Zr/Ti摩尔比对锶锆钛复合氧化物在可见光下光催化性能的影响

通过分步沉积法制备了不同Zr/Ti 摩尔比的锶锆钛(SZT)复合氧化物催化剂, 以X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、紫外-可见(UV-Vis)漫反射光谱等表征手段考察不同Zr/Ti 摩尔比下SZT催化剂的结构形态, 以可见光下光催化降解亚甲基蓝为模型反应考察样品的光催化活性. 结果表明: Zr/Ti 摩尔比<1 时SZT催化剂发生Zr⁴⁺与Ti⁴⁺同质替换, 引起晶格缺陷, 光催化活性小幅提高; Zr/Ti 摩尔比≥1 时SZT催化剂产生SrZrO₃/Ti_nO_2n-1 (n=4, 9)的新晶相, Ti_nO_2n-1 (n=4, 9)的存在有利于光生电子-空穴的传导与分离, 可大幅提高催化剂光催化活性. 其中, SZT-5/5 表现出最高的光催化活性, 其一级反应速率常数达到0.2133 min^-1, 是同等光照条件下纯SrTiO₃样品(0.0158 min^-1)的13.5倍.     

Two New Metal-organic Frameworks Constructed from 3,4,5-Substituted-1,2,4-Triazole Ligands

Two new complexes,[Zn（L1）2（SCN）2]·H2O（1,L1 = 3,5-dimethyl-4-p-tolyl-4H1,2,4-triazole and [Cd3（L2）6（SCN）6]（2,L2 = 3,5-dimethyl-4-phenyl-4H-1,2,4-triazole）,have been hydrothermally prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and PXRD.Complex 1 crystallizes in monoclinic,space group P21 /n with a = 11.246（13）,b = 9.640（11）,c = 26.13（3）,β = 100.97（3）,V = 1108.5（3） 3,Z = 4,C24 H28 N8 OS2 Zn,Mr = 572.02,Dc = 1.366 g/cm3,μ = 1.065 mm-1,S = 0.992,F（000） = 1184,the final R = 0.0602 and wR = 0.1700 for 2925 observed reflections（I 2σ（I））.Complex 2 crystallizes in triclinic,space group P1 with a = 11.6669（3）,b = 12.0957（2）,c = 14.3674（3）,α = 105.380（3）,β = 91.020（2）,γ = 92.4100（10）o,V = 1952.30（7）3,Z = 1,C66H66N24S6Cd3,Mr = 1725.08,Dc = 1.467 g/cm3,μ = 1.025 mm-1,S = 1.037,F（000） = 870,the final R = 0.0336 and wR = 0.0946 for 7819 observed reflections（I 2σ（I））.In the title complexes,complex 1 is a mononuclear molecule where the centre Zn（II） coordinates to two 3,4,5-substituted 1,2,4-triazole ligands（L1） and two terminal SCN-anions in a tetrahedral environment while six-coordinated centre Cd（II） atoms with octahedral geometry in complex 2 are bridged by virtue of substituted 1,2,4-triazole（L2） in N1,N2-bridging mode and μ2-N,N-SCN-anions into a trinuclear molecule.     

Coherence and Quantum Phase Transition in Spin Models

Based on quantum renormalization group (QRG) method, we investigated quantum coherence and quantum phase transition (QPT) in XXZ chain and XY chain, respectively. The results show that both the geometric quantum coherence and entropic coherecne can accurately indicate the QPT at critical point after enough iteration steps. Moreover, the increasing anisotropy parameter destroys the coherence in the XXZ chain, while enhances it in the XY chain. In addition, focused on the XXZ chain we analyzed the nonanalytic phenomena and scaling behaviors with different theoretical exponents in detail.

     

Y2O3掺杂WO3光催化剂的制备及其性能

采用浸渍法合成了Y2O3 -WO3光催化剂,通过XRD和UV-Vis DRS测试手段对其进行了表征.以对苯二甲酸为探针分子,结合化学荧光技术研究了Y2O3 -WO3表面羟基自由基的生成.以溴百里香酚蓝(BTB)催化降解实验评价了其光催化活性.结果表明:与纯WO3相比,1.2％ Y2O3-WO3样品的吸收带边发生明显红移、在200～800 nm 区域有更强的光吸收.Y2O3-WO3样品的紫外和可见光催化活性随Y2O3含量增加先增加,当Y2O3含量为1.2％时分别达到最大值,然后随Y2O3含量的进一步增加而减小.与纯WO3相比,1.2％ Y2O3-WO3样品明显具有更高的紫外和可见光催化活性以及更大的羟基自由基生成速率.     

