GO/CoFe2O4催化过硫酸盐降解邻苯二甲酸二丁酯效能

为高效地去除水中环境激素类污染物,采用共沉淀法合成了氧化石墨烯负载钴尖晶石铁氧体(GO/CoFe_2O_4)催化剂,催化过硫酸盐(PMS)去除水中邻苯二甲酸二丁酯(DBP).采用SEM、TEM、XPS、XRD对催化剂进行表征,研究不同条件下催化PMS去除水中DBP的效果,提出催化PMS反应机理.结果表明,GO/CoFe_2O_4为颗粒状尖晶石结构,室温下,DBP初始浓度为2μmol/L、催化剂投量为0.1 g/L、PMS浓度为20μmol/L、pH为7时,GO/CoFe_2O_4催化PMS体系对DBP的去除率可达89%,使用5次后催化效果仅降低5%.该新型复合催化剂高效、具有磁性、方便回收,具有良好的工程应用前景.     

N掺杂Co3O4纳米片的制备以及活化过一硫酸盐的性能研究

采用牺牲模板法合成N掺杂Co₃O₄纳米片（N-Co NS）,通过透射电子显微镜（TEM）、原子力显微镜（AFM）和光电子能谱（XPS）对制备材料的形貌结构、化学组成进行分析,并通过催化活化过一硫酸盐（PMS）降解水中双酚A （BPA）来探究催化剂的催化性能.实验结果表明与Co₃O₄纳米颗粒（Co NP）、Co₃O₄纳米片（Co NS）相比,N-Co NS表现出了较高的催化性能.在PMS浓度为2 mmol·L^-1、BPA初始质量浓度为50 mg·L^-1的反应条件下,N-Co NS在10 min内完全降解水中的BPA,表明N掺杂和二维纳米片结构有利于催化剂性能的提升.通过pH及离子影响实验证实N-Co NS在复杂水化学环境中仍具有较高的活性.此外结合自由基捕获实验和电子顺磁共振（EPR）测试证实反应体系中产生了高氧化活性的羟基自由基和硫酸根自由基.     

UV/H2O2降解三氯生动力学及反应机理

为考察紫外催化过氧化氢工艺降解三氯生的降解效能,利用动力学模型对三氯生的表观降解速率进行模拟.考察氧化剂投加量、三氯生浓度、NOM质量浓度和p H对三氯生降解速率的影响.结果表明,H_2O_2的投加量小于1 mmol/L时,三氯生的降解速率随H_2O_2浓度的增加而增加,而当H_2O_2的投加量大于1 mmol/L时,由于H_2O_2对HO·的捕获作用增强,三氯生的降解速率随H_2O_2投加量的增加而降低.当三氯生的初始浓度增加时,体系中HO·的稳态浓度随之降低,导致三氯生降解的表观速率降低.体系中存在NOM时,三氯生的降解速率显著降低,主要是由于NOM能够与三氯生竞争光子和HO·.三氯生去质子化后更快地被UV/H_2O_2降解,其去质子化形态的摩尔吸光系数变大,而且其与HO·的二级反应速率更快.通过LC/MS-MS检测UV/H_2O_2氧化TCS得到6种产物,推测TCS的降解途径主要是通过脱氯反应和羟基化反应.     

PMS/Fe0体系中自由基产率比及莠去津降解动力学

针对水体中存在的难降解农药莠去津（ATZ）污染问题,提出零价铁活化过氧单硫酸盐（PMS/Fe⁰）降解水中的ATZ,研究不同工艺参数（溶液pH、PMS投加量、Fe⁰投加量、ATZ初始浓度）条件下ATZ的降解动力学。采用硝基苯（NB）和ATZ竞争实验的方法,原位鉴定PMS/Fe⁰体系的自由基种类,并进一步基于稳态假设定量推导得到自由基产率比的公式。最后,研究了模拟地下水条件下PMS/Fe⁰对ATZ的降解规律。结果表明：ATZ降解的假一级速率常数(k_obs),随pH的增加而降低,随ATZ初始浓度的增加而降低,随Fe⁰投量增加而增加,随PMS的投量先增加后降低,在PMS投量为25μmol/L时最大。NB和ATZ的竞争实验结果表明,PMS/Fe⁰体系中的活性物种为硫酸根自由基（SO^-₄·）和羟基自由基（·OH）,且两种自由基的产率比为10.5∶1。在模拟地下水条件下,Fe⁰和PM...     

