Effect of Manganese Valence on Specific Capacitance in Supercapacitors of Manganese Oxide Microspheres

Manganese oxides have attracted great interest in electrochemical energy storage due to high theoretical specific capacitance and abundant valence states. The multiple valence states in the redox reactions are beneficial for enhancing the electrochemical properties. Herein, three manganese microspheres were prepared by a one-pot hydrothermal method and subsequent calcination at different temperatures using carbon spheres as templates. The trivalent manganese of Mn₂O₃ exhibited multiple redox transitions of Mn³⁺/Mn²⁺ and Mn⁴⁺/Mn³⁺ during the intercalation/deintercalation of electrolyte ions. The possible redox reactions of Mn₂O₃ were proposed based on the cyclic voltammetry and differential pulse voltammogram results. Mn₂O₃ microsphere integrated the advantages of multiple redox couples and unique structure, demonstrating a high specific capacitance and long cycling stability. The symmetric Mn₂O₃//Mn₂O₃ device yielded a maximum energy density of 29.3 Wh kg⁻¹ at 250 W kg⁻¹.     

Controlling domain orientation of liquid crystalline block copolymer in thin films through tuning mesogenic chemical structures

Controlling the macroscopic orientation of nanoscale periodic structures of amphiphilic liquid crystalline block copolymers (LC BCPs) is important to a variety of technical applications (e.g., lithium conducting polymer electrolytes). To study LC BCP domain orientation, a series of LC BCPs containing a poly(ethylene oxide) (PEO) block as a conventional hydrophilic coil block and LC blocks containing azobenzene mesogens is designed and synthesized. LC ordering in thin films of the BCP leads to the formation of highly ordered, microphase‐separated nanostructures, with hexagonally arranged PEO cylinders. Substitution on the tail of the azobenzene mesogen is shown to control the orientation of the PEO cylinders. When the substitution on the mesogenic tails is an alkyl chain, the PEO cylinders have a perpendicular orientation to the substrate surface, provided the thin film is above a critical thickness value. In contrast, when the substitution on the mesogenic tails has an ether group the PEO cylinders assemble parallel to the substrate surface regardless of the film thickness value. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 532–541     

Properties of In situ polymerized poly(3,4‐ethylenedioxythiophene)/alumina composites for energy storage applications

Composites formed by poly(3,4‐ethylenedioxythiophene) and alumina (PEDOT/Al₂O₃) have been prepared by in situ anodic polymerization. For this purpose, the stability of 1:1 and 4:1 monomer:alumina aqueous solutions has been examined as a function of the pH (2.3, 4.0, 7.0, 8.8, or 10.8). Results indicate that the monomer behaves as a dispersant that remains stable at the studied basic pHs despite they are close to the isoelectric point of alumina. Although the thermal stability of the composites is considerably affected by the pH of the reaction medium, its influence on the surface morphology is very small. Independently, of the synthetic conditions, the electrochemical properties were better for PEDOT/Al₂O₃ than for pure PEDOT, reflecting that alumina particles promote the charge mobility. The highest specific capacitance (SC; 141 F/g), which was 55% higher than that obtained for pure PEDOT, was achieved for the composite prepared at pH = 8.8 using a 4:1 monomer:alumina ratio. These conditions favor the participation of OH^– groups as secondary doping agents without degrading the polymer matrix and enhance the specific surface of the films, facilitating the ionic mobility. On the other hand, application of a multi‐step polymerization strategy has shown that interfaces originated by consecutive steps enhance the SC. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1131–1141     

In situ PM‐IRRAS studies of organothiols and organosilane monolayers–ZnO interfaces at high water activities

In situ photoelastic‐modulated Fourier transform infrared reflection absorption spectroscopy has been applied for the investigation of interfacial stability of organothiol and organosilane monolayer films on nanocrystalline zinc oxide thin films. It has been shown that for octadecyltriethoxysilane films, exposure to high water activities results in physisorption of water in the cross‐linked film. This high water activity at the interface leads to a reversible wet de‐adhesion of the interfacial silanol groups from the ZnO surface. However, the organothiol seems to form a denser monolayer and a stable by S–Zn bond that is resistant to the competition with adsorbed water. The reversible attachment for cross‐linked organosilanol films has been demonstrated for the first time by means of an in situ spectroscopic method on model ZnO surfaces. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation of different graphene nanostructures for hydrogen adsorption

In this study, different types of graphene were synthesized to investigate hydrogen adsorption capacity at different pressures (0–34 bar) at room temperature (298 K). Graphene and nanoporous graphene were prepared by Chemical Vapor Deposition (CVD) method, using methane as a carbon source at a temperature of 900 °C over copper plates and nickel oxide nanocatalyst. The nickel oxide nanocatalyst was prepared by sol–gel method, whereas graphene oxide was prepared through modified Hummer's method. The products were characterized by X‐ray diffraction, field emission‐scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller and Raman spectroscopy. The adsorption of hydrogen was done by volumetric method. High adsorption capacity was achieved in nanoporous graphene because of its high pore volume (2.11 cm³/g) and large specific surface area (850 m²/g). Hydrogen adsorption values for nanoporous graphene, graphene and graphene oxide were determined as 2.56, 1.70 and 0.74 wt%, respectively. In addition, the hydrogen adsorption of graphene nanostructures fitted nicely to the selected two‐parameter and three‐parameter adsorption isotherm models. The adsorption isotherm model coefficients have been found for a 0–34 bar pressure range. The parameter values for all adsorbents showed proper conformity to the model and experimental data. Copyright © 2016 John Wiley & Sons, Ltd.     

