芴基张力半导体结构和光电性质的理论研究

[4]Cyclo-9, 9-dimethyl-2, 7-fluorenylene ([4]CF) was used as a model compound to explore the steric strain effect on the structures and photoelectrical properties of materials. A series of strained cyclic polyfluorene materials, [n]CFs (n=3-8), was designed. It was found that the strain energy decreased and the energy gap increased as the number of n and ring diameter increased. The ionization potential and electronic affinity tended to increase and decrease as the strain energy decreased at the same number of [n]CFs, respectively. With a balance between hole and electron reorganization energies in the system, these compounds demonstrated great potential as ambipolar materials. It was also found that [n]CFs showed an obvious blue shift in their emission spectra wavelengths (λ_em2) as the strain energy decreased. Steric strain provides a powerful tool for the design of multifunctional semiconductors in organic optoelectronics.     

一种基于咔唑的新型磷光主体材料的合成及光电性能

设计并合成了一种基于咔唑的新型的磷光主体材料, 即9-(6-(9-咔唑基)己基)咔唑(hCP), 对其结构及性能进行了表征. 研究结果表明: hCP分子中两个咔唑与烷基链是非共平面的, 由于长烷基链的缠绕, 因而具有较高的三线态能级(3.01 eV)和较高的玻璃化温度(93℃); 以hCP为主体材料, 与绿光磷光染料三(2-苯基吡啶)合铱(Ir(ppy)₃)掺杂作为发光层, 制备了磷光电致发光器件, 其器件的最大电流效率为15.1 cd·A^-1, 相对于4,4'-N,N'-二咔唑基联苯(CBP)为主体材料的参考器件, 显著提高了34.8%.     

Influence of Modification of Counter Electrode on Photoelectric Properties of Dye-sensitized TiO2 Solar Cells

A dye-sensitized nanocrystalline TiO2 solar cell(DYSC) was assembled, of which counter electrode was modified already by platinum, nickel and carbon. It was found that the DYSC had better photoelectric performance when the electrode was modified by platinum than by nickel and carbon. The influence of the incidence light wavelength on the incidence monochromatic photoelectric conversion effieieney(IPCE) was investigated.The result shows that the IPCE mainly depends on the short-circuit current density(Isc) of a DYSC, and the IPCE reaches 48.32% under the irradiation with the wavelength of 560 nm when the counter electrode of a DYSC was modified by platinum. The influence of incident light intensity on the photoelectric properties of a DYSC was also investigated. It was found that the Isc and open-circuit voltage(Voc) increased and the fill factor(ff) of the DYSC decreased with the increase of the incident light intensity.     

The impact of regiochemistry of conjugated molecules on the performance of organic electronic devices

Organic photovoltaics and field-effect transistors have attracted considerable attention due to the easy fabrication,low cost,light weight,and flexibility.Unsymmetrical conjugated building blocks are widely utilized for the design of new organic π-functional materials in order to achieve high-performance electronic devices,which has become a hot research topic in recent years.In this review,we summarized some typical organic π-functional materials with regioregular conjugated backbones with unsymmetrical electron-deficiency moieties and focused on the influence of regiochemistry on the final device performance.     

不同溶剂对聚醚砜酮基炭膜结构及气体分离性能的影响

为考察不同溶剂对聚醚砜酮(PPESK)炭膜结构和性能的影响,以PPESK为前驱体,分别以NMP,CHCl3,C2H2Cl4,DMAc为溶剂制备气体分离炭膜。并采用红外光谱、热重分析、X射线衍射和气体渗透等测试手段对所制膜的化学结构、炭膜的微结构和气体的分离性能进行了表征。结果表明,溶剂的溶度参数、沸点、挥发性以及原膜中溶剂的含量等导致所制备聚合物膜形成不同的化学结构,改变它在预氧化和炭化过程的结构变化规律,使形成炭膜表现出不同的炭结构、孔隙结构和表观柔韧性,最终影响炭膜的气体渗透性和分离选择性。     

Sensitivity of the Multiple Functional Moieties of Amino Acids for the Self-Assembly of Au Nanoparticles on Different Physicochemical Properties

