Co3O4催化臭氧氧化降解水中酮基布洛芬的研究

以Co(NO₃)₂·6H₂O和尿素为原料制备了9种Co₃O₄催化材料，考察了其对水中酮基布洛芬(KTP)的催化臭氧氧化降解效能。结果表明，与单独臭氧氧化相比，所制备的Co₃O₄对水中KTP的催化臭氧氧化降解率提高了12.0%～63.8%，且在n[Co(NO₃)₂·6H₂O]:n(尿素)=4:1、煅烧温度400℃下制备得到的Co₃O₄催化剂催化活性最高。SEM、XRD、FTIR、XPS、BET等表征分析显示，该Co₃O₄催化剂表面呈覆盖细小微粒的球状颗粒，晶相为立方相，且表面含有丰富的羟基，表面羟基密度为1.075×10^-5 mol/m²。机理研究证实，Co₃O₄对水中KTP的非均相催化臭氧氧化降解...     

Co3O4-MMT催化剂的制备及其N2O催化分解性能

以MMT为载体，采用原位聚合-配位沉积法制备3种不同Co负载量的Co₃O₄-MMT催化剂。采用N₂物理吸附、XRD和TEM对载体和催化剂进行表征，并在连续流动微反装置上考察其N₂O催化分解性能。结果表明，与Co₃O₄催化剂相比，Co₃O₄-MMT催化剂的比表面积显著增大，且活性组分Co₃O₄具有较高的分散状态。Co₃O₄-MMT催化剂的催化活性随着Co含量的增加先升后降，其中0.015Co-MMT表现出最佳的催化活性，其活性远高于Co₃O₄催化剂，同时，该催化剂还表现出良好的催化稳定性和较好的杂质气体耐受性。     

BiVO4/Bi2Fe4O9的制备及光降解有机废水性能的研究

采用水热法制备具有高效可见光催化性能的BiVO₄/Bi₂Fe₄O₉复合光催化剂,通过SEM、XRD等一系列表征手段对样品进行了形貌和结构的表征。最后通过在一定的条件下降解目标污染物亚甲基蓝(MB)溶液对催化剂的光催化性能进行了探究。结果表明：BiVO₄以100～500 nm颗粒状形态均匀的修饰在片状Bi₂Fe₄O₉的表面。当BiVO₄的修饰量为15%时,光催化剂在可见光下对MB溶液的降解效率最高,高达51.92%。通过对照实验发现BiVO₄/Bi₂Fe₄O₉的催化效率比Bi₂Fe₄O₉单体高了4.45倍,比BiVO₄单体高了1.29倍。另外,根据实验结果对BiVO₄/Bi₂F...     

不同形貌氧化钴活化过一硫酸盐降解硝基酚

通过控制形貌制备具有高活性晶面的金属氧化物可提高硝基酚的降解效果,以硝酸钴和乙酸钴为原料,制备了八面体、立方块和棒状Co₃O₄,通过X射线衍射（XRD）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）对催化剂进行表征,表明合成的Co₃O₄粒径均匀、纯度较高。以3种不同形貌的Co₃O₄为催化剂,在pH值为8.0条件下活化过一硫酸盐（PMS）降解不同种类的硝基酚,采用高效液相色谱和总有机碳分析仪测定反应前后硝基酚和总有机碳含量（TOC）变化。3种Co₃O₄在Co₃O₄/PMS体系降解硝基酚时表现出不同的催化活性：棒状Co₃O₄ > 立方块Co₃O₄ > 八面体Co₃O₄,并且对不同硝基酚的降解效率存在显著的差异性。3种Co₃O₄在pH值为8.0下活化PMS所析出的Co²⁺含量较低,且均表现出良好的循环利用性。自由基淬灭实验和电子自旋共振（ESR）测试表明Co₃O₄/PMS体系降解硝基酚是通过自由基和非自由基机制共同协作完成的,起作用的活性氧化物种主要为羟基自由基（·OH）、硫酸根自由基（SO₄^·-）和单线态氧（¹O₂）。     

