Photogenerated carrier transfer mechanism and photocatalysis properties of TiO_2 sensitized by Zn(Ⅱ) phthalocyanine

The Zn(Ⅱ) phthalocyanine sensitized TiO2(ZnPc-TiO2) nanoparticles were prepared by hydrothermal method via impregnation with ZnPc.The as-prepared photocatalysts were characterized by X-ray diffractometry(XRD) and diffuse reflectance spectroscopy(DRS),and the surface photovoltage spectroscopy(SPS) and photocatalytic degradation of rhodamine B(RhB) were studied under illuminating.The experimental results indicate that TiO2 sensitized by ZnPc extends its absorption band into the visible region effectively,and the sensitized TiO2 has higher activity than TiO2(Degussa P-25) under the simulated solar light and the visible light.Based on the DRS and SPS results,the mechanism about the photogenerated carrier transfer between TiO2 and ZnPc is proposed.At a lower ZnPc content(≤0.20 μmol/g),ZnPc monomer acts as the electron donor,which provides the photoinduced electrons to the conduction band of TiO2.These photoinduced electrons can transfer to molecular oxygen(O2),leading to the formation of active species,such as superoxide/hydroxide radicals and singlet oxygen,which is beneficial to the photocatalytic reaction.While at a higher ZnPc content(0.20 μmol/g),the formation of ZnPc dimer results in the decrease of photocatalytic activities of ZnPc-TiO2 photocatalyst.     

Zn（Ⅱ）-NaOH-H2O体系中锌溶解平衡模型的构建

本文利用电算指数法及平衡法对Zn（Ⅱ）-NaOH-H2O体系热力学进行了深入研究,揭示了在氢氧化钠浓度在0-300 g/L范围内,锌的分布形式及溶解规律,构建了锌在氢氧化钠溶液中的溶解平衡模型,并对热力学计算结果进行实验验证和差异分析.结果表明：锌溶解平衡浓度计算值与实验值的相对偏差的绝对平均值为0.1298%,这说明热力学模型是正确的,所选数据的准确性较好.     

AgBr/TiO2（001）纳米片可见光光催化剂的制备

以暴露高能面（001）面的TiO2纳米片为载体,NaBr和CTAB分别为溴源,通过浸渍-沉积法合成AgBr/TiO2（001）纳米片复合可见光催化剂。采用X射线衍射（XRD）、透射电镜（TEM）、X射线光电子能谱（XPS）、紫外-可见光谱（UV-Vis）等手段对其进行了表征。在可见光（λ〉420nm）的辐照下,通过降解甲基橙来评价合成样品的可见光催化性能,探讨AgNO3的用量、不同溴源和F-在TiO2纳米片表面残留对催化性能的影响。结果表明,以NaBr为溴源制备Ag/AgBr@TiO2复合催化材料,当AgNO3添加量为0.313 5g时,其综合效果最优;而以CTAB为溴源制备的样品其催化活性明显高于以NaBr为溴源制备的样品;TiO2纳米片表面残留F-离子对活性略有影响。     

TiO2／Mg（OH）2复合材料对有机污水中甲基橙的光催化降解动力学的研究

采用溶胶一凝胶法制备了纳米TiO2,并以TiO2和镁盐溶液为前驱物用氨气鼓泡法制得了TiO2／Mg（OH）2复合材料．利用氢氧化镁在水溶液中较强的吸附能力和TiO2对有机物的催化降解作用,研究TiO2／Mg（OH）2复合材料对有机污水中的甲基橙暗反应吸附规律和光反应催化降解性能．结果表明：当Ti02／Mg（OH）2加入量为1g·L^-1。时,在可见光下照射180min后,对有机污水中含20mg·L^-1的甲基橙的降解率达到98．00％,同时在同等条件下选用国家标准（30mg·L^-1亚甲基蓝溶液）作为参照时,降解率可达99．20％．TiO2／Mg（OH）2复合材料对污水中甲基橙的催化降解反应较好地符合Langmuir动力学模型,可用一级反应动力学方程进行描述．     

