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。     

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.     

Al18 B4O33Bi／AI复合材料室温阻尼和力学性能

为提高Al¹⁸ B⁴O³³ w/Al复合材料的室温阻尼性能,通过原位反应向复合材料的界面引入了低熔点金 属Bi.研究了涂层质量分数对涂覆后复合材料室温力学性能和阻尼性能的影响．结果表明,复合材料的力学 性能随着涂层质量分数的增加而降低;复合材料的阻尼性能则随涂覆量的增加而增加．涂覆复合材料的室温 阻尼值不仅强烈依赖于晶须表面涂覆物的质量分数而且依赖于应变振幅．涂覆复合材料在较低应变条件 (4×10_-4)下出现一个由位错机制产生的阻尼峰．当应变振幅超过6x10_-4,界面滑移成为主要的阻尼机制     

SO2浸出软锰矿体系连二硫酸锰的生成机制

副产物连二硫酸锰(MnS₂O₆)生成是限制废气二氧化硫还原浸出软锰矿副产硫酸锰工艺工业化应用的技术瓶颈和关键科学问题。迄今,MnS₂O₆的生成机制尚未明确,难以为探究其工艺控制措施提供有效理论依据。基于此,本文研究了SO₂浸出软锰矿体系MnS₂O₆的生成机制,阐明了MnS₂O₆生成速率控制步骤和动力学过程。首先基于反应体系理论分析,提出基于表面吸附和电化学模型的自由基生成机制可用于解释MnS₂O₆的生成机制,其生成速率微观上取决于自由基HSO₃形成速率,宏观上主要取决于体系H^₊和HSO- 3浓度,两者的反应级数均为1,推导的理论生成速率方程为 。随后通过动力学实验考察了体系SO₂浓度、pH和温度对MnS₂O₆生成的影响,研究结果表明,MnS₂O₆生成速率随体系酸度和温度的升高呈现先快速减小后趋势趋缓,随体系SO₂浓度的升高而升高,H^₊和SO₂浓度对MnS₂O₆生成速率的反应级数分别为-0.057和0.9954,反应的活化能为6894.05 J/mol。最后基于液相SO₂解离平衡关系,推导得到H^₊浓度和HSO- 3浓度对MnS₂O₆生成速率的反应级数分别为0.943和0.996,与理论速率方程的级数非常接近。研究结果验证了对MnS₂O₆生成机制的解释和动力学推导过程, 可为该工艺工业化应用时MnS₂O₆生成特性及抑制方法研究提供理论依据和有效途径。     

KMnO4/NaOH溶液吸收SO2/NO的动力学研究

在典型湿法烟气脱硫系统运行条件下,研究了平面传质搅拌反应器中KMnO₄/NaOH溶液同时吸收SO₂和NO的动力学,确定了反应级数、反应速率常数以及活化能.实验结果表明,NO的吸收速率随着入口NO分压和KMnO₄浓度的增加而提高.在吸收剂溶液中加入NaOH可以提高NO的吸收速率,烟气中O₂的体积分数对于NO和SO₂的吸收速率几乎没有影响.当同时吸收烟气中的SO₂和NO时,SO₂会降低NO的吸收速率,而NO对SO₂的吸收速率几乎没有影响.在KMnO4/NaOH溶液中NO的吸收速率对NO相间浓度和KMnO4浓度均为一级反应,平均反应速率常数为5.79×103 m³/(mol•s),活化能为26.85 kJ/mol.     

3A分子筛和Al2O3复合载体催化剂的催化特性

为探究3A分子筛和Al₂O₃复合载体催化剂的结构特征以及对甲苯的催化特性,采用等体积浸渍法制备Al₂O₃与3A分子筛不同掺混比的载体镍基催化剂,并对催化剂进行XRD、H₂-TPR、BET等特性分析,在固定床反应器中对催化剂催化甲苯的特性进行研究. 结果表明:催化剂中活性组分Ni主要以氧化镍NiO和镍铁合金Ni₃Fe的形式存在;Al₂O₃催化剂的比表面积和孔容随着Fe负载量的增加而减小,而不同掺混比催化剂的比表面积和孔容随着γ-Al₂O₃占比的增加而逐渐增大;甲苯的转化率随着反应温度的增加而逐渐增加,但是随着Fe负载量的增加而先增加后下降;对于不同掺混比的催化剂,随着γ-Al₂O₃占比的增加,催化剂的活性逐渐增强而后减弱,甲苯的转化率因此先增大后减小;当反应温度为700 ℃,水碳比为2,停留时间0.6 s,γ-Al₂O₃占比为60%时,甲苯转化率最高.     

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.     

