四氨基酞菁锌负载二氧化硅纳米粒子的合成及其对细胞毒性的研究

通过在无极核微乳液中水解乙烯基三乙氧基硅烷(TEVS)和3-氨丙基三乙氧基硅烷(APTES),制备了疏水性光敏剂-2,9,16,23-四氨基酞菁锌负载的表面带有正电荷的二氧化硅纳米粒子(SiO2@ ZnPc( NH2)4).通过透射电镜(TEM)、Zetasizer Nano-ZS粒度仪(DLS)、紫外-可见分光光度计...     

硼酸亲和杂化毛细管整体柱选择性富集蒲公英中的活性物质

以四乙氧基硅烷,N-氨乙基-3-氨丙基三乙氧基硅烷,3-甲基丙烯酰氧丙基三甲氧基硅烷作为前驱,4-乙烯基苯硼酸为单体,在毛细管中原位制备硼酸亲和杂化整体柱,该柱可在中性条件下选择性的富集顺式二羟基生物分子,实现了对蒲公英中活性成分咖啡酸及绿原酸的选择性富集。     

氨丙基官能化HMS介孔分子筛的合成及表征

沿S0I0路径,以十六胺为模板剂,以3-氨丙基三乙氧基硅烷为有机硅源,通过与TEOS共水解沉淀合成了氨丙基官能化HMS介孔分子筛.采用粉末X-射线衍射分析、N2吸/脱附、扫描电镜分析、高分辨透射电镜分析、傅立叶变换红外分析以及元素分析等表征手段,对所合成的材料进行表征.氨丙基官能化HMS介孔分子筛具有worm-like孔道结构,且较为均一的孔径分布.研究了前体硅源中3-氨丙基三乙氧基硅烷含量的变化对氨丙基官能化HMS介孔分子筛的相结构及织构性能的影响.傅立叶变换红外分析表明,NH2-CH2-CH2-CH2有机基团分布在杂化HMS介孔孔道中.     

聚γ—（β—氰乙基）胺丙基硅氧烷铑配合物的合成与催化性能

γ－氨丙基三乙氧基硅烷与丙烯腈加成，得到γ－（β－氰乙基）胺丙基三乙氧基硅烷。后者依次与气相法二氧化硅、三氯化铑作用，合成了聚γ－（β－氰乙基）胺丙基硅氧烷铑配合物。它对烯烃与三乙氧基硅烷的硅氢加成反应具有良好的催化活性。     

聚γ-(β-氰乙硫基)两基硅氧烷铑配合物的合成与催化硅氢化性能

γ-巯丙基三乙氧基硅烷与丙烯腈加成，得到γ－（β-氰乙硫基）丙基三乙氧基硅烷，后者依次与气相法二氧化硅、三氯化铑作用，合成了聚γ-（β-氰乙硫基）丙基硅氧烷铑配合物，研究了其催化烯烃与三乙氧基硅烷硅氢加成反应的特性。     

高分子膜湿度传感器的制备

近年来对高分子电解质湿敏材料的研制十分活跃,本文报道以聚γ-氨丙基三乙氧基硅烷季铵化合物的湿敏材料及其元件性能。 试剂 γ-氨丙基三乙氧基硅烷(盖县化工厂),使用前蒸馏,折光指数n_D~(20)为1.4190;碘甲烷、十六烷基三甲基溴化铵、甲苯、无水乙醇皆为分析纯。     

四氧化三铁磁性纳米微粒表面的氨基化修饰

以3-氨丙基三乙氧基硅烷(APTES)作为氨基化试剂,通过硅烷化反应使其键合于Fe3O4纳米颗粒表面,制备了表面氨基化的磁性Fe3O4纳米复合颗粒;利用红外光谱分析了产物的化学键合特征,利用电位滴定测定了合成产物表面的-NH2含量,探讨了活化方式、反应溶剂、投料比、温度、时间等因素对氨基化修饰效果的影响.结果表明,APTES成功地包覆在磁性Fe3O4纳米微粒表面;在乙醇-水体系中,在Fe3O4与APTES投料比3∶8、温度60℃下反应12h,得到的Fe3O4纳米颗粒表面APTES修饰效果最佳,表面-NH2含量高达1 400±50μmol·g-1.     

