微波辅热-甲醇还原法制备M相二氧化钒粉体

为获得具有良好相变特性的M相VO_2粉体,本文以V_2O_5为原料、甲醇作还原剂,采用微波辅热制备M相VO_2粉体.探讨了微波辅热功率、填充度、反应温度、反应时间、甲醇用量因素对制备VO_2的影响,采用X射线衍射(XRD)、差示扫描量热法(DSC)和扫描电子显微镜(SEM),对产物进行了物相、相变和形貌特征的表征.结果表明:在微波辅热功率为1 000 kW,填充度为0.7,反应温度为250℃时,反应时间为60 min,V_2O_5质量与甲醇体积比为5∶3时,得到B相的VO_2粉体;B相的VO_2再经过800℃高温热处理后完全转化为具有相变功能的M相,M相VO_2粉体纯度为99.20%,产率为92.30%,相变点温度为68.6℃,晶体形貌呈现较匀称的棒状结构,长度为1～2μm.     

Eu~(2+)激活的BaO-SrO—SiO_2体系光致发光的研制

(Ba,Sr)SiO_3:Eu~(2+)发光材料采用A.R.试剂合成并加以提纯过的BaCO_3、SrCO_3、H_2SiO_3、Li_2CO_3Eu_2(C_2O_4)_3为原料。在合成发光材料过程中,选用正交式验法进行实验条件的探索。得到了发光材料最佳组成为(Ba_(0.8),Sr_(0.2))_(0.98)Eu_(0.01),SiO_3或Ba_(0.98) Eu_(0.01)Li_(0.01)SiO_3;最佳实验条件为灼烧温度为1150℃,H_2气流量为4ml/min。并用日本岛津产RF-510荧光光谱仪测试了发光材料的激发光谱和发光光谱。     

V_2O_5掺杂Bi_2WO_6微纳米纤维的静电纺丝制备及光催化性能

以柠檬酸铋铵[Bi(NH_3)_2C_6H_7O_7·H_2O]、仲钨酸铵(H_(42)N_(10)O_(42)W_(12))、偏钒酸铵(NH_4VO_3)和聚乙烯吡咯烷酮(PVP)为原料,采用静电纺丝法成功制备前驱体PVP/Bi_2W_(1-x)V_xO_(6-δ)纤维毡,通过缓慢控温处理制得Bi_2W_(1-x)V_xO_(6-δ)微纳米纤维。采用X射线衍射光谱(XRD)、傅立叶红外光谱(FT-IR)、场发射扫描电子显微镜(FE-SEM)、X射线光电子能谱(XPS)和紫外-可见漫反射光谱(UV-Vis)对样品进行了表征。以亚甲基蓝(MB)光降解为模型反应,研究Bi_2W_(1-x)V_xO_(6-δ)样品光催化性能。结果表明,所有掺杂V_2O_5的样品光催化活性均高于纯Bi_2WO_6样品。其中VO_(2.5)掺杂量为3%(原子分数)时光催化效果最好,可见光下120 min内对初始浓度为10mg/L的MB溶液的降解率可达到86.9%,较纯Bi_2WO_6样品提高15%。     

EuW_2O_6(OH)_3荧光粉的水热法合成及发光性能

以Eu_2O_3和Na_2WO_4·2H_2O为原料,采用水热法合成了属纯单斜相结构的EuW_2O_6(OH)_3红色荧光粉,分别采用XRD、FT-IR、SEM、PL测试手段对产物的物相组成、颗粒形貌和发光性能等进行了表征。结果表明,pH值对样品形貌有显著影响,pH=6时可以得到均匀规则的球状粉体。在394nm光的激发下,EuW_2O_6(OH)_3荧光粉的617nm发射峰在pH=6时达到最大值。     

红色荧光粉Ba_(4-4x)B_(11)O_(20)F∶4xEu~(3+)的制备及发光性能

以BaCO_3、BaF_2、H_3BO_3和氧化铕(Eu_2O_3)原料,采用高温固相反应法制备了一系列新型荧光材料Ba_(4-4x) B_(11)O_(20)F∶4xEu~(3+)(x=0.06、0.08、0.10、0.12、0.14)。利用XRD、SEM和荧光分光光度计对粉体结构、形貌和发光性能进行表征,并研究了铕离子(Eu~(3+))掺杂量对Ba_(4-4x)B_(11)O_(20)F∶4xEu~(3+)发光性能的影响。研究结果表明在激发波长为465nm的条件下,材料的发射峰主要位于592、598、616、654和700nm处;随着Eu~(3+)离子浓度的增大,样品的发光强度先增大后减小,最佳掺杂浓度为x=0.12。     