���������ӵ���ײ���������ʲ����������

建立了包含两种正离子的碰撞等离子体鞘层的流体模型,通过四阶龙格-库塔法模拟了碰撞对含有两种正离子的等离子体鞘层中的离子密度和速度分布产生的影响。结果表明,对于两种正离子的等离子体来说,鞘层中无论哪种离子与中性粒子碰撞频率的增加,该种离子的密度和速度分布都将呈现波动变化,密度是先增加后降低,速度是先降低后增加;而另一种离子的密度和速度呈单调变化。鞘边正离子的含量越少,受自身与中性粒子的碰撞频率增加,鞘层中该种离子密度先增加后降低的变化位置就越远离等离子体的鞘层边界。同时发现该种离子密度分布受自身碰撞频率增加,降低的幅度变化非常小。另外发现电子碰撞器壁产生的二次电子发射系数对质量较轻的离子影响要大一些。     

Interaction behavior study of HCl on (ZnS)n (n = 1–12) clusters and HCl effect on Hg0 adsorption

The interaction behavior of HCl and (ZnS)_n (n = 1–12) clusters and HCl effect on Hg⁰ adsorbed by (ZnS)_n have been studied theoretically. The combined genetic algorithm and density functional theory (GA-DFT) method has been used to obtain the structures of (ZnS)_nHCl and (ZnS)_nHgHCl (n = 1–12) clusters. The structural properties of (ZnS)_nHCl and (ZnS)_nHgHCl have been analyzed. The adsorption energies and interaction energies have been calculated. Bond length and bond order analysis has revealed that S H and Zn Cl bonds form after HCl adsorbed on (ZnS)_n clusters, while Hg⁰ can only weakly bind with (ZnS)_nHCl clusters. According to thermodynamic adsorption analysis, the formation of (ZnS)_nHCl clusters from (ZnS)_n and HCl are spontaneous because of their negative Gibbs free energy changes. The formation of (ZnS)_nHgHCl from (ZnS)_nHCl and Hg are nonspontaneous for n = 1–4 and 9, and the Gibbs free energy changes have small negative values for other sizes. Electron localization function and noncovalent interaction (NCI) analysis of (ZnS)₁₀HgHCl manifest that Hg and its nearest Zn form zinc amalgam. Projected density of state study has been performed to obtain the interaction nature of HCl and (ZnS)_n clusters and Hg⁰ adsorption on (ZnS)_nHCl clusters. Based on our study, HCl is chemical adsorbed by (ZnS)_n clusters except (ZnS)₄ cluster. After (ZnS)_n adsorbs HCl, Hg⁰ can physically adsorb on (ZnS)_nHCl clusters. The strength of Hg⁰ on (ZnS)_nHCl is comparable to that of Hg⁰ on (ZnS)_n, indicating that HCl can hardly affect the adsorption of Hg⁰ on ZnS clusters.     

一类非线性偏微分方程组的直接解法

根据Hopf-Cole变换法和试探函数法的基本思想,引入一个变换,并把它应用于求解(2+1)维破裂孤子方程组、(2+1)维Nizhnik-Novikov-Vesslov方程组和(2+1)维Broer-Kaup方程组,得到了这三个方程组的许多新的解析解,包括孤波解和奇异行波解.该方法也适用于其它方程组.     

A Biomass-Ligand-Based Ru(III) Complex as a Catalyst for Cycloaddition of CO2 and Epoxides to Cyclic Carbonates and a Study of the Mechanism

Aiming highly efficient conversion of greenhouse gas CO₂ to cyclic carbonates, a biomass Ru(III) Schiff base complex catalyst ( SalRu ) was constructed by employing a derivative of Lignin degradation (5-aldehyde vanillin). The SalRu catalyst had a remarkable conversion for epoxides into corresponding cyclic carbonates even at atmospheric pressure of CO₂ without the presence of co-catalyst. As the condition at 120 °C and 2 MPa CO₂ the conversion reached to 94 % with selectivity at 99 % after 8 h. 32 % cyclic carbonate production was obtained even under 0.2 MPa CO₂ pressure. The epoxide activation and ring opening, CO₂ insertion and cyclic carbonate formation were illuminated explicitly through the of characteristic absorption peaks changing, which further providing direct and visual evidence for the mechanism proposing. This study has important theoretical significance for the comprehensive utilization of environmental pollutants and energy.     

NMR observation of a high temperature phase transition in the organic superconductor (TMTSF)2ClO4

A high temperature phase transitional behavior in the organic superconductor (TMTSF)₂ClO₄ (tetramethyltetrafulvalenium-perchlorate) was manifest in our ¹H NMR measurements. Our observations are discussed in the light of a dimensional crossover of the electronic transport.     

侧链含查尔酮基团的聚(甲基)丙烯酸酯的光交联特性

采用红外光谱、热重分析、紫外光谱和荧光光谱对侧链含查尔酮基团的聚（4-甲基丙烯酰氧基-4'-二甲氨基查尔酮）（PMADMAC）和聚（4-丙烯酰氧基查尔酮）（PAC）的光交联特性进行了研究。随着光照时间的增加,PMADMAC和PAC聚合物光致环加成反应迅速进行,波长短的紫外线更易使得聚合物发生[2+2]环加成反应。与溶液状态相比,固体薄膜状态下的光交联反应速率较慢。PMADMAC聚合物更容易发生光致环加成反应,其光交联速率要比PAC聚合物快,环加成反应也更彻底。采用荧光光谱研究了聚合物的发光特性,发现PAC聚合物无荧光,而PMADMAC聚合物具有溶剂极性敏感的荧光特性。在PMADMAC聚合物的稀溶液中,随着365 nm紫外光照时间的增加,荧光强度迅速降低,其荧光特征波长在紫外光照射后发生蓝移。 PMADMAC和PAC聚合物的热稳定性较好,光交联后形成热不稳定的环丁烷结构,其热稳定性有所降低。