复合掺杂氧化物La0.5Sr0.5CoO2.91的性能和稳定性

采用固相反应法和柠檬酸-硝酸盐溶胶-凝胶低温自蔓延燃烧法（简称柠檬酸法）合成了La0.5Sr0.5CoO2．91（LSC）复合氧化物。借助XRD和SEM对不同制备方法合成粉体的晶体结构和晶粒形貌进行了研究。结果表明：固相反应法可制得均一钙钛矿结构的LSC氧化物，柠檬酸法除制得LSC氧化物外，还有LaSrCoO4相的生成。柠檬酸-硝酸盐溶胶-凝胶低温自蔓延燃烧法合成粉体的粒度相对较小。为研究以Ce0．9Gd0.1O1．95（GDC）为电解质的固体氧化物燃料电池阴极材料的性能，将LSC粉体与GDC粉体按6：4（质量比）制备了固体氧化物燃料电池（SOFC）的阴极片。在空气气氛下使用直流四探针法研究了烧结样品300～800℃的电导率，发现由柠檬酸法得到粉体制备的阴极片的电导率值较高。将制备的样品置于马弗炉中800℃条件下烧结800h，比较失效前后电导率的变化情况，并借助XRD，SEM等测试手段分析样品电导率变化的原因。分析发现，失效后两种样品的电导率值都有所降低，且样品中都有新相生成，晶体形貌有较大的变化。     

不同碳酸铵试剂对共沉淀法制备的GDC粉性状的影响

近年来工作温度在500￣700℃的中温固体氧化物燃料电池(IT-SOFC)受到广泛关注。稀土掺杂氧化铈尤其是钐、钆掺杂氧化铈在中温下的离子电导率远高于钇掺杂氧化锆(YSZ),是较为理想的IT-SOFC电解质材料。由于掺杂氧化铈难于烧结,不便于制备致密的电解质膜,通过提高掺杂氧化铈粉体细度来降低其烧结温度,是近年来该材料应用领域的一个研究热点。已有各种合成掺杂氧化铈纳米粉的报道,如采用共沉淀法、固态反应法、水热处理法、燃烧法、溶胶-凝胶法等等。其中碳酸盐共沉淀法由于具有成本低、设备简单以及合成粉体细度高等优点而倍受青睐。通…     

SOFC阴极材料LSM的合成及性能研究

分别采用固相法、甘氨酸-硝酸盐燃烧法和溶胶-凝胶法制备了固体氧化物燃料电池阴极材料La0.8Sr0.2MnO3(LSM)。将合成的粉体在不同的温度下烧结,并通过XRD确定粉末成相最低烧结温度为900℃;利用扫描电镜(SEM)对合成的粉体进行微观结构的观察和分析;采用Van-der Pauw四电极法测量片状阴极的直流电阻进而计算电导率;采用三电极法研究LSM阴极材料的电化学性能;结果表明,溶胶-凝胶法制备的LSM阴极与电解质的界面阻抗最小。同时,将3种方法制备的LSM应用到多孔阳极支撑型的固体氧化物燃料电池上,制备成全电池,并采用四电极法对全电池的输出性能进行测试分析,结果表明,溶胶-凝胶法制备的LSM阴极材料电化学性能良好,最大输出功率密度达317mW.cm-2。因此,溶胶-凝胶法合成的LSM粉末能够有效满足固体氧化物燃料电池阴极材料的要求。     