水热-溶胶-凝胶法制备钠离子电池正极材料Na_3V_2(PO_4)_3/C及其性能研究

分别采用溶胶凝胶法和水热-溶胶-凝胶法合成了钠离子电池正极材料Na_3V_2(PO_4)_3/C。用XRD、SEM、恒流充放电等对样品进行了表征。研究表明,两种方法合成的Na_3V_2(PO_4)_3/C样品均为纯相,呈多孔状结构,采用水热-溶胶-凝胶法制备出的Na_3V_2(PO_4)_3/C样品颗粒尺寸更小,更有利于钠离子脱嵌,有利于提高材料的电化学性能。溶胶-凝胶法制备的样品在0.1和2C倍率下首次放电比容量为98.3和31.3mAh/g,水热-溶胶-凝胶法制备的样品在0.1和2C倍率下首次放电比容量高达111.9和94.1mAh/g,电化学性能得到明显改善。     

M_0.8V_5.2O_(13)用作锂蓄电池阴极

V_6O_(13)用作常温锂蓄电池的阴极,不需要严格的化学计量,易于制取,比能量高,并有优良的充放电循环性能。我们曾对非计量 V_6O_(13)(VO_(2.19))作电池的循环测试,电流密度为1mA/cm~2时,有高而稳定的比容量。Abraham 指出用其它金属取代部分钒的可能性。本文拟用金属 M(Ti、W、Co)取代 V_6O_(13)中一部分 V,合成M_(0∶8)V_(5∶2)O_(13)化合物。用它为阴极材料,装配电池,测试电化学性能,并与计量 V_6O_(13)比较。     

近紫外白光LED用Ba_3Y_(1-x-y)B_3O_9∶xEu~(3+),yBi~(3+)高效红色荧光粉的制备与发光性能

采用传统高温固相法在较低温度下制备Eu~(3+)/Bi~(3+)共掺杂Ba_3YB_3O_9红色荧光粉,利用XRD仪和荧光光谱仪对样品Ba_3Y_(1-x-y)B_3O_9∶xEu~(3+),yBi~(3+)的晶体结构和发光性质进行了表征。XRD结果表明,Ba_3Y_(1-x-y)B_3O_9∶xEu~(3+),yBi~(3+)为纯相晶体。激发和发射光谱表明,样品可以被近紫外350～420 nm波段激发,最强激发峰位于393 nm,发射光谱呈现出Eu~(3+)的特征峰,谱带峰值位置在593 nm、613 nm,分别对应~5D_0-~7F_1、~5D_0-~7F_2特征跃迁。最强发射对应的掺杂浓度是0.12 mol。Ba_3Y_(0.87)B_3O_9∶0.12Eu~(3+),0.01Bi~(3+)的CIE坐标为(0.643,0.356)时最接近标准红色坐标,获得极佳的演色性。样品Ba_3Y_(1-x-y)B_3O_9∶xEu~(3+),yBi~(3+)可以用作近紫外激发三基色白光LED的红色荧光粉。     

锂离子电池正极材料铁掺杂V_6O_(13)的制备及电化学性能

为有效提高V_6O_(13)正极材料在高锂状态下的放电比容量和改善循环性能,使用一种先制备前驱体再水热合成的方法制备铁掺杂V_6O_(13)。运用XRD,SEM和XPS表征铁掺杂V_6O_(13)的物相、形貌以及表面元素价态,并对铁掺杂V_6O_(13)的电化学性能进行研究与分析。掺杂不同数量的铁可以得到不同形貌且电化学性能各异的铁掺杂V_6O_(13)。其中0.02样品的有序堆垛纳米片的厚度最大(600~900nm),纳米片之间的空隙最大。铁掺杂V_6O_(13)样品的放电性能均好于纯V_6O_(13),其中0.02样品的电化学性能最好,首次放电比容量为433mAh·g-1,100次循环后的容量保存率为47.1%。     

掺杂 Al_2O_3对 Ba_2Ti_9O_(20)相形成的影响

本文研究了在BaO-TiO_2-SnO_2固相反应系统中掺杂 Al_2O_3对 Ba_2Ti_9O_(20)相形成的影响。实验结果表明,即使掺杂少量的 Al_2O_3,在反应过程中 Ba_2Ti_9O_(20)相也变得更容易形成。微观结构分析结果表明,Ba_2Ti_9O_(20)晶体结晶时,由于具有层状结构特征,往往会出现结构层间应力;这种应力会严重制约Ba_2Ti_9O_(20)晶体的形核和长大。掺杂少量 Al_2O_3后,能形成与 Ba_2Ti_9O_(20)晶体共生的 BaAl_2Ti_6O_(16)晶体;这种共生机制抑制了应力的发展。Al_2O_3改善了 Ba_2Ti_9O_(20)结晶的动力学条件,促进了 Ba_2Ti_9O_(20)相的形成。     

