钛源,采用尿素辅助水热法合成了介孔TiO2微球,利用XRD、FESEM和比表面积分析仪对样品的晶型、形貌和比表面积进行分析,探讨了尿素加入量对TiO2微球的颗粒尺寸、比表面积、孔径和孔容的影响。采用刮涂法,用所合成的介孔TiO2微球制备了染料敏化太阳能电池(DSSC)的光阳极,结果表明,尿素用量为1.2g合成的介孔TiO2微球所组装的电池在模拟太阳光的照射下(100mW/cm2,AM1.5),光电转换效率为6.2%,明显高于商用P25纳晶所组装的电池光电转换效率(4.24%)。     

Investigation of Eu-doped mesoporous titania phosphor with enhanced luminescence

A novel mesoporous TiO2 phosphor doped with Eu was synthesized through a facile hydrothermal synthesis method using cetyltrimethylammonium bromide as structure template reagent. The samples were characterized by X-ray diffraction, N2 adsorption-desorption, scanning electron microscope, high-resolution transmission electron microscopy, ultraviolet visible diffuse reflectance, X-ray photoelectron spectroscopy, and three dimensional Photoluminescence. The X-ray diffraction results demonstrated that the products were anatase type with polycrystalline. N2 adsorption-desorption analysis showed that the samples were of high ordered double mesoporous structures. Eu-doped mesoporous TiO2 indicated the typical fluorescent spectra of Eu3+ ion occurred: the excited-states at 5L6 (394 nm), 5D2 (465 nm) and 5D1 (535 nm); the main emission peaks at 592 and 617 nm, corresponding with the transitions 5D0 --> 7F1 and 5D0 --> 7F2, respectively. Meanwhile, the phenomena of Eu(3+)-doped mesoporous TiO2 phosphor with efficient nonradiative energy transfer from the mesoporous TiO2 host to the activator Eu3+ ions was observed and possible emission mechanism was proposed. High dispersion of Eu in mesoporous TiO2 matrix was responsible for enhanced luminescence.     

TiO2@SBA-15的合成及其光解性能

以水热沉积法在介孔SBA-15上固载TiO2纳米粒子制得光催化剂TiO2@SBA-15,探讨了TiO2负载量对催化效果的影响.以包括N2吸附-脱附、紫外漫反射光谱(DRS)等手段在内的多种技术手段表征了催化剂的结构.研究结果表明适宜负载量的锐钛矿晶型TiO2纳米粒子可均匀分散在载体SBA-15上,N2吸附-脱附进一步表明载体介孔结构得以保持.适宜TiO2负载量的催化剂20 mg紫外光照25 min可将100 mL的10 mg·L-1亚甲基蓝降解完全.