Fe2O3/CoFe2O4复合光催化剂的制备及性能研究

本文以硝酸钴和氯化铁为主要原料制备了Fe₂O₃∕CoFe₂O₄复合光催化材料。利用X射线衍射仪(XRD)和紫外-可见吸收光谱(UV-VIS)对样品的结构和光吸收性能进行了表征。并在可见光照射下,通过催化降解罗丹明B(RHB)溶液考察各催化材料的催化效果。结果表明,制备的复合催化材料是以CoFe₂O₄为主的面心立方尖晶石结构。在反应时间为8.5 h、反应温度为135℃和煅烧温度为500℃时,制备的Fe₂O₃复合量为3%的复合催化剂性能最好,光催化降解2 h后,罗丹明B降解率可达到96.62%。     

ZIF-67衍生Co3O4/g-C3N4复合材料光催化降解盐酸四环素废水的研究

将ZIF-67与g-C₃N₄按一定质量比复合制备Co₃O₄/g-C₃N₄复合光催化材料,并以此来提高Co₃O₄的光催化性能。利用XRD、SEM和FT-IR对复合材料结构、性能和元素分布进行表征。结果表明,当盐酸四环素(TC-HCl)质量浓度为3 mg/L、质量分数为3%的Co₃O₄/g-C₃N₄投加量为15 mg且pH为中性时,催化剂光催化性能最佳,90 min降解盐酸四环素效率达到了91.1%。3%Co₃O₄/g-C₃N₄复合光催化剂重复使用5次后,其降解率仍可达到88.5%,表明该材料具有一定的光催化稳定性和重复利用性。体系自由基捕获实验证明,产生了·O^-₂、h⁺、·OH...     

Co3O4/HY选择性催化苯甲醇氧化合成苯甲醛的研究

以HY分子筛为载体,采用水热法合成了系列Co₃O₄/HY复合分子筛催化剂,通过XRD、SEM、EDS、FT-IR、BET等手段对Co₃O₄/HY进行表征,并对Co₃O₄/HY分子筛催化氧气液相氧化苯甲醇合成苯甲醛的性能进行研究。结果表明,Co₃O₄的引入未破坏分子筛的骨架结构,且Co₃O₄在HY晶体表面形成片层蜂窝状多孔结构,可有效增加催化剂样品的介孔孔容和外表面积,增加催化活性。但Co₃O₄负载过量易出现堆叠现象,使得介孔孔容和外表面积降低,不利于氧化反应进行。以1.0-Co₃O₄/HY为催化剂,在适宜的反应条件下苯甲醇的转化率和苯甲醛的选择性分别达到73.2%和95.8%;催化剂重复使用5次,依然表现出较好的催化活性。     

Co3O4镀银对BH4-水解的抑制及在DBFC中的应用

硼氢化物水解是导致直接硼氢化物燃料电池（DBFC）燃料效率下降的主要问题之一。将Co₃O₄用于DBFC阳极催化剂并通过镀银处理以降低水解反应。以CoCl₂·6H₂O为原料制备Co₃O₄，并通过银镜反应对其进行镀银处理，制得Co₃O₄@Ag。通过X射线衍射（XRD）、扫描电子显微镜（SEM）和能谱（EDS）对其进行物理表征，通过交流阻抗（EIS）、计时电流（CA）和电池测试对其电化学性能进行表征。结果表明，利用银镜反应成功地将Ag引入到催化剂体系，且Co₃O₄@Ag催化材料的含银量为2%。电化学测试表明，与Co₃O₄相比Co₃O₄@Ag具有更高的电催化活性。以Co₃O₄@Ag为阳极催化剂组装的燃料电池在室温下最大功率密度（55 mW·cm^-2）和比容量（971 mA·h·g^-1）较Co₃O₄分别提高了44.7%和32.1%，阳极催化剂性能得到显著提高。Ag在抑制水解反应的同时与Co₃O₄体现了协同催化的作用。     

