石墨烯薄膜修饰TiO2纳米管光电极制备及性能

为提高TiO₂光催化剂的可见光催化活性,采用阳极氧化法制备了高度有序的TiO₂纳米管,利用阳极电化学沉积构筑了石墨烯薄膜修饰的TiO₂纳米管光电极,并利用扫描电子显微镜、X-射线光电子能谱及紫外-可见漫反射光谱对其表观形貌、组成结构及光吸收性能进行表征．结果表明:石墨烯有效地修饰在TiO₂纳米管表面,且以透明薄膜形式存在．此外,石墨烯薄膜修饰显著拓展了TiO₂纳米管的可见光响应范围．以甲基蓝为探针分子,考察了阳极沉积电压及沉积时间对所制备石墨烯薄膜／TiO₂纳米管光电极光催化性能的影响．结果表明:阳极沉积电压为+0.8 V、沉积时间为10 min时,制备的石墨烯薄膜／TiO₂纳米管光电极对甲基蓝的光催化降解效果最佳．模拟太阳光下光照120 min对甲基蓝的降解率为65.9％,是纯TiO₂纳米管光电极的1.35 倍．     

具有可见光响应的改性纳米TiO2研究进展

通过改性可以改变TiO₂只有在紫外光激发下才显示出较高光催化效率的特点,使其在可见光范围也显示出较高的活性。本文综述了纳米TiO₂改性方面的研究进展,指出通过元素掺杂、贵金属修饰、聚合物修饰、半导体复合、染料敏化等手段对TiO₂进行改性,可以减小纳米TiO₂禁带,提高纳米TiO₂对可见光的响应性和量子效率。分析认为,实验室制备的改性纳米TiO₂可见光光催化效果已经比较理想,解决回收难、工程易操作性等问题是未来的发展方向。     

模板法合成三维菊花状TiO2纳米花及其性能

为了解决一维、二维纳米材料在降解有机污染物时,易发生团聚、催化活性低、难以回收利用等问题,以TiO₂(P25)和NaOH为原料,ZnO为模板,采用水热法合成了三维菊花状TiO₂纳米花．运用扫描电子显微镜、X射线衍射仪、氮气吸附脱附、紫外-可见漫反射、傅立叶红外等手段对合成的样品进行测试分析. 结果表明:其花瓣是由TiO₂纳米颗粒通过自组装定向排列而成的链状结构,构成纳米花的粒子晶粒尺寸约15 nm,花状结构尺寸约为5 μm,结晶性良好,为锐钛矿相;比表面积为102.3 m²／g,平均孔径为17.41 nm;以亚甲基蓝为目标污染物,在紫外光照射下对其进行光催化性能实验,80 min亚甲基蓝的降解率为98％,催化活性高于P25,显示出较强的光催化活性．     

TiO2/石墨烯复合材料的水热法合成与光催化性能

为了提高TiO₂的光催化性能,采用水热法一步制备了TiO₂/石墨烯(TiO₂/RGO)复合物．采用XRD、FT-IR、RS、UV-Vis DRS、TEM等测试方法对其进行了表征,并研究了不同质量比的复合物在可见光下对甲基橙(MO)的光催化降解．结果表明:在TiO₂/RGO复合物中,TiO₂以10 nm左右的颗粒均匀地分散在石墨烯层上;与在同等条件下制备的TiO₂相比,TiO₂/RGO复合物在可见光区吸收明显增强,吸收边缘红移了20 nm;质量比为1∶0.005的TiO₂/RGO复合物,2 h内的降解率达到74.79％．可见将石墨烯与TiO₂复合,能够有效地提高TiO₂的可见光催化性能．     

KBrO3协同载贵金属TiO2光催化降解阿莫西林

为提高二氧化钛光催化去除阿莫西林的效率,利用光沉积法制备了载贵金属TiO₂催化剂 (M／TiO₂,M为Ru、Rh、Pd、Ag、Ir、Pt或Au),研究紫外光(365 nm)下KBrO₃协同M／TiO₂光催化降解阿莫西林的活性,并以KBrO₃协同Rh／TiO₂研究实验条件对催化活性的影响．结果表明：M／TiO₂光催化降解阿莫西林的催化活性与贵金属的功函数密切相关;KBrO₃对不同M／TiO₂光催化降解阿莫西林的反应均具有很好的协同效果;在Rh载量为0.1％(质量分数)、催化剂质量浓度为0.15 g／L、KBrO₃浓度为0.5 mmol／L、溶液pH为5的条件下,20 mg／L的阿莫西林溶液90 min光催化降解率达100％,且该反应符合一级反应动力学模型．     

