碳化钨-石墨烯插层复合物的制备及作为甲醇氧化助催化剂的性能研究

直接甲醇燃料电池(DMFCs)作为一种环境友好、高效的新能源,对解决世界目前面临的“能源危机”与“环境危机”这两大问题有着至关重要的意义,具有较广阔的应用前景.目前,甲醇氧化催化剂仍然以 Pt基为主,但是 Pt价格昂贵,且容易受甲醇氧化中间产物的毒化,从而影响了 DMFCs的商业化进程.碳化钨(WC)作为非贵金属催化剂,在催化方面具有类铂的性能.在 WC上负载适量的 Pt,可以通过两者的协同效应加强催化剂的抗 CO中毒能力.但是,由于 WC的导电性能不佳,比表面积较小,因此寻找合适的载体显得尤为必要.在碳载体中,石墨烯(RGO)具有优良的导电性以及独特的片层结构,是电催化剂的理想载体.以 RGO为载体, WC为插层物质制备的 WC-RGO插层复合物具有化学稳定性好、电导率高且电化学活性面积大等优势.但是,由于石墨烯表面光滑且呈惰性,同时使用传统的碳化方法制备的碳化钨颗粒较大,因此,制备较小颗粒且分散均匀的 WC-RGO插层复合物具有较大难度.一般以偏钨酸铵和氧化石墨烯(GO)为前驱体制备 WC-RGO插层复合物,但是由于偏钨酸根和 GO都带负电,因此不能成功地将偏钨酸根引入到石墨烯的片层结构中,造成 WC-RGO插层复合物组装上的困难.本文采用硫脲成功地合成了具有高分散性 WC纳米颗粒插层在少层 RGO里的 WC-RGO插层复合物.硫脲((NH2)2CS)作为阴离子接受器,具有较强的结合阴离子形成稳定复合物的能力,同时它也是合成具有片层结构的过渡金属硫化物的原料之一.因此在 WC-RGO插层复合物组装过程中,硫脲既作为锚定及诱导剂,又是制备片层二硫化钨(WS2)的硫源.材料具体制备方法如下：首先利用浸渍法,将偏钨酸根阴离子([H2W12O40]6?)牵引到(NH2)2CS改性过的 GO上形成[H2W12O40]6?-(NH2)2CS-GO前驱体;然后将前驱体放入管式炉中还原碳化,前驱体先反应生成 WS2;由于 WS2自身的2D片层结构,反应中可以得到 WS2-RGO插层复合物,接着原位碳化生成 WC-RGO插层复合物.碳化钨-石墨烯负载铂电催化剂(Pt/WC-RGO)通过微波辅助法制得,并采用 X射线衍射、扫描电子显微镜、透射电子显微镜及激光拉曼光谱等手段对其结构与形貌进行了表征.结果显示,在 WC-RGO插层复合物中, WC的平均粒径为1.5 nm, RGO的层数约为5层.在甲醇电氧化反应中,相比于商用 Pt/C催化剂, Pt/WC-RGO插层复合物催化剂具有更高的电化学活性面积(ECSA)和较高的峰电流密度(246.1 m2/g Pt,1364.7 mA/mg Pt),分别是 Pt/C的3.66和4.77倍.我们分别利用 CO溶出伏安法、计时电流法及加速耐久性试验法验证了 Pt/WC-RGO催化剂优秀的抗 CO中毒能力及稳定性. Pt/WC-RGO催化剂特殊的插层结构,在增加 WC与 Pt接触机会以加强协同作用的同时,促进了催化过程中质量及电荷的转移,因而具有比 Pt/C更高的催化活性.可见,通过制备WC-RGO插层复合物可降低 Pt用量,从而大大地降低燃料电池中电催化剂的成本.同时,我们使用的是一种高效,可大批量生产纳米材料的方法,有助于催化剂的商业化.     

Independent Components Analysis of the Overlapping Voltammetric Signals

This paper introduces the Independent Components Analysis (ICA) to voltammetry and extends possibility of the qualitative and quantitative analysis of binary mixtures of similar oxidation/reduction potentials. It was demonstrated that even in the case of distance between peaks potentials equal to 10 mV, determinations may be realized according to typical validation criteria. The methodology was presented using the simulated data and capabilities and limitations of the method were described. Further, the usefulness of ICA was presented for voltammograms registered during simultaneous determination of copper and antimony, and thallium and indium. The results of high practical importance for chemical analysis were achieved and documented. In the quantitative analysis a property was extensively used, that ICA is an unsupervised method.     