This paper investigates the extent of the self-assembly process of Au nanoparticles, depending on the nature of structural and functional moieties of various amino acids (l-cystine, glutathione, l-cysteine and N-acetyl cysteine) and their influence on the plasmon sensitivity and electrokinetic parameters in correlation with the catalysis of p-nitrophenol reduction. DLS particle size analysis revealed that the hydrodynamic size 10–20 nm of Au nanospheres was increased to 135–550 nm, 100–460 nm and 130–240 nm after the addition of l-cystine, l-cysteine and glutathione, respectively, in contrast to no significant change of particle size (15–60 nm) after N-acetyl cysteine addition. This difference in the extent of aggregation as a function of structures of amino acids is further evidenced by lengthy tubular arrays formation by glutathione as compared to branched chain like morphology obtained by l-cystine through TEM. FTIR studies further confirmed the binding of amino acids to Au nanospheres via –SH followed by linking of adjacent nanoparticles through H-bonding. Due to the conformational diversity of amino acids, the surface adsorbed –SH, –COO^? and –NH₃ ⁺ species over assembled Au nanoparticles led to the alteration of zeta potential and conductance, thus affected the catalysis for the reduction of p-nitrophenol as compared to unmodified Au nanoparticles.     

Effects of the Brookite Phase on the Properties of Different Nanostructured TiO2 Phases Photocatalytically Active Towards the Degradation of N-Phenylurea

Different sol-gel synthesis methods were used to obtain four nanostructured mesoporous TiO₂ samples for an efficient photocatalytic degradation of the emerging contaminant N-phenylurea under either simulated solar light (1 Sun) or UV light. Particularly, two TiO₂ samples were obtained by means of as many template-assisted syntheses, whereas other two TiO₂ samples were obtained by a greener template-free procedure, implying acidic conditions and, then, calcination at either 200 °C or 600 °C. In one case, anatase was obtained, whereas in the other three cases mixed crystalline phases were obtained. The four TiO₂ samples were characterized by X-ray powder diffraction (followed by Rietveld analysis); Transmission Electron Microscopy; N₂ adsorption/desorption at −196 °C; Diffuse Reflectance UV/Vis spectroscopy and ζ-potential measurements. A commercial TiO₂ powder (i. e., Degussa P25) was used for comparison. Differences among the synthesized samples were observed not only in their quantitative phase composition, but also in their nanoparticles morphology (shape and size), specific surface area, pore size distribution and pH_IEP (pH at isoelectric point), whereas the samples band-gap did not vary sizably. The samples showed different photocatalytic behavior in terms of N-phenylurea degradation, which are ascribed to their different physico-chemical properties and, especially, to their phase composition, stemming from the different synthesis conditions.     

电化学法制备部分还原氧化石墨烯薄膜及其光电性能

提供了一种快速制备氧化石墨烯(GO)薄膜的方法, 并通过调节GO薄膜的含氧量来调控其能级结构.采用阳极电泳及阴极电化学还原联用的方法在F掺杂SnO₂(FTO)导电玻璃上制备出不同层数及含氧量的GO薄膜, 并通过扫描电镜(SEM)、X射线衍射(XRD)、紫外可见(UV-Vis)光谱、X射线光电子能谱(XPS)、拉曼光谱及电化学分析对样品进行表征. 用20-350 s 不同时间电泳沉积得到层数约为77-570层的GO薄膜. 经过不同时间阴极还原的GO薄膜的禁带宽度为1.0-2.7 eV, 其导带位置及费米能级也随之改变. GO作为p型半导体, 与FTO导电膜之间会形成p-n 结, 在光强为100 mW·cm^-2的模拟太阳光照射下, 电泳300 s 且电化学还原120 s时GO薄膜阳极光电流密度达到5.25×10^-8 A·cm^-2.     

