Pd纳米晶修饰TiO2纳米管阵列光电极的制备及性能

为提高TiO₂的可见光催化性能,采用阳极氧化法在Ti箔上原位生成TiO₂纳米管阵列,再利用阴极电沉积法制备了贵金属Pd纳米晶修饰的TiO₂纳米管阵列光电极,并利用扫描电子显微镜（SEM）、X-射线光电子能谱（XPS）及紫外-可见漫反射光谱（UV-vis DRS）对其表观形貌、表面形态及光吸收性能进行表征．结果表明:Pd纳米晶有效地修饰在TiO₂纳米管阵列的表面,且以Pd⁰形式存在．此外,Pd纳米晶修饰明显拓展了TiO₂纳米管阵列的可见光响应范围．以甲基蓝为模型污染物,重点考察阴极沉积电压及沉积时间对其光催化性能的影响．结果表明:阴极沉积电压为-0.8 V、沉积时间为10 min对甲基蓝的光催化降解效果最佳,且符合拟一级反应动力学模型．模拟太阳光下光照120 min对甲基蓝的降解率可达71.4％,是纯TiO₂纳米管阵列光电极的1.5 倍．     

石墨烯薄膜修饰TiO2纳米管光电极制备及性能

为提高TiO₂光催化剂的可见光催化活性,采用阳极氧化法制备了高度有序的TiO₂纳米管,利用阳极电化学沉积构筑了石墨烯薄膜修饰的TiO₂纳米管光电极,并利用扫描电子显微镜、X-射线光电子能谱及紫外-可见漫反射光谱对其表观形貌、组成结构及光吸收性能进行表征．结果表明:石墨烯有效地修饰在TiO₂纳米管表面,且以透明薄膜形式存在．此外,石墨烯薄膜修饰显著拓展了TiO₂纳米管的可见光响应范围．以甲基蓝为探针分子,考察了阳极沉积电压及沉积时间对所制备石墨烯薄膜／TiO₂纳米管光电极光催化性能的影响．结果表明:阳极沉积电压为+0.8 V、沉积时间为10 min时,制备的石墨烯薄膜／TiO₂纳米管光电极对甲基蓝的光催化降解效果最佳．模拟太阳光下光照120 min对甲基蓝的降解率为65.9％,是纯TiO₂纳米管光电极的1.35 倍．     

水环境中不同浓度TiO2纳米颗粒混凝工艺去除效果

为了探究水环境中不同质量浓度TiO₂ 纳米颗粒(NPs)混凝工艺去除影响因素及与浊度去除规律的区别,研究了在超声预处理后投加表面活性剂(LAS)对TiO₂ NPs分散稳定性的影响,通过烧杯实验分别考察了混凝剂(聚合氯化铝,PAC)投加量及pH对不同质量浓度TiO₂ NPs和浊度去除的影响,及pH对TiO₂ NPs表面Zeta电位的影响机制．结果表明,在250 W超声处理10 min后加入20 mg／L的LAS获得的纳米悬浮液稳定性最好;不同混凝剂投加量下,TiO₂ NPs和浊度的去除规律呈相近趋势,TiO₂ NPs初始质量浓度为0.5,1和2 mg／L时,PAC最优投加量为3 mg／L,对应TiO₂ NPs和浊度最大去除率分别为46.2％、60.2％、68.8％和23.2％、43.6％、47.6％．TiO₂ NPs初始质量浓度为5 mg／L时,PAC最优投量为4 mg／L,TiO₂ NPs和浊度最大去除率分别为77.64％和54.08％．pH对TiO₂ NPs表面Zeta电位有明显影响,进而影响TiO₂ NPs的去除效果．     