Electrical,optical, and structural characterization of p‐type N‐doped SnO thin films prepared by thermal oxidation of sputtered SnNx thin films

We present a study of electrical and optical properties of nitrogen‐doped tin oxide thin films deposited on glass by the DC Magnetron Sputtering method. The deposition conditions to obtain p‐type thin films were a relative partial pressure between 7% and 11% (N₂ and/or O₂), a total working pressure of 1.8 mTorr and a plasma power of 30 W. The deposited thin films were oxidized after annealing at 250°C for 30 minutes. X‐ray diffraction results showed that the as‐deposited thin films exhibit a Sn tetragonal structure, and after annealing, they showed SnO tetragonal structure. X‐ray photoelectron spectroscopy results showed the presence of nitrogen in the samples before and after annealing. The measured physical parameters of the thin films were optical band gap between 1.92 and 2.68 eV, resistivity between 0.52 and 5.46 Ωcm, a concentration of p‐type carriers between 10¹⁸ and 10¹⁹ cm^?3, and a Hall mobility between 0.1 and 1.94 cm²V^?1s^?1. These thin films were used to fabricate p‐type thin film transistors.     

Helical Mesoporous Tantalum Oxide Nanotubes: Formation,Optical Activity,and Applications

Nanomaterials with helical morphologies have attracted much attention owing to their potential applications as nanosprings, chirality sensors and in chiral optics. Single‐handed helical Ta₂O₅ nanotubes prepared through a supramolecular templating approach are described. The handedness is controlled by that of the organic self‐assemblies of chiral low‐molecular‐weight gelators (LMWGs). The chiral LMWGs self‐assemble into single‐handed twisted nanoribbons through H‐bonding, hydrophobic association, and π‐π stacking. The Ta₂O₅ nanotubes are formed by the adsorption and polycondensation of Ta₂O₅ oligomers on the surfaces and edges of the twisted organic nanoribbons followed by removal of the template. The optical activity of the nanotubes is proposed to originate from the chiral defects on the inner surfaces of the tubular structures. Single‐handed twisted LiTaO₃ nanotubes can also be prepared using Ta₂O₅ nanotubes.     

纳米氧化铈在催化氧化木质素制备芳香化合物中的应用研究

木质素是自然界中唯一大规模可再生的含芳环聚合物.通过催化氧化的方法,定向解聚木质素得到芳香类化合物,具有非常重要的价值.近年来,氧化铈作为载体在木质素的多相催化氧化反应中表现较好性能.然而,对于氧化铈直接作为催化剂,并探讨其纳米结构与性能之间的研究未见报道.研究结果表明:纳米氧化铈直接作为催化剂时,对于木质素的催化氧化反应具有较好的性能,顺序为氧化铈纳米八面体纳米四方体纳米球纳米棒.纳米八面体表现出最优的催化性能,以其作为催化剂,对乙醇木质素进行催化氧化,得到了大量芳香酸及其酯类化合物.     

氧化铜-过氧化聚吡咯-还原氧化石墨烯复合膜修饰电极非酶检测葡萄糖

先以氧化石墨烯(Graphen oxide,GO)为阴离子掺杂剂,采用电化学聚合法制备了聚吡咯-氧化石墨烯复合膜(PPy-GO)。分别在0.10 mol/L Na Cl和0.10 mol/L NaOH溶液中对其进行还原和过氧化处理,制得过氧化聚吡咯-还原氧化石墨烯复合膜(OPPy-ERGO)。再以此OPPy-ERGO复合膜为载体,采用电化学沉积法制备了氧化铜-过氧化聚吡咯-还原氧化石墨烯复合膜修饰电极(CuO-OPPy-ERGO/CCE)。通过扫描电镜和电化学方法对此电极进行表征,研究了葡萄糖在此修饰电极上的电化学行为。结果表明,此电极对葡萄糖的电氧化过程表现出高的催化活性和良好的抗干扰能力。在0.20 mol/L NaOH溶液中,安培法检测葡萄糖的线性范围为5.0×10~(-7)~1.0×10~(-3)mol/L,检出限(3Sb)为2.0×10~(-7)mol/L,灵敏度为121.8μA/(mmol·L~(-1))。该电极用于血清中葡萄糖含量的测定,加标回收率为96.0%~110.1%。     

纳米金-还原氧化石墨烯修饰葡萄糖氧化酶传感器的制备及其电流法检测饮料中的葡萄糖

利用纳米金(Au NPs)与还原氧化石墨烯(rGO)复合纳米材料制备了葡萄糖氧化酶生物传感器并用于饮料中葡萄糖含量的检测。将壳聚糖作为还原剂及稳定剂,通过一步法合成了Au NPs-rGO复合材料,并通过物理吸附固定葡萄糖氧化酶(GOx)来制作GOx生物传感器。该传感器在磷酸盐缓冲溶液(0.1 mol/L,p H6.0)中,-0.45 V(vs.Ag/Ag Cl)电位下电流法检测葡萄糖含量,线性检测范围为0.01~0.88 mmol/L,灵敏度为22.54μA·mmol-1·L·cm-2,检出限为1.01μmol/L,且表观米氏常数为0.497 mmol/L。该传感器用于多种饮料中葡萄糖含量的直接检测,结果满意。