聚N-[5-(8-羟基喹啉)甲基]苯胺/介孔五氧化二钒杂化材料的制备与表征

采用原位插层聚合法制备出层状有序的聚N-[5-(8-羟基喹啉)甲基]苯胺/介孔五氧化二钒(PNQA/Meso-V2O5)杂化材料.结果显示,PNQA插入后,Meso-V2O5的层间距由2.4nm增加到2.81nm,得到的杂化材料仍保持良好的层状结构.杂化材料的室温电导率比Meso-V2O5高出3个数量级.荧光分析表明,在乙醇介质中杂化材料的发射谱带与PNQA相比蓝移22nm,杂化材料的荧光量子产率(26%)明显高于PNQA(10%).     

具有伸展链构象聚苯胺/蒙脱土混杂纳米复合物的合成与表征

报道了具有聚苯胺伸展链构象的聚苯胺／ 粘土（ Ｐ Ａｎ／ Ｍ Ｍ Ｔ） 混杂纳米复合物的合成与表征．用插层聚合的方法将聚苯胺分子链嵌入层状蒙脱土的片层之中,从而得到一种高电导率的聚苯胺／ 层状硅酸盐混杂纳米复合物．通过 Ｘ 射线衍射（ Ｘ Ｒ Ｄ） ,付立叶红外（ Ｆ Ｔ Ｉ Ｒ） ,四探针电导率测量以及定性和定量的电子光谱分析等手段对产物进行了表征,结果表明,９０ ％ 以上的聚苯胺的分子链被插入蒙脱土的片层中间．由于聚苯胺分子链在受限的纳米空间生成,聚苯胺以伸展的单分子链构象存在．该构象在苯胺的通常聚合中不可能生成．通过对聚合过程进行吸收光谱监测,发现该聚合是扩散控制过程．     

脉冲激光法制备修饰纳米Eu_2O_3/聚苯胺导电杂化薄膜

采用聚焦脉冲激光法(PLA-IT/SFL)制备修饰纳米Eu2O3/聚苯胺有机溶胶及其杂化薄膜材料。考察了制备条件对修饰纳米Eu2O3/聚苯胺有机溶胶荧光性能的影响。TEM显示Eu2O3粒子粒径约为15 nm且其在聚苯胺中有较高的稳定性。荧光光谱表明该杂化薄膜材料在紫外光照射下发出强烈的红光,且荧光强度达2.53×105a.u。杂化薄膜材料的电导率为1.13×10-2S.cm-1。热分析表明该杂化薄膜比导电性聚苯胺(PAN-HCSA)薄膜具有更好的热稳定性。该杂化薄膜材料可望用于电致发光领域。     

聚苯胺/H2W2O7层状复合材料的制备研究

以层状钨基氧化物(H2W2O7)为无机主体, 用正庚胺改性后的正庚胺/H2W2O7复合物(HTT)为中间体, 通过离子交换、层间O2引发聚合等步骤成功制备了聚苯胺/H2W2O7层状复合材料(PANI/H2W2O7). X射线衍射、扫描电子显微镜、红外光谱及差热分析结果表明: 聚苯胺分子已成功地嵌入H2W2O7层间, 层状结构没被破坏, 层间距变至1.19 nm; 聚苯胺的嵌入还大大提高了材料的热稳定性. 讨论了无机主体与有机客体之间的相互作用、聚苯胺在层间的排布形式及苯胺和聚苯胺插入层间的反应机理.     

盐酸掺杂聚苯胺的制备及性能研究

本文用溶液聚合法制备盐酸掺杂聚苯胺,测定了体系酸度对聚苯胺电导率的影响,及盐酸掺杂聚苯胺在不同条件下经过热处理后的电导率,采用TGA、XRD等方法,研究了热处理过程对聚苯胺结构的影响。结果表明,当热处理温度为90℃时,电导率高于初始值,当热处理温度高于100℃时,电导率开始下降,到达220℃时,电导率下降了约4个数量级。在氮气中聚苯胺电导率的衰减比空气中小,聚苯胺经热处理后在浓硫酸中的溶解性会明显降低。本文还探讨了去掺杂、氧化和化学交联等盐酸掺杂聚苯胺的热降解机理。     

