TiO2-SiO2二维大孔薄膜的制备及其光催化活性研究

本文采用改进的溶胶-凝胶法制备了具有锐钛矿晶型结构和较小晶粒尺寸的TiO₂-SiO₂溶胶,并以聚苯乙烯(PS)小球为模板,采用旋涂法制备了新型大孔TiO₂-SiO₂复合薄膜,探究了煅烧温度、不同硅钛比以及溶胶添加量对所制备的大孔薄膜形貌及光催化活性的影响,并考察了该薄膜真空活化前后(Ti³⁺掺杂后)在紫外及模拟太阳光下光催化降解有机污染物罗丹明B的活性。通过Raman、DRS、SEM、EPR等方法对薄膜进行表征,发现制备的复合薄膜具有高透明度、良好附着力及优异的光催化活性。     

TiO2与碳纳米管的复合及光催化协同作用*

TiO₂与碳纳米管均是近15年来最受关注的功能材料。将TiO₂与碳纳米管复合构建的TiO₂/碳纳米管兼有两种材料的特点及优点,在许多领域得到广泛研究。本文基于国内外最新研究进展,系统综述了近年来逐步建立起来的制备TiO₂/碳纳米管的方法,着重介绍了混合法、化学气相沉积法、静电纺丝法、溶胶-凝胶法、水热溶剂热法等几种比较主要的方法。并且以TiO₂ /碳纳米管在光催化领域的应用研究为侧重点,详细分析了碳纳米管在促进TiO₂光生电子-空穴分离、增强可见光吸收等方面的协同作用。文章最后指出相关研究中有待解决的问题,并对此类材料的发展趋势做了展望。     

耐高温核/壳结构TiO2/SiO2复合气凝胶的制备及其光催化性能

以钛酸四丁酯为源, 采用苯胺-丙酮原位生成水溶胶-凝胶法, 在乙醇超临界干燥过程中用部分水解的钛醇盐和硅醇盐对TiO₂凝胶进行超临界修饰制备了具有核/壳纳米结构的块体TiO₂/SiO₂复合气凝胶. 制备的复合气凝胶具有优异的机械性能, 其杨氏模量可达4.5 MPa. 复合气凝胶同时具有极好的高温热稳定性. 经过1000 ℃热处理后, 线性收缩由纯TiO₂气凝胶的31%降至复合气凝胶的10%, 且比表面积由纯TiO₂气凝胶的31 m²·g^-1提升至复合气凝胶的143 m²·g^-1. 此外, 该复合气凝胶经1000 ℃热处理后具有优异的光催化降解亚甲基蓝的性能. 其优异的光催化性能得益于TiO₂/SiO₂复合气凝胶1000 ℃处理后高的比表面积和小的颗粒尺寸. 优良的耐热性能、力学性能和光催化性能使获得的具有核/壳纳米结构的TiO₂/SiO₂复合气凝胶在光催化领域具有良好的应用前景.     

微波辅助合成ZnO-TiO2及其可见光催化脱硝活性

通过对比水热溶胶凝胶法与微波辅助溶胶凝胶法制备的复合TiO₂的光催化性能,最终采用耗时较短且结晶度更好的微波辅助溶胶凝胶法制备了不同复合比例的ZnO-TiO₂材料。ZnO-TiO₂复合材料比表面积和孔容孔径尺寸较TiO₂材料均有明显增大,表面酸性更强,能带结构有利于电子空穴的高效分离,催化还原活性与选择性更强。经光催化脱硝实验优化出ZnO与TiO₂最佳复合比为0.2,对于初始质量浓度为6.83 mg/m³的NO_x,在65 W节能灯照射的光源条件下,可见光催化脱除效率高达85%,NO_x质量浓度提高至13.67 mg/m³,在通入氨氮比为1:1的NH₃后,脱硝效率高达96%,比纯TiO₂的提高43%,质量浓度适用范围较前期研究拓宽近六倍。机理分析认为,整个反应可分成吸附与光催化两个部分,其中,吸附是该反应的速控步骤,NO在吸附氧的作用下被氧化为NO     

粉末状和薄膜状TiO2对敌敌畏的光催化降解

在光照条件下,光催化剂TiO₂有很强的氧化能力,能有效降解水中的有机污染物^[1],因而日益受到人们的关注.目前,研究最多的胶体溶液和颗粒悬浮体系因其难于分离、回收而限制了实际应用,因此催化剂固定问题急需解决.近年来,国内外对TiO₂薄膜催化剂做了许多探索^[2,3],取得了一些进展.本文用溶胶-凝胶法制备了一种粉末状TiO₂光催化剂和两种薄膜型TiO₂光催化剂,并进行了结构和形貌的表征,对敌敌畏稀释液做了光催化降解实验,并与粉末状TiO₂进行对比.结果表明:薄膜TiO₂催化剂优于粉末TiO₂催化剂.     