KMnO4氧化降解雌酮反应动力学与氧化产物

为探讨KMnO_4氧化降解雌酮(E1)的效能和反应机理,在假一级条件下,研究KMnO_4氧化降解E1的动力学规律,利用三重四级杆串联线性离子阱液相-质谱联用仪(LC-MS/MS)对KMnO_4氧化降解E1的产物进行分析.结果表明,KMnO_4氧化降解E1符合假一级动力学规律,且假一级动力学常数Kobs(s-1)随着KMnO_4浓度的增加呈线性增加,二级反应动力学常数k(L·mol~(-1)·s~(-1))随着pH的升高而增大.通过与HOCl和O_3氧化E1对比,在中性p H附近,KMnO_4氧化E1的二级反应动力学常数与HOCl相当,但远低于O_3.然而,实际水体中KMnO_4的除污染效能明显高于HOCl和O_3,主要是由于HOCl和O_3在实际水体中的消耗速度比较快,有效剩余浓度低,而KMnO_4在实际水体中的消耗速度比较慢.LC-MS/MS测定KMnO_4氧化降解E1产物的结果表明,KMnO_4易氧化进攻E1苯环上的活性位酚羟基,形成一系列羟基化、醌型、羧酸化芳香开环产物,并且有效降低其内分泌干扰活性.     

TiO2/ML-Ti3C2复合纳米材料的制备及其光催化性能

通过水热技术在二维(2D)多层材料Ti_3C_2 (multi-layer Ti_3C_2, ML-Ti_3C_2)的表面及层间原位晶化和生长锐钛矿相TiO_2纳米球,制备出TiO_2/ML-Ti_3C_2复合纳米材料。采用XRD、SEM、氮吸附等表征技术对TiO_2/ML-Ti_3C_2纳米复合材料进行分析表征,并以亚甲基蓝(MB)为模拟污染物,对纯TiO_2和TiO_2/ML-Ti_3C_2复合纳米材料的光催化性能进行了评价。实验结果表明,两种材料的耦合抑制了Ti O_2中光生电子-空穴对的湮灭,延长了复合光催化剂中载流子寿命,拓宽了复合材料的光谱响应范围。在紫外光照射下,以TiO_2/ML-Ti_3C_2复合纳米材料为光催化剂,200 mg/L的MB溶液在20 min内几乎完全脱色,降解率为98.98%。TiO_2/ML-Ti_3C_2纳米复合材料的光催化性能优于纯TiO_2和Ti_3C_2, Ti_3C_2优异的电子传输能力和超强的吸附性能优化了TiO_2的光催化性能。本研究为使用光催化技术处理废水提供了一种新的思路,具有一定的实际应用前景。     

CuO/Fe_3O_4活化过一硫酸盐降解RhB

以铁氰化钾、三水硝酸铜为前驱体,采用共沉淀法制得中间产物,将中间产物置于马弗炉煅烧,得到CuO/Fe_3O_4磁性纳米颗粒。利用X射线衍射仪、扫描电子显微镜、X-射线光电子能谱仪对催化剂进行物相、形貌和表面元素的表征。选择罗丹明B(RhB)等多种染料为目标污染物,建立的氧化体系在10 min内可以完全降解体系中的RhB(体系条件:30℃,CuO/Fe_3O_4 0.3 g/L,PMS 0.4 mmol/L,RhB 30μmol/L,初始pH=8.0)。实验结果表明制备的CuO/Fe_3O_4可以高效地活化过一硫酸盐降解RhB。     

不同煅烧温度对碳纳米管活化PMS降解四环素的性能研究

环境中大量监测出的四环素类抗生素对于生态系统和人类健康造成了严重的威胁,碳基催化剂活化过一硫酸盐（PMS）降解水中四环素的技术因其环境友好以及无二次污染而受到广泛关注,但其催化氧化效果有待提升。本文采用不同煅烧温度下的碳纳米管（CNTs）活化过一硫酸盐（PMS）降解水中四环素（TC）,同时考察了PMS浓度、CNT投加量以及初始pH值等反应条件对四环素降解的影响。结果表明,煅烧温度为950℃下处理的CNTs具有最佳的活化PMS的性能,且当初始pH为9、CNT投加量为0.4 g/L、PMS与TC的物质的量浓度比为20：1时TC达到最佳的讲解去除效果。     

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.     