热处理对聚四氟乙烯-聚苯胺系列导电复合膜性能的影响

对电化学制备的聚四氟乙烯-聚苯胺系列导电复合膜进行热处理,采用热重、红外和X衍射等手段研究了在空气和真空氛围中,热处理对复合膜的电导率及力学性能的影响。热分析结果表明：此系列复合膜在100～180°C失重较少,在此温度区间内对聚苯胺-聚四氟乙烯复合膜热处理,其电导率在空气和真空氛围中均随热处理温度升高而下降,聚苯胺-聚四氟乙烯-银复合膜在空气氛围中的电导率也随热处理温度升高而下降,两种复合膜的强度不变,断裂伸长率降低;聚苯胺-聚四氟乙烯-银复合膜在真空氛围中经120°C热处理后电导率提高最显著,力学强度也有所提高,但断裂伸长率降低。X衍射研究表明复合膜经180°C热处理后结晶度降低。红外分析结果表明聚苯胺-聚四氟乙烯复合膜经180°C热处理,发生了磺基水杨酸的脱掺杂和聚苯胺的结构热氧化、分子链的断裂和交联,复合膜电导率降低。     

聚苯胺/顺丁橡胶复合导电膜的制备与性能(Ⅱ)

采用再掺杂方法制得了樟脑磺酸掺杂的聚苯胺(PAn-CSA),用溶液共混法制备PAn／BR导电复合膜．研究了聚苯胺与顺丁橡胶(BR)复合膜在间甲酚二次掺杂前后电导率的变化。实验表明:CSA对聚苯胺有较好的掺杂作用;二次掺杂使PAn复合膜电导率明显提高,其导电渗滤阈值略有降低,使卷曲的二次掺杂PAn链展开并通过分子链间的相互作用而自行组成导电通路．     

反应温度对衣康酸掺杂聚苯胺性能的影响

以衣康酸为掺杂剂,过硫酸铵为引发剂,采用化学氧化聚合法在不同的反应温度下合成聚苯胺(PANI)。计算其产率和电导率,并测定掺杂态聚苯胺的各项性能指标。通过电阻测试、傅立叶红外光谱测试(FT-IR)、紫外-可见光谱测试(UV-vis)、电子探针分别对产物的导电性、化学结构、紫外可见光谱和微观形貌进行了表征。结果表明,低温有利于减缓链终止的速度使得产物分子链较长,从而使载流子的传输更容易进行,产物电导率高;而温度高于10℃会使聚苯胺氧化断链,使产物电导率下降。以反应温度为10℃时电导率最高,为1.29×10-2(S·cm-1),且具有最高的产率为111.2%,微观形貌为纳米棒状结构。     

掺杂质子酸的类型对聚苯胺结构和电导率的影响

采用化学氧化聚合法以苯胺为单体，过硫酸铵为氧化剂，在不同质子酸的水溶液中合成聚苯胺，考察质子酸对聚苯胺电性能影响，并通过傅立叶红外吸收光谱（FTIR）和紫外可见光吸收光谱（UV－vis)研究聚苯胺掺杂前后结构的变化。结果表明，龙质子酸掺杂后聚 胺具有导电性是因为其分子链上电荷离城形成了共轭结构，具有不同质子酸中生成的聚苯胺氧化程度不同；分子链共轭程度与掺杂酸对阴离子大小有关，掺杂质子酸对阴离子越大，聚苯胺分子链共轭程度越大，电导率也就越高。     

SiO_2负载磷钨钒杂多酸杂化材料的制备及其氧化脱硫性能的研究

利用磷酸氢二钠、偏钒酸纳和钨酸钠为原料,合成了具有Keggin结构的磷钨钒杂多化合物(H5PW10V2O40),并与1-丁基-3-甲基咪唑溴(BmimBr)离子液体反应生成一种杂多酸杂化材料([Bmim]5PW10V2O40)。利用红外光谱(FT-IR)、X射线衍射光谱(XRD)和紫外可见光谱(UV-vis)对所合成的杂多酸杂化材料进行表征。结果表明,[Bmim]5PW10V2O40具有咪唑阳离子基团和Keggin型杂多阴离子基团的结构特征,并且两种基团之间存在相互作用。以SiO_2为载体制备负载型的杂多酸杂化材料催化剂[Bmim]5PW10V2O40/SiO_2,以H2O_2作为氧化剂,考察该催化剂对模拟油中DBT的氧化性能,并优化氧化反应条件,在反应温度40℃,O/S物质的量比为3.0的条件下,反应50min,模拟油品中的DBT的转化率可以达到100%。催化剂可以通过离心法分离,经过干燥之后,可以循环使用至少七次,而对DBT的氧化活性没有降低。     

Insights into the H_2O/V_2O_5 Interface Structure for Optimizing Water-splitting

The interaction of water(H2O) with metal oxide surfaces is of fundamental importance to various fields of science, ranging from batteries to catalysis. In particular, vanadium pentoxide(V2O5) has been widely used as electrode materials for aqueous-battery and catalysts. Herein, theoretical(density functional theory) study gives atomic-scale insights into water monolayers in V2O5 and single-molecule adsorption and dissociation at three low-index surfaces and oxygen-vacancy V2O5(001) surface. The H2O/V2O5 interface structure was identified. The results show that H2O is adsorbed on the stoichiometric V2O5(001) surface with physisorption mechanism, and the dissociation hardly occurs. Water adsorbs as an intact monomer with a computed binding energy of 0.75 eV. The formation of ordered water overlayers has been observed on V2O5(001) surface, suggesting a locally ordered superstructure of molecular water. The molecular H2O adsorption on oxygen-vacancy V2O5(001) surface is stronger than that on the stoichiometric V2O5(001) surface, and H2O can undergo dissociative chemisorption to form a surface hydroxyl group and a H adatom. V2O5 can take the oxygen from H2O, which is consistent with the experimental results.     