TiO2对Ni/Al2O3催化剂CO甲烷化性能的影响

采用溶胶凝胶法制备了一系列不同TiO₂含量的TiO₂-Al₂O₃复合载体,并通过浸渍法制备了NiO/TiO₂-Al₂O₃催化剂。分别考察了不同TiO₂含量的NiO/TiO₂-Al₂O₃催化剂及反应温度对CO甲烷化催化性能的影响。实验结果表明,当复合载体中TiO₂质量分数为30%,反应温度为350～450 ℃时,催化剂催化活性较高。利用N₂吸附-脱附(BET)、X射线衍射(XRD)及H₂程序升温还原(H₂-TPR)等手段对催化剂物化性能进行了表征。结果表明,加入适量的TiO₂能抑制镍铝尖晶石NiAl₂O₄物种的生成,改善NiO的表面分散性能,避免大晶粒NiO的形成,也改善了催化剂的还原性能,从而提高催化剂的CO甲烷化活性。     

N掺杂空心TiO2微球的合成与表征

采用无皂乳液聚合合成的聚苯乙烯(PS)微球为模板、氨水/三乙醇胺为催化体系, 通过溶胶-凝胶方法合成了PS/TiO₂(核/壳)复合微球, 然后通过煅烧制备了N掺杂、锐钛型空心TiO₂微球. 在反应体系中三乙醇胺扮演双重角色, 既是TiO₂生成及包覆过程的抑制剂又是空心TiO₂微球的N掺杂剂. 改变氨水、三乙醇胺和钛酸正丁酯用量可控制TiO₂壳的形态和尺寸. 氨水用量增加, PS/TiO₂复合微球的壳表面变得粗糙|三乙醇胺用量增加, 壳表面变得光滑|钛酸正丁酯用量提高导致壳层变厚. 改变三乙醇胺用量可调节空心TiO₂微球中的N掺杂量|N掺杂空心TiO₂微球具有可见光响应和光催化作用.     

纳米二氧化钛/碳纳米管复合催化剂光催化性能及碳纳米管组分的作用

运用溶胶-凝胶及低温水热法合成纳米TiO₂/碳纳米管复合催化剂, 以甲基橙为目标降解物考察复合物的光催化活性. 运用X光衍射、透射电镜、Brunauer-Emmett-Teller低温氮气吸附、差热-热重分析及紫外-可见漫反射吸收光谱等表征催化剂. 结果表明, 与单纯纳米TiO₂相比, 溶胶-凝胶法制备的复合催化剂的光催化活性显著提高, 实验条件下复合的碳纳米管最适含量为3%(碳纳米管/TiO₂, 重量百分比), 复合催化剂经在缓和氧化气氛中焙烧处理可在保持碳纳米管热稳定前提下获得纳米TiO₂的充分晶化. 观察到了低温水热合成的复合催化剂的甲基橙降解活性的进一步提升, 复合催化剂中纳米TiO₂在碳纳米管表面分散均匀, TiO₂和碳纳米管组分间的紧密和充分键合及低温水热条件下催化剂的大比表面积、超细粒径以及碳纳米管的热稳定等有利于复合催化剂的光催化活性. 进一步地, 探讨了复合催化剂中适量碳纳米管组分的光活性促活机制.     

TiOx/SiO2复合载体上高分散Au催化剂的CO氧化性能

负载型Au催化剂中金与载体间存在相互作用,载体性质能够影响Au纳米颗粒分散度及稳定性.本文通过表面溶胶-凝胶(SSG)法制备了TiO_x/SiO₂复合载体,以期增加氧化物载体表面配位不饱和度从而使其具有较高的金属分散性,并利用低能离子散射(LEIS)谱、X射线光电子能谱(XPS)、X射线衍射(XRD)、透射电子显微镜(TEM)及N₂物理吸附(BET)等手段对载体及催化剂进行表征分析.实验表明TiO_x/SiO₂复合载体表面TiO_x分散性良好,没有形成明显的TiO₂晶相,且与SiO₂间形成Ti―O―Si键.与Au/TiO₂相比, Au/TiO_x/SiO₂催化剂中Au纳米颗粒的分散性更好,因而CO氧化活性显著提高. TiO_x/SiO₂复合载体上的TiO₂膜是Au的主要表面键合位,导致Au与载体间相互作用增强,从而使得Au纳米颗粒抗烧结能力提高,同时催化剂反应稳定性得到改善.     

