Ultrasonic radiation to enable improvement of direct methanol fuel cell

To improve DMFC (direct methanol fuel cell) performance, a new method using ultrasonic radiation is proposed and a novel DMFC structure is designed and fabricated in the present paper. Three ultrasonic transducers (piezoelectric transducer, PZT) are integrated in the flow field plate to form the ultrasonic field in the liquid fuel. Ultrasonic frequency, acoustic power, and methanol concentration have been considered as variables in the experiments. With the help of ultrasonic radiation, the maximum output power and limiting current of cell can be independently increased by 30.73% and 40.54%, respectively. The best performance of DMFC is obtained at the condition of ultrasonic radiation (30 kHz and 4 W) fed with 2 M methanol solution, because both its limiting current and output power reach their maximum value simultaneously (222 mA and 33.6 mW, respectively) under this condition. These results conclude that ultrasonic can be an alternative choice for improving the cell performance, and can facilitate a guideline for the optimization of DMFC.     

隔膜式电解槽生物膜阴极降解苯酚的过程及其条件的优化

以炼油废水中的主要污染物苯酚为目标污染物, 采用不同生物膜电极反应器对苯酚进行降解, 从而寻找出降解苯酚的最佳反应途径. 研究结果表明, 运用隔膜式电解槽生物膜阴极区域对苯酚废水进行处理, 其苯酚的去除效果虽然没有在生物膜阴极与阳极相混合的混合式反应器中处理效果好, 但在18 h内苯酚浓度降解到0, 并且其化学需氧量(COD)去除率最高, 在16 h内COD去除率达到80%. 对于隔膜式电解槽生物膜阴极区域的降解条件优化后发现, 电流设定为5 mA, 初始苯酚质量浓度低于200 mg/L, 温度为35 ℃时, 苯酚降解效果最佳.     

荧光探针法研究铜离子-姜黄素体系中1O2的反应机理及在O2·-存在下1O2的测定

以1,3-二苯基异苯并呋喃(1,3-Diphenylisobenzofuran, DPBF)为荧光探针, 研究了姜黄素(Curcumin, CUR)在铜离子催化下产生的单线态氧(1O2), 其反应机理为姜黄素与溶液中的氧分子快速作用产生O2·-和H2O2等活性氧物种, 同时Cu2+与姜黄素形成复合物, 再与H2O2形成过氧化物过渡态, 过氧化物进一步与H2O2发生类Haber-Weiss反应生成1O2, 且只有Cu2+和Cu+离子可催化姜黄素并产生1O2. 1O2在1.37×10-8～3.66×10-7 mol/L浓度范围内与荧光强度下降值ΔIF有良好的线性关系, 检出限为4.12×10-9 mol/L.     

氧弹燃烧-离子色谱法测定煤中氯含量

建立了氧弹燃烧-离子色谱测定煤中氯含量的方法.在加有(NH4)2CO3溶液和过量氧气的氧弹中燃烧煤样,释放的氯被(NH4)2CO3溶液吸收,过滤溶液后, 采用离子色谱外标法测定滤液中氯的浓度,最后计算出煤中氯的含量.色谱工作条件:淋洗液为1.8 mmol/L Na2CO3与1.7 mmol/L NaHCO3混合液,流速1 mL/min;再生液为40 mmol/L H2SO4,流速0.5 mL/min;进样量20 μL.色谱标准工作曲线线性相关系数0.9996;10次测定1 mg/L Cl-标准溶液的均值为1.0012 mg/L,相对标准偏差为1.34%;8个煤样加标回收率为90.7%～104.3%;测定标准物质GBW11119 及GBW11120的相对误差分别为1.75%和1.36%;对比研究显示,氧弹燃烧-离子色谱测定8个煤样(除两个煤样外)氯含量结果远高于艾士卡剂混合熔样-离子色谱测定结果,表明艾士卡剂混合熔样过程由于煤样未处于完全密闭状态导致部分氯的散失.     

甲烷在清洁 Pd(111) 及氧改性的 Pd(111) 表面解离的密度泛函理论研究

 采用广义梯度近似 (GGA) 的密度泛函理论 (DFT) 并结合平板模型, 研究了 CH4 在清洁 Pd(111) 及 O 改性的 Pd(111) 表面发生 C朒 键断裂的反应历程. 优化了裂解过程中反应物、过渡态和产物的几何构型, 获得了反应路径上各物种的吸附能及反应的活化能. 结果表明, CH4 采用一个 H 原子指向表面的构型在 Pd(111) 表面的顶位吸附, CH3 的最稳定的吸附位置为顶位, OH, O 和 H 的最稳定吸附位置均为面心立方. CH4 在清洁 Pd(111) 表面裂解的活化能为 0.97 eV, 低于它在 O 原子改性 (O 没有参与反应) 的 Pd(111) 表面的活化能 1.42 eV, 说明表面氧原子抑制了 CH4 中 C朒 键的断裂. 当亚表面 O 原子和表面 O 原子 (O 参与反应) 共同存在时, C朒 键断裂的活化能为 0.72 eV, 低于只有表层氧存在时的活化能 (1.43 eV), 说明亚表面的 O 原子对 CH4 分子的活化具有促进作用. CH4 在 O 原子改性的 Pd(111) 表面裂解生成 CH3 和 H, 以及生成 CH3 和 OH 的反应活化能分别为 1.42 和 1.43 eV, 说明 CH4 在 O 原子改性的 Pd(111) 表面发生这两种反应的难易程度相当.     