Ba2Ti9O20陶瓷流延浆料的流变性能和流延成型研究

以BaCO3和TiO2粉末为原料,采用固相反应法合成Ba2Ti9O20的粉体,并以此粉体为主要原料添加适量的分散剂、粘结剂及塑性剂,采用流延法制备Ba2Ti9O20陶瓷膜片。研究了不同种类和配比的溶剂、不同种类和含量的分散剂对Ba2Ti9O20流延浆料的流变特性的影响。结果表明,当选用异丙醇和甲苯(体积比为75:25)为溶剂,固含量Ba2Ti9O2054wt%,分散剂蓖麻油0.5wt%,粘结剂聚乙烯醇缩丁醛5wt%,塑性剂聚乙二醇5wt%时,流延浆料的流变性能较好,浆料的粘度为9.1Pa.s。     

Ba0.8Sr0.2Ti0.5Mn0.5O3纳米晶体的合成及气敏性质研究

采用复合碱媒介法(CHM),在合成BaMnO3和Ba0.5Sr0.5MnO3的基础上,以Sr(NO3)2、BaCO3以及MnO2和TiO2为原料,在200℃、24h的生长条件下,用20%的Sr离子替代20%的Ba离子,用50%的Ti离子替代50%的Mn离子成功合成了Ba0.8Sr0.2Ti0.5Mn0.5O3纳米晶体。采用XRD、SEM及EDS对产物的晶相、形貌和成分进行了分析,对Ba0.8Sr0.2Ti0.5Mn0.5O3制作的电极进行了气敏性质的测定。     

前驱溶液的碱浓度对BiVO4粉体的微波水热法制备及光催化性能的影响

以Bi(NO3)3·5H2O和NH4VO3为原料,采用微波水热法在200℃不同前驱液碱浓度下制备了BiVO4粉体。利用XRD、FE-SEM、BET、UV-Vis等手段研究了前驱液碱浓度对BiVO4晶型、结构及形貌的影响,并对不同前驱液碱浓度下合成粉体的光催化性能进行了研究。溶于纯水获得的粉体是单斜相和四方相1～3μm八面体结构的BiVO4混晶。溶于HNO3和NaOH溶液时制得粉体为纯单斜相3μm大小球状BiVO4,NaOH增加到4mol/L时为2μm大小鱼排骨状BiVO4的混晶。光催化结果表明,紫外光下光催化活性顺序为:BiVO4(纯水)>BiVO4(4mol/L NaOH)>BiVO4(2mol/L NaOH),可见光下光催化活性顺序为:BiVO4(4mol/L NaOH)>BiVO4(纯水)>BiVO4(2mol/L NaOH)。     

Vanadium pentoxide nanobelts and nanorolls: from controllable synthesis to investigation of their electrochemical properties and photocatalytic activities

Uniform V(2)O(5)· xH(2)O nanobelts with high aspect ratios and ultra-long V(2)O(5)· xH(2)O nanorolls with novel scroll-like structures were synthesized on a large scale by a simple hydrothermal growth route using NH(4)VO(3) as the raw material in the presence of different acids at 180?°C for 24?h. Their morphologies were observed by scanning electron microscopy (SEM). X-ray powder diffraction measurement and thermal gravimetric analysis revealed the composition of nanobelts and nanorolls to be V(2)O(5)·0.9H(2)O and V(2)O(5)·0.6H(2)O, respectively. The possible mechanisms of formation of the nanobelts and nanorolls were schematically elucidated based on the layered structure of vanadium pentoxide. In addition, corresponding anhydrous V(2)O(5) nanostructures with better crystallinity were obtained by calcining the precursors of V(2)O(5)·0.9H(2)O nanobelts or V(2)O(5)·0.6H(2)O nanorolls. Furthermore, we have investigated the electrochemical intercalation properties with Li(+) and the photocatalytic activities of the synthesized V(2)O(5)·0.9H(2)O nanobelts, V(2)O(5)·0.6H(2)O nanorolls and their corresponding post-annealing products. It was observed that the morphologies and compositions of the synthesized products had an evident influence on the electrochemical intercalation properties with Li(+) and photocatalytic activities.     

