Bi2WO6量子点(QDs)修饰Bi2MoO6-xF2x异质结的构筑及其催化活性增强机理

采用简单沉积-沉淀法合成了Bi₂WO₆@Bi₂MoO_6-xF_2x（BWO/BMO6-xF2x）异质结,借助XRD、XPS、TEM、SEM、EDS、UV-Vis-DRS、PC和EIS等测试技术对其组成、形貌、光吸收特性和光电化学性能等进行系统表征,并以模型污染物罗丹明B（RhB）的光催化降解作为探针反应来评价Bi₂WO₆@Bi₂MoO_6-xF_2x异质结的光催化活性增强机制。形貌分析表明,所得Bi₂MoO₆微球由大量厚度为20~50 nm的纳米片组成;FE-SEM和HR-TEM分析表明,尺寸约为10 nm的Bi₂WO₆量子点均匀沉积在Bi₂MoO_6-xF_2x微球表面,形成新颖的Bi₂WO₆@Bi₂MoO_6-xF_2x异质结;与纯Bi₂MoO₆或者Bi₂WO₆相比,1∶1Bi₂WO₆@Bi₂MoO_6-xF_2x异质结表现出更好的光催化活性和光电流性质,其对RhB光催化降解的表观速率常数分别为纯BMO和BWO的6.4和11.6倍。PC和EIS图谱分析表明,Bi₂WO₆量子点表面沉积显著提高Bi₂MoO_6-xF_2x光生电子/空穴的分离效率和迁移速率;活性物种捕获实验证明了·O₂^-和h⁺是主要的活性物种。根据实验结果,探讨了F^-掺杂和Bi₂WO₆量子点之间的协同效应对Bi₂MoO₆的光催化活性的影响机制。     

新半金属Fe2LaO4磁电性能的第一性原理计算

利用基于密度泛函理论的第一性原理赝势法设计并优化了含稀土元素的新半金属Fe₂LaO₄。详细计算了其电荷分布,分子磁矩等磁电性能，并结合配位场理论分析了其电子结构。结果表明，Fe₂LaO₄是一种含稀土元素的铁磁性的新ⅡB型半金属；它的稳定相晶格常数约为0.623 nm，分子磁矩约为1.0μ_B；Fe₂LaO₄属软铁磁性半金属；La较多的外层电子增强了Fe₂LaO₄内部的库仑斥力,导致了配合物ML₄和ML₆均受强场作用,从而使Fe₂LaO₄具有软铁磁性；考虑自旋分布后ML₄和ML₆的电子结构分别为a_1g¹↑a_1g¹↓t_1u³↑t_1u³↓e_g²↑e_g²↓t_2g³↑t_2g³↓和a_1g¹↑a_1g¹↓t_1u³↑t_1u³↓t_2g³↑t_2g³↓e_g²↑e_g²↓e_g^*1↑,这些电子属于分子轨道。     

溴代烷烃与活性氮的反应发光研究

在流动余辉装置上, 利用N₂空心阴极放电制备活性氮, 研究了活性氮与溴代烷烃(CHBr₃、CH₂Br₂、C₂H₅Br、C₄H₉Br) 反应的化学发光.上述所有反应中, 在550～750 nm波段均观察到了较强的NBr (b¹Σ+→X³Σ^-)跃迁发射谱. 同时在活性氮与CHBr₃和CH₂Br₂的反应中, 在流动管下游还观察到了CN (A²π, B²π→X²Σ⁺)的发射谱. 验证性的实验表明, 激发态NBr (b¹Σ⁺)是由二步过程形成: N(⁴S)与溴代烷烃反应生成NBr (X³Σ^-), 再通过N₂ (A ³Σ_u⁺)分子能量转移到激发态NBr (b¹Σ⁺); 而激发态的CN是通过N(⁴S) + CBr→CN(A, B) + Br过程形成的.     