模板法合成三维菊花状TiO2纳米花及其性能

为了解决一维、二维纳米材料在降解有机污染物时,易发生团聚、催化活性低、难以回收利用等问题,以TiO₂(P25)和NaOH为原料,ZnO为模板,采用水热法合成了三维菊花状TiO₂纳米花．运用扫描电子显微镜、X射线衍射仪、氮气吸附脱附、紫外-可见漫反射、傅立叶红外等手段对合成的样品进行测试分析. 结果表明:其花瓣是由TiO₂纳米颗粒通过自组装定向排列而成的链状结构,构成纳米花的粒子晶粒尺寸约15 nm,花状结构尺寸约为5 μm,结晶性良好,为锐钛矿相;比表面积为102.3 m²／g,平均孔径为17.41 nm;以亚甲基蓝为目标污染物,在紫外光照射下对其进行光催化性能实验,80 min亚甲基蓝的降解率为98％,催化活性高于P25,显示出较强的光催化活性．     

具有可见光响应的改性纳米TiO2研究进展

通过改性可以改变TiO2只有在紫外光激发下才显示出较高光催化效率的特点,使其在可见光范围也显示出较高的活性。本文综述了纳米TiO2改性方面的研究进展,指出通过元素掺杂、贵金属修饰、聚合物修饰、半导体复合、染料敏化等手段对TiO2进行改性,可以减小纳米TiO2禁带,提高纳米TiO2对可见光的响应性和量子效率。分析认为,实验室制备的改性纳米TiO2可见光光催化效果已经比较理想,解决回收难、工程易操作性等问题是未来的发展方向。     

TiO2对高C3S熟料烧成的影响

通过外掺TiO₂来改善高C₃S熟料的烧成.配制7个生料样品,其潜在矿物组成均为w(C₃S)=75%、w(C₃A)=7%、w(C4AF)=18%,TiO₂掺量分别为0、05%、10%、15%、20%、25%、30%,在设定的高温下煅烧成熟料,通过化学分析、XRD、SEM/EDS等方法,研究了TiO₂对熟料易烧性、矿相形成、C₃S晶体形貌和熟料强度等的影响.结果表明,掺入少量TiO₂明显提高了熟料的易烧性;当TiO₂掺量小于2%时,f-CaO随TiO₂掺量的增加而显著降低;当TiO2掺量超过2%后,f-CaO随TiO₂掺量的变化不大;当TiO₂掺量达到3%时,在1 350和1 400 ℃温度煅烧的熟料中均发现了CaO·TiO₂新相;掺2%TiO2在1 400℃煅烧条件下的熟料,TiO₂在C₃S中的固溶量约1.7%;掺入适量的TiO₂,熟料中C₃S结晶比较完整、均匀,熟料强度较高.适当掺入TiO₂对改善高C₃S熟料的烧成和提高其强度都是有利的.     

TiO2/石墨烯复合材料的水热法合成与光催化性能

为了提高TiO₂的光催化性能,采用水热法一步制备了TiO₂/石墨烯(TiO₂/RGO)复合物．采用XRD、FT-IR、RS、UV-Vis DRS、TEM等测试方法对其进行了表征,并研究了不同质量比的复合物在可见光下对甲基橙(MO)的光催化降解．结果表明:在TiO₂/RGO复合物中,TiO₂以10 nm左右的颗粒均匀地分散在石墨烯层上;与在同等条件下制备的TiO₂相比,TiO₂/RGO复合物在可见光区吸收明显增强,吸收边缘红移了20 nm;质量比为1∶0.005的TiO₂/RGO复合物,2 h内的降解率达到74.79％．可见将石墨烯与TiO₂复合,能够有效地提高TiO₂的可见光催化性能．     