受体强度及D/A比对D-A型共轭聚合物几何结构和电子性质的影响研究

以Thieno[3,2-b]thiophene(TT)为电子供体(D),Benzo[c][1,2,5]thiadiazole(BT)、[1,2,5]thiadiazolo[3,4-g]quinoxaline(Td Q)、和Benzobis[1,2,5]thiadiazole(BBT)为电子受体(A),设计了供体-受体摩尔比(D/A比)分别为1∶1和2∶1的6种供体-受体交替排列的D-A型共轭聚合物.采用杂化的密度泛函方法(B3LYP),在6-31G(d)理论水平下研究了其几何结构和电子性质.研究发现,电子受体接受电子的能力和D/A比对基于TT的D-A型共轭聚合物的几何结构和电子性质有重要影响.对于D/A比相同的聚合物,电子受体接受电子的能力增强,聚合链上桥键的键长缩短,供体环上的碳碳双键的平均键长(L_(AD))增大而碳碳单键平均键长(L_(AS))减小.对由相同电子供体和受体构成的聚合物,D/A比增加,桥键变长.电子受体对D/A比为2∶1的聚合物的性质影响有显明的规律.当电子受体接受电子的能力增强,聚合物的能隙(Eg)变窄、价带(W_(VB))和导带(W_(CB))变宽、载流子有效质量(m_H和m_L)减小.研究发现,p-TdQ-TT和p-BBT-DTT能隙窄,能带相对较宽、载流子有效质量小,可能是的潜在的本征导电聚合物材料.     

Perylene‐based Solution‐processable Conjugated Molecules for Optoelectronic Applications: Synthesis and Comparison of Different Substituents on the Optical,Thermal, and Electrochemical Properties

A series of small organic molecules were synthesized by exploiting the bay and imide positions of the perylene nucleus. The synthesized compounds 1 – 11 were characterized by spectroscopic and elemental analyses. These molecules show yellowish color in solution and are highly soluble in dichloromethane. Compound 7 shows a bandgap of 1.7 eV and a Stokes shift of 27. From these results, we infer that this compound can serve as structural template in the design of organic electronics. Moreover, compound 7 shows higher T_d (370°C) and T_g (132°C) values, which reflect its high thermal stability.     

固体氧化物催化剂酸碱性质对 1,2-丙二醇转化反应的影响

 采用 X 射线衍射、热重、NH3 程序升温脱附、CO2 程序升温脱附等手段研究了 Al2O3, MgO, CaO 和 KNO3 改性 MgO 催化剂的结构和酸碱性质, 并在固定床反应装置上考察了上述催化剂气相催化转化 1,2-丙二醇反应性能. 结果表明, 催化剂表面的酸碱性对 1,2-丙二醇气相转化反应的产物分布有显著影响. Al2O3 催化剂上的产物以丙醛和丙酮为主; MgO 催化剂上的主要产物为丙酮醇; CaO 催化剂上丙酮和丙烯醇选择性相对较高; KNO3 改性 MgO 催化剂上环氧丙烷选择性显著升高. 结合不同催化剂酸碱性质及其反应结果, 提出了 1,2-丙二醇气相转化的 6 个主要反应途径, 明确了各反应途径与催化剂酸碱性质的关系.     

不同电性的纳米银对甲基橙光谱学性质的影响

通过吸收光谱和荧光光谱等手段研究了正/负电性纳米银对不同pH值的甲基橙(MO)溶液光谱学性质的影响.研究结果表明,正电性纳米银(P-Ag)与甲基橙作用形成新的复合物,吸收光谱表现为复合物体系的性质.负电性纳米银(N-Ag)与甲基橙静电排斥作用,相互作用较弱,吸收光谱仅表现为两者简单叠加.在正电性纳米银-甲基橙体系中,S1→S0荧光明显增强.当溶液pH=2.1时,荧光增强比率最大,当pH=4.8时,荧光增强比率最小;S2→S0荧光减弱,且与体系的pH值关系不大.在负电性纳米银-甲基橙体系中,仅少量纳米银存在条件下,S1→S0荧光略增强.在溶液pH=2.1时,荧光增强比率最大;S2→S0荧光明显减弱,且与体系的pH值关系不大.分析认为,不同电性的纳米银对甲基橙光谱学性质影响不同,与纳米银与甲基橙分子间相互作用、纳米银的局域场增强效应以及无辐射能量转移作用等密切相关.     