白光LED用Sr0.955Al2Si2-xTixO8：Eu2+荧光粉的晶体结构和光谱特性

由高温固相反应制得Sr_0.955Al₂Si_2-xTi_xO₈：Eu²⁺（x=0~1.0）系列试样,研究了Ti⁴⁺置换Si⁴⁺对其晶体结构和光谱特性的影响。Ti⁴⁺以类质同相替代Si⁴⁺进入晶体晶格中,形成了连续固溶体,其晶胞参数a,b,c,β和晶胞体积V随Ti⁴⁺置换量呈线性递增。Ti⁴⁺置换Si⁴⁺对晶胞参数c的影响显著,b其次,a最小。荧光激发谱为宽带,位于230~400nm,由267nm、305nm、350nm和375nm 4个峰拟合成,表观峰值位于351nm;随着Ti⁴⁺置换量的增加,半高宽（FWHM）从105nm减小到93nm。发射光谱位于380~600nm,表观峰值位于407nm,可由406nm和441nm两峰拟合而成并且随Ti⁴⁺置换量增加线性红移,Ti⁴⁺进入晶格对长波长发射中心影响较少;Ti⁴⁺置换量为1.0时,表观发射峰位从407nm红移至417nm;利用试样荧光光谱和VanUitert经验公式,得出SrAl₂Si₂O₈：Eu²⁺中Sr²⁺的配位数为9。随着Ti⁴⁺置换量Si⁴⁺进入基质晶格,造成Eu-O距离变小,使得Eu²⁺所处的晶体场强度增强,发光中心Eu²⁺的5d能级分裂增大,造成Eu²⁺最低发射能级重心下移,两拟合谱峰峰位均呈线性红移。     

三元体系YCl3-CdCl2-H2O和四元体系YCl3-CdCl2-HCl(～8.8%)-H2O (25 ℃)的相平衡及其固相新化合物的研究

The equilibrium solubilities of the ternary system YCl₃-CdCl₂-H₂O, the quaternary system YCl₃-CdCl₂-HCl(～8.8%)-H₂O were determined at 25 ℃ and the phase diagrams were constructed. The results show that the ternary system was complicated with six equilibrim solid phases CdCl₂·2.5H₂O, CdCl₂·H₂O, 8CdCl₂·YCl₃·15H₂O (8∶1 type), 4CdCl₂·YCl₃·13H₂O(4∶1 type), 5CdCl₂·2YCl₃·26H₂O (5∶2 type) and YCl₃·6H₂O. The quaternary system was also complicated with four equilibrim solid phase CdCl₂·H₂O, 4CdCl₂·YCl₃·13H₂O (4∶1 type), 5CdCl₂·2YCl₃·26H₂O(5∶2 type) and YCl₃·6H₂O. Among the three new compounds 8CdCl₂·YCl₃·15H₂O, 4CdCl₂·YCl₃·13H₂O and 5CdCl₂·2YCl₃·26H₂O, 8CdCl₂·YCl₃·15H₂O was a kind of metastable compound only in ternary system, and it was changed into 4CdCl₂·YCl₃·13H₂O with time. Both 4∶1 type and 5∶2 type existed in ternary and quaternary system, but they were also congruently soluble compounds in quaternary system. They have been prepared from the system and have been characterized by XRD, TC-DTG and DSC.     

钙钛矿型LaxSr1－xNi1－yCoyO3光电催化活性研究

用甘氨酸-硝酸盐燃烧合成法, 制备La_xSr_1－xNi_1－yCo_yO₃复合氧化物的陶瓷粉末, 对钙钛矿氧化物进行了XRD结构分析. 在通氧或不通氧下测试氧还原和氧析出的循环伏安曲线. 结果表明: 该氧电极具有双功能催化特性, 但不完全可逆. 利用汞灯作为激发光源, 进行几种水溶性染料和五种混合染料光解实验, 利用紫外-可见、红外以及人工神经网络光度法研究La_xSr_1－xNi_1－yCo_yO₃的催化性能. 结果表明: La_xSr_1－xNi_1－yCo_yO₃ (x＝0.7, 0.9, 1; y＝0.3, 0.75)复合氧化物都具有较强光催化特性; La_xSr_1－xNi_1－yCo_yO₃的光催化活性高于La_xSr_1－xNiO₃, 这与B位离子(Ni^2—, Co^2－)的电子构型有关; Co^2＋的加入可使La_xSr_1－xNiO₃的光催化活性有所提高.     