Gd_(0.2)Ce_(0.8)O_2包覆固体氧化物燃料电池Ni-ScSZ复合阳极制备及性能表征

应用双层流延法制备Ni-ScSZ阳极支撑体-ScSZ电解质复合膜素坯,经共烧结得到复合膜.以硝酸铈和硝酸钆为原料,柠檬酸作燃料,由燃烧合成法制备Gd0.2Ce0.8O2(GDC)包覆的Ni-ScSZ阳极.X-射线衍射(XRD)和电子显微镜(TEM和SEM)分析显示,Ni-ScSZ阳极颗粒表面的包覆层是由直径小于100 nm的GDC微粒构成,并与Ni-ScSZ阳极颗粒紧密烧结在一起.实验表明,2.0%(by mass)GDC包覆的Ni-ScSZ阳极具有较佳的性能,以其组装的单电池在850℃用H2或CH4作燃料的最大功率密度分别是825和848 mW/cm2,而由无包覆的Ni-ScSZ作阳极的单电池,功率密度分别是584和586 mW/cm2.由两种阳极材料组装的单电池,分别在700℃于CH4气氛下作长时间发电实验,发现2.0%(by mass)GDC包覆的Ni-ScSZ阳极比Ni-ScSZ阳极具有较好的抗碳沉积性能.     

缓冲溶液法制备氧化钐稳定氧化锆纳米粉体及其表征

以硝酸盐为前驱体、NH3·H2O-NH4HCO3为复合沉淀剂，采用缓冲溶液法制备了含4％～12％（摩尔分数）Sm2O3的ZrO2粉体。通过X射线衍射、透射电镜及比表面吸附法等对所得粉体的相结构、形貌和粒度进行了测定。所得粉体经冷等静压成形后，在1300～1500℃下烧结5h，得到烧结体。采用阿基米德法（水介质）测定了烧结体的密度，采用扫描电镜对烧结体的微结构进行了观测，并通过交流阻抗谱法测定了烧结体的电导率。实验结果表明：当Sm2O3掺杂量大于8％时，在600℃煅烧共沉淀物可得到具有立方结构的氧化钐稳定氧化锆（SSZ）粉体，其颗粒形状规则，粒径在10～20nm。随着Sm2O3掺杂量的增加和烧结温度的升高，烧结体的相对密度增加，1500℃烧结的掺杂12％Sm2O3的ZrO2（12SSZ）烧结体的相对密度为96．91％。在500～800℃的测量范围内，SSZ烧结体的电导率与温度成线性关系，12SSZ在800℃时的电导率可达0．043S·cm^-1，电导活化能为0．72eV。     

Ce_(1-x)Sc_xO_(2-x/2)固体电解质的微观结构及电性能研究

研究了Sc_2O_3掺杂CeO_2基电解质材料的微观形貌和电性能。采用溶胶凝胶法制备了Sc_2O_3掺杂CeO_2基电解质粉体, Sc_2O_3掺杂量分别为6%, 8%, 10%。采用单向压力法将电解质粉体压制为圆片状素坯,分别在1400, 1450, 1500℃下,空气中烧结制备电解质材料。研究分析了不同掺杂比例及不同烧结温度对电解质的相组成、微观形貌及电导率的影响。实验结果表明:低温下, Sc_2O_3能溶于CeO_2中形成固溶体,随着Sc_2O_3掺杂量由6%增加到10%(摩尔分数,下同),晶胞参数减小;高温烧结时溶于CeO_2中的Sc_2O_3会析出,且随着烧结温度的升高析出量增加;当Sc_2O_3掺杂量为8%、烧结温度为1500℃时,在750℃时Sc_2O_3掺杂CeO_2电解质电导率最大为8.78×10~(-3) S·cm~(-1),活化能为1.220 eV。     

YxTi2On(1.7≤x≤2.1)系固态电解质的共沉淀法合成及电导率研究

以TiCl3、YCl3溶液和氧化钛、氧化钇为原料,通过共沉淀法和固相法制备了YxTi2On(1.7≤x≤2.1,x=1.7,1.8,1.9,2.0,2.1)系烧绿石型固态电解质样品。粉体经700℃处理后在透射电镜下可见其粒径小于100 nm的晶粒。用共沉淀法制得的样品通过1500℃/5 h烧结后的相对密度近94%,且比用固相法经1550℃/5 h烧结所获相同组成样品的相对密度明显要高。X衍射表明样品A(x=1.7)的主晶相为烧绿石和二氧化钛,而样品D(x=2.0)和E(x=2.1)都为烧绿石。从扫描电镜照片可见,样品E的晶界随着烧结温度的提高变得更清晰,晶体生长也更充分。随着Y2O3含量的增加,YxTi2On(1.7≤x≤2.1)系电解质的电导率随之增加。用共沉淀法所得样品的电导率明显高于相应固相法所得样品。随烧结温度和测量温度的提高,样品E的电导率增加。     

