基于膦酸基的高温质子交换膜的研究进展

提高质子交换膜燃料电池(PEMFCs)的工作温度,不但可以提高电催化剂的活性以及电催化剂对原料气中CO等杂质气体的耐受能力,少用甚至不用Pt 等贵金属作电催化剂,还可以简化PEMFCs的水热管理系统,提高PEMFCs的综合能量转化效率. 实现高温PEMFCs的核心是开发能够适用于高温PEMFCs的高温质子交换膜(HT-PEM),是PEMFCs的研究热点. 在众多HT-PEM候选材料中,基于膦酸基的质子交换膜材料是最具前途的候选材料之一,是制备HT-PEM的主要研究方向. 本文综述了基于膦酸基的HT-PEM的研究进展,讨论了膦酸基参与的质子传导机理,比较了纯聚合物膦酸膜、膦酸基接枝改性膜、酸-碱两性膜、掺杂型复合膜的电导率、物理化学稳定性、机械性能等. 最后,展望了基于膦酸基的HT-PEM的发展趋势.     

Bi_2O_3掺杂对Ag(Nb_(0.8)Ta_(0.2))O_3陶瓷结构和介电性能的影响(英文)

本文研究了Bi2O3掺杂对Ag(Nb0.8Ta0.2)O3陶瓷的结构和介电性能的影响。X射线衍射(XRD)结果表明,Bi2O3的掺杂可以使陶瓷中Ag+被还原并析出,且银析出的量随Bi2O3掺杂量的增加而不断增加,这可能源自于Bi3+对Ag+的取代。在一定范围内增大Bi2O3掺杂量可提高Ag(Nb0.8Ta0.2)O3陶瓷的室温介电常数,降低介电损耗,并使温度系数向负值方向移动。当Bi2O3的掺杂量约为3.5wt%时,样品具有较大的介电常数(ε=672)和较小的介电损耗(tanδ=7.3×10-4)。     

氮掺杂长竹节状碳纳米管的制备及其生长机理

采用电弧放电法,通过阳极棒与不锈钢片的共蒸发,制备了氮掺杂长竹节状碳纳米管(NDLBLCNTs)。借助扫描电子显微镜(SEM)、场发射高分辨透射电子显微镜(HRTEM)及其附带能量色散X射线(EDX)光谱仪和电子能量损失谱(EELS)、透射电子显微镜(TEM)等表征方法,对产物的形貌、结构和组成进行表征。表征结果表明,NDLBLCNTs的长度在640~835 nm之间,其内径在23~35 nm之间,外径在28~47 nm之间;且在每一节"竹节"与另一节"竹节"的连接处形成的内腔中均有一个黑色纳米颗粒,其直径尺寸以及产物中的NDLBLCNTs的含量均与熔化、蒸发的不锈钢片的面积有关。对NDLBLCNTs的生长机理进行了简单的探讨。     

Influence of Gd doping on the absolute quantum efficiency and lifetime of EuxGd1-x（TTA）3phens

Absolute quantum yield （Ф） is one of the most important parameters to evaluate the potential of novel materials. Lanthanide complexes EuxGd1-x（TTA）3phens are synthesized with the ratio of Gd3＋ dopant concentration ranging from 10% to 90% to improve the absolute quantum yield. EuxGd1-x（TTA）3phens possess similar infrared and ultraviolet spectra, showing that they have similar molecular structures. The absolute emission quantum yields of EuxGd1-x（TTA）3phens are determined using a fluoromax-4 spectrofluorometer equipped with an integrating sphere. The fluorescence lifetimes of the EuxGd1-x（TTA）3phens are measured in the same experiment. It was found that both absolute quantum yields and fluorescence lifetimes of EuxGd1-x（TTA）3phens are of quasi-periodic variation with the change of the Gd3. dopant concentrations. The absolute quantum efficiency and fluorescence lifetime vary with respect to the Gd content in an opposite fashion, indicating that the rate of energy absorption by the EuxGd1-x（TTA）3phens and the conversion to light energy is critical for the absolute quantum efficiency. The radiative rate constant Kr and non-radiative rate constant Knr are calculated. The dependence of Kr and Knr on the Gd3＋ dopant concentrations is very similar to that of absolute quantum efficiency. The radiation rate constant Kr and absolute quantum efficiency have a linear relationship.     

