高分散Fe-N-C氧还原反应电催化剂及其在直接甲醇燃料电池中的应用

氧还原反应(ORR)是燃料电池和金属空气电池等洁净发电装置中阴极的主要反应,该反应动力学过程慢,电化学极化严重. Pt基电催化剂具有较好的ORR活性,然而Pt资源有限、价格昂贵,研制高活性、低成本的代Pt电催化剂意义重大.经过几十年的探索,研究者发现将含有C, N和Fe等元素的前体进行高温热处理得到的Fe-N-C电催化剂对ORR具有良好的活性,然而在高温热解过程中Fe容易发生聚集而形成大块颗粒,导致Fe的利用率不高,影响了电催化剂的ORR活性.
　　本文分别以聚吡咯和乙二胺四乙酸二钠(EDTA-2Na)为C和N的前驱体,利用高温热解形成的富含微孔的碳材料对铁前体的吸附及锚定作用,获得了一种Fe高度分散的Fe-N-C电催化剂.采用物理吸脱附技术、高分辨透射电镜(HRTEM)和扫描电镜对Fe-N-C及其制备过程中相关电催化剂的孔结构及表面形貌进行了表征.结果表明,在第一步热解过程中, EDTA-2Na的Na对碳材料起到了活化作用,形成富含微孔的N掺杂碳材料(N-C-1),其BET比表面积达到1227 m2/g,孔径约1.1 nm.在第二步热解过程中, N-C-1有效地抑制了Fe的聚集,产物Fe-N-C中的Fe元素均匀地分布在碳材料中,其比表面积高达1501 m2/g.
　　电化学测试结果表明,在碱性介质(0.1 mol/L NaOH)中, Fe-N-C电催化剂对ORR具有良好的催化活性, ORR起始电位(Eo)为1.08 V (vs. RHE),半波电位(E1/2)0.88 V,电子转移数n接近4, H2O2产率<3%,与商品20%Pt/C(Johnson Matthey)接近.电化学加速老化测试结果表明, Fe-N-C的E1/2未发生明显变化,而Pt的负移45 mV,表明Fe-N-C具有很好的稳定性;在酸性介质(0.1 mol/L HClO4)中, Fe-N-C的Eo为0.85 V, E1/2为0.75 V,其E1/2比Pt/C负移约0.15 V,表明在酸性介质中Fe-N-C对ORR的催化活性还有待提高.采用TEM、X射线衍射、X射线光电子能谱以及穆斯堡尔谱等方法研究了电催化剂构效关系.结果表明, Fe-N-C较好的ORR活性主要来自于高分散的Fe-N4结构,此外, N(吡啶N和石墨N)掺杂的C也对反应具有一定的催化活性.
　　与Pt/C相比, Fe-N-C电催化剂具有很好的耐甲醇性能.本文对比了Fe-N-C和Pt/C作为阴极催化剂的直接醇类燃料电池(DMFC)性能,采用质子交换膜的DMFC最大功率密度分别为47(Fe-N-C)和79 mW/cm2(Pt/C),而采用碱性电解质膜的则分别为33(Fe-N-C)和8 mW/cm2(Pt/C).结合半电池结果表明, Fe-N-C电催化剂在碱性介质中具有比Pt更为优秀的催化活性和稳定性,有望用作DMFC阴极代Pt催化剂.     

Electrocatalytic activity of porous nanostructured Fe/Pt-Fe electrode for methanol electrooxidation in alkaline media

An electrochemical approach to fabricate a nanostructured Fe/Pt-Fe catalyst through electrodepo-sition followed by galvanic replacement is presented. An Fe/Pt-Fe nanostructured electrode was prepared by deposition of Fe-Zn onto a Fe electrode surface, followed by replacement of the Zn by Pt at open-circuit potential in a Pt-containing alkaline solution. Scanning electron microscopy and energy-dispersive X-ray techniques reveal that the Fe/Pt-Fe electrode is porous and contains Pt. The electrocatalytic activity of the Fe/Pt-Fe electrode for oxidation of methanol was examined by cyclic voltammetry and chronoamperometry. The electrooxidation current on the Fe/Pt-Fe catalyst is much higher than that on flat Pt and smooth Fe catalysts. The onset potential and peak potential on the Fe/Pt-Fe catalyst are more negative than those on flat Pt and smooth Fe electrodes for methanol electrooxidation. All results show that this nanostructured Fe/Pt-Fe electrode is very attractive for integrated fuel cell applications in alkaline media.     