沸石负载Mn,N共掺杂TiO2及光催化性能

为提高传统TiO₂光催化剂的可见光催化活性,本文采用溶胶-凝胶法合成了Mn,N共掺杂TiO₂光催化剂,改善了传统TiO₂光生载流子易复合的问题;进一步采用沸石作为载体对改性后的TiO₂样品进行负载,解决了传统光催化剂存在的难分离回收问题,以达到光催化剂可重复使用的目的.借助X-射线衍射仪、扫描电子显微镜、紫外分光光度计、傅立叶变换红外光谱仪等测试手段对Mn,N共掺杂TiO₂光催化剂的结构、元素组成、微观形貌和光催化降解性能进行系统分析与研究.研究结果表明,沸石负载Mn,N共掺杂TiO₂的样品较未改性的TiO₂样品具有更高的光催化降解活性,在可见光照射下,在最优掺杂条件下获得的TiO₂光催化剂在60 min内对孔雀石绿的降解率可达到97%,这主要归因于锰离子掺杂能够对TiO₂光生载流子的复合产生抑制作用,促进光生电荷分离,与此同时氮元素掺杂可有效拓宽TiO₂半导体光催化剂光响应范围.此外,经过5次循环使用后,对孔雀石绿的降解率没有较大程度的减弱,依然能够维持在88%以上,表明沸石负载Mn,N共掺杂TiO₂的样品具有较好的光催化循环稳定性.     

SO2-4对块体纳米晶铜阳极极化行为的影响

为了揭示SO₂^-4对块体纳米晶铜耐蚀性能的影响规律,利用电化学方法,结合X射线衍射、能谱分析、扫描电镜等表面分析技术,研究了惰性气体沉积原位温压法制备的块体纳米晶铜在不同质量分数（0.3%、1.3%、2.3%、3.3%和4.3%）Na₂SO₄溶液中的阳极极化行为.结果表明,随着SO₂^-4的增多,纳米晶铜的致钝电流密度增大,而致钝电位降低.在0.3%的Na₂SO₄溶液中加入1%的NaCl,纳米晶铜阳极极化行为发生明显变化,Cl^-在纳米晶铜表面形成难溶于水的CuCl保护钝化膜,纳米晶铜致钝电流密度降低,活化-钝化过渡区电流密度下降速率显著减小.     

氯氧化铋/氧化亚铜复合材料的制备及其可见光催化性能

通过水热法成功制备了BiOCl/Cu₂O 复合材料, 是一种良好的可见光响应的光催化剂。通过X 射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-vis) 和电化学阻抗谱(EIS) 等分析方法对BiOCl/Cu₂O 复合材料进行表征分析。以酸性橙(AO7) 为目标污染物进行光催化降解实验, 探究了BiOCl/Cu₂O 复合材料的光催化性能和降解机制。XRD 结果表明, 随着BiOCl 含量的增多, BiOCl 的衍射强度逐渐上升。SEM 结果表明, BiOCl 小纳米片附着在相对较大的八面体Cu₂O 表面形成复合结构。通过UV-vis 和EIS 分析结果可知, 复合材料的带隙相较于Cu₂O 略微增大但其阻抗明显变小。降解实验结果表明, 质量比为3 : 5 的BiOCl/Cu₂O 复合材料在90 min时的可见光催化降解率(56.8%) 明显高于Cu₂O 的降解率(26.3%), 其降解速率常数(0.009 3 min^-1) 是纯Cu₂O(0.003 3 min^-1) 的2.8 倍。自由基捕获实验表明BiOCl/Cu₂O 复合材料光催化过程中起主要作用的活性物种是超氧自由基(·O_{2^- )。6 次循环降解实验后光催化剂BiOCl/Cu2O(3 : 5) 对AO7 的降解率仍可达到48.3%。BiOCl 与Cu2O形成的异质结构在一定程度上降低了表面转移电阻, 加快了光催化过程中光生电子的转移速率, 提高了光生电子和空穴的分离率, 增强了光催化效果。}     