第一性原理研究:Mg2+掺杂尖晶石型LiMn2O4的电子结构

尖晶石 LiMn₂O₄ 正极材料是在原有锂电池正极材料 LiCoO₂ 、LiNiO₂ 、LiMnO₂ 的基础上研发出来的优选 正极材料, 它相较于 LiCoO₂ 材料价格更加低廉热稳定性加强且安全性能有所提高。采用 Mg²⁺ 掺杂 LiMn₂O₄正极 材料, 利用基于密度泛函理论的第一性原理对 LiMg_0.5Mn_1.5O₄ 晶格常数与能带结构、态密度进行计算与分析。结 果表明: 新材料 LiMg_0.5Mn_1.5O₄ 的空间群为 F4332, 掺杂后晶胞参数 a 明显减小, 晶胞体积收缩; 掺杂量为 0.5 时明 显比掺杂量 0.125 时 Fermi 能量和能量密度高。Mg ²⁺ 掺杂能影响 LiMn₂O₄ 的晶体结构, 形成更加稳定的共价键。 掺杂量会改变 LiMn₂O₄ 的空间群影响到结构稳定性, 所以掺杂量不宜过大。     

Fe2O3对污泥与底泥制备轻质陶粒性能的影响

为研究在以污水污泥和河道底泥为主要原料制取轻质陶粒过程中,Fe₂O₃质量分数对陶粒性能的影响,对陶粒的物理性能、表面形态、抗压强度和晶体构成进行研究,结果表明,Fe₂O₃质量分数在3.5％～7％时,可取得松散容重和表观密度较高、吸水率比较小、抗压强度较高的陶粒．扫描电子显微镜(SEM)分析表明,随着Fe₂O₃质量分数的增加,陶粒表面玻璃化效果明显．在Fe₂O₃质量分数为5％时,可得到致密性较好、表面微孔分布均匀的陶粒．Fe₂O₃质量分数在3.5％～7％时,陶粒的抗压性能良好(14 MPa以上)．X射线衍射分析(XRD)表明,陶粒中主要晶体为石英、钠钙长石、蓝晶石和赤铁矿,内部以稳定的硅酸盐晶体为主．随着Fe₂O₃质量分数的增加,更多的Fe₂O₃可以在高温条件下转换为晶体结构的赤铁矿．在利用污水污泥与河道底泥制取轻质陶粒的过程中,控制Fe₂O₃质量分数在3.5％～7％较合适．     

球形Cu2O@HP-β -CD 合成、表征及类芬顿去除水中亚甲基蓝的研究

利用液相沉淀法制备 Cu₂O@HP-β-CD, 通过 XRD、SEM、FT-IR 对 Cu₂O@HP-β-CD 的结构进行表征, 并研究其对亚甲基蓝 (MB) 的类芬顿催化降解性能。XRD 图谱显示样品的衍射峰为纯 Cu₂O, HP-β-CD 与 Cu 摩尔比为 1 : 1 时样品 SEM 形貌为 500 nm, 大小均一的球形。Cu₂O@HP-β-CD 类芬顿体系降解 MB 的实验结果表明, 当HP-β-CD 与 Cu 摩尔比为 1 : 1, 加入浓度为 20 mmol/L 的 H₂O₂, 100 min 时 MB 去除率达到 96.1%。相同条件下, 液相法单一合成的 Cu₂O 的 MB 去除率为 54.4%; Cu₂O@HP-β-CD 的一级动力学反应速率常数为 0.027 76 min^?1 , 高于 Cu₂O 的反应速度常数 (0.007 4 min^?1)。Cu₂O@HP-β-CD 的自由基捕获实验表明了·OH 在催化降解过程中起主要作用。     

Ba3La2Ti2Ta2O15: A new microwave dielectric of A5B4O15-type cation-deficient perovskites

The synthesis, structure and properties of a new A5B4O15-type cation-deficient perovskite Ba3La2Ti2Ta2O15 were discribed. The compound was prepared by the conventional solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）. The results reveal that the compound is successfully synthesized. The compound crystallizes in the trigonal system with unit cell parameter a=5.6730（2） A, c=11.6511（2） A, V=324.93（1） A^3 and Z=1. The microwave dielectric properties of the ceramic are studied using a network analyzer, and it shows a high dielectric constant of 45.1, a high quality factors with Q×fof21 029 GHz, and a positive τf of 5.3 ppm℃^-1.     

Electrical conductivity of （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts

The effects of contents of AlF3 and Al2O3, and temperature on electrical conductivity of （Na3AlF6-40%K3AlF6）- AlF3-Al2O3 were studied by continuously varying cell censtant （CVCC） technique. The results show that the conductivities of melts increase with the increase of temperature, but by different extents. Every increasing 10 ℃ results in an increase of 1.85 × 10^-2, 1.86× 10^-2, 1.89 × 10^-2 and 2.20 × 10^-2 S/cm in conductivity for the （Na3AlF6-40%K3AlF6）-AlF3 melts containing 0%, 20%, 24%, and 30% AlF3, respectively. An increase of every 10 ℃ in temperature results an increase about 1.89× 10^-2, 1.94 × 10^-2, 1.95 × 10^-2, 1.99× 10^-2 and 2.10× 10^-2 S/cm for （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts containing 0%, 1%, 2%, 3% and 4% Al2O3, respectively. The activation energy of conductance was calculated based on Arrhenius equation. Every increasing 1% of AlF3 results in a decrease of 0.019 and 0.020 S/cm in conductivity for （Na3AlF6-40%K3AlF6）-AlF3 melts at 900 and 1 000 ℃, respectively. Every increase of 1% Al2O3 results in a decrease of 0.07 S/cm in conductivity for （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts. The activation energy of conductance increases with the increase in content of AlF3 and Al2O3.     

