固态反应制备纳米钙钛矿型物质及其反应机理

以TiCl₄和碱土金属氢氧化物为原料, 采用低温固态反应合成了钙钛矿纳米晶. 首先, TiCl₄水解制备高活性TiO₂•H₂O (H₂TiO₃), 再分别与碱土金属氢氧化物按物质的量比1∶1均匀混合研磨1 h后, 在一定温度下反应. XRD分析显示产物均为钙钛矿型物质. TEM形貌观察, 粒子均匀, 分散性较好, 平均粒径小于80 nm. 通过对不同反应温度和反应时间产物的XRD分析推断出了化学反应为该低温固态反应速度控制步骤, 并分析了影响反应温度的可能因素.     

立方体形PbS纳米晶的制备

在60～100 ℃下，以醋酸铅为铅源，硫代乙酰胺为硫源，乙二胺为溶剂，制备了立方体形的PbS纳米晶，采用XRD、TEM、SAED、SEM等对合成的产物进行了形貌和结构的表征。结果表明得到的产物为单晶的立方体形PbS，颗粒大小均匀。并且随着反应时间的延长，反应温度的升高，硫源比例的增加，立方体变大。通过控制不同的反应条件，可以合成边长从几十个纳米到几百个纳米的立方体形PbS晶体。     

有机固废燃烧/气化过程As、Pb释放特性及热力学研究

在固定床反应器上,研究了不同种类有机固废在800-1100℃不同温度下燃烧/气化过程As、Pb的释放特性以及灰的组成成分,探究了CaO、SiO₂、Al₂O₃对气化过程中重金属As、Pb迁移转化的影响。结果表明,有机固废气化过程As、Pb的释放率整体上随温度升高而升高,且气化过程As、Pb的释放率明显低于燃烧;灰产率随温度升高而降低,灰中主要含有CaO、Al₂O₃和SiO₂;热力学研究表明,在高温下气化过程主要生成气态As和Pb,而燃烧过程则会生成大量的As₂O₃和PbO,As和Pb的单质沸点相比氧化物更高,因此,气化过程As、Pb的释放率比燃烧过程要低;在900℃以下CaO、SiO₂、Al₂O₃会与As、Pb反应生成Ca₃(AsO₄)₂、Ca₂PbO_4...     

污泥焚烧中铅的形态转化及脱除的热力学平衡研究

利用热力学平衡模型预测了污泥焚烧过程中铅的形态转化和迁移规律, 并采用系统吉布斯自由能最小的原理对Al₂O₃, SiO₂, TiO₂和CaO 4种吸附剂吸附污泥燃烧中铅的效果进行了模拟计算. 探讨了痕量元素Pb与S, Cl的相互作用及S和Cl的存在对吸附剂与Pb反应的影响. 研究结果表明, 污泥焚烧中Pb的形态转化受到S, Cl及矿物质的影响较大. 有S存在情况下, Pb在低温条件下主要以固态PbSO₄存在, 温度较高时以气态PbO存在; Cl较易和Pb结合形成低沸点的金属氯化物而导致Pb的挥发, 并且Cl含量的增加会加速Pb的挥发. 4种吸附剂对污泥焚烧中Pb都有一定的脱除能力, 其中Al₂O₃可以在较宽温度范围对Pb进行捕集, 而CaO对Pb的化学吸附能力较差. 由于S, Cl与Pb有更强的反应性, 因此S, Cl的存在对吸附剂与铅的反应有抑制作用, 使有效吸附的温度范围变窄, 吸附效率降低, 甚至失去脱除Pb的能力, 并且Cl的影响大于S.     

不同形貌纳米氧化锌的水热法合成

以氯化锌为锌源,以氢氧化钠为碱源,采用水热法合成了不同形貌的纳米氧化锌;探讨了晶化时间、晶化温度、表面活性剂十六烷基三甲基溴化铵(CTAB)对纳米ZnO形貌的影响.结果表明:不添加CTAB时,在120℃下反应24h得到的纳米氧化锌为颗粒状,而在160℃下反应24h得到的纳米氧化锌为片状.当添加CTAB后,在120℃可得到片状氧化锌,而在160℃可得到颗粒状氧化锌.     

共沉淀法合成Pb3Nb2O8纳米粉

在PbO-Nb₂O₅-KOH-H₂O体系中,于90℃下得到纳米级Pb₃Nb₂O₈陶瓷粉.原料来源及配比、溶液碱度及合成温度对产物物相的形成有较大影响.在Pb₃Nb₂O₈的合成中,必须以可溶性铌酸盐和醋酸铅作为反应原料,同时以KOH调节体系中铌酸盐的聚集状态.当n(Pb)/n(Nb)接近1/1,KOH浓度在1～3mol/L时,得到Pb₃Nb₂O₈纯相,当KOH浓度大于3mol/L时容易生成反应活性较低的PbO,产生杂相.     