纳米Mn-Zn铁氧体的制备和研究

Nanosize manganese zinc ferrites were fabricated by hydrothermal precipitation route using Fe₂(SO₄)₃, ZnSO₄·7H₂O, MnSO₄·H₂O as material, then some calcinated at 500 ℃ and studied by XRD, TEM, IR and VSM. The results showed that the products were spinel crystal structure and uniformly sized nanoparticles (15～25 nm) with little aggregation. The analysis of IR showed that the superficial water can be eliminated, but that was embedded in crystal lattice can not be removed by calcinating. The effect Zn content x on the lattice (a) of nanosize Mn_1-xZn_xFe₂O₄ was also discussed. The lattice of nanosize Mn_1-xZn_xFe₂O₄ decreases with x increasing; and its value deviated the standard lattice (a₀) of normal size manganese zinc ferrites. A lot of water was absorbed during the hydrothermal process owing to the large surface of nanosize particles. The change of magnetic properties of Mn_xZn_1-xFe₂O₄ with x increasing was studied: nanosize Mn_xZn_1-xFe₂O₄ particles synthesized by us exhibited peculiar magnetic properties curve with Zn content (x) increasing, Superparamagnetic behaviors of the synthesized ZnFe₂O₄ samples were confirmed by magnetic characterization, which can be explained by the difference between the distribution of the metal ions (Mn²⁺, Zn²⁺ and Fe³⁺) among the tetrahedral (A) and the octahedral (B) sites of nanosize ferrite and that of bulk ferrite.     

VB2n-(n=8~12)团簇几何结构、电子及热力学特性的理论研究

基于卡里普索结构预测程序和密度泛函理论的第一性原理计算,搜索确定了VB_2n^-（n=8~12）团簇的基态和亚稳态结构。结果发现,V原子的掺杂完全改变了原硼团簇的结构并提高了原体系的稳定性。掺杂体系基态结构分别呈现高对称性的鼓状（VB₁₆^-：C_2v）、管状（VB₁₈^-：C_2v和VB₂₀^-：C_s）及笼状（VB₂₂^-：C₂和VB₂₄^-：D_3h）结构。基于基态结构,研究了体系的电荷转移和极化率,拟合出了光电子能谱、红外和拉曼谱图,分析了流变键和芳香特性。最后,研究了体系的热力学特性,讨论了温度对热力学参数的影响。     

不同温度下VUV光激发的Pr3+离子的发光性质

The luminescent properties of Pr³⁺-doped LaB₃O₆, SrAl₁₂O₁₉, SrB₄O₇ and NaYF₄ in the vaccum ultraviol-et (VUV) range at different temperatures were investigated under the excitation of high-energetic synchrotron radiation. For Pr³⁺ ions in LaB₃O₆, SrAl₁₂O₁₉ and SrB₄O₇, only the parity-forbidden ¹S₀→4f² transitions were observ-ed in the emission spectra at relatively low temperature; but the parity-allowed 4f5d→4f² transitions appeared simultaneously when the temperature was high enough. And the intensity of broad 4f5d→4f² emission increased relative to the intensity of ¹S₀→4f² emissions with increasing temperature. Then the thermal equilibrium model of energy levels was employed to the lowest 4f5d state and ¹S₀ state of Pr³⁺ in the three hosts. The calculated curves were in good agreement with the experimental values, indicating the occurrence of the thermal excitation from ¹S₀ state to 4f5d states at high temperatures when the lowest 4f5d state lies higher than ¹S₀ state and the photon energy is high enough.     