Cu2O/Cu2S 复合材料制备及可见光催化降解甲基橙的研究

通过水热法制备Cu₂O/Cu₂S 复合材料对甲基橙(MO) 进行光催化降解实验。在Cu₂O 中引入S 元素, 通过 改变Cu/S 投加摩尔比, 从而得到不同Cu/S 的复合材料。利用XRD、SEM、UV-vis、EIS 等手段对材料进行表征, 并 对MO 进行光催化降解实验。XRD 结果表明, 随着S 含量的增多, Cu₂S 的衍射强度逐渐上升, Cu₂O 的f111g 晶面 衍射强度逐渐降低。SEM 结果表明Cu₂S 能较好地包覆在Cu₂O 八面体的表面。通过UV-vis 和EIS 结果计算得知, 复合材料带隙为1.49 eV, 电荷转移电阻大幅降低。降解实验结果表明复合材料最佳Cu/S 投加摩尔比为15 : 1, 其在 100 min 时对MO (100 mL, 10 mg/L) 降解率达到91.4%, 明显高于纯Cu₂O 对于MO 的降解率(60.3%)。猝灭实验表 明了?OH 和 ?O₂ ^-在光催化过程中起到主要作用。     

水环境中不同浓度TiO2纳米颗粒混凝工艺去除效果

为了探究水环境中不同质量浓度TiO₂ 纳米颗粒(NPs)混凝工艺去除影响因素及与浊度去除规律的区别,研究了在超声预处理后投加表面活性剂(LAS)对TiO₂ NPs分散稳定性的影响,通过烧杯实验分别考察了混凝剂(聚合氯化铝,PAC)投加量及pH对不同质量浓度TiO₂ NPs和浊度去除的影响,及pH对TiO₂ NPs表面Zeta电位的影响机制．结果表明,在250 W超声处理10 min后加入20 mg／L的LAS获得的纳米悬浮液稳定性最好;不同混凝剂投加量下,TiO₂ NPs和浊度的去除规律呈相近趋势,TiO₂ NPs初始质量浓度为0.5,1和2 mg／L时,PAC最优投加量为3 mg／L,对应TiO₂ NPs和浊度最大去除率分别为46.2％、60.2％、68.8％和23.2％、43.6％、47.6％．TiO₂ NPs初始质量浓度为5 mg／L时,PAC最优投量为4 mg／L,TiO₂ NPs和浊度最大去除率分别为77.64％和54.08％．pH对TiO₂ NPs表面Zeta电位有明显影响,进而影响TiO₂ NPs的去除效果．     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi_0.45Co_0.10Mn_0.45O₂ was synthesized from Li₂CO₃ and a triple oxide of nickel, cobalt and manganese at 950 °C in air. The structures and characteristics of LiNi_0.45Co_0.10Mn_0.45O₂, LiCoO₂ and LiMn₂O₄ were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi_0.45Co_0.10Mn_0.45O₂ has a layered structure with hexagonal lattice. The commercial LiCoO₂ has sphere-like appearance and smooth surfaces, while the LiMn₂O₄ and LiNi_0.45Co_0.10Mn_0.45O₂ consist of cornered and uneven particles. LiNi_0.45Co_0.10Mn_0.45O₂ has a large discharge capacity of 140.9 mA · h/g in practical lithium ion battery, which is 33.4% and 2.8% above that of LiMn₂O₄ and LiCoO₂, respectively. LiCoO₂ and LiMn₂O₄ have higher discharge voltage and better rate-capability than LiNi_0.45Co_0.10Mn_0.45O₂. All the three cathodes have excellent cycling performance with capacity retention of above 89.3% at the 250th cycle. Batteries with LiMn₂O₄ or LiNi_0.45Co_0.10Mn_0.45O₂ cathodes show better safety performance under abusive conditions than those with LiCoO₂ cathodes. Foundation item: Project(50302016) supported by the National Natural Science Foundation of China; Project(2005037698) supported by the Postdoctoral Science Foundation of China     

LiNi0.4Co0.2Mn0.4O2与LiMn2O4共混正极材料电化学性能

为开发具有优良循环性能和安全性能的大型锂离子电池的正极材料,将不同比例的LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和Li Mn2O4材料进行共混,研究了LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和Li Mn2O4共混以及共混比例(10∶0、8∶2、7∶3、6∶4、5∶5、0∶10)对锂离子电池的首次放电性能、循环性能和倍率性能以及交流阻抗和循环伏安曲线的影响,并采用扫描电镜对电极材料进行了表征.研究结果表明,共混比例会影响材料的电化学性能,8∶2,7∶3和6∶4配比的混合材料的体积比容量、循环性能和倍率性能要好于纯LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和Li Mn2O4材料.其中,8∶2配比的材料性能最好.     