沸石负载Mn,N共掺杂TiO2及光催化性能

为提高传统TiO₂光催化剂的可见光催化活性,本文采用溶胶-凝胶法合成了Mn,N共掺杂TiO₂光催化剂,改善了传统TiO₂光生载流子易复合的问题;进一步采用沸石作为载体对改性后的TiO₂样品进行负载,解决了传统光催化剂存在的难分离回收问题,以达到光催化剂可重复使用的目的.借助X-射线衍射仪、扫描电子显微镜、紫外分光光度计、傅立叶变换红外光谱仪等测试手段对Mn,N共掺杂TiO₂光催化剂的结构、元素组成、微观形貌和光催化降解性能进行系统分析与研究.研究结果表明,沸石负载Mn,N共掺杂TiO₂的样品较未改性的TiO₂样品具有更高的光催化降解活性,在可见光照射下,在最优掺杂条件下获得的TiO₂光催化剂在60 min内对孔雀石绿的降解率可达到97%,这主要归因于锰离子掺杂能够对TiO₂光生载流子的复合产生抑制作用,促进光生电荷分离,与此同时氮元素掺杂可有效拓宽TiO₂半导体光催化剂光响应范围.此外,经过5次循环使用后,对孔雀石绿的降解率没有较大程度的减弱,依然能够维持在88%以上,表明沸石负载Mn,N共掺杂TiO₂的样品具有较好的光催化循环稳定性.     

纳米Al2O3改性环氧胶黏剂和钢铁附着机理的研究

通过拉拔法测定纳米Al₂O₃改性环氧胶黏剂和钢铁之间的附着强度,并结合环氧胶的表面能参数测定以及X射线光电子能谱(XPS)分析,对纳米Al₂O₃提高环氧胶和钢铁附着力的机理进行研究.表面能测定结果表明,添加纳米Al₂O₃使环氧胶的极性增加;XPS能谱分析结果表明,当纳米Al₂O₃质量分数达到2%时,环氧胶中形成新的羧基极性基团;进一步研究发现,当纳米Al₂O₃质量分数为1%时未形成新的羧基基团,当纳米Al₂O₃质量分数为8%时单位接触面积上新的羧基基团的数目较2%时少,这与附着强度的变化规律是一致的.因此,纳米Al₂O₃改性的环氧胶黏剂与钢铁的附着强度的增强是由于Al₂O₃与环氧胶的相互作用形成了新的羧基极性基团．     

负载纳米TiO2石英砂功能集料-水泥石的界面粘结性能

光催化水泥基材料是先进建筑功能材料的研究热点之一,但传统内掺法制备的TiO₂-水泥基复合材料中TiO₂有效利用率低、经济效益差。针对此问题,采用负载法制备纳米TiO₂功能集料（QST）,并将QST集料负载于普通水泥砂浆表面。研究QST集料对水泥砂浆干缩性能的影响,通过拉拔法测试QST集料与水泥石的界面粘结力;采用SEM、EDS、MIP等微观测试方法,研究纳米TiO₂对集料-水泥石界面过渡区水化产物、孔结构的影响。结果表明：与普通石英砂集料相比,表面负载纳米TiO₂的石英砂功能集料可减少水泥砂浆的干缩,提高集料-水泥石的界面粘结力。在QST集料-水泥石的界面过渡区,纳米TiO₂促进了水泥浆体的水化,减少了界面过渡区Ca(OH)₂的富集,细化并改善了界面过渡区的孔结构。     

Powder Quartz/Nano-TiO<Subscript>2</Subscript> Composite: Mechanochemical Preparation and Photocatalytic Degradation of Formaldehyde

Powder quartz (PQ)/nano-TiO₂ composite was prepared by a mechanochemical method. Based on as-prepared PQ/nano-TiO₂ composite, we prepared interior paints and investigated the degradation efficiency of formaldehyde (DEF). Scanning electron microscopy showed that nano-TiO₂ got well dispersed by the adding of PQ. Thermogravimetric analysis indicated that the mass ratio of 4:1 was a relatively good proportion for the most production of PQ/nano-TiO₂ composite. Fourier transform-infrared spectrometry showed that the peak position of Ti-O-Si bond varied with the milling time. At the early stage, no characteristic peak of Ti-O-Si bond was observed, while at the later stage, new peaks at 902 cm^-1 and 937 cm^-1 appeared. Meanwhile, PQ/nano-TiO₂ composite-based interior paint exhibited significant DEF of 96.3% compared to that consisting of sole nano- TiO₂ of 92.0% under visible light illumination. As an abundant mineral resource, PQ would make interior paints with HCHO purifying effect much more efficient and cheaper.     

