金属离子掺杂的TiO2薄膜的制备及其光催化降解甲苯的性能

 采用溶胶-凝胶法制备了负载于铝板上掺杂金属离子的TiO2薄膜光催化剂,并通过空气中甲苯光催化降解实验评价了其光催化活性. 结果表明,Pt和Fe的掺杂对TiO2薄膜的光催化活性起促进作用,甲苯降解率分别提高了17%和6%; Ag的掺杂引起催化剂失活; Mn的掺杂未对TiO2薄膜的光催化活性起明显促进作用. XRD结果表明,掺杂金属离子前后TiO2均为锐钛矿相; TEM观察到薄膜催化剂微观结构为球形颗粒,粒径分布均匀,平均粒径为19 nm; 紫外漫反射光谱表明,Pt-TiO2薄膜催化剂的反射率几乎为0,表明其对光的吸收能力很强,因而Pt掺杂的TiO2薄膜光催化降解甲苯的活性最高.     

核-壳式纳米SnO2/TiO2光催化剂的制备和性能

 以纳米SnO2·nH2O胶体粒子为基质,采用活性层包覆法制备了纳米SnO2/TiO2复合光催化剂,并用R,TEM,XPS和XRD等手段进行了表征. 采用敌敌畏的光催化降解反应对所制催化剂的活性进行了评价. 结果表明,SnO2/TiO2为核-壳结构,粒径约为12 nm. SnO2/TiO2的光催化活性受TiO2含量及SnO2·nH2O乙醇溶液含水量的影响. 最佳条件为SnO2/TiO2中TiO2含量为56.45%,SnO2·nH2O乙醇溶液含水量为20%. 所制SnO2/TiO2光催化活性比纯TiO2显著提高,且光催化活性稳定,可重复使用.     

CNTs/TiO2多孔复合膜的组装及光催化性能

提出了一种在掺氟的SnO2(FTO)导电玻璃上组装碳纳米管(CNTs)/Fe-Ni/TiO2多孔复合膜光催化剂的新方法.采用喷涂热解法(SPD)将掺杂镍和铁的含有嵌段聚合物P123的二氧化钛前驱体溶胶涂覆在FTO导电玻璃上,制备Fe-Ni/TiO2多孔膜,再采用化学气相沉积法(CVD)在Fe-Ni/TiO2膜上原位生长CNTs,得到CNTs/Fe-Ni/TiO2多孔复合膜光催化剂.CNTs/Fe-Ni/TiO2复合膜具有多级孔结构特征,在TiO2表面原位生长的CNTs不但具有较好的石墨化结构,且CNTs较均匀地分布在整个膜层的孔中.考察了CNTs/Fe-Ni/TiO2复合膜光催化剂的结构和性能,并通过降解甲基橙溶液评价了复合膜的光催化活性.结果表明,CNTs的复合及铁和镍的掺杂等改性显著提高了TiO2膜材料的光催化活性.     

RE/TiO2用于NO2-光催化氧化的研究

 以稀土盐和钛酸丁酯为原料,采用溶胶－凝胶法制备了掺杂稀土\r\n光催化剂RE／TiO2（RE＝La,Ce,Er,Pr,Gd,Nd,Sm）,并用XRD,\r\nDRS和IR等手段对RE／TiO2进行了表征;以NO－2为目标降解物,考察了\r\n其光催化氧化活性．结果表明,适量RE的掺入,可有效扩展TiO2的光谱\r\n响应范围,有利于NO－2的吸附,使光催化活性均有不同程度的提高．\r\n其中掺杂Gd样品的光催化活性最高．掺杂量是影响光催化活性的重要因\r\n素,一般最佳掺杂量为w（RE）≈0．5％．     

La2O3掺杂TiO2光催化剂的制备和性能

采用溶胶-凝胶法制备了La2O3掺杂TiO2纳米光催化剂，并通过XRD、TEM、BET和XPS等手段进行了表征．掺入La2O3后，阻止了TiO2从锐钛矿晶型向金红石晶型的转变，使TiO2的粒径减小，比表面积增大．以甲基橙为光催化降解反应模型化合物，考察了光催化剂的活性．测定了甲基橙在纯TiO2和La2O3掺杂TiO2光催化剂上的吸附常数．考察了pH、H2O2对降解性能的影响．讨论了光催化活性与催化剂性质的关系．     