H5PMo10V2O40/SBA-15催化剂的制备及其催化性能

以Keggin型杂多酸H5PMo10V2O40为主体,SBA-15介孔分子筛为载体,利用溶胶-凝胶法制备了不同负载量的H5PM10V2O40/SBA-15负载型催化剂,通过XRD、FTIR、TEM、H2-TPR和N2吸脱附法对样品进行了分析和表征,并将制得的负载型催化剂应用于苯氧化苯酚的反应中,研究了不同条件(温度、时间和催化剂用量等)下的催化性能.研究结果表明:H5PMo10V2O40杂多酸能均匀地分散于SBA-15孔道中且SBA-15的六方介孔结构并未发生改变:较好地解决了活性组分大量溶脱的问题;与H5PMo10V2O40杂多酸相比,H5PMo10V2O40/SBA-15催化剂在苯氧化为苯酚的反应中具有更高的转化率和更好的选择性,当反应温度为70℃,催化剂的使用量为0.25 g,反应时间为2 h和H5PMo10V2O40负载量为60%时苯酚的选择性达到了82.53%.     

V2O5表面氧和晶格氧的热脱附性能

V_2O_5是一种重要的烃类选择氧化催化剂,ESR研究表明,在V_2O_5/SiO_2上存在有O~-,O~(2-)和O_3~-等物种。但是氧吸附物种的ESR研究迄今仍局限于较低温度,与实际催化反应条件尚存相当差距。用程序升温脱附(TPD)法研究,恰好能补其不足。但是关于V_2O_5表     

Highly stable aqueous rechargeable Zn-ion battery: The synergistic effect between NaV_6O_(15) and V_2O_5 in skin-core heterostructured nanowires cathode

The aqueous rechargeable Zn-ion batteries based on the safe,low cost and environmental benignity aqueous electrolytes are one of the most compelling candidates for large scale energy storage applications.However,pursuing suitable insertion materials may be a great challenge due to the strong electrostatic interaction between Zn^{^(2+})and cathode materials.Hence,a novel NaV₆O₁₅/V₂O₅ skin-core heterostructure nanowire is reported via a one-step hydrothermal method and subsequent calcination for high-stable aqueous Zn-ion batteries(ZIBs).The NaV₆O₁₅/V₂O₅ cathode delivers high specific capacity of 390 m Ah/g at 0.3 A/g and outstanding cycling stability of 267 m Ah/g at 5 A/g with high capacity retention over 92.3%after 3000 cycles.The superior electrochemical performances are attributed to the synergistic effect of skin-core heterostructured NaV₆O₁₅/V₂O₅,in which the sheath of NaV₆O₁₅ possesses high stability and conductivity,and the V₂O₅ endows high specific capacity.Besides,the heterojunction structure not only accelerates intercalation kinetics of Zn²⁺transport but also further consolidates the stability of the layers of V₂O₅ during the cyclic process.This work provides a new perspective in developing feasible insertion materials for rechargeable aqueous ZIBs.     

固相球磨法制备丙烷氧化脱氢V2O5/NiO催化剂

以不同温度焙烧制备的NiO和V2O5为前驱物,采用固相球磨法制备了V2O5/NiO催化剂,考察了前驱物的焙烧温度对该催化剂丙烷氧化脱氢制丙烯反应性能的影响,并采用x射线衍射、N2物理吸附、电感耦合等离子体原子发射光谱、透射电子显微镜、H2程序升温还原和x射线光电子能谱等对催化剂进行了表征.结果表明,固相球磨法制备的V2O5/NiO催化剂表现出较好的丙烷氧化脱氢制丙烯催化性能,当以400℃焙烧的氧化物为前驱体时,V2O5/NiO催化剂表面含有较多的未完全还原氧物种Oδ-,因而表现出了较高的丙烯选择性.在475℃反应时,丙烷转化率可达20.1%,丙烯选择性达到71.2%.     