空气中合成固溶体荧光粉Ba2(Zn, Mg)Si2O7:Ce3+,Eu2+,Eu3+及其发光特性

采用高温固相法在空气中合成了Ba_1.97-yZn_1-xMg_xSi₂O₇:0.03Eu,yCe³⁺系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba_1.97-yZn_1-xMg_xSi₂O₇:0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu²⁺离子的4f⁶5d¹-4f⁷跃迁,590~725 nm红光区窄带谱源于Eu³⁺的⁵D₀-⁷F_J (J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu³⁺在Ba_1.97-yZn_1-xMg_xSi₂O₇基质中被还原成了Eu²⁺;当x=0.1时,荧光粉Ba_1.97Zn_0.9Mg_0.1Si₂O₇:0.03Eu的绿色发光最强,表明Eu³⁺被还原成Eu²⁺离子的程度最大。当共掺入Ce³⁺离子后,形成Ba_1.97-yZn_0.9Mg_0.1Si₂O₇:0.03Eu,yCe³⁺荧光粉体系,其发光随着Ce³⁺离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba_1.96Zn_0.9Mg_0.1Si₂O₇:0.01Ce³⁺,0.03Eu的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba₂Zn_0.9Mg_0.1Si₂O₇基质中的能量传递与发光机理。     

化学沉积镍-铁-磷合金和它的伏安行为(英文)

在以次亚磷酸钠为还原剂 ,硼酸为缓冲剂和柠檬酸钠为络合剂的碱性介质中 ,研究了镍_铁_磷合金化学沉积条件 (pH值 ,温度及 [Fe2 + ]/([Ni2 + ]+[Fe2 + ])物质的量比 )对沉积速率和镀层组成的影响 ;并由此建立镀液稳定的最佳沉积工艺 .实验表明 ,镀液中硫酸亚铁对沉积镍_铁_磷合金有阻碍作用 (降低了化学沉积速率 ) ,造成镀层中铁含量不高 (小于 2 0 % ) ,使用循环伏安技术研究了镍_铁_磷合金的电沉积机理 .结果发现铁对次亚磷酸钠的氧化不起催化作用 ,提高镀液温度和pH值有增加沉积速率之效     

聚硅硫酸铝在中原油田注水处理中的应用

用硅酸钠和硫酸铝制备了聚硅硫酸铝 (PASS)混凝剂 ,应用于中原油田废水的混凝处理 .考察了硅铝配比、熟化时间、水样pH值和温度等因素对混凝性能的影响 ,并与聚合硫酸铁 (PFS)、聚合氯化铝 (PAC)进行比较 .结果表明PASS在降低悬浮物 (SS)和总铁量、增大絮凝体的直径、加快沉降速度等方面均优于PFS和PAC ,在常温下的混凝性能尤其显著 .     

Interactions in iron gall inks

Simple iron gall inks composed of gallic acid, ferrous sulfate, and gum arabic and in some cases also of copper(II) sulfate were prepared. The process of iron ion complex formation with gallic acid was investigated using UV-VIS spectroscopy, pH measurements, and by monitoring the concentration changes of Fe(II) ions. The admixture of Fe(II) ions to gallic acid induced a bathochromic shift of absorption bands at 215 nm and 265 nm in the UV-VIS spectra. Formation of a new absorbance band in the visible area was also observed and used to calculate the initial rate of complex formation. Concurrently, the pH values and the concentration of Fe(II) ions in the solution decreased. Gum arabic significantly enhanced the complex formation and its stability. On the contrary, the addition of Cu(II) ions to the solution decelerated the complex formation considerably. Dedicated to Professor L’ubomír Lapčík, DrSc., in honor of his 70th birthday     

Coagulation effect and floc properties of polyferric silicate sulphate and polyferric sulphate in the Yellow River water treatment

Two inorganic polymer coagulants,polyferric silicate sulphate(PFSS) and polyferric sulphate(PFS),were comparatively evaluated in the Yellow River water treatment.The removal efficiency of turbidity and UV254 were investigated,and the zeta potential was measured.An online laser scatter instrument was used to determine the size distribution of flocs formed in the coagulation processes.Compared with PFS,PFSS forms flocs with higher growth rates and larger sizes.The formed flocs were exposed to a series of shea...     

