多溶剂响应自折叠水凝胶（英文）

本文基于寡聚乙二醇甲醚甲基丙烯酸酯(OEGMA)和2-甲基-2-丙烯酸-2-(2-甲氧基乙氧基)乙酯(MEO_2MA)设计了一种自折叠水凝胶.在室温下,P(MEO_2MA-co-OEGMA)凝胶能够在多种溶剂中自折叠形成三维结构.凝胶不均匀膨胀导致内应力增强,从而使得片状凝胶可以在三维结构和二维形状之间进行可逆转换.研究表明,凝胶组成、固化气体环境和成型过程对水凝胶的自折叠过程起着重要的影响.     

从可溶性单源分子前驱体采用溶胶凝胶法制备ZnO/TiO2 纳米复合物

合成了单源分子前驱体Cl₂TiZn(dmae)₄ (dmae为2-二甲基乙醇胺),并以乙醇为溶剂,加入等摩尔量的水对其进行可控水解得ZnO/TiO₂纳米复合凝胶,经pH=9沉淀,在200、400和600 oC 烧结得到不同的产物T₂₀₀、T₄₀₀、T₆₀₀. XRD分析表明未烧结产物为无定形粉末并随着烧结温度升高晶型改善. ZnO呈纤锌矿结构(六方晶系),TiO₂呈板钛矿型结构(正交). BET分析和扫描电镜表明颗粒的大小随着烧结温度的提高而增加. 红外光谱证明Zn-O和Ti-O的特有的振动频率,OH基团烧结后的产物中被去掉. 所有的样品都显示良好的光催化活性, 且T₆₀₀活性最高.     

Density Functional Theory Study on Electronic and Magnetic Properties of Mn-doped (MgO)n (n=2～10) Clusters

利用密度泛函理论方法优化了纯的和M_n原子掺杂的(MgO)_n (n=2～10)团簇的几何结构. 在Mn原子掺杂的氧化镁结构中, 获得了一系列的同分异构体和与之相对应的总能量.MnMg_n-1O_n(n=2～10)的几何构型显示Mn原子优先取代低配位的Mg原子. 结构稳定性分析表明,除了(MgO)₁₀团簇外,其它纯的和掺杂结构的平均结合能均随着团簇的增大而增强. MnMg_n-1O_n团簇的二阶能量差结果表明MnMg₅O₆和MnMg₈O₉比相邻的团簇表现出更高的相对稳定性. 除了MnMgO₂团簇的磁矩为3.00 μB外,其它掺杂结构的磁矩均为5 μB左右. 它们的磁性主要受电荷转移大小、原子在结构中的位置以及结构尺寸所影响.     

Reaction of C2HCl2+O2: Combined TR-FTIR Spectroscopy and Electronic Structure

用时间分辨傅立叶变换红外发射光谱(TR-FTIR)和G3MP2//B3LYP/6-311G(d,p)水平的电子结构计算研究了环境化学中重要的二氯代乙烯自由基C₂HCl₂和O₂分子的基元反应通道和机理. 通过0.5 cm^-1高分辨的TR-FTIR发射光谱观察到三种振动激发态产物CO₂、CO和HCl,由光谱拟合得到CO和HCl的振动态分布,结合电子结构计算的反应势能曲线,提出反应机理和能量上最可能的反     

光腔衰荡光谱研究PH2自由基在465-555 nm的光谱

采用光腔衰荡光谱记录了465-555 nm范围内PH₂自由基在射流冷却条件下的吸收光谱. 在超声射流条件下对氩载气中的PH₃和SF₆混合物直流放电产生PH₂自由基. 得到了7个有精细转动结构的振转谱带,并归属为PH₂自由基?²A₁- Χ²B₁电子跃迁的0⁰₀、2ⁿ₀、2ⁿ₁ (n=1-3)跃迁. 在已有的基础上,重新归属每一个振转谱带的转动量子数和转动项值;进一步精细化转动常数、离心畸变常数和自旋转动相互作用常数. 另外还简单讨论了每个K结构受到其它电子态的微扰.     