Co3O4/4A分子筛活化PMS处理高盐AO7废水研究

采用浸渍-焙烧法制备Co₃O₄/4A分子筛复合催化剂,用于活化过一硫酸盐（PMS）处理高盐酸性橙7（AO7）废水。采用扫描电镜、X-射线衍射仪、红外光谱仪等对复合催化剂进行表征,同时考察其稳定性。考察复合催化剂活化PMS对AO7模拟废水的处理效果,结果表明,当Co₃O₄/4A分子筛投加量为0.2 g/L、PMS投加量为0.7 mmol/L、pH为9时,高盐（Na₂SO₄,10 g/L）废水中AO7浓度可在20 min内由15 mg/L左右降至接近0,去除率达99%以上,同时催化剂钴离子溶出量约为0.36 mg/L,低于《地表水环境质量标准》（GB3838-2002）中规定的1 000μg/L。     

ZIF-67及其母液衍生Co3O4催化氨硼烷水解制氢

采用常规液相沉淀反应合成了沸石咪唑酯金属有机骨架化合物ZIF-67,并对母液进行浓缩结晶以回收钴基化合物。通过高温焙烧的方式将ZIF-67及其母液转化为2种Co₃O₄(记作Co₃O₄-S和Co₃O₄-L)作为氨硼烷水解的催化剂前驱体。考察了反应液中氨硼烷浓度、催化剂浓度和反应温度对体系产氢速率的影响,并进行动力学分析。结果表明:Co₃O₄-S为多孔多面体结构而Co₃O₄-L为纳米颗粒;增加反应液中氨硼烷浓度和催化剂浓度有助于提升体系的产氢速率;经4次循环使用后,Co₃O₄-S催化产氢速率无衰减,Co₃O₄-L催化产氢速率为初始值的78%。     

Phase diagram of the Al2O3-HfO2-Y2O3 system

The phase diagram of the Al₂O₃-HfO₂-Y₂O₃ system was first constructed in the temperature range 1200-2800 °C. The phase transformations in the system are completed in eutectic reactions. No ternary compounds or regions of appreciable solid solution were found in the components or binaries in this system. Four new ternary and three new quasibinary eutectics were found. The minimum melting temperature is 1755 °C and it corresponds to the ternary eutectic Al₂O₃ + HfO₂ + Y₃Al₅O₁₂. The solidus surface projection, the schematic of the alloy crystallization path and the vertical sections present the complete phase diagram of the Al₂O₃-HfO₂-Y₂O₃ system.     

A bi-layered composite cathode of La0.8Sr0.2MnO3-YSZ and La0.8Sr0.2MnO3-La0.4Ce0.6O1.8 for IT-SOFCs

A bi-layered composite cathode of La_0.8Sr_0.2MnO₃ (LSM)-YSZ and LSM-La_0.4Ce_0.6O_1.8 (LDC) was fabricated for anode-supported solid oxide fuel cells with a thin YSZ electrolyte film. The cell with the bi-layered composite cathode displayed better performance than the cell with the corresponding single-layered composite cathode of LSM-LDC or LSM-YSZ. At 650 °C, the cell with the bi-layered composite cathode gave a higher maximum power density than the cells with the single-layered LSM-LDC and LSM-YSZ composite cathodes, by 52% and 175%, respectively. The impedance spectra results show that the thin LSM-YSZ interlayer not only improves the cathode/electrolyte interface but also reduces the polarization resistance of the cathode. The activation energy for oxygen reduction on the bi-layered composite cathode is much smaller than that on LSM-YSZ composite cathode, and it is suggested that the special redox property of Ce⁴⁺/Ce³⁺ in LDC facilitates the oxygen reduction process on the bi-layered composite cathode. The cell with the bi-layered composite cathode operated quite stably during a 100 h run.     