聚合硅酸硫酸铁和聚合硫酸铁处理黄河水的效果及其絮体特性研究

采用聚合硅酸硫酸铁(PFSS)和聚合硫酸铁(PFS)两种无机高分子混凝剂处理黄河水,考察了两种混凝剂对浊度和UV254的去除效果,并结合混凝过程中絮体zeta电位的变化,分析了两种混凝剂的混凝机理.通过激光粒度仪在线观察混凝过程中絮体的生长情况,发现PFSS比PFS生成的絮体生长速度快,尺寸大.对形成的絮体施加不同强度的剪切力,通过观察絮体粒径的变化来比较絮体的强度,发现PFSS生成的絮体强度较大.研究了在不同剪切强度和不同剪切时间下絮体的破碎程度和絮体的恢复能力(分别以破碎因子Bf和恢复因子Rf表示),发现在强剪切力和长剪切时间下Bf和Rf均较大;在相同条件下PFSS生成絮体的Bf较小而PFS生成絮体的Rf较大,这表明前者的抗剪切能力较强,而后者具有更强的再生能力.     

Uniform nanosized goethite particles obtained by aerial oxidation in the FeSO4-Na2CO3 system

Pure goethite particles in the nanometer size range (from approximately 200 to approximately 80 nm) with an elongated shape (axial ratio from approximately 5 to approximately 8) useful as iron precursors for magnetic recording have been prepared by oxidation of the suspensions resulting from the addition of sodium carbonate to Fe(II) sulfate aqueous solutions under a restrictive set of experimental conditions (Fe(II) concentration, carbonate/Fe(II) mole ratio, temperature, and air flow rate). In all cases, the goethite particles were formed by a dissolution-recrystallization mechanism through an intermediate green-rust phase. The particle size was determined by the carbonate/Fe(II) ratio (which controls the formation pH), the FeSO(4) concentration, and the air flow rate. The smallest particles (length 80 nm) were obtained for a high carbonate/Fe(II) mole ratio (>/=3), a low Fe(II) concentration (0.075 mol dm(-3)), and an air flow rate of 2 dm(3) min(-1). The goethite particles were also characterized by the electron diffraction and high-resolution TEM finding that they were monocrystalline, having the crystalline c axis parallel to the longest particle dimension.     

Characterisation and coagulation performance of polysilicate-ferric-zinc

A new type of coagulant, polysilicate-ferric-zinc (PSFZn) with different Fe/Zn molar ratios, was synthesised using water glass (industrial grade, w(SiO₂) = 21 mass %, ρ = 1.34 × 10³ kg m^?3, modulus = 3.2), FeSO₄ · 7H₂O, ZnSO₄, and NaClO₃ by way of co-polymerisation in the same (Fe + Zn)/Si molar ratio based on polysilicate-ferric (PSF). The effect of the Fe/Zn molar ratios on the morphology and structure was systematically investigated using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) analysis. Three samples, namely PSFZn4, PSFZn1, and PSFZn0.25, represented Fe/Zn molar ratios of 4, 1, and 0.25, respectively, and were selected for a comparative study while a constant (Fe + Zn)/Si molar ratio equal to 1 was maintained. Accordingly, PSFZn was found to be a complex compound rather than a simple mixture of raw materials. With the decrease in Fe/Zn, a great change occurred in the surface morphology, from a tetrahedral cluster structure to a lamellar structure. The Fe—O and Fe—O—Si bonds were gradually replaced by Zn—O and Zn—O—Si. However, the crystalline peaks were more obvious with the increase in the number of zinc ions; hence the new polymer would be formed from iron, zinc, and polysilicate. In addition, the coagulation performance of PSFZn was investigated using a surface water sample. PSFZn4 exhibited a better coagulation performance than the other PSFZn coagulants. Additionally, the trends in changes in pH with different coagulation times after adding PSFZn were studied relative to PSF and FS. The replacement of zinc ions with iron ions could effectively counter the rapid decrease in pH. The effect of settling time on the coagulation efficiency was also investigated. PSFZn4 exhibited a better settlement performance than PSF and poly aluminium chloride (PAC). Hence, the partial substitution of zinc salt with iron salt not only addresses the inadequacies of iron salt but also improves the coagulation efficiency of zinc salt in water treatment.     

