还原氧化石墨烯表面聚苯胺纳米阵列的制备及电化学电容性能

本文以阳极氧化铝(AAO)膜为模板,通过恒电位法在自组装还原氧化石墨烯(rGO)膜表面制备有序聚苯胺(PANI)纳米线阵列。通过拉曼光谱和场发射扫描电子显微镜分别对其结构和微观形貌进行了表征,并对PANI纳米线阵列的电化学电容性能进行了测试。结果表明,rGO膜表面可电沉积PANI,电沉积得到的PANI纳米线阵列具有比PANI薄膜材料更高的电容和比电容。     

Development of an Electrochemical Sensor Nanoarray for Hydrazine Detection Using a Combinatorial Approach

The combinatorial screening of different metallic nanoparticles as electrocatalysts was investigated and efficiently applied for the detection of hydrazine. In a first step, glassy carbon microspheres decorated with metallic nanoparticles (Au, Pd, and Ag) were abrasively attached on the surface of a basal plane pyrolytic electrode giving a ‘multi–metal’ nanoarray. In a second step, electrodes modified with only one type of metallic nanoparticles allowed the identification of Pd as the unique catalytic material. In addition, a carbon‐epoxy composite electrode loaded with the Pd nanoparticles was then constructed for a practical use. The carbon‐epoxy composite nanoarray electrode was found to have excellent characteristics as for the sensing of hydrazine with a limit of detection of 2 μM.     

A controllable synthetic route to Cu,Cu2O,and CuO nanotubes and nanorods

Reducing Cu(OH)4(2-) with hydrazine hydrate and glucose in the presence of a structure-directing surfactant at room temperature gave Cu and Cu2O nanotubes/nanorods, respectively, whereas facile hydrothermal treatment of Cu(OH)4(2-) precursor resulted in CuO nanotubes/nanorods.     

An improved sensitivity non-enzymatic glucose sensor based on a CuO nanowire modified Cu electrode

CuO nanowires have been prepared and applied for the fabrication of glucose sensors with highly enhanced sensitivity. Cu(OH)(2) nanowires were initially synthesised by a simple and fast procedure, CuO nanowires were then formed simply by removing the water through heat treatment. The structures and morphologies of Cu(OH)(2) and CuO nanowires were characterised by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The direct electrocatalytic oxidation of glucose in alkaline medium at CuO nanowire modified electrodes has been investigated in detail. Compared to a bare Cu electrode, a substantial decrease in the overvoltage of the glucose oxidation was observed at the CuO nanowire electrodes with oxidation starting at ca. 0.10 V vs. Ag/AgCl (saturated KCl). At an applied potential of 0.33 V, CuO nanowire electrodes produce high and reproducible sensitivity to glucose with 0.49 microA/micromol dm(-3). Linear responses were obtained over a concentration range from 0.40 micromol dm(-3) to 2.0 mmol dm(-3) with a detection limit of 49 nmol dm(-3) (S/N = 3). The CuO nanowire modified electrode allows highly sensitive, low working potential, stable, and fast amperometric sensing of glucose, thus is promising for the future development of non-enzymatic glucose sensors.     

Enhanced Raman scattering as a probe for 4-mercaptopyridine surface-modified copper oxide nanocrystals.

We report on the application of Raman scattering as a probe to study 4-mercaptopyridine (4-Mpy) surface-modified CuO nanocrystals. Enhanced Raman scattering from 4-Mpy adsorbed on CuO nanocrystals was observed. The Raman signals displayed 10(2) enhancement compared with those of 4-Mpy in solution. We compared the Raman spectra of 4-Mpy molecules adsorbed on CuO nanocrystals and Ag, Cu substrate. A particular feature of the semiconductor substrate that was different from the metal substrate was revealed. The excitation wavelength-dependent behavior was clearly observed.     

Cu/活性炭催化剂：水合肼还原制备及催化甲醇氧化羰基化

以活性炭为载体,水合肼为还原剂制备了负载型Cu/活性炭催化剂,考察了水合肼/硝酸铜物质的量的比对催化甲醇气相氧化羰基化性能的影响,并采用XRD、XPS、H2-TPR和SEM等手段对催化剂进行了表征。结果表明,不加入还原剂水合肼时,催化剂中仅有CuO;随着水合肼/硝酸铜物质的量的比的增加,二价铜逐步被还原为Cu2O和/或单质Cu0,未被还原的Cu(OH)2在催化剂干燥过程中分解形成分散态CuO存在于催化剂表面。当水合肼/硝酸铜物质的量的比为0.75时,催化剂的催化性能最好,碳酸二甲酯的时空收率为120.62 mg.(g.h)-1,选择性为74.51%,甲醇转化率达到3.88%。在93 h反应时间内,催化剂都保持了较高的反应活性和选择性。此时铜物种以Cu2O和分散态CuO为主,Cu2O是主要的活性物种。     