邻菲咯啉锌（Ⅱ）配合物[Zn（phen）3]·（ClO4）2的水热合成、晶体结构及光谱性质

用水热法合成了一种新的配合物[Zn（phen）3].（ClO4）2,并用X-射线衍射分析、元素分析、红外光谱、紫外光谱及荧光光谱对其结构进行了表征。配合物的晶体结构属于单斜晶系,空间群为P21/n,晶胞参数为a=1.355 36（14）nm,b=2.559 3（3）nm,c=2.077 1（2）nm,β=109.04°,V=6.810 8（12）nm3,Z=8,Dc=1.570g.cm-3,μ=0.942 mm-1,F（000）=3 280。该配合物中心离子是一个典型的八面体配位构型。     

Effects of H3PO4 and Ca（H2PO4）2 on mechanical properties and water resistance of thermally decomposed magnesium oxychloride cement

The effects of H3PO4 and Ca（H2PO4）2 on compressive strength, water resistance, hydration process of thermally decomposed magnesium oxychloride cement （TDMOC） pastes were studied. The mineral composition, hydration products and hydration heat release were analyzed by XRD, FT-IR, SEM and TAM air isothermal calorimeter, etc. After being modified by H3PO4 and Ca（HzPO4）2, the properties of the TDMOC are improved obviously. The compressive strength increases from 14.8 MPa to 48.1 MPa and 37.1 MPa, respectively. The strength retention coefficient （Kn） increases from 0.38 to 0.99 and 0.94, respectively. The 24 h hydration heat release decreases by 10% and 4% and the time of hydration peak appearing is delayed from 1 h to about 10 h. The XRD, FT-IR and SEM results show that the main composition is 5Mg（OH）z＇MgCIz＇8H20 in the modified TDMOC pastes. The possible mechanism for the strength enhancement was discussed. The purposes are to extend the potential applications of the salt lake magnesium resources and to improve the mechanical properties of TDMOC.     

红磷单质光催化剂在能源转化和环境净化领域的研究进展

单质红磷（red P）作为一种新型的可见光响应的半导体光催化剂,具有合适的带隙、独特的电子结构、稳定的化学性质、价廉易得等优点,在可见光光催化能源转化和环境保护领域受到人们的广泛关注.综述了近年来红磷单质光催化剂的物化性质、制备方法、改性研究以及红磷基纳米复合光催化剂的催化原理,并对红磷单质光催化剂的发展方向及应用前景进行了展望.

     

Preparation of TiO2 photocatalyst loaded with V2O5 for O2 evolution

TiO₂ photocatalysts loaded with V₂O₅ were prepared via a modified hydrolysis process, and characterized by X-ray diffraction, transmission electron microscopy, Raman spectra and diffuse reflectance UV-Vis spectra measurements. The photocatalytic activity of V₂O₅/TiO₂ was investigated by employing splitting of water for O₂ evolution. The results indicate that V₂O₅ loading can pronouncedly improve the photocatalytic activity of TiO₂ with Fe³⁺ as an electron acceptor under UV or visible light irradiation. The optimum mass fraction of the loaded V₂O₅ is 8%, and the largest speed of O₂ evolution for 8%V₂O₅ (mass fraction) loaded TiO₂ catalyst is 118.2 μmol/(L·h) under UV irradiation, and 83.7 μmol/(L·h) under visible light irradiation.     

Fe_3O_4-TiO_2磁性光催化剂的制备与性能

采用化学共沉淀法制备磁性纳米Fe3O4作为磁载体,以溶胶-凝胶法制备了Fe3O4-TiO2磁性光催化剂,采用X射线衍射(XRD)、紫外-可见(UV-Vis)漫反射等手段对其进行表征。以亚甲基蓝水溶液为模拟污染物,测试了Fe3O4-TiO2磁性光催化剂的光催化性能,光照90min后,亚甲基蓝的脱色率可达到96.6%,相同条件下TiO2对亚甲基蓝的脱色率为93.6%。在外加磁场作用下,Fe3O4-TiO2磁性光催化剂的平均回收率为85.6%,TiO2离心分离平均回收率为62.7%,Fe3O4-TiO2磁性光催化剂在保证高催化活性的前提下实现了高效回收。     

