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51.
Menggang Li Zhonghong Xia Yarong Huang Lu Tao Yuguang Chao Kun Yin Wenxiu Yang Weiwei Yang Yongsheng Yu Shaojun Guo 《物理化学学报》2020,36(9):1912049-0
Direct methanol fuel cells (DMFCs), as one of the important energy conversion devices, are of great interest in the fields of energy, catalysis and materials. However, the application of DMFCs is presently challenged because of the limited activity and durability of cathode catalysts as well as the poisoning issues caused by methanol permeation to the cathode during operation. Herein, we report a new class of Rh-doped PdCu nanoparticles (NPs) with ordered intermetallic structure for enhancing the activity and durability of the cathode for oxygen reduction reaction (ORR) and achieving superior methanol tolerance. The disordered Rh-doped PdCu NPs can be prepared via a simple wet-chemical method, followed by annealing to convert it to ordered phases. The results of transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), power X-ray diffraction (PXRD) analysis and high resolution TEM (HRTEM) successfully demonstrate the formation of near-spherical NPs with an average size of 6.5 ± 0.5 nm and the conversion of the phase structure. The complete phase transition temperatures of Rh-doped PdCu NPs and PdCu are 500 and 400 ℃, respectively. The molar ratio of Rh/Pd/Cu in the as-synthesized Rh-doped PdCu NPs is 5/48/47. Benefitting from Rh doping and the presence of the ordered intermetallic structure, the Rh-doped PdCu intermetallic electrocatalyst achieves the maximum ORR mass activity of 0.96 A·mg-1 at 0.9 V versus reversible hydrogen electrode (RHE) under alkaline conditions—a 7.4-fold enhancement compared to the commercial Pt/C catalyst. For different electrocatalysts, the ORR activities follow the sequence, ordered Rh-doped PdCu intermetallics > ordered PdCu intermetallics > disordered Rh-doped PdCu NPs > disordered PdCu NPs > commercial Pt/C catalyst. In addition, the distinct structure endows the Rh-doped PdCu intermetallics with highly stable ORR durability with unaltered half-wave potential (E1/2) and mass activity after continuous 20000 cycles, which are higher than those of other electrocatalysts. Furthermore, the E1/2 of the Rh-doped PdCu intermetallics decreases by only 5 mV after adding 0.5 mol·L-1 methanol to the electrolyte, while the commercial Pt/C catalyst negatively shifts by 235 mV and a distinct oxidation peak can be observed. The results indicate that the ORR activity of the Rh-doped PdCu intermetallic electrocatalyst can be well maintained even in the presence of poisoning environment. Our results have demonstrated that Rh-doped PdCu NPs with ordered intermetallic structures is a potential electrocatalyst toward the next-generation high-performance DMFCs. 相似文献
52.
The actual structure of the vanadium phosphate K6(VO)2(V2O3)2(PO4)4(P2O7) has been determined, using a much larger single crystal than previously used for the isostructural Rb-phase. The actual supercell is four times larger than the corresponding orthorhombic subcell with , , , α=β=γ=90°. The structure resolution, performed in the triclinic space group C-1, shows that the P2O7 groups alone are responsible for the superstructure, all the other atoms keeping the atomic positions of the orthorhombic subcell. This structural study shows a perfect ordering of the P2O7 groups in the actual structure, in contrast to the results obtained from the subcell. Concomitantly, the V4+ and V5+ are found to be ordered in the form of [110] stripes. 相似文献
53.
采用溶剂挥发自组装结合提拉法,在石墨纤维表面制备有序介孔碳(Ordered mesoporous cabon,OMC)涂层,并开展其对水中氯苯类有机污染物的固相微萃取(SPME)测定.扫描电镜(SEM)结果显示,制备的OMC涂层完整,与基体结合紧密,厚度约为7μm.透射电镜(TEM)、X射线衍射(XRD)和氮吸附脱附结果证实,OMC涂层具有规整二维六方特征,比表面积和孔容分别为369.7 m2/g和0.28 cm3/g.以氯苯类污染物为分析对象,采用顶空固相微萃取与氢火焰气相色谱联用法对OMC涂层的萃取性能进行全面的评价,优化萃取时间和温度、解吸时间、搅拌速率、离子强度及顶空体积等萃取条件,并与商品化涂层进行比对.结果表明,最佳萃取条件为:萃取时间30 min,萃取温度50℃,脱附时间2 min,盐浓度0.35 g/mL,顶空体积15 mL.在最佳萃取条件下,检出限在0.05~0.15 μg/L之间;在1~1000 μg/L线性范围内,线性关系良好;7次平行样测定的相对标准偏差为4.1% ~6.4%.制备的OMC涂层的峰面积是商用聚二甲基硅氧烷/二乙烯基苯(Polydimethylsiloxane/divinylbenzene,PDMS/DVB)涂层的2倍,商用聚丙烯酸酯(Polyacrylate,PA)涂层的18倍.将此涂层应用于两种实际水样中,4种氯苯均未检出,添加浓度为20 μg/L时,样品回收率分别为99.4%~114.5%和92.3%~ 97.0%. 相似文献
54.
