KzLa2Ti3O10的制备和光催化产氢性能

通过聚合-配合方法和溶胶-凝胶方法，制备了具有层状钙钛矿结构复合氧化物K2La2Ti3O10光催化剂，采用X射线衍射（XRD）、紫外-可见漫反射光谱（DRS）、扫描电镜（SEM）等手段进行表征：以I-为电子给体，比较了制备方法对K2L。2Ti3O10分解水产氢活性的影响。研究结果表明，溶-凝胶法制备的KELaETi3O10比聚合-配合法制备的K2LaETi3O10光催化产氢活性要高出1倍左右，且制备条件友好，所得K2La2Ti3O10具有较好的单相性：获得了以I-为电子给体，溶胶-凝胶法制备的K2La2Ti3O10分解水的最佳实验条件：产氢的最佳pH值为11,5，RuO2的负载量为0.2％～0.3％。     

纳米TiO_2/Cu_2O复合物的可见光降解活性艳红和分解水制氢的机理

采用溶胶-凝胶法和化学沉积法制备纳米TiO2/Cu2O复合粉体。可见光光催化实验结果表明:TiO2/Cu2O复合粉体具有较高的可见光降解活性和分解水制氢性能。根据TiO2和Cu2O的导带和价带位置以及TiO2、Cu2O和TiO2/Cu2O复合粉体的可见光光催化实验结果,提出TiO2/Cu2O复合粉体的可见光光催化机理:在可见光照射下,Cu2O导带上产生的电子转移到TiO2的导带上,Ti4+捕获这些电子后成为Ti3+,这些被捕获的电子具有很长的寿命,能转移到复合粉体和溶液的界面。在光降解活性艳红的过程中,这些电子与吸附氧结合后可最终形成过氧化物自由基或氢氧自由基,从而氧化有机物;而在分解水制氢过程中,这些电子与H+结合后可形成H2。光照后TiO2/Cu2O复合粉体的XPS表征显示Ti3+的存在,证明机理理论的正确性。     

硫氧化物La3NbS2O5的硫化合成及其光催化活性

采用H2S硫化的方法合成硫氧化物La3NbS2O5,并通过X射线衍射(XRD)、紫外?可见漫反射(DRS)、场发射扫描电镜(FE-SEM)等技术对其进行表征和分析,研究硫化条件与光催化分解水产氢活性的关系。结果表明：与传统固相法比较,硫化法使La3NbS2O5在更低的温度和更短的反应时间(1 h)合成;合成的La3NbS2O5粒子呈规则的盘子状,粒径为0.1?0.6μm,粒子表面光滑;在1073 K硫化1 h制得的La3NbS2O5具有极高的产氢活性,大约为固相法制得La3NbS2O5的产氢活性的1.83倍。     

高活性TiO_2薄膜电极的制备及其光电化学性能

以Ti(n-OC4H9)4和CH3COOK为原料,采用溶胶-凝胶法在导电玻璃基底上制备K2Ti2O5薄膜,进一步以K2Ti2O5薄膜为前躯体,用离子交换法获得TiO2纳米薄膜电极。利用X射线衍射(XRD)和扫描电子显微镜(SEM)分析薄膜的组成和表面特征;以草酸为有机污染物代表,通过光电化学技术考察薄膜的光电化学活性。结果表明:TiO2纳米薄膜具有锐钛矿晶型,其粒径随着K2Ti2O5薄膜制备温度的降低而减小,约为30～150nm;TiO2纳米薄膜在0.1mol/LNa2SO4溶液中具有典型的光电化学活性以及较高的稳定性,比在含少量草酸的溶液中采用溶胶-凝胶法制备的TiO2薄膜具有更强的光激发和更稳定的光电流响应性能,TiO2薄膜电极的平带电位发生负移,负移值为0.140V(vsSCE),饱和光电流密度为0.32mA/cm2。     

溶胶-凝胶法制备La2O3纳米粉体

以普通La2O3,硝酸,聚乙二醇为原料,利用溶胶-凝胶法制备了纳米La2O3粉体,利用TG-DTA,XRD,TEM等各种测试方法对干凝胶300℃灼烧所得前驱体粉末的分解过程及最终形成的纳米氧化镧粉体进行了分析和表征,并研究了浓度、搅拌和分散剂聚乙二醇(PEG)添加量等因素的改变对La2O3粉体的粒径、形态的影响.实验结果表明,在适当工艺参数下,可以制得平均粒径小于50 nm的La2O3粉体.     