超低密度SiO2气凝胶的制备及成型研究

 以正硅酸乙酯(TEOS)为硅源，采用酸碱二步催化溶胶-凝胶法，结合超临界干燥技术制备了超低密度SiO₂气凝胶,最低密度为3.4 mg/cm³；进一步结合成型工艺，在解决了模具设计和脱模技术后制备了具有不同密度的柱状和微型套筒样品，密度10～50 mg/cm³。研究了水、催化剂、稀释剂对二步溶胶-凝胶过程的影响，获得了制备低密度SiO₂气凝胶的最佳条件。利用扫描电镜、孔径分布及比表面积测试仪等对SiO₂气凝胶微结构进行了研究。结果表明，获得的超低密度SiO₂气凝胶具有较好的纳米网络，平均孔径18.9 nm，还具有高比表面积898 9 m²/g。     

Nd掺杂对Bi4Ti3O12铁电薄膜的微结构和铁电性能的影响

利用溶胶-凝胶法在Pt/Ti/SiO₂/Si(100)衬底上制备了Nd掺杂Bi₄Ti₃O₁₂(Bi_4-xNd_xTi₃O₁₂, x=0.00,0.30,0.45,0.75,0.85,1.00,1.50)铁电薄膜样品.研究了Nd掺杂对Bi₄Ti₃O₁₂薄膜的微结构和铁电性能的影响.研究结果表明:Nd掺杂未改变Bi₄Ti₃O₁₂薄膜的基本晶体结构.在掺杂量x<0.45时,Nd³⁺只取代类钙钛矿层中的A位Bi³⁺.当x=0.45时,样品剩余极化强度达最大值,在270kV·cm^-1的电场下为32.7μC·cm^-2.掺杂量进一步增加时,结构无序度开始明显增大,Nd³⁺开始进入(Bi₂O₂)²⁺层,削弱其绝缘层和空间电荷库的作用,导致材料剩余极化逐渐下降.当掺杂量x达到1.50时,掺杂离子最终破坏(Bi₂O₂)²⁺层的结构,材料发生铁电-顺电相变.     

金属醇盐法制备Ta2O5气凝胶

 以乙醇钽为前驱物,采用金属醇盐溶胶-凝胶技术,获得了Ta₂O₅湿凝胶,分析了不同条件下的溶胶-凝胶过程,并初步探讨了凝胶过程机理。Ta₂O₅的溶胶-凝胶过程主要受到水量、催化剂用量及钽源浓度等因素的影响：体系在强酸性条件下凝胶,且随着酸性的增强,体系凝胶时间明显缩短;当水量较少时,凝胶时间随水量的增加而增加,但当水量增加到一定程度时,体系凝胶时间基本不变;实验证明,通过增大溶剂用量,体系凝胶时间延长,气凝胶理论密度降低。通过对溶胶-凝胶过程的控制,结合超临界干燥技术,获得了密度低至44 mg/cm³的Ta₂O₅气凝胶样品。     

Zn在水锰矿和δ-MnO2表面吸附结构的EXAFS研究

用延展X射线吸收精细结构光谱(EXAFS)研究了重金属Zn(Ⅱ)在水锰矿(γ-MnOOH)和δ-MnO₂表面吸附产物的微观结构.结果表明,在0.1M NaNO₃介质中,pH7.5时Zn(Ⅱ)离子主要是通过共用水合Zn离子的氧原子及水锰矿表面上的氧原子结合到水锰矿固体表面上.第一配位层(Zn-O层)的Zn-O原子平均间距为2.00±0.01A,该键长是由于六配位的Zn(H₂O)₆²⁺及其四配位的水解产物Zn(OH)₂或Zn(OH)₄^2－以一定比例混合吸附于水锰矿表面面形成的.第二配位层(Zn-Mn层)存在两个Zn-Mn原子间距,即R₁=3.07±0.02A和R₂=3.54±0.02,分别对应水锰矿结构单元MnO₆八面体与Zn-O多面体两种结合方式:共用两个氧原子的边边结合和共用一个氧原子的角-角结合.pH5.50时,吸附在δ-MnO₂表面上Zn²⁺以六配位的八面体水合离子形式存在.水合锌离子八面体从δ-MnO₂层状结构的空位上下方,与δ-MnO₂的结构单元MnO₆八面体通过共用O原子给合,形成角-角结合的弱吸附.Zn-O原子平均间距为2.07±0.01A,Zn-Mn平均原子间距为3.53±0.01A.EXAFS分析表明,Zn在水锰矿表面吸附不可逆性较强,而在δ-MnO₂表面吸附很可逆,这与Zn和两种锰矿间的结合方式有关.     