Modification of nano-TiO2 by Al2O3 in-situ coating

A novel technology of in-situ coating Al₂O₃ on the surface of H₄TiO₄ was developed to prevent the aggregation of nano-TiO₂ powders and improve the dispersibility and thermal stability in the way of forming a uniform coating layer. The heterogeneous nucleation was conducted to prepare the precursor of nano-TiO₂ and then Al₂O₃ was coated on the surface of precursor. The effects of Al₂O₃ in-situ coating on the properties of nano-TiO₂ were investigated. The results show that H₄TiO₄ can be dispersed well under alkaline condition (pH 8.5) and the heterogeneous nucleation can be controlled easily. The optimized uniform coating layer is obtained by adding 5% (mass fraction) and 10% of Al₂O₃ and the aggregation of nano-TiO₂ powders is effectively inhibited and the dispersibility is obviously improved. The crystal sizes of TiO₂ powders are 12.3, 11.4 and 8.7 nm after coating 0,5% and 10% of Al₂O₃ respectively. Al₂O₃ on the surface of particulates in amorphous phase could increase the thermal stability of nano-particles after calcined at 550 °C. Foundation item: Project(04GK2007) supported by Hunan Industrial Key Project of Science and Technology     

Study on method and mechanism for simultaneous desulfurization and denitrification of flue gas based on the TiO2 photocatalysis

Based on the TiO₂ photocatalysis mechanism, a new method of simultaneous desulfurization and denitrification from flue gas was proposed. Preparation of TiO₂ photocatalyst, design of photocatalysis reactor and influencing factors for simultaneous removal of SO₂ and NO, and removal mechanism of SO₂ and NO were studied. After the optimal values of concentration of O₂ in flue gas, the relative humidity of flue gas and the irradiation time in the photocatalysis reactor were used, the efficiencies of removal for SO₂ and NO can be achieved above 98% and about 67%, respectively. According to the results of removal products analysis, the removal mechanism of SO₂ and NO based on TiO₂ photocatlysis can be put forward, namely, SO₂ was oxidized to SO₃ partly, the bulk of NO was oxidized to NO₂, and both were removed by resorbing finally.     

Effect of pH values on photocatalytic properties of Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript> synthesized by hydrothermal method

Highly crystalline orthorhombic Bi₂WO₆ powders were hydrothermally synthesized from aqueous solutions of Na₂WO₄ · 2H₂O and Bi (NO₃)₃ · 5H₂O over a wide range of pH. The effect of pH on morphologies, sizes and properties of the Bi₂WO₆ crystals was investigated. The band gaps of the as-prepared Bi₂WO₆ were determined from the onset of the absorption edge of UV-vis diffuse reflectance spectra. The methyl orange photodegradation was employed as a probe reaction to test the photocatalytic activity of the as-prepared samples under visible light irradiation. The photocatalytic activities of methyl orange degradation under visible light irradiation are strongly dependent on the pH used in the synthesis. The highest efficiency is observed at pH=7. Funded by the PCSIRT, the National Natural Science Foundation of China (Nos. 50532030 and 50625206) and the Zhejiang Provincial Natural Science Foundation of China (No. Z4080021)     

铈碳共掺杂TiO_2脱除烟气汞的实验研究

采用自主设计的光催化台架,在实验室中研究了Ce和C共掺杂的TiO_2在光催化脱汞方面的效率,并与Ce和C的单一掺杂及纯TiO_2进行对比,用以确定Ce和C在光催化反应中各自的作用及共掺杂后的相互影响.     