溶胶-凝胶法制备纳米复合Mo-La2O3阴极

采用溶胶-凝胶法制备出平均粒径小于60nm的Mo-La2O3粉末。将所制备出的纳米复合Mo-La2O3粉末经冷压、热压工艺后烧结成纳米复合Mo-La2O3阴极。发现用溶胶-凝胶法制备的Mo-La2O3阴极组织均匀，晶粒细小，La2O3粒子晶粒大多在100nm以下，且弥散分布在晶内及晶界上。在燃弧实验中发现用溶胶．凝胶法制备的纳米复合Mo-La2O3阴极击穿点分布存阴极表面的大部分面积上，烧蚀坑浅，且击穿优先发生在La2O3相上。     

稀土增强Al2O3掺杂钼基复合粉体的制备

采用溶胶-凝胶法制备了稀土掺杂Al2O3增强钼基复合材料的粉体,研究了在La2O3与Al2O3在不同掺杂量对粉体的影响。结果表明:采用溶胶凝胶法制得La2O3/Al2O3/Mo混合粉体的平均粒径为1～2μm。Al2O3对粉体的均匀性、颗粒分布、粒径大小有一定的影响,Al2O3添加量的增加对粉体的团聚有分散作用。当Al2O3含量为15vol%、La2O3添加量小于2.5%时,La2O3对粉体粒径无明显细化作用。     

Y2Cu2O5光催化剂的制备及模拟太阳光催化产氢

分别用固相法和液相法制备Y2Cu2O5光催化剂,利用热重差热分析(TG-DTA)、X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见光漫反射光谱(UV-Vis DRS)等技术对光催化剂进行表征。在模拟太阳光照射条件下,以草酸(H2C2O4)为牺牲剂对所制得的光催化剂制氢性能进行评价,考察制备方法和牺牲剂类型等因素对其产氢性能的影响以及光催化剂的稳定性能。结果表明:溶胶凝胶法所得样品中含有Y2O3杂质,为Y2Cu2O5与Y2O3的混合物;固相法所得样品为纯净的Y2Cu2O5,具备较高的光催化产氢活性。用固相法制备的光催化剂Y2Cu2O5,当其用量为0.8 g/L、草酸为牺牲剂且初始浓度为0.05 mol/L时,表现出最佳光催化产氢活性,其产氢量为3.78mmol/(h.g)。但Y2Cu2O5在草酸溶液中不稳定,会与草酸反应生成Y2(C2O4)3.2H2O,导致产氢活性降低。     

溶胶-凝胶法制备Ru-Ir-Ti/Ti阳极涂层及性能研究

应用溶胶.凝胶法制备Ru-Ir/Ti/Ti氧化物阳极涂层.SEM、XRD、电子探针、极化曲线、电流效率实验表明,由溶胶-凝胶法制备的氧化物涂层比热分解法制备的氧化物涂层的分散性好、形成固溶体充分、电流效率高:由溶胶-凝胶法制备的氧化物涂层的失效是由于生成不导电的TiO2引起,而由热分解法制备的氧化物涂层的失效是由于活性氧化物涂层的溶解引起.     

第二相粒子大小对Mo-La2O3阴极电子发射性能的影响

利用溶胶-凝胶、氢气还原及热压工艺制备了纳米复合Mo-4La2O3（质量分数,%）阴极材料,其显微组织中La2O3粒径小于100 nm,而常规Mo-4La2O3阴极中La2O3粒径为200~300 nm。在真空击穿实验中发现La2O3粒径对于阴极电子发射性能有显著的影响,纳米复合阴极的电子发射能力远高于常规阴极的发射能力,其电子发射点遍布整个阴极表面,而常规阴极电子发射点只是集中在一小块区域。通过建立金属-半导体电子相互作用模型,计算并绘制了Mo及La2O3中电子隧穿几率随La2O3粒径变化的关系曲线,解释了纳米复合阴极电子发射能力强的原因。     

Fe-15Ce合金在H2-CO2、H2-H2S及H2-H2S-CO2气氛下的腐蚀

研究了600℃时Fe-15Ce合金在H2-CO2、H2-H2S及H2-H2S-CO2 3种气氛中的腐蚀行为，Fe-15Ce合金腐蚀后发生了Ce的内氧化或形成了复杂的腐蚀产物膜，而未出现Ce的选择性氧化或硫化，这主要是合金中存在着两相及Ce在Fe中极低的溶解度的结果。Fe-15Ce合金在本实验条件下的氧化-硫化腐蚀速度低于相同温度、压力下的纯硫化。     

用氢-氧取代氧-乙炔作焊接切割的必要性及可行性

阐述了用氢代乙炔的必要性．通过时HGQU2000／315火焰电孤焊割机的考察和试用证实了用氢代乙炔的可行性，比较了两种气体的性质并提出了使用特性差异和注意事项．提出了进一步探索的问题。     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

IrO2-MnO2中间层Ti/RuO2-TiO2-SnO2电极制备及性能

通过热分解法制备了含IrO2-MnO2中间层Ti/RuO2-TiO2-SnO2电极,采用SEM、EDX、XRD、CV等检测方法对中间层进行表征,同时采用强化加速寿命试验对电极电化学稳定性进行表征。结果表明:450℃时前躯体完全氧化并形成固溶体,制备的中间层晶粒细小,表面结构致密,电化学孔隙率小。添加中间层使Ti/RuO2-TiO2-SnO2电极强化寿命由未加中间层的7.5h提高到995.8h,远高于国家标准20h。     