Immobilization of porphyrins in poly(hydroxymethylsiloxane)

Three tetracationic porphyrins differing in the position of charged nitrogen atoms on the peripheral substituents — 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP4), 5,10,15,20-tetrakis(N-methylpyridinium-2-yl)porphyrin (TMPyP2), 5,10,15,20-tetrakis(4-trimethylammoniophenyl) porphyrin (TMAPP), and hydrophobic 5,10,15,20-tetraphenylporphyrin (TPP), were immobilized by adsorption and encapsulation in poly(hydroxymethylsiloxane) (PHOMS). The so prepared porphyrin-PHOMS composites were characterized by porosimetry, scanning electron microscopy, fluorescence and diffuse reflectance UV-VIS spectroscopy. It was found that porphyrins are immobilized in the PHOMS matrix in the free base monomer form Their irradiation produced singlet oxygen O₂(¹Δ_g) with the lifetime of 10–30 μs.     

绿色氧化合成苯乙酮的研究

研究了以氧气为氧化剂、液相氧化乙苯合成苯乙酮反应的各种影响因素,在优化的反应条件(冰乙酸20mL、乙苯5mL、醋酸钴用量为乙苯的4.2%(物质的量)、Br/Co=2.5(物质的量)、氧气流速为100mL/min、常压、温度80℃和反应时间4h)下,乙苯转化率达到99.94%,苯乙酮收率达到98.49%.     

Enhanced Catalytic Activity and Unexpected Products from the Oxidation of Cyclohexene by Organic Nanoparticles of 5,10,15,20‐Tetrakis‐(2,3,4,5,6‐pentafluorophenyl)porphyrinatoiron(III) in Water by Using O2

The catalytic oxidation of alkenes by most iron porphyrins using a variety of oxygen sources, but generally not dioxygen, yields the epoxide with minor quantities of other products. The turnover numbers for these catalysts are modest, ranging from a few hundred to a few thousand depending on the porphyrin structure, axial ligands, and other reaction conditions. Halogenation of substituents increases the activity of the metalloporphyrin catalyst and/or makes it more robust to oxidative degradation. Oxidation of cyclohexene by 5,10,15,20‐tetrakis‐(2,3,4,5,6‐pentafluorophenyl)porphyrinato iron(III), ([Fe^III(tppf₂₀)]) and H₂O₂ is typical of the latter: the epoxide is 99 % of the product and turnover numbers are about 350. 1 – 4 Herein, we report that dynamic organic nanoparticles (ONPs) of [Fe^III(tppf₂₀)] with a diameter of 10 nm, formed by host–guest solvent methods, catalytically oxidize cyclohexene with O₂ to yield only 2‐cyclohexene‐1‐one and 2‐cyclohexene‐1‐ol with approximately 10‐fold greater turnover numbers compared to the non‐aggregated metalloporphyrin in acetonitrile/methanol. These ONPs facilitate a greener reaction because the reaction solvent is 89 % water and O₂ is the oxidant in place of synthetic oxygen sources. This reactivity is unexpected because the metalloporphyrins are in close proximity and oxidative degradation of the catalyst should be enhanced, thus causing a significant decrease in catalytic turnovers. The allylic products suggest a different oxidative mechanism compared to that of the solvated metalloporphyrins. These results illustrate the unique properties of some ONPs relative to the component molecules or those attached to supports.     

复合金属氧化物Sn-Sb-Mn/陶瓷粒子电极体系的电催化性能

通过热分解法制备了复合金属氧化物Sn-Sb-Mn/陶瓷粒子电极, 分别采用扫描电子显微镜(SEM)、能量色散X 射线能谱(EDS)、X射线衍射(XRD)和N2吸附-脱附等技术对电极的形貌、晶相组成、比表面积和孔径分布进行了表征. 考察了该三维粒子电极系统的析氧特性, 采用循环伏安法分析了三维系统的电催化性能, 并且进行了电化学催化降解苯酚的试验. 结果表明, 制备的陶瓷粒子电极涂层比表面较大、孔结构发达, 有利于电催化反应; 电催化降解主要发生在电化学析氧区; 粒子电极系统对苯酚降解作用显著, 明显高于二维电极系统, 苯酚的去除率为92.3%, 总有机碳(TOC)的去除率为66.7%. 研究结果表明, 该三维粒子电极系统具有优良的电催化性能.     

CeZrYLaO对Fe基整体式稀薄甲烷催化燃烧性能的影响

采用共沉淀法制备了高性能低铈储氧材料Ce_0.35Zr_0.55Y_0.07La_0.03O_1.95(OSM,储氧材料)和胶溶法制备了耐高温、高比表面的La-Al₂O₃并以它们为载体,制备了一系列整体式铁基催化剂。考察了该系列催化剂对甲烷稀薄燃烧的催化性能,并用低温N₂吸附-脱附,储氧能力(oxygen storage capacity,OSC),XRD,XPS和H₂-TPR等测试手段对载体和催化剂进行了表征。活性测试结果表明所制得的整体式催化剂Fe/OSM+La-Al₂O₃可在50 000 h^-1的高空速条件下使含量为1%的甲烷在474 ℃起燃,565 ℃完全转化;低温氮吸附-脱附测试结果表明,所制得的Ce_0.35Zr_0.55Y_0.07La_0.03O_1.95经1 050 ℃焙烧5 h后的BET比表面积达33 m²·g^-1,孔容为0.14 mL·g^-1;La-Al₂O₃经1 050 ℃焙烧5 h后的BET比表面积达125 m²·g^-1,孔容为0.46 mL·g^-1,是优良的催化剂载体;OSC测试结果表明,加入储氧材料(oxygen storage material(OSM))能增加催化剂的储氧性能,有利于催化活性的提高;XRD测试结果表明,OSM以均一固溶体存在;XPS测试结果表明,Fe₂O₃与OSM载体之间的相互作用最强;H₂-TPR测试结果表明,加入OSM能增加催化剂的还原性能,从而提高了催化活性。