Coexistence of antiferromagnetic and ferromagnetic in Mn-doped anatase TiO2 nanowires

A series of Mn-doped TiO_2 nanowires (NWs) were prepared by hydrothermal method at the mole fraction of Mn changing from 0 to 12.0%. X-ray powder diffraction (XRD) analysis shows that all the samples have pure anatase structure. SEM and TEM studies show that the diameter and the length of the Mn-doped TiO_2 NWs are larger than those of the undoped TiO_2 NWs. Energy dispersive X-ray spectroscopy (EDX) reveals that the samples are composed of Ti, Mn and O. According to magnetization measurements, all samples show ferromagnetic behavior, but only the undopedTiO_2 NWs are completely ferromagnetic with a saturated magnetization about 1.0 mA·m~2/kg. Mn-doped TiO_2 samples exhibit antiferromagnetic and ferromagnetic (AF-FM) behaviors simultaneously. Photoluminescence (PL) spectra demonstrate the existence of MnO_2 sublattice. These observations indicate that an AF-WF crossover is induced by the coexistence of TiO_2 sublattice and MnO_2 sublattice.     

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.     

Enhanced photocatalytic activity of （La, N） co-doped TiO2 by TiCl4 sol-gel autoigniting synthesis

(La, N) co-doped TiO2 photocatalysts were synthesized using TiCl4 sol-gel autoigniting synthesis (SAS) starting from a plished in the formation of TiO2 nanocrystals. The prepared samples were characterized by using X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS) and UV-vis diffuse reflectance spectra. The results indicated that nitrogen and lanthanum were incorporated into the lattice and interstices of titania nanocrystals, which resulted in narrowing the band gap and promoting the separation of photoexcited hole-electron pairs, respectively, and showing expected red-shifts and enhanced photocatalytic activity under visible light. The mechanism on nitrogen doping and enhancement in photocatalytic activity of (La, N) co-doped titania by SAS was discussed in detail.     

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.     

p-n异质结TiO_2/NiO光催化剂的制备及其性能研究

采用溶胶凝胶和浸渍煅烧相结合的方法,制备出了具有p-n异质结结构的球形二氧化钛表面负载氧化镍颗粒的复合光催化剂.利用XRD、TEM、UV-Vis和PL等方法对催化剂的晶相组成、微观结构、吸光性能和光致发光性能等进行了表征.结果表明氧化镍晶粒与二氧化钛晶粒紧密接触形成p-n异质结.氧化镍颗粒的负载使复合光催化剂的吸收带边发生了明显的红移,并进入了可见光区.形成的p-n异质结促进了二氧化钛光生电子和空穴的分离,从而降低了其本征发光光强度.通过在可见光条件下对亚甲基蓝的降解研究了其光催化性能,结果表明,氧化镍颗粒的负载使二氧化钛的光催化效果在可见光区有了显著地提高,并在一定范围内随着氧化镍含量的增加光催化效果也随之提高.     

稀土修饰TiO2光催化降解甲基橙反应机理

采用溶胶-凝胶法制备纯的及掺杂不同量Ce的TiO2纳米粒子,利用UV-Vis漫反射光谱及XRD等对所制备样品进行表征,以紫外灯为光源,甲基橙水溶液的脱色为模型反应,研究了CeO2/TiO2的光催化降解反应活性.实验发现:掺杂Ce的TiO2纳米粒子反射光谱特性向可见光方向红移到了500nm;掺杂Ce的TiO2纳米粒子比纯的TiO2纳米粒子对光的吸收率高、吸收能力强;掺杂的Ce4+仅有少量进入TiO2晶格中,而大部分的Ce4+没有进入TiO2晶格中,而是以小团簇的CeO2形态均匀地分散在TiO2纳米粒子中或者是覆盖在其表面上,说明了掺杂Ce能提高TiO2光催化反应活性,且掺杂Ce最佳浓度是2.0mol%.光催化降解反应机理可能有两种途径,一种途径是掺杂离子协同光催化降解甲基橙反应机理,另一种途径是光敏剂与掺杂离子协同光催化降解甲基橙反应机理.     

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．