基于约束非平衡溶剂化理论的对硝基苯胺π-π*光谱移动 (cited: 1)

采用共沉淀法制备不同组分类水滑石前驱体Co-M-Al和Co-M-Ce-Al (M=Zn, Ni, Cu)复合氧化物催化剂催化分解N₂O. 结果表明,Co-M-Al系列氧化物催化剂的催化活性Co-Ni-Al系列>Co-Zn-Al系列>Co-Cu-Al系列;CeO₂添加使得催化剂催化活性进一步提高,N₂O分解温度T₅₀和T₉₀均下降80 oC;继续负载碱金属K也使氧化物催化剂催化活性提高,N₂O分解温度T₅₀和T₉₀下降约50 oC.     

Thermoresponsive Gold Polymer Nanohybrids with a Tunable Cross‐Linked MEO2MA Polymer Shell

Gold nanoparticles (AuNPs) are functionalized with a thermoresponsive polymer shell of a cross‐linked poly(2‐(2‐methoxyethoxy)ethyl methacrylate) (P(MEO₂MA)). To provide a covalent attachment of the polymer to the NP surface, AuNPs are first modified using butanoic acid to develop the encapsulation with the biocompatible thermoresponsive polymer formed by free‐radical precipitation polymerization. Both the MEO₂MA concentration and the shell cross‐linking density can be varied and, in turn, the thickness and the shells' free volume can be fine‐tuned. By downscaling the size of the polymeric shell, the lower critical solution temperature (LCST) is decreased. The LCST in the nanohybrids changes from 19.1 to 25.6 °C when increasing the MEO₂MA content; it reaches almost 26 °C for P(MEO₂MA) (bulk). The maximum decrease in the volume of the nanohybrids is around 40%, resulting in a modification of the light scattering properties of the system and causing a change in the turbidity of the gel network. The sizes of the nanohybrids are characterized using both transmission electron microscopy and dynamic light scattering measurements. Optical properties of the colloidal systems are determined using the derived count rate measurements as an alternative to absorbance or transmittance measurements, confirming the colloidal stability of the nanohybrid systems.     

Synthesis and Characterization of pH- and Temperature-sensitive Hydrogels of Poly (Styrene-alt-Maleic Anhydride)-co-Pluronic for Drug Release

A pH- and temperature-sensitive hydrogel of poly(styrene-alt-maleic anhydride) -co-Pluronic P123 (PSMA-P123) was prepared by the reaction of anhydride groups (MA) on PSMA with the hydroxyl groups on Pluronic (triblock polyethylene oxide-co-polypropylene oxide-co-polyethylene oxide, HO(CH₂CH₂O)₂₀(CH₂CH(CH₃)O)₇₀ (CH₂CH₂O)₂₀OH). The effect of proportions between PMSA and P123 on the gel fraction was determined. The effects of pH value and temperature on swelling ratio of the hydrogels were evaluated. Scanning electron microscopy was used to observe the morphology of the hydrogels. Differential scanning calorimetry was employed to characterize the thermo-sensitivity of the hydrogel. The drug-release behavior of the hydrogels was investigated by using chloromycetin as a model drug. The effect of temperature and pH on the release of chloromycetin from the hydrogels was studied. These results showed that PSMA-P123 hydrogels, being pH- and temperature-sensitive and reversible, appeared to be of potential for biomedical materials, especially for drug release applications.     