溶液燃烧法合成Co3O4纳米粉体及热处理研究

分别以氨基乙酸、柠檬酸、葡萄糖为燃料,Co(NO_3)_2·6H_2O为氧化剂,采用溶液燃烧法合成Co_3O_4粉体,并对氨基乙酸为燃料合成的Co_3O_4粉体在500℃、600℃和700℃热处理,研究其结构、微观形貌和磁学性能。研究表明各燃料配制的前驱体溶液在300℃均可发生燃烧反应合成Co_3O_4粉体,以氨基乙酸为燃料时,合成粉体的颗粒较大,中间有气孔,分散性好,残留少量的氨基乙酸。n(氨基乙酸)∶n(硝酸钴)=1.11∶1时合成的Co_3O_4粉体600℃热处理后得到了高纯度、分散性好、平均径向尺寸80nm的Co_3O_4纳米粉体。以氨基乙酸为燃料合成的Co_3O_4产物在600℃和700℃热处理后,其矫顽力和剩磁值都比500℃热处理后的要小。     

Synthesis of nanoparticles of barium lanthanum hafnium oxide by a modified combustion process

Barium lanthanum hafnium oxide, a complex perovskite ceramic, has been synthesized as nanoparticles by a modified combustion process for the first time. The Ba, La, and Hf ions required for the formation of Ba2LaHfO5.5 were obtained in solution by dissolving in boiling nitric acid a stoichiometric mixture of BaCO3, La2O3, and HfO2 that had been heated at 1200 degrees C for 4 h. By complexing the ions with citric acid and using ammonia as fuel, it was possible to get Ba2LaHfO5.5 as nanoparticles in a single-step combustion process. The powder obtained by the present combustion process was characterized by X-ray diffraction, BET surface area analysis, differential thermal analysis, thermogravimetric analysis, infrared spectroscopy, and scanning and high-resolution transmission electron microscopy. According to the results of X-ray and electron diffraction, the powder synthesized through the combustion process showed single-phase barium lanthanum hafnium oxide. The transmission electron microscopic investigations showed a grain size of 42 nm, with a standard deviation of 8 nm. The nanoparticles of Ba2LaHfO5.5 synthesized by the present combustion technique could be sintered to > 97% of the theoretical density at a relatively low temperature of 1425 degrees C. Scanning electron microscopic studies on the sintered Ba2LaHfO5.5 samples showed that the final grain size of the sintered specimen was < 500 nm.     

pH对化学沉淀法制备纳米Al_2O_3粉体的影响

以硫酸铝铵、碳酸氢铵为原料,采用化学沉淀法,在不同pH条件下制备Al2O3的前驱体NH4Al(OH)2CO3,再经不同温度焙烧得到Al2O3粉体;利用扫描电镜、X射线衍射等分析手段对Al2O3粉体进行表征。结果表明,反应溶液pH的增大能降低Al2O3的相转变温度,但pH越大,所得到的Al2O3粉体越容易团聚;控制反应溶液的pH为9¹0,焙烧温度为800℃左右,可得到结晶度高的γ-Al2O3粉体,其平均晶粒径约为12 nm。     

Structural phase transition of tungsten-doped vanadium dioxide nanopowders prepared by thermolysis

Tungsten-doped vanadium dioxide (VO2) nanopowders were prepared by thermolysis of (NH4)5[(VO)6(CO3)4(OH)9] x 10H2O at low temperature, with active white powdery tungstic acid used as a substitutional dopant. The composition and microstructure of the powders were examined by X-ray diffraction, transmission electron microscope, and differential scanning calorimetry. The change in electrical resistance due to the S-M transition was measured from 0 to 150 degrees C by the four-probe method. Hysteresis loops and differential scanning calorimetry analysis of the samples indicated that the phase-transition temperature of VO2 nanopowders was 67.15 degrees C. For tungsten-doped VO2 nanopowders, the temperature was reduced to 26.46 degrees C. After sintering the nanopowders, Tc rose from 26.46 degrees C to 34.85 degrees C with the sizes increasing to the bulk. A significant direct correlation between particle size and Tc was confirmed. The results indicated that white powdery tungstic acid is exceptionally effective as a dopant for reducing transition temperature.     

水热温度对二氧化钛结构及光催化活性的影响

以四氯化钛、环氧丙烷和乙醇为原料,采用水热法在不同温度下分别合成了金红石相纳米二氧化钛及板钛矿相与金红石相混晶结构的纳米二氧化钛,并利用X射线衍射(XRD)、透射电镜(TEM)和N2吸附-脱附对其进行了表征。以甲基橙为探针研究了不同水热温度对二氧化钛光催化活性的影响。     

开放体系下碳热还原氮化法制备(Ti、W、Mo、V)CN固溶体粉末的研究

在开放体系下,采用碳热还原氮化的方法制备出了(Ti、W、Mo、V)CN固溶体粉末。结合XRD、SEM等分析测试手段对该过程中的物相以及显微形貌的演变进行了研究。结果表明(Ti、W、Mo、V)CN合成过程中物相演变遵循以下顺序:TiO2(anatase)→TiO2(rutile)→Ti4O7→Ti3O5→Ti(N、O)→(Ti、Mo…)N→(Ti、W、Mo、V)CN,1700℃可合成相组成单一、游离碳和氧分别为0.11%、0.28%的(Ti、W、Mo、V)CN固溶体粉。