Electronic properties of polyoxometalate derivatives [(C2B9H11) M'M5O18]n‐ (M' = TiIV,MoVI, WVI; M = MoVI,WVI): Protonation,Electronic Spectra,and Redox Properties

Density functional theory is used to study the electronic structures and properties of Lindqvist‐type polyoxometalates‐supported organometallic compounds [LM'M₅O₁₈]^n– (L = [C₂B₉H₁₁]^2– (Cb), [C₅H₅]^– (Cp); M' = Ti^IV, Mo^VI, W^VI; M = Mo^VI, W^VI). [(Cb)M'M₅O₁₈]^n– are a series of novel compounds designed in this work, based on related experiment. The calculated results reveal that the Cb ligand is able to form a σ, 2π triple bond with M', which is similar to the bond character in [(Cp)M'M₅O₁₈]^n–. However, comparing with the protonation, electronic spectra and redox properties of [(Cp)M'M₅O₁₈]^n– and [M'M₅O₁₉]^n–, [(Cb)M'M₅O₁₈]^n– species show the advantageous electronic properties owning to the superior electron donating ability of the Cb ligand. © 2015 Wiley Periodicals, Inc.     

木质纤维素催化转化制备能源平台化合物

可再生生物质资源的能源化利用能有效缓解能源短缺和环境恶化的双重压力。木质纤维素类生物质原料通过催化转化途径可以转化成为用途广泛的平台化合物,如呋喃类化合物、多元醇和有机酸及其酯类衍生物等。以这些平台化合物为原料,通过基元反应的转化可以制备高附加值的生物质基液体燃料。基于上述背景,本文概述了国内外木质纤维素通过不同催化转化途径制备各种新能源平台化合物的研究进展。目前木质纤维素制备新能源平台化合物的可行途径主要包括液体酸催化、固体酸催化、离子液体催化和多功能材料催化。在介绍这些催化途径的同时,重点讨论了所使用的催化剂,分析了仍然存在的问题和可能的解决措施,同时对今后该领域的研究前景进行了展望。     

3D-structured carbon-coated MnO/graphene nanocomposites with exceptional electrochemical performance for Li-ion battery anodes

MnO has a high theoretical capacity, moderate discharge plateau, and low polarization when it is used as the anode material in lithium battery. However, the issues that limit its application are its poor conductivity and large volume changes, which can easily result in the collapse of electrode structure during long-term cycling. In the present work, a carbon-coated MnO/graphene 3D-network anode material is synthesized by an electrostatic adsorption of dispersed precipitates precipitation method. The MnO nanoparticles coated by carbon are uniformly distributed on the surface of graphene nanosheets and form a 3D sandwich-like nanostructure. A carbon layer is coated on the surface of MnO nanoparticles, which slows down the volume expansion in the process of lithium intercalation. The graphene nanosheets are cross-linked through carbons in this 3D nanostructure, which provides mechanical support and effective electron conduction pathways during the charge-discharge. The electrochemical tests indicate that the prepared 3D carbon-coated MnO/graphene electrode exhibits an excellent rate capacity of 1247.3 and 713.2 mAh g^?1 at 100 and 1000 mA g^?1, respectively. The capacity is 792.2 mAh g^?1 after long cycle at a current density of 1000 mA g^?1. The specific capacity is higher than that of MnO-based composite lithium anode materials currently reported. The superior rate and cycling performances are attributed to the unique 3D-network structure, which provides an effectively conductive network, buffers volume expansion, and prevents falling and aggregation of MnO in the charge and discharge process of the electrode materials. The 3D-structured carbon-coated MnO/graphene anode material will have an excellent application prospect.

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Graphical abstract Cyclic performance at 1 A g^?1 and SEM images (inset) of the 3D-structured carbon-coated MnO/graphene nanocomposite.

     

多金属氧簇与倍半硅氧烷簇构筑的哑铃形杂化分子Langmuir膜和Langmuir-Blodgett膜

以两个形状杂化分子(Shape Hybrid Molecules)为目标分子, 研究了它们在气液界面上形成Langmuir膜的过程和Langmuir-Blodgett (LB)膜的聚集态结构. 杂化分子是由Wells-Dawson型磷钨氧簇(Polyoxometalates, POMs)和T₈型的倍半硅氧烷簇(Polyhedral Oligosilsesquioxane, POSS), 通过对苯二甲酸有机连接链(OL)用共价键构筑的具有杂化性质和哑铃形状的簇-簇杂化分子(POM-OL-POSS). 这两种杂化分子的差别在于POSS段中, 外围有机基团的尺寸不同. 在实验中, 采用Langmuir和LB膜技术, 了解POSS外围的七个取代基变化导致的分子尺寸变化对Langmuir膜形成过程和LB膜结构的影响. 采用Langmuir技术测定了表面压-平均分子面积(π-A)等温曲线和π-A循环等温曲线, 跟踪并研究了这两个杂化分子在水表面上形成Langmuir膜的过程. 实验结果表明, 两个杂化分子都表现出良好的两亲性, 从气相变化到固相的过程中, 杂化分子经历了从分散到集中的过程. 将这些膜转移到基片上, 得到单层的LB膜, 再利用原子力显微镜(AFM)和透射电子显微镜(TEM)研究了LB膜的表面形貌和聚集态结构. 由于POM段中含有钨和钒金属, 可以直接用TEM观察聚集态结构, 发现了在气-液和液-固相转变过程中, LB膜中杂化分子的聚集态结构都呈现涨落特征, 一种凝聚态物理中由相转变导致结构涨落的重要物理现象. 本研究获得的结果能够帮助我们以及这个领域的研究者们继续优化杂化分子的结构, 进一步构筑具有有序结构的膜和本体材料.     