SnO2-TiO2复合颗粒的形态结构及其光催化活性

在气溶胶反应器中,利用TiCl4高温氧化反应制备超细TiO2,采用均匀沉淀法在TiO2表面沉积SnO2,制备SnO2-TiO2复合颗粒,应用TEM、EDS、XRD、BET比表面积测试等手段对粒子进行表征。以活性艳红X-3B溶液为处理对象,考察复合颗粒的光催化活性。结果表明SnO2-TiO2复合颗粒的光催化活性较纯气相合成超细TiO2有较大提高,SnO2最佳含量为15.3%,SnO2-TiO2复合颗粒光催化活性的提高归因于不同能级半导体之间光生载流子的输运和分离。     

纳米复合Y2O3／TiO2的制备、表征及其光催化性能研究

采用溶胶－凝胶法制备复合半导体Y2O3／TiO2,掺入Y2O3会阻碍锐钛矿晶相的出现,掺入浓度越大,TiO2锐钛矿（101）峰强度减小越大,平均晶粒直径与颗粒直径减小,比表面积增大;Y2O3／TiO2具有高热稳定性与高比表面积,由于量子尺寸效应,掺入Y2O3使光催化剂的拉曼峰发生微小位移,在380－460nm范围内,使反射率增强,以亚甲基蓝与甲基橙溶液光 经降解为模型反应,掺入Y2O3,复合光催化剂对亚甲基蓝溶液的光催化脱色降解一级动力学常数明显低于纯TiO2的;掺入5％的10％Y2O3,复合光催化剂对甲基橙溶液的光催化脱色降解一有动力学均常数高于纯TiO2的,掺入浓度太高反而有害,讨论了掺入Y2O3后光物理性质的变化与其光催化活性的关系。     

掺Ce^3＋纳米TiO2的制备及光催化性能

用溶胶-凝胶法技术制备了掺杂Ce^3＋的纳米TiO2复合粒子，并对其进行了XRD，TEM和DRS表征及光催化活性检验。水中苯酚的Ce^3＋／TiO2光催化降解效果和矿化率分别采用降解率和COD表征。结果表明，未经掺杂的TiO2与掺杂Ce^3＋的TiO2均为锐钛和金红石的混合晶型；掺杂抑制了TiO2晶粒的生长，使得TiO2粒径明显变小，其颗粒大小为10mm左右。用DRS表征微粒的光吸收能力和光吸收带边移动情况，发现掺杂导致了TiO2光吸收能力增强及吸收带边红移。通过对苯酚的光催化氧化降解研究，发现铈的掺杂量有一适宜值，当Ce^3＋在0．08％-0．4％之间时，随着掺杂量的增加光催化活性提高；当Ce^3＋在0．5％～3．0％之间时，随着掺杂量的增加光催化活性降低；Ce^3＋=0．4％时，TiO2光催化活性最高。     

溶胶-凝胶法制备TiO2/玻璃膜和光催化降解玫瑰红B的研究

以Ti(OC4H9)4为原料采用溶胶－凝胶法制备了纳米TiO2／玻璃薄膜光催化剂，用X射线衍射法对催化剂的物相、粒径进行了表征。结果表明，薄膜中TiO2为锐钛矿晶型，粒径15－25nm。用X射线光电子能谱法分析膜的化学组成。磨擦学实验表明，TiO2／玻璃膜具有良好的减磨和抗磨性能。水中染料玫瑰红B的光催化氧化降解实验结果表明，TiO2膜对玫瑰红B玫解有很高的催化活性，其降解反应对时间和浓度均为一级反应，反应速率可用Langmuir-Hinshelwood方程描述。     

掺磷二氧化钛的制备及其光催化性能研究

以TiCl4为原料,在低温下分别制备了纯二氧化钛和掺磷二氧化钛水溶胶,通过XRD、TEM、FT-IR、UV-vis等进行了表征。结果表明,两类样品中的TiO2颗粒均呈锐钛矿型晶相结构,粒径小于10nm,但是掺磷二氧化钛比纯二氧化钛的结晶度更高,颗粒分散更均匀,且禁带宽度和吸光度也有一定的增大,同时掺磷二氧化钛中的磷有效地溶入二氧化钛晶格中。通过对亚甲基兰的光催化降解表明,掺磷二氧化钛水溶胶的光催化性能比纯二氧化钛水溶胶大约提高了2倍。     