低介Ba(Al0.98Co0.02)2Si2O8-Ba5Si8O21基LTCC微波介质陶瓷的研究

采用传统固相反应法,按摩尔比合成0.7Ba(Al_0.98Co_0.02)₂Si₂O₈?0.3Ba₅Si₈O₂₁(BACS-BS)基陶瓷,分析Li₂O-B₂O₃(1wt%)(L-B)烧结助剂对其烧结特性、相组成和微波介电性能的影响,探讨0.7BACS-0.3BS+1wt%(L-B)陶瓷理论与实验介电常数(ε_r)的差异。结果表明:添加1wt%(L-B)烧结助剂能有效降低0.7BACS-0.3BS基陶瓷的烧结温度(950 ℃),但严重影响其微波介电性能;在950℃烧结的0.7Ba(Al_0.98Co_0.02)₂Si₂O₈-0.3Ba₅Si₈O₂₁+1wt%(Li₂O-B₂O₃)陶瓷具有较好的微波介电性能,其ε_r=7.56, Q×f=13 976 GHz, τ_f=?6.32 ppm/℃;0.7BACS-0.3BS+1wt%(L-B)复合陶瓷与Ag电极有很好的化学相容性,这为其在LTCC技术的应用奠定了良好的基础。     

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.     

Electrolysis expansion performance of semigraphitic cathode in [K3AlF6/Na3AlF6]-AlF3-Al2O3 bath system

The electrolysis expansion of semigraphitic cathode in [K₃AlF₆/Na₃AlF₆]-AlF₃-Al₂O₃ bath system was tested by self-made modified Rapoport apparatus. A mathematical model was introduced to discuss the effects of α _CR (cryolite ratio) and β _KR (elpasolite content divided by the total amount of elpasolite and sodium cryolite) on performance of cathode electrolysis expansion. The results show that K and Na (potassium and sodium) penetrate into the cathode together and have an obvious influence on the performance of cathode electrolysis expansion. The electrolysis expansion and K/Na penetration rate increase with the increase of α _CR. When α _CR=1.9 and β _KR=0.5, the electrolysis expansion is the highest, which is 3.95%; and when α _CR=1.4 and β _KR=0.1, the electrolysis expansion is the lowest, which is 1.28%. But the effect of β _KR is correlative with α _CR. When α _CR=1.6 and 1.9, with the increase of β _KR, the electrolysis expansion and K/Na penetration rate increase. However, when α _CR=1.4, the electrolysis expansion and K/Na penetration rate firstly increase and then decrease with the increase of β _KR. Foundation item: Project (2005CB623703) supported by the Major State Basic Research and Development Program of China; Project (2008AA030502) supported by the National High-Tech Research and Development Program of China     

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.     

Ca0.9Ce0.1Ti0.8Al0.2SiO5在水热作用下的化学稳定性

通过固相法合成掺铈榍石固溶体(Ca0.9 Ce0.1Ti0.8Al0.2SiO5),采用PCT粉末浸泡试验法,借助X射线衍射(XRD)、扫描电镜(SEM)、电感耦合等离子体发射光谱(ICP-OES)等分析测试手段,研究掺铈榍石固溶体在热液作用下的稳定性.实验结果表明,掺铈榍石固化体在不同条件下(温度150～ 200℃,0.476～1.554 MPa,pH值5～9),都具有良好的稳定性.随着浸泡时间的增加,各元素的归一化浸出率逐渐降低并保持在较低水平.     

Preparation and electrical-magnetic properties of Co0.6Cu0.16Ni0.24Fe2O4/MWCNTs composites

Co0.6Cu0.16Ni0.24Fe2O4/multi-walled carbon nanotube nanocomposites (CCNF/MWCNTs) were synthesized by solution filling method.The phase structure,thermal stability,morphology and electrical-magnetic properties of the samples were characterized by means of modern testing technology.The effect of iron concentration,filling time,sintering temperature on their electrical and magnetic performance was discussed.The results indicated that conductivity was related to the content of MWCNTs,while the magnetism correlated with the volume fraction of the filled CCNF in the composites.When the optimal condition satisfied the filling time of 18 h,ferric concentration of 0.25 mol L-1 and sintering temperature of 350°C,the prepared composite had the best magnetic loss performance,and its minimum reflection loss reached-22.47 dB on 9.76 GHz,the available bandwidth was beyond 2.0 GHz.Hence,the obtained composite can be used as advancing absorption and shielding material due to its favorable microwave absorbing property.