反射吸收红外光谱法研究铝表面硅烷试剂膜的结构与性能

采用反射吸收红外光谱法（RA－IR）研究了铝金属表面涂覆乙炮基三乙氧基硅烷（VS），环氧基三乙氧基硅烷（GS）和γ－氨丙基三乙氧基硅烷（γ-APS）溶液成膜后结构及膜与金属表面之间结合状态，比较并探讨了不同处理工艺条件下硅烷溶液在金属铝材上成膜后膜的特性。以指导硅烷用作金属表面处理新技术的优化和实用化处理过程。     

氨基修饰介孔SiO2的合成及对其对Hg2+、 Ni2+和Mn2+的吸附

利用介孔SiO₂微球（MSM）作为基底,对其表面进行氨基修饰,合成了氨基修饰介孔SiO₂微球（MSM/NH₂）,其结构和性能经TEM, XRD和元素分析表征。结果表明：MSM/NH₂ 1.0［3-氨丙基三乙氧基硅烷（APTES）用量为1.0 mL］对Hg²⁺、 Ni²⁺和Mn²⁺的5次循环吸附效率的平均值均超过92.0%。     

微接触印刷技术转移Au纳米粒子及氧化石墨烯复合图案及其性质研究

通过改良的“Hummers方法”制得氧化石墨烯,利用聚二甲基硅氧烷（PDMS）弹性印章的微接触印刷技术,以Au膜和氧化石墨烯溶液为“墨水”,通过二次印章转移,分别将Au纳米粒子和氧化石墨烯（Graphene Oxide,GO）转移至修饰了(3-氨基丙基)三乙氧基硅烷（APTES）的ITO基底（APTES/ITO）表面. 利用场发射扫描电子显微镜（FE-SEM）、原子力显微镜（AFM）等表征图案,结果表明转移的AuNPs和GO组成的复合图案均匀,致密性较好. 利用表面电势显微镜（Surface Potential Microscope,SEPM,KFM）测定了各部分的表面电势,以APTES/ITO基底表面为表面电势零点,各部分表面电势大小为：APTES/ITO > GO > Au（0,-11.6,-44.2 mV）.     

Heats of adsorption using temperature programmed adsorption equilibrium: application to the adsorption of CO on Cu/A12O3 and H2 on Pt/Al2O3

A new simple analytical procedure is described that allows the determination of the heats of adsorption (denoted E(theta)) of adsorbed species at several coverages (theta's) using a single experiment. This procedure is an extension of an original method previously developed (denoted AEIR: adsorption equilibrium infrared spectroscopy). A mass spectrometer is used to determine the amounts of gas (in the present study, CO and H2) either desorbed from or adsorbed on a metal supported catalyst (4.7% Cu/Al2O3 and 2.9% Pt/Al2O3) during the perturbation of the adsorption equilibrium due to a controlled change of the adsorption temperature (Ta) at a quasi-constant adsorption pressure (Pa). These amounts allow us to follow the evolution of the adsorption equilibrium coverage (theta(e)) with Ta at the quasi-constant partial pressure (Pa). Then, the curve theta(e) = f(Ta) provides Etheta = f(theta) with the support of an adsorption model. This procedure presents several advantages as compared to the TPD methods, in particular, considering the theoretical supports linked to the exploitation of the experimental data. As compared to AEIR, the TPAE procedure allows one to study the heats of adsorption of adsorbed species that are not detectable by IR. However, it is not adapted if surface reactions occur in parallel to adsorption/desorption processes.     