Synthesis of flower-like cuo hierarchical nanostructures as an electrochemical platform for glucose sensing

Flower-like CuO hierarchical nanostructures were synthesized on copper foil substrate through a simple wet chemical route in alkaline media at room temperature. SEM images collected at different reaction times revealed the transformation of initially formed Cu(OH)₂ nanowires to flower-like CuO nanostructures. The hierarchical structure of the as-prepared CuO showed high electrocatalytic activity towards the oxidation of glucose making it a promising electrode material for the development of non-enzymatic glucose sensor. The amperometric sensor exhibited a wide linear response to glucose ranging from 4.5 × 10^?5 to 1.3 × 10^?3 mol L^?1 (R ² = 0.99317) at fixed potential of 0.3 V. The detection limit was 6.9 × 10^?6 mol L^?1 (LOD = 3σ/s) with a sensitivity of 1.71 μA μmol^?1 cm^?2. Moreover, the developed sensor offers a fast amperometric response, good selectivity and stability.     

Sensitive and Rapid Flow Injection Amperometric Hydrazine Sensor using an Electrodeposited Gold Nanoparticle Graphite Pencil Electrode

A gold (Au) nanoparticle-modified graphite pencil electrode was prepared by an electrodeposition procedure for the sensitive and rapid flow injection amperometric determination of hydrazine (N₂H₄). The electrodeposited Au nanoparticles on the pretreated graphite pencil electrode surface were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction spectroscopy, and electrochemical impedance spectroscopy. Cyclic voltammograms showed that the Au nanoparticle-modified pretreated graphite pencil electrode exhibits excellent electrocatalytic activity toward oxidation of hydrazine because the highly irreversibly and broadly observed oxidation peak at +600?mV at the pretreated graphite pencil electrode shifted to ?167?mV at the Au nanoparticle pretreated graphite pencil electrode; in addition, a significant enhancement in the oxidation peak current was obtained. Thus, the flow-injection (FI) amperometric hydrazine sensor was constructed based on its electrocatalytic oxidation at the Au nanoparticle-modified pretreated graphite pencil electrode. The Au nanoparticle-modified pretreated graphite pencil electrode exhibits a linear calibration curve between the flow injection amperometric current and hydrazine concentration within the concentration range from 0.01 to 100?µM with a detection limit of 0.002?µM. The flow injection amperometric sensor has been successfully used for the determination of N₂H₄ in water samples with good accuracy and precision.     

Electrospun rhodium nanoparticle-loaded carbon nanofibers for highly selective amperometric sensing of hydrazine

A novel one-step method has been carried out for synthesizing high-quality rhodium nanoparticle-loaded carbon nanofibers (nano-Rh/CNF) for the first time by using an electrospinning technology. The new hybrid material shows high electrocatalytic activity for hydrazine oxidation and can be potentially used for the amperometric sensing of hydrazine with high sensitivity and good selectivity.     

Derivatives (Cu/CuO,Cu/Cu2O,and CuS) of Cu superstructures reduced by biomass reductants

Metallic Cu is considered as the promising functional material owing to its high conductivity and harmlessness. Here, metallic Cu which presents a unique interconnected and continuous structure (Cu superstructure) is prepared using Magnolia grandiflora leaves as the biomass reductant, a green process which avoided the release of harmful gases and massive energy consumption. What's more, Cu/CuO, Cu/Cu₂O, and CuS nanosheets with different sizes were fabricated using Cu superstructure as the substrate via facile methods, and the morphology is regulated by controlling the relevant factors. The electrochemical sensors based on the three derivations were fabricated to study the sensing performance of glucose. The unique structure of nanosheets encapsulating Cu superstructure guarantees the excellent conductivity of Cu/CuO and Cu/Cu₂O composites. Moreover, the electrochemical stability is improved owing to the nanosheet protective layer. Although no metallic Cu was maintained in CuS, the integrated multilayer nanosheets endow CuS with short channels for fast interlayer electronic transmission and with structural stability.     

用俄歇电子能谱分析Y-Ba-Cu-O超导薄膜与衬底的界面互作用

高T_c的Y-Ba-Cu-O超导材料在弱电方面进入实用的一个重要条件,就是需要制备出优质的超导薄膜。已有多种制备超导薄膜的方法见报道。用蓝宝石或Si衬底制备超导薄膜,通常会由于薄膜与衬底强烈的界面反应使其零电阻温度大为降低,严重时甚至变成非超导。而我们在实验中发现,YSZ(掺钇稳定立方氧化锆)衬底在高温下与薄膜的界面反应也较为严重。在YSZ衬底上沉积一层Ag缓冲层则可以减轻薄膜与村底的相互作用。     

A novel hydrazine electrochemical sensor based on the high specific surface area graphene

An ultrasensitive platform is presented for the determination of hydrazine by combining the high specific surface area and higher electrical conductivity of poly(sodium styrenesulfonate) (PSS) graphene nanocomposite film with amperometric detection. The PSS-graphene were synthesized by the Hummers method and used to modify a glassy carbon electrode. The material was characterized by scanning electron microscopy and is found to be suitable for sensing hydrazine. The overpotential of hydrazine on the modified electrode is 0.31 V which is lower than in many electrochemical sensors. The calibration curve for hydrazine is linear in the range from 3.0 to 300 µmol L^?1, and the detection limit is as low as 1 µmol L^?1. This is the first report in which such a high sensitivity and low limit of detection has been achieved. It is concluded that PSS graphene represents an efficient electron mediator for sensing hydrazine.     