不同干燥过程对超细TiO2粉体性质的影响

考察了采用不同干燥工艺制备的TiO2粉体在粒子形貌、颗粒大小与分布、晶相组成以及比表面积和孔结构等织构和结构性质方面的差异。结果表明，利用常规的干燥方法，由水凝胶脱水所得的颗粒，颗粒间严重团聚，颗粒粒径大且分布不均匀，比表面积和孔体积最小；由醇凝胶直接脱水，则可以显著提高粉体的织构性能．而采用超临界流体干燥法则可以进一步提高粉体的性能，比表面积由水凝胶的4．88m2·g－1增大到113．8m2·g－1，提高了近30倍；孔体积由0．027cm3·g－1增大到0．41cm3·g-1．大约提高了15倍；而且其能够有效地防止粒子间的团聚，较好地保持了湿凝胶的网络结构，使颗粒尺寸降低且分布均匀，可重复性好．     

不同配体对钌多吡啶配合物与DNA的作用和荧光性质的影响

Two polypyridyl ligands DCHIP (2-hydro-3，5-dichlorophenyl-imidazo[4，5-f][1，10] phenanthroline)，MDHIP(2，4-dihydrophenyl-imidazo[4，5-f][1，10]phenanthroline) and their ruthenium(Ⅱ) complexes [Ru(phen)₂MDHIP]²⁺ and [Ru(phen)₂DCHIP]²⁺ were prepared. Their DNA-binding properties were studied by spectroscopic methods and viscosity measurements. The results indicated that the complexes both bound to DNA by partial intercalation mode， but [Ru(phen)₂DCHIP]²⁺ exhibited stronger binding affinity for DNA than [Ru(phen)₂MDHIP]²⁺ due to the different planarities and steric effects of ligands. On the other hand， after binding to DNA， the fluorescence intensity of [Ru(phen)₂MDHIP]²⁺ decreased， while the fluorescence intensity of [Ru(phen)₂ DCHIP]²⁺ increased.     

沉淀剂和Ag含量变化对甲醛降解性能的影响

采用不同沉淀剂制备CeO₂-Co₃O₄复合金属氧化物载体,通过浸渍负载不同含量Ag获得Ag/CeO₂-Co₃O₄催化剂.借助氮气物理吸附、XRD、Raman和H₂-TPR等手段研究了催化剂的物理化学性质.结果表明：当WHSV=30 000 mL·g^-1·h^-1时,催化剂能表现出良好的催化氧化甲醛性能,在≤ 90℃时实现甲醛的完全转化.草酸沉淀能有效降低Ce-Co氧化物的结晶度,使得Co²⁺含量增加,提供更多的氧空位,促进了氧分子的活化与迁移,从而提高了催化活性.随着Ag含量增加,使得由草酸沉淀制备的Ag/CeO₂-Co₃O₄催化剂的活性增强,且金属与载体间的相互作用也增强,当Ag负载量为1%（重量百分比）时活性最佳.     

焙烧温度对ZnO粉体结晶及光学性能的影响

以草酸铵和醋酸锌为原料,采用直接沉淀法制备ZnO粉体,考察了焙烧温度对粉体结晶和光学性能的影响。 采用热重分析（TGA-DTA）、X射线衍射、紫外-可见漫反射（UV-Vis）、荧光分光光度计（FS）和扫描电子显微镜（SEM）等方法对样品进行了分析。 结果表明,制备的前驱物为C2O4Zn·2H2O,最低焙烧温度400 ℃,随着焙烧温度的提高,粉体结晶度提高,一次粒径增大;600 ℃焙烧后有较强紫外发光峰,粉体由200 nm的粒子排列成层叠状;900 ℃焙烧后有较强可见发光峰,粉体粒子大于500 nm,团聚严重;粉体有较强的紫外吸收,吸收峰有蓝移。     

不同结构氧化锌对CIIR/ENR共混胶的气体阻隔性能和力学性能的影响

以重量比为90∶10的氯化丁基橡胶/环氧天然橡胶共混胶为基体,用密炼法将三种不同结构的氧化锌（普通条状氧化锌、片状氧化锌和纳米结构氧化锌）分散到基体中,研究不同结构的氧化锌对共混胶力学性能和气体阻隔性能的影响.结果表明片状氧化锌和纳米氧化锌复合胶比普通氧化锌复合胶强度下降,伸长率提高.片层氧化锌复合体系硫磺用量提高到2.0份,综合力学性能达到最好,且片状氧化锌能够赋予复合胶最佳的气体阻隔性能,比普通氧化锌体系提高了50％.     