MPEGMAA/G-570/DEM/AMPS新型酯类聚羧酸系减水剂的制备

以甲基丙烯酸聚乙二醇单甲醚酯600（MPEGMAA600）、 γ-甲基丙烯酰氧基丙基三甲氧基硅烷（G-570）、马来酸二乙酯（DEM）和2-丙烯酰胺-2-甲基丙磺酸（AMPS）为原料,过硫酸钾 硫酸亚铁为引发剂,合成了G-570/MPEGMAA/DEM/AMPS酯类聚羧酸系减水剂,其结构和组成经傅立叶变换红外光谱（FT-IR）和凝胶色谱（GPC）表征。通过正交实验确定最佳合成工艺为:MPEGMAA与DEM、 AMPS和G-570的摩尔比为1.0:1.0:2.0:0.4,过硫酸钾-硫酸亚铁总质量占聚合单体总质量的0.4%,于45 ℃聚合反应8 h,单体转化率为91.71%,水泥初始净浆流动度为225 mm。通过X-射线衍射（XRD）和热重（TG-DTG）分析对加入该减水剂的硬化水泥石微观结构进行了分析。结果表明：该减水剂链段中含有酯基、氨基、磺酸基、醚键、硅氧键等基团,平均相对分子质量分布集中,峰值大都集中在1.2~1.7万。同时,该减水剂可以延缓24 h内水泥水化。     

聚硅酸硫酸铁/壳聚糖复合絮凝剂的制备及其在废水处理中的应用

制备了无机高分子复合絮凝剂聚硅酸硫酸铁（PFSS）和助凝剂壳聚糖（CTS）,考察了影响合成及絮凝剂应用的因素,探讨了其组成、投加量以及pH值对城市废水絮凝效果的影响,通过对模拟废水和城市废水絮凝试验,得出最佳的合成和应用条件：n（Fe）∶n（Si）=1∶1,PFSS的碱化度为1.5,聚合硫酸铁（PFS）的pH=2,聚硅酸（PS）的活化时间为1.5 h;n（PFSS）∶n（CTS）=5∶1,投加量为(20+4) mg/L,pH值的范围为6～9,沉降时间为15 min。 复合絮凝剂（PFSS-CTS）在最佳条件下浊度、色度、COD的去除率分别达到95.04%、91.26%和83.45%。     

掺Fe~(3+) A-TiO_2的合成及其对酸性红B的光催化降解性能

以硫酸氧钛和FeCl_3·6H_2O为主要原料,采用水热法合成了掺Fe~(3+)的纯锐钛矿型A-TiO_2催化剂,其结构经FT-IR和X-射线衍射表征。以波长365nm紫外灯为光源,酸性红B为降解对象,研究了其光催化降解性能。实验结果表明:掺Fe~(3+)有利于提高TiO_2的催化性能,当掺Fe~(3+)量为0.2mol%时,A-TiO_2的光催化性能最强;当掺Fe~(3+)A-TiO_2投放量为400mg·L~(-1),于20℃降解时间40min,对10mg·L~(-1)酸性红B溶液(pH=5)的降解率最大(95.11%)。