β-PbO2纳米棒及Pb3O4纳米晶的制备与表征

利用NaClO在碱性溶液中与Pb(Ac)2进行氧化反应直接合成出直径为10－20nm、长度为400nm、长径比达20以上的纯相β－PbO2纳米棒，对所得β－PbO2在420℃下进行热解，得到晶粒尺寸为20nm左右的Pb3O4。对液相氧化反应的温度、时间、氧化剂浓度、pH等因素的影响进行了详细研究，获得了最佳合成反应条件，所得产物利用粉末X射线衍射和透射电子显微镜分析进行了表征。     

Zn-MOF模板法制备ZnO/C/SNTs及其药物缓释性能

采用超声法一步合成了SiO₂包覆金属-有机骨架[Zn₆(OH)₃(BTC)₃(H₂O)₃] ·7H₂O(Zn-MOF, BTC=1,3,5-均苯三羧酸根)纳米晶, 在N₂保护下, 热解Zn-MOF@SiO₂获得了ZnO/C/SNTs复合物, 进而与布洛芬(HIBU)反应合成药物组装体Zn(IBU)₂/C/SNTs. 通过透射电子显微镜(TEM)、 傅里叶变换红外光谱仪(FTIR)、 高分辨透射电子显微镜(HRTEM)和X射线衍射仪(XRD)对样品的结构和形貌进行表征. 结果显示, Zn-MOF@SiO₂呈棒状, 具有清晰的核/壳结构, 形貌单一, 分散性良好. 煅烧后SNTs结构稳定, 形貌基本不变. 载药实验表明, 药物组装体的载药量为752 mg/g, 并具有良好的pH响应性能.     

介观结构SiO2/CdO纳米复合物为前驱体原位水热合成半导体CdSe和CdS纳米晶

以高度有序的介观结构SiO₂/CdO纳米复合物为前驱体,在硒源或硫源存在的还原性条件下,利用原位水热反应,合成了介观结构SiO₂/CdSe及SiO₂/CdS纳米复合物,除去SiO₂后,得到半导体CdSe及CdS纳米晶.通过X射线衍射(XRD),高分辨率透射电镜(HRTEM),X射线能散射谱(EDX)及选区电子衍射(SAED)等手段对产物进行了组成和结构表征.结果表明,介观结构SiO₂主体材料在合成过程中起到了一定的形貌和尺寸限制作用,得到的CdSe和CdS均为直径在8 nm左右的类球形六方相纳米晶.     

Anti-solvent assisted treatment for improved morphology and efficiency of lead acetate derived perovskite solar cells

An efficient solution-processable route employing Pb(Ac)₂ as lead source and anti-solvent treatment to achieve fully covered and homogenous perovskite films is reported.     

On synthesis, structure, and thermal stability of mercury and lead sulfates and oxide sulfates

Reactions between HgO, PbO, or PbO₂ and 2.5–95 wt.% H₂SO₄ are studied at temperatures up to the boiling point of the acid. Depending on the oxide reactant, the H₂SO₄ concentration, and synthesis temperature, HgSO₄, Hg₃O₂(SO₄), PbSO₄ and Pb₂O(SO₄) are obtained as identified reaction products. The thermal stability of HgSO₄, Hg₃O₂(SO₄), PbSO₄, Pb₂O(SO₄), and PbO₂ is examined and the results supplement and modify earlier findings. The redetermined crystal structure of Hg₃O₂(SO₄) on the basis of powder neutron diffraction data shows that its space group (P3₁) is of lower symmetry than earlier reported (P3₁2₁).     

Formation of monodispersed PVP-capped ZnS and CdS nanocrystals under microwave irradiation

Poly (N-vinyl-2-pyrrolidone) (PVP)-capped ZnS, CdS nanoparticles were prepared by a microwave method from Zn(Ac)₂ or Cd(Ac)₂ and thiourea in N,N-dimethylformamide (DMF) solution. The reaction process was monitored by the temporal evolution of the absorption spectrum. With PVP as stabilizer, monodispersed semiconductor nanoparticles, which showed high quantum size effect, have been obtained. Further study showed that the microwave irradiation could influence selectively the nucleation and growing rates of different semiconductor nanoparticles.     