石墨烯、Sm和Pr共掺杂TiO2复合光催化剂性能研究

以钛酸四丁酯为基底,采用溶胶―凝胶法制备了纳米级半导体TiO₂光催化材料,使用还原氧化石墨烯(RGO)、稀土元素Sm和Pr共掺杂制备了改性半导体TiO₂光催化材料。分别对所制备的光催化材料进行XRD、SEM、PL等表征,结果表明,TiO₂、RGO/TiO₂、RGO/Sm³⁺/TiO₂、RGO/Pr³⁺/TiO₂为锐钛矿相,RGO/Sm³⁺/TiO₂获得了较窄禁带宽度、较小晶粒尺寸以及光致发光强度低的改性光催化材料。以亚甲基蓝(MB)为目标污染物,在降解MB模拟污染物的实验中,85 min时RGO/Sm³⁺/TiO₂的降解率达到99.2%。这说明RGO和稀土元素的掺入能够明显的影响催化材料的性能。     

Solubility in the Na2Cr2O7-(NH4)2Cr2O7-K2Cr2O7-H2O system

Solubility in the Na₂Cr₂O₇-(NH₄)₂Cr₂O₇-K₂Cr₂O₇-H₂O four-component water-salt system at 25, 50, and 75°C was studied for the first time. Phase field boundaries for individual salts and potassium and ammonium dichromate solid solutions, monovariant lines, and invariant points were determined. Experimental data were used to optimize the looped isohydric process of potassium dichromate preparation involving additional salts.     

Polymorphism in the Sc2Si2O7-Y2Si2O7 system

This paper examines the structural changes with temperature and composition in the Sc₂Si₂O₇-Y₂Si₂O₇ system; members of this system are expected to form in the intergranular region of Si₃N₄ and SiC structural ceramics when sintered with the aid of Y₂O₃ and Sc₂O₃ mixtures. A set of different compositions have been synthesized using the sol-gel method to obtain a xerogel, which has been calcined at temperatures between 1300 and 1750 °C during different times. The temperature-composition diagram of the system, obtained from powder XRD data, is dominated by the β-RE₂Si₂O₇ polymorph, with γ-RE₂Si₂O₇ and δ-RE₂Si₂O₇ showing very reduced stability fields. Isotherms at 1300 and 1600 °C have been analysed in detail to evaluate the solid solubility of the components. Although, the XRD data show a complete solid solubility of β-Sc₂Si₂O₇ in β-Y₂Si₂O₇ at 1300 °C, the ²⁹Si MAS-NMR spectra indicate a local structural change at x ca. 1.15 (Sc_2−xY_xSi₂O₇) related to the configuration of the Si tetrahedron, which does not affect the long-range order of the β-RE₂Si₂O₇ structure. Finally, it is interesting to note that, although Sc₂Si₂O₇ shows a unique stable polymorph (β), Sc³⁺ is able to replace Y³⁺ in γ-Y₂Si₂O₇ in the compositional range 1.86?x?2 (where x is Sc_2−xY_xSi₂O₇) as well as in δ-Y₂Si₂O₇ for compositions much closer to the pure Y₂Si₂O₇.     

KCl-KBO2-K2CO3, K2MoO4-KBO2-K2CO3, and K2WO4-KBO2-K2CO3 ternary systems

phase diagrams of KCl-KBO₂-K₂CO₃, K₂MoO₄-KBO₂-K₂CO₃, and K₂WO₄-KBO₂-K₂CO₃ ternary systems were studied by a calculation-experimental method and differential thermal analysis (DTA). The coordinates of ternary eutectics were determined to be E ₁: 622°C, 8.5 mol % KBO₂, 56.5 mol % KCl, and 35 mol % K₂CO₃; E ₂: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂MoO₄; E ₃: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂WO₄. The specific heats of melting of the eutectics were determined.     