ACTIVITY OF La_2O_3 IN LIQUID La_2O_3-CaF_2 AND La_2O_3-CaF_2-CaO-SiO_2 SLAGS

用石墨为还原剂,将渣中La_2O_3还原入液态Sn,以测定1500℃下La_2O_3-CaF_2和La_2O_3-CaF_2-CaO-SiO_2渣中La_2O_3的活度.对La_2O_3-CaF_2系,并用Gibbs-Duhem积分法求得CaF_2的活度. 根据液态渣的离子结构模型,对上述二渣系中La_2O_3的活度数据进行了简单的讨论.     

Mechanoluminescence in BaSi2O2N2:Eu

Mechanoluminescence (ML), a general term for the phenomenon in which light emission occurs during any mechanical action on a solid, can be divided roughly into two classes: destructive ML and non-destructive ML. For practical use in high-end applications (e.g. pressure sensors), materials with non-destructive ML properties are preferred. This paper reports on the strong non-destructive ML in BaSi₂O₂N₂:Eu. When irradiated in advance with ultraviolet or blue light, this phosphor shows intense blue-green light emission upon mechanical stimulation such as friction or pressure. The ML has an emission band peaking at 498 nm, which is ～4 nm red-shifted compared to the steady-state photoluminescence. The origin of the ML is discussed and related to the persistent luminescence of BaSi₂O₂N₂:Eu. The same traps are responsible for both phenomena. Based on the occurrence of ML in this phosphor, we were able to show that the predominant crystallographic structure of BaSi₂O₂N₂:Eu belongs to space group Cmc2₁.     

氢分子在贮氢材料Li2MgN2H2表面的吸附与解离

采用第一性原理计算方法研究了Li-Mg-N-H体系贮氢材料的放氢产物Li2MgN2H2的吸氢反应过程中的过渡态、表面电子态密度和表面能。结果表明:氢分子在Li2MgN2H2低指数表面中最低能量(100)表面的Mg-Mg-Li穴位吸附位置能够形成最稳定的吸附结构并发生解离,氢分子吸附能为-0.1898eV,解离能约为0.84eV(81kJ/mol),表明该反应所需的反应活化能仍较高,吸氢反应速度缓慢。     

Thermodynamic evaluation of phase equilibria in the CaCl2-MgCl2-CaF2-MgF2 system

The phase diagram of the CaCl₂-CaF₂-MgCl₂-MgF₂ reciprocal ternary system was calculated thermodynamically from available data on the common-ion binary subsystems and from available data on the CaCl₂-MgF₂ join. This join is very nearly quasibinary and divides the system into two quasiternary systems: the CaCl₂-MgF₂-CaF₂ system with a ternary eutectic calculated at 724 +-5 °C and the CaC₂-MgF₂-MgCl₂ system with a ternary eutectic calculated at 561 +-5 °C.     

High temperature corrosion of Fe-Cr-Mn-alloys in H2-H2S and H2-H2O-H2S gas mixtures

The sulfidation of Fe-20% Cr-30% Mn, Fe-25%Cr-20%Mn and Fe-25% Cr was studied at 700°C in H₂-H₂S and the oxidation and sulfidation in H₂-H₂O-H₂S after preoxidation in H₂-H₂O. The sulfidation rate is strongly increased for the Mn-containing alloys, layers of (Mn,Cr)S and (Mn,Fe)Cr₂S₄ are formed. Also the oxidation rate is enhanced compared to Fe-25% Cr by formation of MnCr₂O₄ instead of Cr₂O₃. The sulfidation after preoxidation leads to internal and external sulfidation of the Mn-containing alloys. With increasing oxygen pressure p(O₂) = 10^?26…10^?22 atm. of the H₂-H₂O-H₂S mixtures the sulfidation is suppressed, for the higher oxygen pressure 10^?23 and 10^?22 atm. fast oxidation prevails under formation of MnCr₂O₄. Manganese cannot increase the sulfidation resistance of alloys, in spite of the stability and low degree of disorder of its sulfide, since the mixed sulfide (Mn,Cr)S is formed which has a high degree of disorder, high diffusivities and high growth rate according to the doping effect of trivalent Cr³⁺.     

The Quasi-Ternary System Cu2Se-Ga2Se3-GeSe2

The quasi-ternary system Cu₂Se-Ga₂Se₃-GeSe₂ was investigated using the methods of differential thermal and x-ray analysis. An isothermal section at 770 K and a liquidus surface projection of the phase diagram were constructed. The existence of the quaternary phase CuGaGeSe₄, the boundaries of solid solutions ranges of the system compounds were established.