Investigation of hydrogen transport through Mm(Ni3.6Co0.7Mn0.4Al0.3)1.12 and Zr0.65Ti0.35Ni1.2V0.4Mn0.4 hydride electrodes by analysis of anodic current transient

Hydrogen transport through such metal-hydride electrodes as Mm(Ni_3.6Co_0.7Mn_0.4Al_0.3)_1.12 and Zr_0.65Ti_0.35Ni_1.2V_0.4Mn_0.4 was investigated in 6 M KOH solution by using potentiostatic current transient technique. From the shape of the anodic current transient and the dependence of the initial current density on the discharging potential, the boundary conditions at the electrode surface were established during hydrogen extraction from the as-annealed and as-surface-treated electrodes. Especially, it was experimentally confirmed that the diffusion-limited boundary condition is no longer valid at the electrode surface during hydrogen transport in case hydrogen diffusion is coupled with either the interfacial charge transfer reaction or the hydrogen transfer reaction between adsorbed state on the electrode surface and absorbed state at the electrode sub-surface. From the transition behaviour of the boundary condition, it was further recognised that the boundary condition at the electrode surface during hydrogen transport is not fixed at the specific electrode/electrolyte system by itself, but it is rather simultaneously determined even at any electrode/electrolyte system by the potential step and the nature of the electrode surface, depending upon e.g. the presence or absence of the surface oxide scales.     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Effect of HfO2 content on the microstructure and piezoelectric properties of (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃–xHfO₂ [BNBT–xHfO₂] lead-free ceramics were prepared using the conventional solid-state reaction method. Effects of HfO₂ content on their microstructures and electrical properties were systematically studied. A pure perovskite phase was observed in all the ceramics with x=0–0.07 wt%. Adding optimum HfO₂ content can induce dense microstructures and improve their piezoelectric properties, and a high depolarization temperature was also obtained. The ceramics with x=0.03 wt% possess optimum electrical properties (i.e., d₃₃~168 pC/N, k_p~32.1%, Q_m~130, ε_r~715, tan δ~0.026, and T_d~106 °C, showing that HfO₂-modified BNBT ceramics are promising materials for piezoelectric applications.     

Mixed oxides Ca2Fe2O5 and Ca2Co2O5 as anode materials for Li-ion batteries

The electrochemical performance of mixed oxides, Ca₂Fe₂O₅ and Ca₂Co₂O₅ for use in Li-ion batteries was studied with Li as the counter electrode. The compounds were prepared and characterized by X-ray diffraction and SEM. Ca₂Fe₂O₅ showed a reversible capacity of 226 mAh/g at the 14th cycle and retained 183 mAh/g at the end of 50 cycles at 60 mA/g in the voltage window 0.005-2.5 V. A reversible capacity in the range, 365-380 mAh/g, which is stable up to 50 charge-discharge cycles is exhibited by Ca₂Co₂O₅ in the voltage window, 0.005-3.0 V and at 60 mA/g. This corresponds to recycleable moles of Li of 3.9±0.1 (theoretical: 4.0). Significant improvement in the cycling performance and attainable reversible capacity were noted for Ca₂Co₂O₅ on cycling to an upper cut-off voltage of 3.0 V as compared to 2.5 V. Coulombic efficiency for both compounds is >98%. Electrochemical impedance spectroscopy (EIS) data clearly indicate the reversible formation/decomposition of polymeric surface film on the electrode surface of Ca₂Co₂O₅ in the voltage window, 0.005-3.0 V. Cyclic voltammetry results compliment the galvanostatic cycling data.     

Synthesis of Bi0.5(Na0.7K0.2Li0.1)0.5TiO3 powders through the molten salt method

The Bi_0.5(Na_0.7K_0.2Li_0.1)_0.5TiO₃ powder synthesis through molten salt method was investigated in the temperature range of 650–700 °C for 2–4 h. The XRD results indicated that the optimal synthesizing temperature for molten salt method was 700 °C, significantly lower than that for conventional processing route of solid state reaction method, where a calcining temperature of 850 °C was needed. The SEM results revealed better crystallization of the powders obtained through molten salt method, compared with those through the conventional processing route of solid state reaction method.     