Sc2MgGa2 and Y2MgGa2

Scandium magnesium gallide, Sc₂MgGa₂, and yttrium magnesium gallide, Y₂MgGa₂, were synthesized from the corresponding elements by heating under an argon atmosphere in an induction furnace. These intermetallic compounds crystallize in the tetragonal Mo₂FeB₂‐type structure. All three crystallographically unique atoms occupy special positions and the site symmetries of (Sc/Y, Ga) and Mg are m2m and 4/m, respectively. The coordinations around Sc/Y, Mg and Ga are pentagonal (Sc/Y), tetragonal (Mg) and triangular (Ga) prisms, with four (Mg) or three (Ga) additional capping atoms leading to the coordination numbers [10], [8+4] and [6+3], respectively. The crystal structure of Sc₂MgGa₂ was determined from single‐crystal diffraction intensities and the isostructural Y₂MgGa₂ was identified from powder diffraction data.     

Zur Kenntnis der Dialkalimetalldichalkogenide β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 und Rb2Te2

On Dialkali Metal Dichalcogenides β-Na₂S₂, K₂S₂, α-Rb₂S₂, β-Rb₂S₂, K₂Se₂, Rb₂Se₂, α-K₂Te₂, β-K₂Te₂ and Rb₂Te₂ The first presentation of pure samples of α- and β-Rb₂S₂, α- and β-K₂Te₂, and Rb₂Te₂ is described. Using single crystals of K₂S₂ and K₂Se₂, received by ammonothermal synthesis, the structure of the Na₂O₂ type and by using single crystals of β-Na₂S₂ and β-K₂Te₂ the Li₂O₂ type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na₂O₂ type to the Li₂O₂ type will be explained by means of the examples α-/β-Na₂S₂ and α-/β-K₂Te₂. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb₂S₂ is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.     

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

[(n‐Bu)₂Sn(O₂PPh₂)₂] ( 1 ), and [Ph₂Sn(O₂PPh₂)₂] ( 2 ) have been synthesized by the reactions of R₂SnCl₂ (R=n‐Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

The alkali hypophosphites KH2PO2, RbH2PO2 and CsH2PO2

The structures of the hypophosphites KH₂PO₂ (potassium hypophosphite), RbH₂PO₂ (rubidium hypophosphite) and CsH₂PO₂ (caesium hypophosphite) have been determined by single‐crystal X‐ray diffraction. The structures consist of layers of alkali cations and hypophosphite anions, with the latter bridging four cations within the same layer. The Rb and Cs hypophosphites are isomorphous.     

Syntheses,Spectroscopic Studies,and Crystal Structures of Me2Sn(O2PPh2)2, Ph2Pb(O2PMe2)2, and Ph2Pb(O2PPh2)2

Me₂Sn(O₂PPh₂)₂ ( 1 ), Ph₂Pb(O₂PMe₂)₂ ( 2 ), and Ph₂Pb(O₂PPh₂)₂ ( 3 ) have been synthesized by the reactions of Me₂SnCl₂ or Ph₃PbCl with the corresponding diorganophosphinic acid in methanol. X‐ray diffraction studies show that the diorganophosphinate groups behave as double bridges between the metal atoms leading to polymeric ring‐chain structures with M₂O₄P₂ (M = Pb, Sn) eight‐membered rings. The organic groups bonded to the metal atoms are in trans‐position in the resulting octahedral arrangement around the metal atoms. The IR and the mass spectra were reported and discussed.     

Thermal decomposition of Me3SnO2PCl2, Me2Sn(O2PCl2)2 and Ph3SnO2PCl2

TG and DTA studies on Me₃SnO₂PCl₂, Me₂Sn(O₂PCl₂)₂ and Ph₃SnO₂PCl₂ were carried out under dynamic argon atmosphere. The results show that the decomposition proceeds in different stages leading to the formation of Sn₃(PO₄)₂ as a stable product. This compound was characterized by IR spectroscopy. Decomposition schemes involving reductive elimination reactions were proposed.