The hydrophilization of polystyrene substrates by 172-nm vacuum ultraviolet light

This paper describes the photochemical surface modification of polystyrene (PS) substrates using vacuum ultraviolet (VUV) light 172 nm in wavelength. We have particularly focused on the effects of atmospheric pressure during VUV irradiation on the obtained surface's wettability and the stability of the wettability, in addition to its chemical structure, morphology, and photooxidation rate. Samples were photoirradiated with VUV light under pressures of 10, 10(3), or 10(5) Pa. Although, in each case, the originally hydrophobic PS surface became highly hydrophilic, the final water-contact angle and photooxidation rate depended on the atmospheric pressure. The samples treated at 10 Pa were less wettable than those prepared at 10(3) and 10(5) Pa due to the shortage of oxygen molecules in the atmosphere. The minimum water-contact angles of the samples treated at 10, 10(3), and 10(5) Pa were about 8 degrees, 0 degrees, and 0 degrees, respectively. With the samples prepared at 10 and 10(3) Pa, photooxidation reactions proceeded in the topmost region closest to the surface, while at 10(5) Pa photooxidation was found to be greatly enhanced in the deeper regions, as evidenced by angle-resolved X-ray photoelectron spectroscopy. Photoetching rates were determined through atomic force microscope observation of microstructured PS samples prepared by a simple mesh-contact method. As estimated from AFM images of the latticed microstructures obtained, the rates of samples prepared at 10(3) and 10(5) Pa were about 1.5 and 1.3 nm/min, respectively. However, no photoetched features were observable on the sample surface prepared at 10 Pa. Hydrophilic stability also varied greatly depending on atmospheric pressure. The hydrophilicity of samples treated at 10 and 10(3) Pa gradually decreased as they were exposed to air. On the other hand, the sample surface prepared at 10(5) Pa showed excellent hydrophilicity even after being left in air for 30 days.     

Studies on oxygen chemical surface exchange and electrical conduction in thin film nanostructured titania at high temperatures and varying oxygen pressure

We report on oxygen surface exchange studies in ～450-nm-thick nanocrystalline titania films with an average grain size of ～13 nm by electrical conductivity relaxation along with the conductivity measurements at varying temperatures and oxygen partial pressures (pO(2)s). By electrochemical impedance spectroscopy technique, the high temperature conductivity was measured in the pO(2) range from ～10(-16) to ～10(-6) Pa at temperatures from 973 to 1223 K and activation energy, ΔE(a), for conduction was estimated as ～3.23 eV at pO(2) ～10(-11) Pa. Under reducing atmosphere (pO(2) < 10(-6) Pa), two distinct n-type conduction regimes were observed and corresponding predominant defects are discussed while, at high pO(2) regime (pO(2) >10(-6) Pa), ionic conduction appears dominant leading to a conductivity plateau. The surface relaxation was observed to have two independent time constants likely originating from microstructural effects. The surface exchange coefficients are measured as ～10(-8)-10(-7) m∕s and ～10(-9)-10(-8) m∕s for each contribution with ΔE(a)s of 2.79 and 1.82 eV, respectively, without much pO(2) dependence across several orders of pO(2) range of ～10(-16)-10(-6) Pa in the temperature range between 973 and 1223 K. The results are of potential relevance to understanding the near-surface chemical phenomena in nanocrystalline titania which is of great interest for energy and environmental studies.     

Construction of lamellar morphology by side-chain crystalline comb-like polymers for gas barrier

A comb-like polymer containing crystallized alkyl side chains and the intermolecular hydrogen bonds between the linking groups was fabricated by grafting long-chain fatty amine onto poly(styrene-co-acrylic acid)_n (P(S-AA)_n, wherein “n” denoted AA feed ratio). The chemical structures and crystallization behaviors of the comb-like polymer P(S-AA)_n-g(p) (wherein “p” denoted the number of side-chain carbon atoms) were analyzed by Fourier transform infrared, gel permeation chromatography, X-ray photoelectron spectroscopy, and X-ray diffractometer, differential scanning calorimetry, atomic force microscopy, respectively. It was found that the lamellar morphology could be generated by controlling the grafting density and side chain length of P(S-AA)_n-g(p). Moreover, it was identified that the hydrogen bonds between amide groups could enhance the crystallinity and then adjust the interlamellar spacing of lamellar phase. As a result, P(S-AA)₇₀-g(18) with the highest degree of crystallinity and closely packed lamellar morphology showed a good gas-barrier performance, and the nitrogen permeability reached 1.78 × 10^?14 cm³·cm/cm²·s·Pa. Furthermore, the permeation switch of the obtained comb-like polymer could reach 500 times traversing the melting point.     