Three-dimensional flower-like NiS2/MoS2 assembly of randomly oriented nanoplate for enhanced hydrogen evolution reaction

The continually worsening energy crisis has stimulated research into energy conversion technology to produce pure hydrogen, H₂. Transition metal-based compounds have attracted great attention as electrocatalysts for hydrogen evolution reaction (HER) as alternatives to commercial, high-cost, and scarce noble metal-based catalysts. In this work, a 3D flower-like NiS₂/MoS₂ is synthesized with the advantages of a three-dimensional (3D) morphology and the compositing of different metal compounds, thus leading to enhanced electrocatalytic performance. The structure of 3D flower-like NiS₂/MoS₂ augments the specific surface areas resulting from nanoplate assemblies as well as the heterointerface ascribed to two different phases of NiS₂ and MoS₂. These characteristics are confirmed by electrocatalytic measurements of the lower overpotential of 165 mV at 10 mA/cm² with high charge transfer ability, thus demonstrating the structure's potential for advanced electrocatalysts for the HER.     

Capillarity induced folding of elastic sheets

Surface tension forces induced by a liquid droplet are used to bend thin elastic sheets into three dimensional structures. The resulting 3D shape may be controlled by tailoring the initial cut of the sheet. We derive the criterion for folding from a balance between elastic and capillary effects and compare it with the experiments. This mechanism can be used for fabrication of three-dimensional micro- or nano-scale objects through the self-folding of planar templates.     

Introducing CdS into two- and three-dimensional photonic crystals

SiO₂/air three-dimensional (3D) periodic structures were fabricated by removing Si layers partially from Si/SiO₂ 3D photonic crystals (PhCs) formed by using autocloning. CdS/SiO₂ 3D periodic structures were formed by introducing CdS into the SiO₂/air structures by the TEA method and photoluminescence (PL) was observed from the introduced CdS. TiO₂/air/CdS two-dimensional (2D) PhCs were also fabricated by introducing CdS into the voids of TiO₂/air 2D periodic structures, in which SiO₂ layers were partially etched out from TiO₂/SiO₂ 2D PhCs fabricated by using autocloning. PL radiating normal to the surface was measured and large polarization dependence was observed.     

In situ investigation of the formation of Cu(In,Ga)Se2 from selenised metallic precursors by X-ray diffraction—The impact of Gallium, Sodium and Selenium excess

The chemical reactions during rapid thermal processing of stacked elemental layers were investigated by angle-dispersive in situ X-ray diffraction. With a time resolution of 5 diffractograms per minute four different solid state reactions resulting in ternary chalcopyrites were identified: (A) CuSe+InSe→CuInSe₂, (B) Cu₂Se+2InSe+Se→2CuInSe₂, (C) Cu₂Se+In2Se₃→2CuInSe₂, (D) Cu₂Se+Ga2Se₃→2CuGaSe₂. All these reactions form pure tenary chalcopyrites. The reaction resulting in the mixed crystal Cu(In,Ga)Se₂ starts not before (B) has begun. The reaction speed of (A) and the fraction of CuInSe₂ formed by (B) depend on Na-doping and Se-pressure, (C) takes place only, if the reaction paths (A) and (B) are suppressed. Reaction (D) is observed only, if 25% In is replaced by Ga in the precursor. The diffractograms were evaluated by Rietveld refinement to give the phase contents of the samples as a function of reaction time.     

Supercritical fluid extraction of rare earth elements,thorium and uranium from monazite concentrate and phosphogypsum using carbon dioxide containing tributyl phosphate and di-(2-ethylhexyl)phosphoric acid

Supercritical fluid extraction (SCFE) using carbon dioxide containing tributyl phosphate (TBP), di-(2-ethylhexyl)phosphoric acid (D2EHPA) and their adducts with HNO₃ is applied for extraction of rare earth elements (REE), thorium (Th) and uranium (U) from monazite concentrate (MC) and phosphogypsum (PG). REE extraction from MC and their separation from Th and U are carried out from the product of MC–Na₂CO₃ baking (MCS), which is obtained under microwave irradiation, after which the phosphates of REE, Th and U present in the MC are converted into their oxides. Up to 50% of REE can be recovered as the adducts of TBP and D2EHPA with HNO₃ from the resulting powdered MCS under SCFE conditions, whereas Th and U remain in the solid phase. After a complete dissolution of the MCS residue in the mixture of 4 M HCl and 0.05 M HF, Th and U are quantitatively extracted using supercritical carbon dioxide (SC CO₂) containing D2EHPA and thus separated from the REE that remain in an acidic solution. The conditions of quantitative isolation of REE, Th and U from PG are determined. The schemes for complex processing of MC and PG aimed at REE recovery and their separation from Th and U are suggested.     