纳米La0.6Sr0.4Co0.2Fe0.8O3-δ阴极粉体的溶液燃烧法合成与性能表征

采用硝酸盐-甘氨酸溶液燃烧法合成了La0.6Sr0.4Co0.2Fe0.8O3-?啄(LSCF)前驱粉体, 通过XRD、BET、FESEM及激光粒度仪等手段对粉体进行表征. 结果表明, 所合成的LSCF粉体为纯钙钛矿结构, 具有高达22.9 m2·g-1的比表面积, 粒度均匀, 平均颗粒尺寸为175 nm. 非等温烧结实验表明该粉体具有良好的低温烧结活性. 在阳极NiO-YSZ(氧化钇稳定氧化锆)负载的电解质YSZ上, 于800 ℃烧结制备LSCF阴极组成的单元电池Ni-YSZ/YSZ/LSCF, 在700 ℃下以H2作燃料时具有良好的电池性能, 最大功率密度为0.97 W·cm-2, 在0.7 V时的功率密度约达到0.83 W·cm-2. 这种无中间缓冲层的低温制备LSCF阴极方法, 简化了电池结构及其制备过程, 同时提高了电池的性能.     

Gd1-xSrxCoO3-δ和Gd0.8Sr0.2Co1-yFeyO3-δ系阴极材料的制备和性能

采用甘氨酸-硝酸盐(GNP)法合成了新型中温固体氧化物燃料电池(IT.SOFC)的阴极材料Gd1-xSrxCoO3-δ(x=0-0.5)和Gd.0.8Sr0.2Co1-yFeyO3-δ(y=0-1),所合成的初始粉体在800℃下煅烧12 h后均形成了钙钛矿结构的单相固溶体.研究发现,Gd1-xSrxCoO3-δ(GSC)的电导率在600℃时达到了559 S·cm-1,由Ce0.8Cd0.2O2-δ(GDC)电解质和GSC-25GDC材料组成的对称电极在600℃和700℃的界面阻抗分别为0.170Ω·cm2和0.064Ω·cm2,活化能仅为87.8 kJ·mol-1,预示其可以作为ITSOFC较为理想的阴极备选材料;随着Fe3 离子含量的增加,Gd0.8Sr0.2Co1-yFeyO3-δ系列阴极材料的热膨胀系数显著降低,但其电导率也急速下降;此外,通过调整Gd0.8Sr0.2CoO3-δ与GDC的比例可以制备出热膨胀系数与GDC电解质匹配、性能良好的Cd0.8Sr0.2CoO3-δ/GDC复合阴极材料.     

Ce0.8Sm0.2O1.9的尿素燃烧法合成与性能

采用以尿素为燃料的燃烧合成法制备Ce0.8Sm0.2O1.9(SDC)氧离子导体材料, 对燃烧合成粉体的物相和显微形态进行了表征, 并研究了燃烧法合成SDC的烧结性能以及烧结体的导电性能. 研究结果表明, 采用尿素燃烧法合成SDC具有简便高效和合成粉体烧结活性高的优点. 经过燃烧过程后即可得到立方萤石结构的纯相SDC粉体, 合成粉体的分散性良好, 为50~150 nm的球形颗粒, 具有高的烧结活性, 在1250 ℃的烧结温度下, 陶瓷样品的相对密度可达到95.1%. 在600和800 ℃的测试温度下, 烧结温度为1250 ℃的陶瓷样品的电导率分别达到5.4×10-2和1.0×10-1 Ω-1·cm-1.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.