一种基于SWNTs/Nafion/CuNPs纳米复合材料的

通过电沉积金属铜于SWNTs/Nafion修饰的玻碳电极表面构建了一种经济且简单易制备的非酶尿酸传感器.采用扫描电镜和能谱仪表征了纳米材料的形貌和成分,并考察了不同扫速和pH值对修饰电极的影响.在优化条件下,尿酸的线性范围为0.1～1000 μmol·L-1,检出限(S/N =3)为0.058 5iμmol·L-1.采用标准加入法检测人体血清中尿酸的回收率为97.2％～103.9％,相对标准偏差(RSD)为0.04％～0.11％.该非酶法与GOD-POD酶法的结果高度一致,且传感器经济易制备、灵敏性高、稳定性好、重现性高.     

One step synthesis of Fe4.4Ni17.6Se16 coupled NiSe foam as self-supported,highly efficient and durable oxygen evolution electrode

The development of cost-effective, durable and high-efficient oxygen evolution reaction (OER) electrocatalysts is an extremely critical technology for the large-scale industrial water electrolysis. Here, a new strategy is proposed to significantly enhance the electrocatalytic activity by forming a hybrid electrode of NiSe and Fe_4.4Ni_17.6Se₁₆ through direct selenization of porous iron-nickel (FeNi) alloy foam via thermal selenization process. The obtained self-supported Fe_4.4Ni_17.6Se₁₆/NiSe hybrid (FNS/NiSe) foam displays outstanding durability and remarkable catalytic activity in 1.0 M KOH with low overpotentials of 242 and 282 mV to achieve the current densities of 100 and 500 mA cm^?2, respectively. To the best of our knowledge, it exceeds most of the reported OER electrocatalysts in alkaline electrolytes.     

Solvent-Triggered Self-Folding of Hydrogel Sheets

Intense investigations have been attracted to the development of materials which can reconfigure into 3D structures in response to external stimuli. Herein we report on the design and self-folding behaviors of hydrogels composed of poly(ethylene glycol) methyl ether methacrylate (OEGMA) and 2-(2-methoxyethoxy) ethyl methacrylate (MEO\begin{document}$_{2}$\end{document}MA). Upon immersion into a variety of solvents at room temperature, the resulting P(MEO\begin{document}$_{2}$\end{document}MA-co-OEGMA) hydrogel sheets self-fold into 3D morphologies, and the observed transformation in shape is reversible. We further show that composition of the gel, gaseous environment, and preparation procedure play important roles in the self-folding behavior of the resulting hydrogels. This work provides a facile approach for fabricating self-folding hydrogels.     

二氢嘧啶并[4,5-d]嘧啶类衍生物作为集落刺激因子-1受体激酶抑制剂的分子对接和定量构效关系研究

集落刺激因子-1受体激酶（CSF-1R）属于Ⅲ型受体酪氨酸激酶家族成员,其在调控单核巨噬细胞系中发挥重要作用。CSF-1R及其配体异常表达与肿瘤发展过程密切相关。因此,CSF-1R信号传导可成为抗肿瘤治疗的有吸引力的靶标。本文用比较分子场分析法（CoMFA）和比较分子相似性指数分析法（CoMSIA）研究了54个二氢嘧啶并[4,5-d]嘧啶类CSF-1R激酶抑制剂的三维定量构效关系（3D-QSAR）。基于配体叠合,CoMFA和CoMSIA模型的交叉验证系数（q2）分别为0.725和0.636,拟合验证系数（r2）分别为0.960和0.958,结果表明这两种模型均具有较好的预测能力。所建模型的等势图能直观反映分子不同取代基对活性的影响,其中立体场和疏水场对活性的贡献较大。通过分子对接研究显示,氨基酸残基Cys666、Asp796在配体和受体结合过程中产生作用,分子对接的结合模式与3D-QSAR得到的结果一致。这些信息为进一步优化CSF-1R激酶抑制剂提供了理论基础。