Interaction in the Ga2S3-Y2O2S system

The phase diagram of the Ga₂S₃-Y₂O₂S system has been investigated by differential thermal, X-ray powder diffraction, microstructural, and thermodynamic analyses. It has been established that the system is eutectic, and solubility at 295 K from the Ga₂S₃ side reaches 3 mol % Y₂O₂S. The coordinates of the eutectic point are 14 mol % Y₂O₂S and 1320 K.     

The preparation of NbH5(Me2PCH2CH2Me2)2 and NbHL2(Me2PCH2CH2PMe2)2 (L = CO or C2H4)

MMe₅(dmpe) (M = Nb or Ta, dmpe = Me₂PCH₂CH₂PMe₂) reacts with H₂ (500 atm) and dmpe in THF at 60°C to give MH₅(dmpe)_2? NbH₅(dmpe)₂ readily reacts with two mol of CO or ethylene (L) to give NbHL₂(dmpe)₂. The exchange of the hydride ligand with the ethylene protons in NbH(C₂H₄)₂(dmpe)₂ is not rapid on the ¹H NMR time scale (60 MHz) at 95°C.     

Some studies on the solid solutions in the systems Sr2Nb2O7Eu2Nb2O7 and Sr2Ta2O7Eu2Ta2O7

Preparation of new solid solutions containing divalent europium have been tried in the systems Eu₂Nb₂O₇Sr₂Nb₂O₇ and Eu₂Ta₂O₇Sr₂Ta₂O₇. These solid solutions described as Eu_2xSr_2(1?x)M₂O₇ (M = Nb and Ta) exist in a pure orthorhombic phase in a limited region of x from 0 to about 0.5. The compounds with compositions close to Eu₂M₂O₇ exist but techniques have not been found to prepare them in pure form.     

Phase equilibria and glass formation in the As2S3-TlAs2S2Se2 section of the As2S3-As2Se3-TlS system

Alloys in the As₂S₃-TlAs₂S₂Se₂ section of the As₂S₃-As₂Se₃-TlS ternary system were studied and a phase diagram was constructed using physicochemical methods (differential thermal analysis, microstructural analysis, X-ray powder diffraction, also microhardness and density measurements). The diagram in the As₂S₃-TlAs₂S₂Se₂ section is a non-quasi-binary diagonal section of the As₂S₃-As₂Se₃-TlSe quasi-ternary system. It was found that all the alloys in the section under ordinary conditions are obtained in the vitreous state. At low As₂S₃ concentrations in the section, solid solutions form up to 2.5 mol %, and at low TlAs₂S₂Se₂ concentrations, their extent is 3 mol %.     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…     

High-temperature equilibria and critical phenomena in the Na2CO3-NaCl-H2O and Na2CO3-Na2WO4-H2O systems

Phase equilibria in the Na₂CO₃-NaCl-H₂O and Na₂CO₃-Na₂WO₄-H₂O ternary systems formed by type 1 salts (NaCl, Na₂WO₄) and a type 2 salt (Na₂CO₃) were experimentally studied at temperatures from 425 to 500°C and pressures from 30 to 160 MPa with the contents of type 1 salts from 10 to 30 wt %. Transition from supercritical homogeneous fluid equilibria of the Na₂CO₃-H₂O system to heterogeneous equilibria of the title ternary systems was studied in the presence or absence of liquid phase immiscibility in the type 1 subsystems.     

NaBO2-NaCl-Na2CO3, NaBO2- Na2CO3-NaMoO4, NaBO2- Na2CO3-NaWO4, and NaBO2-NaCl-Na2WO4 ternary systems

The phase diagrams of the NaBO₂-NaCl-Na₂CO₃, NaBO₂-Na₂CO₃-Na₂MoO₄, NaBO₂- Na₂CO₃-Na₂WO₄, and NaBO₂-NaCl-Na₂WO₄ ternary systems were studied by a calculation-experimental method and differential thermal analysis. The coordinates of ternary eutectics were determined: E ₁: 612°C, 16 mol % NaBO₂, 42 mol % NaCl, and 42 mol % Na₂CO₃; E ₂: 568°C, 12 mol % NaBO₂, 28 mol % Na₂CO₃, and 60 mol % Na₂MoO₄; E ₃: 575°C, 12 mol % NaBO₂, 32 mol % Na₂CO₃, and 56 mol % Na₂WO₄; E ₄: 628°C, 8 mol % NaBO₂, 20 mol % NaCl, and 72 mol % Na₂WO₄; and E ₅: 655°C, 9 mol % NaBO₂, 53 mol % NaCl, and 38 mol % Na₂WO₄.