V2O5/TiO2催化剂表面结构FT-IR发射光谱研究(II)

用傅里哀变换红外发射光谱原位考察了V_2O_5/TiO_2催化剂在制备焙烧过程中担载偏钒酸铵的热分解步骤及其形成的表面活性相结构。偏钒酸铵在200 ℃左右分解, 在300 ℃之前完全转化为晶相V_2O_5。担载于TiO_2上的偏钒酸铵在100 ℃左右与TiO_2已产生强的化学作用, 在200 ℃之前已完全分解。对于10%(质量分数)V_2O_5/TiO_2催化剂其担载偏钒酸分解后在1020 cm~(-1)附近出现晶相V_2O_5的特征峰。但在500 ℃进一步焙烧后晶相V_5O_5的峰减弱并在1025—900 cm~(-1)区出现宽峰, 表明部分晶相V_2O_5可能转化为二维高分散的VO_x物种。2%(质量分数)V_2O_5/TiO_2催化剂在焙烧过程中也显示晶相V_2O_5的弱峰, 但同时也观察到属于VO_x物种的宽峰。进一步降低钒担载量, V_2O_5晶相特征峰逐渐消失, 而在1025—900 cm~(-1)区出现二维VO_x物种的宽峰。结果还表明傅里哀变换红外发射光谱是表征氧化物催化剂表面相结构的一种有力的方法。     

两类稀土钒酸盐的合成与结构

通过（１）ＬｎＯＣｌ／Ｖ＿２Ｏ＿５，（２）ＬｎＣｌ３／Ｖ及（３）ＬｎＯＣｌ／ＬｎＣｌ／Ｖ＿２Ｏ＿５／Ｖ的高温固态化学反应，得到两种稀土钒酸盐：Ｌｎ＿６Ｖ＿３Ｃｌ＿（１０）Ｏ＿（１２）（Ｌｎ＝Ｌａ）及Ｌｎ＿４Ｖ＿５Ｓｉ＿４Ｏ＿（２２）（Ｌｎ＝Ｌａ～Ｎｄ）。Ｌａ＿６Ｖ＿３Ｏ＿（１０）Ｏ＿（１２）晶体呈浅色透明片状，其结构可认为是由［Ｌａ＿３（ＶＯ＿４）＿３Ｃｌ］单元插入到ＬａＣｌ３结构单元中而形成的，在结构中沿ｃ轴方向存在一系列截面积为１９．１的空洞。Ｌｎ＿４Ｖ＿５Ｓｉ＿４Ｏ＿（２２）（Ｌｎ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ）晶体呈，黑色针状，其结构可认为是由交替的稀土钒硅酸盐薄层及钒氧金红石层沿ｃ轴堆叠而表现为准二维Ｃｈｅｖｋｉｎｉｔｅ型结构。     

The design and fabrication of Co_3O_4/Co_3V_2O_8/Ni nanocomposites as high-performance anodes for Li-ion batteries

The Co_3O_4/Co_3V_2O_8/Ni nanocomposites were rationally designed and prepared by a two-step hydrothermal synthesis and subsequent annealing treatment. The one-dimensional(1D) Co_3O_4 nanowire arrays directly grew on Ni foam, whereas the 1D Co_3V_2O_8 nanowires adhered to parts of Co_3O_4 nanowires.Most of the hybrid nanowires were inlayed with each other, forming a 3D hybrid nanowires network.As a result, the discharge capacity of Co_3O_4/Co_3V_2O_8/Ni nanocomposites could reach 1201.8 mAh/g after100 cycles at 100 mA/g. After 600 cycles at 1 A/g, the discharge capacity was maintained at 828.1 mAh/g.Moreover, even though the charge/discharge rates were increased to 10 A/g, it rendered reversible capacity of 491.2 mAh/g. The superior electrochemical properties of nanocomposites were probably ascribed to their unique 3D architecture and the synergistic effects of two active materials. Therefore, such Co_3O_4/Co_3V_2O_8/Ni nanocomposites could potentially be used as anode materials for high-performance Li-ion batteries.     

Electrochemical and structural evolution of structured V_2O_5 microspheres during Li-ion intercalation

With the development of stable alkali metal anodes,V₂O₅ is gaining traction as a cathode material due to its high theoretical capacity and the ability to intercalate Li,Na and K ions.Herein,we report a method for synthesizing structured orthorhombic V₂O₅ microspheres and investigate Li intercalation/deintercalation into this material.For industry adoption,the electrochemical behavior of V₂O₅ as well as structural and phase transformation attributing to Li intercalation reaction must be further investigated.Our synthesized V₂O₅ microspheres consisted of small primary particles that were strongly joined together and exhibited good cycle stability and rate capability,triggered by reversible volume change and rapid Li ion diffusion.In addition,the reversibility of phase transformation(a,e,d,c and xLixV₂O₅)and valence state evolution(5+,4+,and 3.5+)during intercalation/de-intercalation were studied via in-situ X-ray powder diffraction and X-ray absorption near edge structure analyses.