二次纳流电喷雾电离耦合超高分辨质谱检测人体呼出气中相对高分子量化合物

二次电喷雾电离源耦合超高分辨质谱(SESI-UHRMS)有望检出人体呼出气中分子量大于300的相对高分子量化合物,这些化合物的发现将有助于更准确地理解呼出气中挥发性有机化合物(VOCs)的来源、产生机制以及SESI源电离机理,更好地实现SESI-UHRMS的转化应用.本研究自组装nanoSESI源(尚无商业产品)耦合四极杆-静电场轨道阱质谱(最高质量分辨率1.2×10~5),考察了该装置对健康人体呼出气中分子量为300~500化合物的检出情况.结果表明,所搭建的nanoSESI-UHRMS装置检测人体呼出气的重现性好、灵敏度高,可检出数十种分子量为300~500的化合物.根据这些化合物在单次呼气过程中信号强度随时间变化的趋势,推断其来源分别为内源性和外源性;各化合物的元素组成主要包括C,H,N和O,环-双键当量(RDB)的均值为(4.5±3.1),表明检出的化合物可能为醛酮或不饱和脂肪酸,容易在SESI源中被电离.本研究初步验证了自组建nanoSESI-UHRMS检测人体呼出气中相对高分子量化合物的可行性,为后续进一步开展方法应用奠定了基础.     

共面闭合断续节理岩体直剪强度特性研究

介绍了节理面和岩桥各自的抗剪强度机制,引入法向变形协调条件,基于Mohr-Coulomb理论,推导了共面闭合断续节理岩体的直剪强度公式。模型试验发现,剪切破坏面以拉剪复合破坏为主,同时岩块中伴随大量的拉张微裂隙。试样的强度和变形具有明显的阶段性,全应力应变曲线主要经历了线弹性增长、节理面错动、次生裂纹起裂稳态扩展、节理面贯通破坏和残余强度5个阶段。对比发现,理论计算结果与试验值吻合较好。     

三种类型汽车的能耗和使用成本的建模研究

本文对电动,传统,混合动力三种类型汽车的能耗和使用成本问题进行了建模、求解及分析．首先定义了电动汽车的能量利用率ηE。根据能量守恒将所有电量转换成汽油消耗量,而传统车型则直接反映到汽油的消耗上,混合动力汽车则综合电动汽车和传统汽车的能耗模型,从而统一能耗水平评价标准．这样,我们就得到了三种不同类型车的能耗模型再进行模型求解以此来分析比较三种类型车哪一种节能效果好．对电动汽车来说,使用成本主要包括驾驶维护成本、报废处理成本,而对传统汽车来说,使用成本主要包括驾驶维护成本、报废处理成本、环境成本和其他成本,混合动力汽车则结合二者使用成本．因此,根据不同车型使用成本类型建立相应的数学模型,按照建立的公式,可以得到电动汽车的使用成本LCC1、传统汽车的使用成本LCC2和混合动力汽车的使用成本LCC3,从而进行模型求解．     

常温直接沉淀法制备ZnO纳米棒

在常温下, 以PEG-400(聚乙二醇400)为表面活性剂, 采用直接沉淀法合成了ZnO纳米棒. 产物用XRD, TEM, SAED和 HRTEM等进行了表征. 结果表明, 所得ZnO为一维的纳米棒, 属于六方纤维矿的单晶结构. ZnO纳米棒的直径在20~40 nm之间, 长度在300~800 nm范围. (0001)面为ZnO纳米棒的生长方向. 讨论了ZnO相的生成和ZnO纳米棒的形成机理以及PEG-400在其形成过程中的作用.     