利用水热法合成得到有序介孔二氧化硅( OMS),采用X射线衍射、N2吸附-脱附、透射电镜等技术对其进行了表征。制备OMS修饰碳糊电极( OMS/CPE),采用循环伏安和交流阻抗技术考察了修饰电极的电化学性能,发现与裸碳糊电极(CPE)相比,OMS/CPE具有更大的电活性面积和更快的电子传导速率。研究了L-色氨酸(L-Trp)在表面活性剂十二烷基磺酸钠(SDS)存在下,在OMS/CPE上的电化学行为和动力学性质,结果表明,OMS和SDS具有良好的协同作用,能明显增加L-Trp的响应信号; SDS存在下,L-Trp在修饰电极上的电化学氧化是2电子和2质子参加的不可逆过程,电极过程受吸附控制。优化了表面活性剂浓度、富集时间、富集电位、介质 pH 值等测定参数,在最优条件下, L-Trp 氧化峰电流与其浓度在8.0×10-8~4.0×10-6 mol/L范围内呈良好线性关系,检出限为7.0×10-8 mol/L(S/N=3)。本方法用于氨基酸口服液样品的加标回收检测,回收率为99.6%~102.6%。 相似文献
55.
One of fluorinated polyimides was synthesized from 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 3,3′-dimethyl-4,4′-diaminodiphenylmethane (DMMDA) by two-steps method, which had good solubility and hydrophilicity. 6FDA-DMMDA polyimide was dissolved in chloroform (CHCl3) and cast on a glass substrate in a humid atmosphere. It was found that 6FDA-DMMDA/CHCl3 solution was easy to form ordered porous structure at high concentration, and the reason was discussed in detail. In addition, the influences of solution concentration, the atmosphere humidity, were also tested. 相似文献
56.
57.
Hong-yu Li Zhi-qiang Chen Hai-qiao Wang Bo Meng Xiao-yu Li 《高分子科学》2007,(2):217-220
Ordered macroporous titania photonic crystals (PCs) and photonic balls were fabricated by functional modified polymer colloidal crystals. The TiO2 PCs and balls formed through this method exhibit no cracks and lacunae in large areas on their surface and their inner structures. 相似文献
58.
Jijun Qiu Weidong Yu Xiangdong Gao Xiaomin Li 《Journal of Sol-Gel Science and Technology》2007,44(3):235-239
Ordered porous TiO2 films, including TiO2 nanotube arrays, are fabricated by a sol-gel dip-coating approach via ZnO nanorod templates obtained from aqueous solution
approach. The results indicate that the morphologies of ordered porous TiO2 films have been great affected by the sol-gel dip-coating cycle number. Open-ended TiO2 nanotube arrays can be obtained in optimum dip-coating cycle numbers. The TiO2 nanotubes with the inner diameter matching well with the diameters of ZnO nanorods, are well assembled and separate each
other. When the cycle number is less than this optimum value, no intact porous TiO2 film can be obtained. As the cycle number is larger than this optimum value, an ordered porous TiO2 film with many throughout holes is formed. The evolutive mechanism of ordered porous TiO2 films is proposed. 相似文献
59.
Emilie Barriau Holger Frey Anton Kiry Manfred Stamm Franziska Gröhn 《Colloid and polymer science》2006,284(11):1293-1301
The preparation of carboxylated hyperbranched polyglycerols of narrow polydispersity was achieved by modification (78–90%) of the hydroxyl end groups via Michael addition of acrylonitrile, followed by hydrolysis. High conversion could only be achieved for low molecular weight starting materials (520 and 1,030 g mol−1). The solution properties of the resulting materials were investigated by dynamic light scattering (DLS), showing the formation of large aggregates with size depending on the pH value. After deposition on a negatively charged mica surface, the structures observed by atomic force microscope (AFM) show the coexistence of aggregates and single macromolecules. Most interesting, in the case of the lower molecular weight sample (PG 520 g mol−1), extended and ordered terrace structures were formed, which are unprecedented for hyperbranched polymers and are of interest for surface modification in general. 相似文献
60.
Luis Rodríguez-Marín 《Journal of Mathematical Analysis and Applications》2008,342(1):371-385
This article deals with derivatives for set-valued maps that take values in ordered vector spaces, in particular it concerns about the relationship between the epiderivatives of a set-valued map and its associated map of infima. When the image space is a real separable Hilbert space ordered by an orthonormal basis, by using a variational technique based on a decoupling of the ordering cone into half-spaces, we show that both epiderivatives coincide under certain hypothesis of compactness and stability. Furthermore we obtain some computation formulas for these derivatives in terms of associated scalar set-valued maps. 相似文献