Equilibrium constants and kinetics of carbon monoxide insertion in alkyl complexes of ruthenium(II)

The equilibrium constants of the reaction of cis, trans-[Ru(CO)₂(PMe₃)₂(CH₃)I] (Mc) with carbon monoxide to give cis, trans[Ru(CO)₂(PMe₃)₂ (COMe)i] (Ac) and trans, trans[Ru(CO)₂(PMe₃)₂(COMe)I] (At) were measured at various temperatures in toluene. The thermodynamic parameters are compared with those obtained for the isoelectronic complexes of iron, and the trend is discussed. The kinetics of the carbonylation reaction of Mc, as well as those of the inverse decarbonylation reaction of At were measured. The kinetics of the carbonylation of the new complex trans, trans-[Ru(CO)₂(PMe₃)₂(CH₃)I] (Mt) were also investigated. All the results afford further support to the previously proposed CO insertion mechanism occurring via methyl migration. The comparison of these kinetic results with those of isoelectronic complexes of iron indicates that ruthenium is more reactive than iron, which is reflected by its greater aptitude to act as catalyst in many processes.     

Stability of Pyrotechnic Composition in Flame Detonator Exposed to Severe Thermal Stimulus

The stability of pyrotechnic composition used in flame detonator was studied at severe temperatures (-70-130℃) for 5 d. For single N-LTNR(normal lead styphnate), camera was used to observe the shape and colour of N-LTNR in the DSC(differential scanning calorimetry) furnace during continuous heating and cooling processes. Based on the DSC-TGA(thermogravimetric analysis) results, it can be seen that when the temperature exceeded 110℃, N-LTNR lost its crystal water, making the energetic material become darker in colour, smaller in dimension, lager in volume and lighter in weight(3.416%); when the temperature was below -40℃, the phenomenon of sample broking, jumping and cracking happened. For the N-LTNR and Pb(N₃)₂(lead azide) double layers, the loss of N-LTNR's crystal water at the temperature higher than 110℃ caused the hydrolysis reaction of Pb(N₃)₂, and the purity of Pb(N₃)₂ measured after the temperature cycling decreased from 98.6% to 95.26%. For the flame detonator, the height and diameter of the flame detonator were measured and no apparent changes of them were found. The p-t(pressure-time) test shows that the peak pressure was decreased by 3.9%. Therefore, the operating temperature of this flame detonator should be limited to -40-110℃.     

三乙酰基丙酮合锰(Ⅲ)的敏化光分解光化学的研究

研究了含硫堇的三乙酰基丙酮合锰(Ⅲ)[简称Mn(AA)₃]溶液的紫外光谱的变化。Mn(AA)₃通过中间体Mn(AA)₂,最终还原形成Mn(Ac)₂。观察了氧对反应的影响。Mn(AA)₃的这一敏化分解还原过程与文献报道的它的直接光解反应是一致的,还讨论了反应机理,并为1100nm处的带,即Mn(AA)₃的电荷转移吸收带提供了新的证据。     

Polarographic studies of mixed hydroxy-complexes of monoethanolamine with cadmium and with lead

The composition and stability of mixed complexes of cadmium or lead with hydroxide and monoethanolamine have been determined polarographically at 25° in aqueous and aqueous methanol solutions at ionic strength 0.1M. For the aqueous solutions the results agree with those of others. In the methanolic systems the previously unreported complexes Cd(MEA)₄(OH), Pb(MEA)(OH)₃, Pb(MEA)₂(OH) and Pb(MEA)₂(OH)₂ were detected.     

水蒸气对高岭土高温吸附铅的影响

使用沉降炉开展了水蒸气对高岭土高温吸附铅影响的实验研究，其中铅的形态为PbO和PbCl₂两种。首先研究了0-20%水蒸气对高岭土吸附PbO（1100-1300 ℃）和PbCl₂（800-1300 ℃）的影响规律，然后基于XRD、SEM和残余羟基率等分析，掌握了水蒸气影响高岭土高温吸附的机理。结果表明，水蒸气可以减少高岭土表面羟基的高温脱落，从而阻碍了PbO吸附、促进了PbCl₂吸附。综合高温下惰性莫来石的出现和高岭土孔隙结构的坍塌等因素，PbO和PbCl₂的最佳吸附温度分别为1200和1000 ℃。     

Cesium lead halide perovskite nanocrystals for ultraviolet and blue light blocking

Using cesium lead halide perovskite nanocrystals, CsPb(Cl/Br)_3, as a light absorber, we report a highly effective UV and blue light blocking film. The CsPb(Cl/Br)_3 nanocrystals are well dispersed in the ethyl cellulose(EC) matrix to compose a UV and blue light shielding film, and the absorption edge of the film is tunable by adjusting Cl to Br ratio using anion exchange. The CsPbCl_2 Br-EC film exhibits a transmittance of 5% at 459 nm, 90% at 478 nm and 95% in the range of 500–800 nm, which makes it excellent for UV and blue light shielding. In addition, the as-prepared EC-CsPb(Cl/Br)_3 film shows excellent photostability under UV irradiation. Results demonstrate that this EC-CsPb(Cl/Br)_3 based materials with sharp absorbance edges, tunable blocking wavelength, and high photostability can be useful for the applications in UV and blue light blocking and optical filters