聚丁二酸丁二酯/纳米高岭土共混体系结晶及力学性能研究

用熔融共混法制备聚丁二酸丁二酯(PBS)/纳米高岭土(nano kaolin)复合降解材料,利用FTIR、DSC、万能拉力机和SEM对其微观结构、结晶、力学性能及分散性进行研究.FTIR光谱分析结果表明,改性剂与nano kaolin发生了化学键合作用;DSC结果表明,在PBS中加入nano kaolin,提高了结晶起...     

负载型钴-钼氮化物的制备及吡啶加氢脱氮活性的研究

以钼磷酸+硝酸钴、仲钼酸铵+硝酸钴、仲钼酸铵为前体活性相组元及γ-Al₂O₃为载体,制备了负载型双(单)组元过渡金属氮化物[(CoMoN-(Ⅰ,Ⅱ,Ⅲ),MoN-Ⅳ],并利用BET、XPS、H₂-TPD及Raman等手段进行了表征;以正己烷+环己烷+吡啶为模型底物考察了上述催化剂的吡啶加氢脱氮活性.与CoMoN-Ⅱ、CoMoN-Ⅲ和MoN-Ⅳ相比,CoMoN-Ⅰ具有较高的吡啶加氢脱氮活性.     

Mixed-phase PdRu bimetallic structures with high activity and stability for formic acid electrooxidation

Aiming at investigating the effect of structure on electrocatalytic properties, Pd(50)Ru(50) nanoparticles (NPs) with three different structures were carefully designed in a one-pot polyol process for application in formic acid electrooxidation. The three structures are: (1) single-phase PdRu nanodendrites (denoted as PR-1), (2) a mixed-phase mixture of PdRu nanodendrites and monometallic Ru NPs (denoted as PR-2), and (3) a mixed-phase mixture of monometallic Pd and Ru NPs (denoted as PR-3). From PR-1 to PR-3, the structure was varied from single-phase to mixed-phase. The relative position of Ru was altered from completely Pd-connected (PR-1), to a mixture of Pd-connected and monometallic (PR-2), and completely monometallic (PR-3). All PdRu NPs outperform the commercial Pd/C. PR-2 exhibits the highest peak current density, but its stability is slightly lower than that of PR-3. When both the current density and the durability are taken into consideration, PR-2 is the best choice of catalyst for formic acid oxidation. It indicates that both the Pd-connected Ru NPs and monometallic Ru NPs in the mixed-phase PR-2 are essential to improve the electrocatalytic properties. Our study also illustrates that the electrochemical active surface area (ECSA) and hydrogen storage capacity of the as-prepared PdRu NPs are greatly enhanced after several hundred scans in formic acid, indicating the possibility for highly restorable catalysts in direct formic acid fuel cells.     

NEPE推进剂固化交联的流变学研究

采用动态流变学方法研究了硝酸酯增塑聚醚(NEPE)推进剂的固化历程. 结果表明, 推进剂固化初期(黏流态)的储能模量(G′)和损耗模量(G″)随时间增加缓慢增大, G′gel)缩短, 但推进剂在凝胶点和固化结束时的储能模量G′_gel(622~781 Pa)和G′_∞(831.1×10³~868.3×10³ Pa)的变化不大. 推进剂在固化初期(反应控制阶段)符合一级反应动力学关系, 推进剂的固化过程符合Hsich动力学模型, 由反应速率常数(k_c)、凝胶时间(t_gel)和特征松弛时间(τ)得到推进剂的表观反应活化能ΔE_c, ΔE_g和ΔE_τ分别为129.6, 122.1和120.6 kJ/mol.