基于膜盘菌属的两种系统发育研究方法的比较研究

以rDNA ITS1-5.8S-ITS2序列作为分子标记,采用直接优化和常规分析两种方法,探讨膜盘菌属内种间及其与相关属间的亲缘关系,并比较了两种建树方法在解决该属内种间关系的效果。以Lachnum spartinae为外群,选取31条序列构建了最小进化树、最大简约树和直接优化树。结果表明,Hymenoscyphus ericae复合种与其他膜盘菌属的成员关系较远,除了H.ericae外,其他膜盘菌形成一个单系群。模式种Hymenoscyphus fructigenus与H.caudatus,H.fucatus,H.scutulus等构成一个高支持率的分支,与另一分支(H.epiphyllus,H.lasiopodium)形成姐妹群。相对于常规的两步分析法,直接优化所产生的系统树与当前形态学特征基本相符合,因而更合理地反映膜盘菌属的分类地位和种间关系,表明该分析方法在真菌系统发育分析中具有较大的应用价值。     

Determination of direct orange 8 in effluent using a polypyrrole modified electrode

Electrochemical studies of direct orange 8 were carried out with a bare glassy carbon electrode (GCE) and a polypyrrole-coated GCE in aqueous acetonitrile medium using voltammetric techniques. One reversible couple around 0.3?V due to the redox reaction of the phenol group, one reduction peak around ?0.4?V due to reduction of the azo group and one oxidation peak around 1.0?V due to oxidation of the amino group were observed. Chronocoulometric studies revealed dye adsorption on the GCE. A square-wave stripping method was developed for the determination of the dye at pH 13.0, and a linear calibration equation obtained. The reproducibility in the measurement of peak currents was confirmed from the RSD value 2.8% at 0.001?mg?mL^?1 concentration. A comparison of the stripping voltammetric method with the UV-Vis spectrophotometric method was made. The determination limits are wider and the RSD value is lower in the stripping voltammetric method. The concentration of the dye present in dye effluent was determined using this method.     

The impact of stochastic lead time reduction on inventory cost under order crossover

We use exponential lead times to demonstrate that reducing mean lead time has a secondary reduction of the variance due to order crossover. The net effect is that of reducing the inventory cost, and if the reduction in inventory cost overrides the investment in lead time reduction, then the lead time reduction strategy would be tenable.We define lead time reduction as the process of decreasing lead time at an increased cost. To date, decreasing lead times has been confined to deterministic instances. We examine the case where lead times are exponential, for when lead times are stochastic, deliveries are subject to order crossover, so that we must consider effective lead times rather than the actual lead times. The result is that the variance of these lead times is less than the variance of the original replenishment lead times.Here we present a two-stage procedure for reducing the mean and variance for exponentially distributed lead times. We assume that the lead time is made of one or several components and is the time between when the need of a replenishment order is determined to the time of receipt.     

Direct amperometric determination of tert-butylhydroquinone in biodiesel

The direct amperometric determination of tert-butylhydroquinone (TBHQ) in biodiesel at an unmodified glassy carbon electrode is reported. A biodiesel aliquot was added into an electrochemical cell containing a 75% (v/v) ethanol-water solution under stirring (with final concentration of 50 mmol L⁻¹ HClO₄). The amperometric method involved the continuous application of three sequential potential pulses to the working electrode (700 mV for 300 ms, 0 mV for 100 ms and −50 mV for 1 s). TBHQ was continuously monitored at the first (direct oxidation) and optionally at the second (reduction) potential pulse while the third potential pulse was applied for cleaning of the electrode surface. For comparison, the samples were also analyzed by high-performance liquid-chromatography and a good agreement between the results was verified. Recovery values for spiked samples were between 90% and 95% and the reproducibility of the proposed method was around 5% (n = 5). The proposed method can be easily adapted for on-site analysis.