不同污泥龄厌氧氨氧化菌的脱氮效能及其动力学特性

为研究不同污泥龄(SRT)条件下厌氧氨氧化菌的脱氮效能和动力学特性,采用一组SBR反应器研究梯度降低污泥龄过程中系统的NO2--N去除负荷(Nr)和NO2--N污泥负荷(Ns),并对各阶段厌氧氨氧化过程动力学特性进行分析.结果表明,污泥龄由21 d梯度降低到12 d,Nr由0.590 kg/(m3·d)降低到0.493 kg/(m3·d),单位MLVSS Ns由0.178 kg/(kg·d)提升到0.297 kg/(kg·d),系统整体的脱氮性能有所下降,但单位质量的厌氧氨氧化菌脱氮效率显著提升;采用莫诺(Monod)模型可以较好地模拟不同污泥龄运行阶段厌氧氨氧化菌的动力学行为,动力学分析表明,随着污泥龄的降低,NO2--N的最大比降解速率vmax由0.406 d-1提高到0.826 d-1,半饱和常数Ks由23.3 mg/L增加到95.3 mg/L,梯度降低污泥龄能够筛选纯化生长速率较快的厌氧氨氧化菌菌种,提升NO2--N的最大比降解速率,但厌氧氨氧化菌对底物的亲和性会逐渐变差,稳定性降低.     

BaZr0.9Y0.1O2.95/Na2SO4 composite with enhanced protonic conductivity

Heterogeneous composite BaZr_0.1Y_0.9O_2.95/Na₂SO₄ was designed and fabricated with Y-doped BaZrO₃ as matrix and Na₂SO₄ as dispersant by conventional powder processing to improve the total conductivity of barium zirconate. The electrical conduction of the composite was studied by electrical and electrochemical methods. Microstructure of the heterogeneous composite was examined by SEM. The experimewtal results show that the protonic conductivity of Y-doped BaZrO₃ is greatly improved upon incorporating Na₂SO₄ in the material. Microstructure observation indicates that a multiphase structure with Na₂SO₄ disperses at the grain boundaries of BaZr_0.1Y_0.9O_2.95. Electromotive force (EMF) measurements under fuel cell conditions reveal that the total ionic transport number of the composite is more than 0.9 at 750 °C. Funded by the National natural Science Foundation of China(No. 50872090)     

Self-Propagating High-Temperature Reduetive Synthesis of TiB2-Al2O3 Composite Powders

TiB2-Al2O3 composite powders were produced by self-propagating high-temperature synthesis（SHS） method with reductive process from B2O3-TiO2-AI system. X-ray diffraction（XRD） and scanning electron microscopy（SEM） analyses show the presence of TiB2 and Al2O3 only in the composite powders produced by SHS. The powders are uniform and free-agglomerate. Transmission electron microscopy （TEM） and high resolution electron microscopy （HREM） observation of microstructure of the composite powders indicate that the interfaces of the TiB2-Al2O3 bond well, without any interfacial reaction products. It is proposed that the good interfacial bonding of the composite powders can be resulted from the TiB2 particles crystallizing and growing on the Al2O3 particles surface with surface defects acting as nucleation centers.     

Effect of La doping on microstructure and ferroelectric properties of Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films prepared by sol-gel method

The Bi4Ti3Oi2 and Bi3.25La0.75Ti3O12 thin films were prepared on the Pt/Ti/SiO2/Si substrate using the sol-gel method. The effect of La doping on the microstructure and ferroelectric properties of Bi4Ti3O12 films were investigated. Both the Bi4Ti3O12 and Bi3.25La0.75Ti3O12 thin films exhibited typical bismuth layered perovskite structure. The 2Pr （remanent polarization） value of Bi3.25La0.75Ti3O12 thin films is 18.6 μC/cm^2, which is much larger than that of Bi4Ti3O12 thin films. And the Bi3.2eLa0.75Ti3O12 films show fatigue-free behavior, while the Bi4Ti3O12 thin films exhibit the fatigue problem. The mechanism of improvement of La doping was discussed.     