Rapid synthesis of water-glass based aerogels by in situ surface modification of the hydrogels

The objective of the present research was to reduce the processing time of water-glass based aerogels synthesized via an ambient pressure drying. For this purpose we employed a co-precursor method for the surface modification in hydrogels using trimethylchlorosilane (TMCS) and hexamethyldisilazane (HMDS). The surface modification resulted in the displacement of pore water from the hydrogels and thereby absolutely avoiding the time-consuming solvent exchange step. The attachment of trymethylsilyl (Si(CH₃)₃) groups to the silica surface was confirmed by the presence of SiCH₃ peaks at 2900, 1400, 1255 and 845 cm⁻¹ in the Fourier Transform Infrared (FTIR) spectra. The differential thermal analysis (DTA) revealed that the aerogels maintain their hydrophobic behavior up to a maximum temperature of 500 °C above which they become hydrophilic. The physical and textural properties of the silica aerogels have been reported and the results have been discussed by taking into account the surface modification and the amounts of the pore water displaced out from the hydrogels.     

Preparation of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles for superthermites by the detonation of an explosive nanocomposite material

This article reports on the preparation of chromium(III) oxide nanoparticles by detonation. For this purpose, a high explosive—hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX)—has been solidified from a solution infiltrated into the macro- and mesoporosity of Cr₂O₃ powder obtained by the combustion of ammonium dichromate. The resulting Cr₂O₃/RDX nanocomposite material was embedded in a cylindrical charge of pure explosive and detonated in order to fragment the metallic oxide into nanoparticles. The resulting soot contains Cr₂O₃ nanoparticles, nanodiamonds, amorphous carbon species and inorganic particles resulting from the erosion by the blast of the detonation tank wall. The purification process consists in (i) removing the carbonaceous species by an oxidative treatment at 500 °C and (ii) dissolving the mineral particles by a chemical treatment with hydrofluoric acid. Contrary to what could be expected, the Cr₂O₃ particles formed during the detonation are twice larger than those of initial Cr₂O₃. The detonation causes the fragmentation of the porous oxide and the melting of resulting particles. Nanometric droplets of molten Cr₂O₃ are ejected and quenched by the water in which the charge is fired. Despite their larger size, the Cr₂O₃ nanoparticles prepared by detonation were found to be less aggregated than those of the initial oxide used as precursor. Finally, the Cr₂O₃ synthesized by detonation was used to prepare a superthermite with aluminium nanoparticles. This material possesses a lower sensitivity and a more regular combustion compared to the one made of initial Cr₂O₃.     

Ionization of hydrogen and deuterium atoms in thermal energy collisions with state-selected Ne(3s 3 P 2,3 P 0) metastable atoms

High resolution energy spectra of electrons and ions resulting from thermal energy collisions of hydrogen and deuterium atoms with state-selected metastable Ne(Ne(3s ³ P ₂,³ P ₀) atoms are reported. The electron spectra for Ne(³ P ₂)+H(D) are very broad: The high energy part due to formation of NeH⁺ (NeD⁺) bound states (associative ionization), amounts to about 30% of the ionizing events, whereas the dominant part of the spectrum including a prominent low-energy peak is due to Penning ionization out of a strongly-attractive entrance potential curve. Comparison of the spectra with quantum mechanical fit calculations yields fairly accurate information on this potential, in particular its well depthD _e [Ne(³ P ₂)?H,D]= 2.0(1) eV. The spectra for Ne(³ P ₀)+H, D are comparatively narrow with much lower cross sections than the one for the Ne(³ P ₂) state. The corresponding entrance channel is a weakly bound van der Waals molecule with a well depth below 0.1 eV. A perturbation calculation of the Ne(3s)+H(1s) potential energy curves at large distances explains the observed difference between the Ne(³ P ₂)+H(D) and Ne(³ P ₀)+H(D) systems. Symmetry arguments are given that the major contribution to the Ne(³ P ₂)+H(D) spectra is due to the² Σ potential.