Comparison of AlPO4- and Co3(PO4)2-coated LiNi0.8Co0.2O2 cathode materials for Li-ion battery

Electrochemical and thermal properties of Co₃(PO₄)₂- and AlPO₄-coated LiNi_0.8Co_0.2O₂ cathode materials were compared. AlPO₄-coated LiNi_0.8Co_0.2O₂ cathodes exhibited an original specific capacity of 170.8 mAh g⁻¹ and had a capacity retention (89.1% of its initial capacity) between 4.35 and 3.0 V after 60 cycles at 150 mA g⁻¹. Co₃(PO₄)₂-coated LiNi_0.8Co_0.2O₂ cathodes exhibited an original specific capacity of 177.6 mAh g⁻¹ and excellent capacity retention (91.8% of its initial capacity), which was attributed to a lithium-reactive Co₃(PO₄)₂ coating. The Co₃(PO₄)₂ coating material could react with LiOH and Li₂CO₃ impurities during annealing to form an olivine Li_xCoPO₄ phase on the bulk surface, which minimized any side reactions with electrolytes and the dissolution of Ni⁴⁺ ions compared to the AlPO₄-coated cathode. Differential scanning calorimetry results showed Co₃(PO₄)₂-coated LiNi_0.8Co_0.2O₂ cathode material had a much improved onset temperature of the oxygen evolution of about 218 °C, and a much lower amount of exothermic-heat release compared to the AlPO₄-coated sample.     

Chemical zoning of calcium aluminoferrite formed during melt crystallization in CaO-SiO2-Al2O3-Fe2O3 pseudoquaternary system

In the CaO-SiO₂-Al₂O₃-Fe₂O₃ pseudoquaternary system, the solid solutions of Ca₂(Al_xFe_1−x)₂O₅, with x<0.7 (ferrite), Ca₂SiO₄ (belite), Ca₃Al₂O₆ (C₃A) and Ca₁₂Al₁₄O₃₃ (C₁₂A₇), were crystallized out of a complete melt during cooling at 8.3 °C/min. Upon cooling to 1370 °C, both the crystals of ferrite with x=0.41 and belite would start to nucleate from the melt. During further cooling, the x value of the precipitating ferrite would progressively increase and eventually approach 0.7. At ambient temperature, the ferrite crystals had a zonal structure, the x value of which successively increased from the cores toward the rims. The value of 0.45 was confirmed for the cores by EPMA. The chemical formula of the rims was determined to be Ca_2.03[Al_1.27Fe_0.68Si_0.02]_Σ1.97O₅ (x=0.65). As the crystallization of ferrite and belite proceeded, the coexisting melt would become progressively enriched in the aluminate components. After the termination of the ferrite crystallization, the C₃A and belite would immediately crystallize out of the melt, followed by the nucleation of C₁₂A₇. The C₁₂A₇ accommodated about 2.1 mass% Fe₂O₃ in the chemical formula Ca_12.03[Al_13.61Fe_0.37]_Σ13.98O₃₃, being free from the other foreign oxides (SiO₂ and P₂O₅).     

Synthesis of LiNi0.9Co0.1O2 from Li2CO3, NiO or NiCO3, and CoCO3 or Co3O4 and their electrochemical properties

Cathode active materials with a composition of LiNi_0.9Co_0.1O₂ were synthesized by a solid-state reaction method at 850 °C using Li₂CO₃, NiO or NiCO₃, and CoCO₃ or Co₃O₄, as the sources of Li, Ni, and Co, respectively. Electrochemical properties, structure, and microstructure of the synthesized LiNi_0.9Co_0.1O₂ samples were analyzed. The curves of voltage vs. x in Li_xNi_0.9Co_0.1O₂ for the first charge–discharge and the intercalated and deintercalated Li quantity Δx were studied. The destruction of unstable 3b sites and phase transitions were discussed from the first and second charge–discharge curves of voltage vs. x in Li_xNi_0.9Co_0.1O₂. The LiNi_0.9Co_0.1O₂ sample synthesized from Li₂CO₃, NiO, and Co₃O₄ had the largest first discharge capacity (151 mA h/g), with a discharge capacity deterioration rate of −0.8 mA h/g/cycle (that is, a discharge capacity increasing 0.8 mA h/g per cycle).