N2/Ar等离子体改性对CuO/TiO2可见光光催化活性的影响

研究了N2/Ar介质阻挡放电处理对负载CuO的TiO2可见光光催化活性的影响.采用X射线衍射、紫外-可见分光吸收光谱、透射电镜、X射线光电子能谱和电子自旋共振进行了表征,详细考察了等离子改性参数包括气氛组成、处理时间和处理功率对改性效果的影响,并通过降解甲基橙溶液考察了可见光光催化活性.结果表明,最佳等离子处理条件为N2与Ar比例为8:2,处理时间为20 min,放电电流为1.0 A.最后,使用改性后的光催化剂对模拟含汞废水进行了处理.     

氮掺杂石墨烯的生长机理及其在乙苯选择性氧化中的应用

以热解氧化石墨烯材料为碳基底,分别使用有机氮源和无机氮源对其进行氮掺杂处理,制备了一系列氮掺杂石墨烯材料.采用透射电子显微镜、扫描电子显微镜、拉曼光谱和X射线光电子能谱等表征方法考察了氮掺杂石墨烯的生长机理.结果表明,随着制备过程中退火温度的改变,氮掺杂石墨烯中不同氮物种的含量有显著差别.这种差异是由不同氮物种化学环境的差异所导致的.所制备的含氮石墨烯材料对乙苯选择性氧化制苯乙酮反应均表现出优良的催化活性.其中,石墨氮的含量对于提高苯乙酮收率起到至关重要的作用.此外,通过氧化剂控制活化的方法可以消除过多的结构缺陷和过量氮掺杂对催化反应的不利影响,有效提升氮掺杂石墨烯的催化活性.     

Parity Alternation of Silicon-doped Ternary Cationic Clusters HC_nSi_2~+(n=1～9)

Systematic study on the electronic/geometrical structures and the parity alternation effect of silicon-doped ternary cationic clusters HCnSi2＋（n = 1 ~9） have been carried out at the coupled cluster level. The ground-state （G-S） isomers of the clusters have been defined. The C, chains of the G-S isomers display polyacetylene-like structures. The even-n cations are more stable than the odd-n ones. Such a trend of even/odd alternation has been elaborated based on concepts of the bond character, atomic charge, incremental binding energy, ionization potential, proton affinity and fragmentation energies of the systems. The findings accord with the relative intensities of HC,,Si2＋ species recorded in the related mass spectrometric experiments.     

Opening Band Gap of Graphene by Chemical Doping: a First Principles Study

Single atom chemically doped graphene has been theoretically studied by density functional theory. The largest band gap, 0.62 eV, appears in arsenic atom doped graphene, then 0.60 eV comes by the tin atom, whose deformations can neither be ignored. It is also found that oxygen and iron single atom embedded graphene can open band gap by 0.52 and 0.54 eV, respectively. Moreover, doping O atom shows little distortion and high stability by charge redistribution. The band gap of Fe doped graphene is opened by orbital hybridization. The other heteroatom doped results are a little inferior to them.     

Tuning of NaTaO_3 Band Structure through Mn~（2＋） Ion Doping and the Enhanced Visible Light Response

Pure and Mn-doped NaTaO3 nanoparticles were synthesized by a simple hydro- thermal method. XRD and XPS results suggested that manganese ions were successfully doped into the NaTaO3 crystalline in Mn2＋ state. UV-vis diffuse reflectance spectra revealed the obvious red-shift in the series of manganese doped NaTaO3 nanoparticles, resulting in a decrease in the band gap of NaTaO3 with the increase of Mn2＋ doping concentration. The photo-degradation experiment indicated that manganese doped NaTaO3 showed good photocatalytic performance and methylene blue（MB） degradation is improved with lower doping concentration of manganese ions under visible light. The simulation of energy band structure by density functional theory unfolded that the substitution of Ta5＋ ions by Mn2＋ ions resulted in an intermediate band（IB） below the bottom of the conduction band（CB）, which was mainly attributed to the state of Mn 3d.     

电喷雾离子化技术制备FeNi(OH)x薄膜及电催化水氧化性能

采用电喷雾离子化沉积技术, 在氟掺杂锡氧化物(FTO)衬底上制备了均匀的无定形铁镍双金属氢氧化物薄膜. 与浸泡法制备的薄膜相比, 该薄膜具有更高的纯度、 更大的比表面积和较高的电催化水氧化性能, 在10 mA/cm ²时的过电位为290 mV, 并在催化反应中表现出良好的稳定性, 为可控合成高催化活性的过渡金属氢氧化物薄膜提供了一种新方法.