Effects of Different Drying Processes on the Material Properties of Bacterial Cellulose Membranes

Summary: Membranes of bacterial cellulose produced by Gluconacetobacter xylinus show a high water and gas permeability that can be altered by different drying techniques. It could be shown that freeze-drying reduces the swellability of the polymer membranes by a factor of 5 while evaporation drying causes a reduction by a factor of 50. The strong decrease of swellability for an evaporation dried membrane could be correlated with a reduction of the absolute number of polymer strands that form the network structure of the membrane, determined with oscillatory shear rheological experiments. The removal of network meshes by a complete aggregation of polymer strands could be confirmed by IR-spectroscopy with an increased degree of intramolecular hydrogen bonding of cellulose strands. In contrast to this, the freeze-drying process shows a slight increase of the number of network meshes due to partial aggregation of free polymer strands. Freeze-dried membranes show a gas permeability two orders of magnitude higher then evaporation dried membranes. The absolute permeability strongly depends on the bacterial strain used for the polymer membrane synthesis and varies by up to 1.5 orders of magnitude for the same drying process. The Young's modulus of the polymer membranes varies with the bacterial strain used, but does not show the same trends as the permeability. Finally, a comparison of the characterized properties shows that only one of the tested strains shows the capability to synthesize membranes that meets the requirements for an application as a wet wound dressing.     

Effects of Different Denaturants on the Properties of a Hot-Pressed Peanut Meal-Based Adhesive

Plant protein-based adhesives could fundamentally solve the problem of formaldehyde-based adhesive releasing formaldehyde, but enhancing bonding strength and water resistance is a necessary measure to realize practical applications. In this study, the effects of different denaturants on the properties of a hot-pressed peanut meal (HPM)-based adhesive before and after crosslinking were studied. Papain, sodium dodecyl sulfate (SDS), urea and crosslinker-polyamide epichlorohydrin (PAE) were used to prepare HPM-based adhesives. The functional groups, bonding strength, thermal behaviors, mass loss, moisture uptake value, viscosity and fracture surface of adhesive samples were analyzed. As a result, (1) papain was used to break HPM protein (HPMP) into polypeptide chains and to reduce the water resistance. (2) SDS and urea unfold the HPMP molecule and expose internal hydrophobic groups to improve the water resistance of the adhesive. (3) A denser network structure was formed by PAE and HPMP molecules, which significantly improved the bonding strength and water resistance of adhesives. In particular, after SDS denaturation and PAE crosslinking, compared with pure HPM adhesive, the wet shear strength increased by 96.4%, the mass loss and moisture uptake value reduced by 41.4% and 69.4%, and viscosity increased by 30.4%. This work provided an essential guide to design and prepare HPM-based adhesives.     

不同掺杂酸对纤维聚苯胺电化学性能的影响

采用界面聚合法通过不同质子酸掺杂分别制备了平均直径约为50,62,95nm的纤维聚苯胺。通过傅里叶变换红外光谱(FT-IR)、扫描电子显微镜(SEM)、透射电镜(TEM)对其化学组成和微观形貌进行了表征,采用循环伏安、恒流充放电和交流阻抗研究了不同质子酸掺杂纤维聚苯胺的超级电容器电容行为,并利用X射线衍射(XRD)、氮气吸脱附及X射线光电子能谱(XPS)等方法对纤维聚苯胺的微观结构进行了深入研究。结果表明:高氯酸(HClO4)掺杂制备的聚苯胺在0.5A/g电流密度下的比容量可以达到397F/g,高于盐酸(HCl,334F/g)和樟脑磺酸(HCSA,383F/g)掺杂聚苯胺的测试结果,纤维的电化学性能主要受其规整度、孔隙率及掺杂度的影响。