磁性Fe3O4微球的溶剂热法合成及光芬顿性能优化

为探究Fe_3O_4微球的光芬顿性能,在200℃条件下,利用溶剂热法成功制备出具有较好分散性、平均粒径(200±0.5)nm的Fe_3O_4微球,并通过对其原料配比的探究进行样品优化.该合成方法所制备出的Fe_3O_4微球在Photo-Fenton降解亚甲基蓝方面有优秀的性能,降解率达95%甚至以上.此外,Fe_3O_4微球具有易回收的优点,仅利用磁场即可将其分离,且回收率超过85%甚至90%.利用回收后的Fe_3O_4微球探究其重复利用率,结果表明,重复利用过程中样品催化降解效率与第一次使用时几乎相同.本研究探究了该样品降解亚甲基蓝的最佳反应条件,其中当反应体系中加入15 mL过氧化氢且为酸性环境下降解效率达到最大.     

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     

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 Mg3(PO4)2-coated Li1.05Ni1/3Mn1/3Co1/3O2 cathode material for Li-ion battery

Mg₃(PO₄)₂-coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), charge/discharge cycling and differential scanning calorimeter (DSC). SEM analysis shows that Mg₃(PO₄)₂-coating changes the morphologies of their particles and increases the grains size. XRD and CV results show that Mg₃(PO₄)₂-coating powder is homogeneous and has better layered structure than the bare one. Mg₃(PO₄)₂-coating improved high rate discharge capacity and cycle-life performance. The reason why the cycling performance of Mg₃(PO₄)₂-coated sample at 55 °C was better than that of room temperature was the increasing of lithium-ion diffusion rate and charge transfer rate with temperature rising. Mg₃(PO₄)₂-coating improved the cathode thermal stability, and the result was consistent with thermal abuse tests using Li-ion cells: the Mg₃(PO₄)₂ coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode did not exhibit thermal runaway with smoke and explosion, in contrast to the cells containing the bare Li_1.05Ni_1/3Mn_1/3Co_1/3O₂. Funded by the National Natural Science Foundation of China (No. 20273047)     

Modification of LiCo1/3Ni1/3Mn1/3O2 cathode material by CeO2-coating

LiCo_1/3Ni_1/3Mn_1/3O₂ was coated by a layer of 1.0 wt% CeO₂ via sol-gel method. The bared and coated LiMn_1/3Co_1/3Ni_1/3O₂ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammogram (CV) and galvanotactic charge-discharge test. The results show that the coating layer has no effect on the crystal structure, only coating on the surface; the 1.0 wt% CeO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ exhibits better discharge capacity and cycling performance than the bared LiCo_1/3Ni_1/3Mn_1/3O₂. The discharge capacity of 1.0 wt% CeO₂-coated cathode is 182.5 mAh·g⁻¹ at a current density of 20 mA·g⁻¹, in contrast to 165.8 mAh·g⁻¹of the bared sample. The discharge capacity retention of 1.0 wt% CeO₂-coated sample after 12 cycles reaches 93.2%, in comparison with 86.6% of the bared sample. CV results show that the CeO₂ coating could suppress phase transitions and prevent the surface of cathode material from direct contact with the electrolyte, thus enhance the electrochemical performance of the coated material.     

Luminescent properties of BaO-La2O3-B2O3 glasses with dopant

The luminescent properties of glasses synthesized in air atmosphere by conventional high temperature process were stud{ed. The emissions spectra of Eu^2 and Eu^3 were observed in BaO-La2O3-B2O3-Eu2O3 glasses.The results show that the broad emission peaks at 430 nm correspond to 5d→4f emission transition of Eu^2 , the sharp emission peaks at 592, 616, 650 and 250 nm correspond to 5^D0→1Fj(j=1--4) emission transition of Eu^3 ,respectively, which indicates that the BaO-La2O3a-B2O3-Eu2O3 glass can convert ultraviolet and green omponents of sunlight into blue and red light so as to increase the intensity of blue and red light, respectively. The luminescent in--tensity of Eu^2 increases with increasing the molar ratio of Tb^3 in BaO-La2O3-B2O3-Eu2O3a-Tb4O3 glasses, whereas the luminescent intensity of Eua^3 decreases. So the luminescent intensity of Eu(Ⅲ,Ⅱ) is influenced by Tb^3 .These phenomena can be explained by electron transfer mechanism; Eu^3 (4f6) Tb^3 (4f^8)→Eu^2 (4f′) Tb^4 (4f′). Taking advantage of the luminescent properties of BaO-La2O3-B2O3-Eu2O3 glasses, light-conversion glass for agriculture can be produced.     