YVO_4基纳米光催化剂制备及其光催化脱汞性能评价

采用水热反应法制备YVO4光催化剂,并通过掺杂C和Sm3+对其进行改性,通过X射线衍射仪(XRD)、扫描电镜(SEM)和比表面积(BET)对其形态、结构、组成和性质进行表征.在紫外光条件下,对YVO4及其改性后的催化剂进行脱除气态元素汞(Hg0)评价,YVO4,YVO4掺碳,YVO4掺Sm3+,YVO4掺Sm3+掺碳催化剂脱汞效率分别为10.5%,9.1%,5.2%,19.6%.其中YVO4∶Sm3+/C效果最好,但也只有19.6%.这可能是紫外光激发了YVO4导带的电子,且电子成功地跃迁到了价带,但由于此反应产生的光生载流子能量较弱,不足以激发自由·OH,只能靠光生载流子直接氧化汞,导致样品不能高效光催化氧化汞.     

A Fundamental DFT Study of Anatase(TiO_2) Doped with 3d Transition Metals for High Photocatalytic Activities

Anatase(TiO_2) has been widely used in photocatalysis. However, it can only absorb near-ultraviolet light with a wavelength below approximately 388 nm due to a wide band gap. Therefore a modification should be made for anatase to increase its capability in utilizing more abundant visible light. We investigated the doped anatase with the most promising 3d transition metal elements, and the results showed that the visible light absorption intensity was increased significantly due to the reduced band gap and the cavitation effects. As compared to other 3d transition metals, Cu was found to be the most effective one in improving anatase photocatalytic effects. In addition, greater Cu concentration doped in the anatase increased the photocatalysis effects but reduced the anatase stability, therefore, an optimized Cu concentration should be considered to optimize the anatase photocatalysis activity.     

GNR-TiO_2/g-C_3N_4异质结构的制备及其性能研究

采用二次凝胶-溶胶法和水热法合成了具有光催化效应的GNR-TiO_2/g-C_3N_4异质结构,并对其性能进行了研究.研究结果表明:GNR-TiO_2/g-C_3N_4异质结构表现出强的光催化活性,并在可见光照射下,对有机物亚甲基蓝有良好的催化效果.这主要归因于石墨烯纳米带作为载体,不仅增加了异质结构的比表面积,还使空穴-电子对的再结合率降低.     

Review:Nanostructured TiO2 for Enhanced Photocatalytic Property by Glancing Angle Deposition Method

物理气相沉积GLAD法在二氧化钛光催化剂的应用

双爽¹,谢拯^1,2,张政军³

（1.清华大学 新型陶瓷与精细工艺国家重点实验室（材料科学与工程学院）,北京 100084;2. 西安高新技术研究所, 西安 710025;3. 清华大学 先进材料教育部重点实验室（材料科学与工程学院）,北京 100084）

创新点说明：

1）通过气相沉积的物理方法,制备垂直或倾斜生长的纳米阵列作为光催化剂,提高催化剂回收效率,减少二次污染;

2）运用掺杂、修饰以及复合其他材料的方法,拓展二氧化钛在可见光范围的利用;

3）通过表征手段分析,分析内在光催化效率提高机理。

研究目的：

通过多种方法,提高气相沉积GLAD法制备的二氧化钛在可见光范围的利用率,分析催化反应提高机理。

研究方法：

磁控溅射、电子束蒸镀、原子层沉积

结果：

1）通过气相物理沉积GLAD方法,制备了垂直或倾斜生长的纳米阵列作为光催化剂,提高回收效率,减少二次污染;

2）利用掺杂、修饰以及复合其他材料的方法,提高二氧化钛在可见光范围的利用率;

3）通过表征手段分析,分析内在光催化效率提高机理。

结论：

1）实现了在特定基底生长纳米阵列光催化剂的制备,提高回收效率减少二次污染;

2）使用化学方法复合窄带隙硫氧化物、贵金属及石墨烯提高催化剂在可见光范围的利用率,并分析其内在增强机理。

关键词：二氧化钛纳米阵列,倾斜生长阴影效应,带隙匹配