Nanocomposite films of V<Subscript>2</Subscript>O<Subscript>5</Subscript>−MoO<Subscript>3</Subscript> xerogel with poly ethylene oxide intercalation

Poly ethylene oxide (PEO)_x−V₂O₅−V₂O₅−MoO₃ (x=0, 0.5, 1) films were prepared by the sol-gel method. The synthesis and structure of the films were investigated by XRD, TG-DTA, FTIR, etc. The results show that V₂O₅−MoO₃ xerogel has a layered structure and its interlayer space increased from 1.3181 nm at x=0 to 1. 7898 nm at x=1 after the nanocomposite films were dried, and PEO in the interlayer changes the interface structure by forming hydrogen bonds with V=0 bands. CV measurement indicates that the intercalation of PEO improves insertion/extration properties of Li⁺ ions in the interlayer. ZHENG Jin-xia: Born in 1976 Funded by the National Natural Science Foundation of China (No. 50172036) and Natural Science Foundation of Hubei Province(No. 2001ABB083)     

Molar heat capacities of La2Mo2O9 and La1.9Sr0.1MO209-δ

The molar heat capacities of La2Mo209 and La1.9Sr0.1MO209-δ were obtained using the differential scanning calorimetry （DSC） technique in a temperature range from 298 to 1473 K. The DSC curve of La2Mo209 showed an endothermal peak around 834 K corresponding to a first-order monoclinic-cubic phase transition, and the enthalpy change accompanying this phase transition is 5.99 kJ/mol. No evident endothermal peak existed in the DSC curve of La1.9Sr0.1MO209-δ, but a broad thermal anomaly existed in its heat capacity curve at around 832 K. In addition, the heat capacity values of La2Mo209 and La1.9Sr0.1MO209-δ began to decrease at 1196 and 1330 K, respectively. The non-transitional heat capacity values of La2Mo209 and La1.9Sr0.1MO209-δ were formulated using multiple regression analysis in two temperature ranges.     

Synthesis and characterization of (PEO)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>−(V<Subscript>0.85</Subscript>Mo<Subscript>0.15</Subscript>)<Subscript>2</Subscript>O<Subscript>5</Subscript> nanocomposite films

(PEO) _x −(V_0.85Mo_0.15)₂O₅(x=0,0.5,1.0) nanocomposite films were prepared by a modified sol-gel method. The structure of the films was analyzed by XRD, and the DC electrical conductivity. Cyclic voltammogram and optical spectral transmittance were investigated. The results show that the (V_0.85Mo_0.15)₂O₅ xerogel has a layered structure and its interlayer space increased from 1.3181 nm at x=0 to 1.7897 nm at x=1.0. The introduction of MoO₃ improved the DC electrical conductivities of the films due to the generation of V₄₊ to maintain the electrical neutrality of the oxides. PEO intercalated in the interlayer of (V_0.85Mo_0.15)₂O₅ oxides has interaction with the oxides, enhancing the amount of Li⁺ ions inserted into the interlayer of the oxides. Moreover, the intercalation of PEO into the interlayer of (V_0.85Mo_0.15)₂O₅ oxides improved the cathodic electrochromic property in near ultraviolet region and anodic electrochromic property in visible range. JIANG Cong-sheng: Born in 1963 Supported by the Science Foundation of Hubei Province (Grant No. 2001ABB083)     

Preparation and characterization of Bi4Ti3O12 platelets by a novel low-temperature molten salt system

Bismuth titanate (Bi₄Ti₃O₁₂) platelets were prepared by molten salt method in a new salt system of CaC_l2-NaCl at 650–750 °C, using bismuth nitrate pentahydrate (Bi(NO₃)₃―H₂O) and titanium butoxide (Ti (OC₄H₉)₄) as raw materials. The synthesis temperature of Bi₄Ti₃O₁₂ platelets was decreased to 650 °C from 900–1100 °C. The phase compositions and crystalline morphology of Bi₄Ti₃O₁₂ platelets were investigated by XRD and SEM. The experimental results indicate that Bi₄Ti₃O₁₂ platelets containing tetragonal and orthorhombic phase with the size of 1–3 μm can be synthesized at 650 °C for 2 h, and the orthorhombic phase becomes the dominant phase at 750 °C for 5 h. The size and proportion of Bi₄Ti₃O₁₂ platelets increase with the increment of the calcining temperature and holding time. The proportion of platelets increases to about ninety percent, and the platelets grow up to about 3–10 μm at 750 °C for 5 h from 1–2 μm at 650 °C for 2 h. This technical route provides a new low-temperature molten salt system for preparing platelets by molten salt methods.