基于双金属MOFs 制备Co3O4/In2O3 复合物及其气敏性能的研究

以硝酸铟(In(NO₃)₃·xH₂O)、对苯二甲酸(H₂BDC)、六水合硝酸钴(Co(NO₃)· 6H₂O) 为原料, 首先采用一锅油浴法合成了含有Co²⁺ 的铟基金属有机框架材料(MOFs) Co²⁺/CPP-3(In) 材料, 然后在450 ℃ 下焙烧制备Co₃O₄/In₂O₃ 复合物气敏材料, 将Co₃O₄/In₂O₃ 复合物的粉体制作成传感器, 并对其气敏性能进行研究。利用扫描电子显微镜和X 射线衍射仪(XRD) 对双金属MOFs Co²⁺/CPP-3(In) 材料和Co₃O₄/In₂O₃ 复合物进行表征, 采用静态配气法测试其气敏性能。结果表明, Co₃O₄/In₂O₃(n_Co : n_In = 0.4 : 1) 样品的形貌保留了其MOFs 前驱体的棒状结构, 棱柱形框架更为突出, 表面呈凹陷状, 棒体中间粗两边细, 六角截面和棒体均布满了孔洞。结合EDX 和XRD 表征结果, Co²⁺/CPP-3(In) MOFs 前驱体完全转化成Co₃O₄/In₂O₃ 复合物; Co₃O₄/In₂O₃(n_Co : n_In = 0.4 : 1) 复合物在 70 ℃ 下对5×10^-6 H₂S 的气敏性能最优, 响应值达到153, 是同条件下纯备In₂O₃对H₂S 响应值的5 倍, 并且有较好的重复性、选择性和稳定性。     

氧空穴对二氧化钛/磷酸银光催化活性的影响机制

采用磷酸银与具有可见光吸收能力的TiO_2基光催化剂相复合的方法,对带有氧空穴的二氧化钛(TiO_2-OV)的复合磷酸银光催化材料的性能进行了研究.采用光处理法成功制备出了具有可见光吸收能力的氧空穴二氧化钛材料,利用化学吸附法成功制备出了磷酸银/氧空穴二氧化钛复合光催化剂.透射电镜结果显示,磷酸银纳米颗粒均匀分散于氧空穴二氧化钛表面,形成结构完美的复合光催化剂;光催化降解罗丹明B实验结果表明,所制备的磷酸银/氧空穴二氧化钛复合光催化剂的光催化活性明显优于磷酸银光催化材料.     

球形LiMn1.5Ni0.5O4材料的嵌脱动力学

为明晰Li Mn1.5Ni0.5O4正极材料的动力学性能,采用水热辅助共沉淀法合成了尖晶石Li Mn1.5Ni0.5O4正极材料,并采用扫描电镜(SEM)、X射线粉末衍射(XRD)和电化学阻抗(EIS)研究了材料的结构和锂离子嵌脱动力学.实验结果表明:共沉淀法制备的Li Ni0.5Mn1.5O4材料颗粒呈均匀球形,且平均粒径较小,粒度分布较窄.在循环过程中,Li Ni0.5Mn1.5O4的电荷转移电阻增大,锂离子扩散系数减小,进而电子电导率和离子电导率下降.温度升高后,Li Ni0.5Mn1.5O4材料的溶液电阻变化不大,但是电荷转移电阻逐渐增大,锂离子扩散系数逐渐减小;此外,随着温度的升高,Li Ni0.5Mn1.5O4材料的溶解速度加快,从而导致SEI膜的厚度增大.Li Ni0.5Mn1.5O4材料的嵌脱锂动力学与温度和循环次数有密切关系.     

Ferroelectric properties of Bi3.4Ho0.6Ti3O12 thin films prepared by sol-gel method

We have prepared the Ho-substituted bismuth titanate (Bi_3.4Ho_0.6Ti₃O₁₂, BHT) thin films on Pt/Ti/SiO₂/Si substrates using sol-gel method. The crystal structure and morphology of the films were characterized using X-ray diffraction and atomic force microscopy. The BHT film shows a single phase of Bi-layered Aurivillius structure and dense microstructure. The 2Pr and 2Ec of the 600-nm-thick BHT film were 38.4 μC/cm² and 376.1 kV/cm, respectively at applied electric field 500 kV/cm. The dielectric constant and dielectric loss are about 310 and 0.015 at a frequency of 1 MHz, respectively. The Pr value decreased to 93% of its pre-fatigue values after 4.46×10⁹ switching cycles at 1 MHz frenquency, and the BHT film shows good insulating behavior according to the test of leakage current. Supported by the Hubei Province Natural Science Foundation (Grant No. 2007ABA309)     

Preparation of LiFePO4 for lithium ion battery using Fe2P2O7 as precursor

In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy（SEM） were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the Cl space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0 μm. During the Li^＋ ion chemical intercalation, radical P2O7^4- is disrupted into two PO4^3- ions in the presence of O^2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.