基于纳米CuO敏感材料的电流型NO2传感器研究

采用浸渍技术在多孔的氧化钇稳定的氧化锆(YSZ)中制备了纳米CuO敏感材料,并以其为敏感电极,YSZ为固体电解质,制备了一种新型的电流型NO2传感器。采用X射线衍射仪和扫描电子显微镜表征了NO2传感器的相组成和微观形貌,应用IM6e型电化学工作站测试了其气敏性能。结果表明,CuO颗粒粒径约为100 nm,且与基体结合紧密。在500～600℃时,传感器对NO2表现出良好的敏感性。在极化电压为-300 mV,NO2体积分数为0～5.0×10-4时,传感器的响应电流值与NO2浓度之间呈良好的线性关系。在被测气体总流量为400 cm3/min时,传感器信号90%的响应和恢复时间均为50 s。传感器响应信号在测试时间内具有良好的稳定性。共存气体O2和CO2对传感器的敏感性几乎没有影响。     

The porous CuO electrode fabricated by hydrogen bubble evolution and its application to highly sensitive non-enzymatic glucose detection

The porous Cu film was deposited on a Pt/Ti/Si substrate by electrochemical deposition accompanied by hydrogen evolution at very high current densities. CuO films with similar morphologies were obtained by subsequent annealing of the porous copper films. The morphology, composition and structure of the porous Cu and porous CuO were investigated by FE-SEM, EDS and XRD methods. The complete transformation of Cu to CuO after annealing was indicated. The sensing performances of the porous CuO film were evaluated in alkaline solution with the porous CuO film showing a wide linearity range from 1 μM to 2.5 mM with sensitivity of 2.9 mA cm⁻² mM⁻¹, and detection limit of 0.14 μM. The sensor showed good selectivity to conventional intermediates such as AA and UA and long term stability.     

Copper-based metal–organic framework decorated by CuO hair-like nanostructures: Electrocatalyst for oxygen evolution reaction

We report a Cu-based metal–organic framework (MOF) decorated by CuO nanostructures as an efficient catalyst for the oxygen evolution reaction (OER). MIL-53(Cu) was synthesized by a hydrothermal approach using 1,4-bezenedicarboxylic acid as organic precursor and further annealed at 300°C to form CuO nanostructures on its surface. The produced electrocatalyst, CuO@MIL-53(Cu), was characterized using various techniques. Under alkaline conditions, the developed electrocatalyst exhibited an overpotential of 801 and 336 mV versus RHE at 10 and 1 mA cm⁻², respectively. The reproducibility of the catalytic performance was validated using several electrodes. It was confirmed that the CuO hair-like nanostructures grown on MIL-53(Cu) using thermal treatment exhibit high OER activity, good kinetics and durability. CuO@MIL-53(Cu) is an economic noble-metal-free OER electrocatalyst. It has potential for application as anode material for sustainable energy technologies like batteries, fuel cells and water electrolysis.     

Low cost, surfactant-less, one pot synthesis of Cu2O nano-octahedra at room temperature

Cu₂O octahedra were successfully synthesized via a novel wet-chemical method using d-glucose and hydrazine as reducing agent at room temperature without the presence of any other surfactant. Presence of d-glucose was important for the stabilization of the evolved copper octahedra and also for facilitating the reduction of the Cu(II) ions. The existence of glucose moieties on the surface as capping agent was confirmed by the FT-IR spectra while there was presence of excess oxygen atoms on the surface leading to the formation of a thin CuO layer at the octahedra surface, as confirmed by the XPS study, probably promoted by the capping glucose. Effect of NaOH concentration on the reaction and the formation of octahedra was also studied. The formation mechanism of obtained Cu₂O octahedra has been discussed. These octahedra were then studied for their photocatalytic properties in degradation of organic dyes, rhodamine B and methyl orange.     

Electrodeposited nano-scale islands of ruthenium oxide as a bifunctional electrocatalyst for simultaneous catalytic oxidation of hydrazine and hydroxylamine

For the first time, an electrodeposited nano-scale islands of ruthenium oxide (ruthenium oxide nanoparticles), as an excellent bifunctional electrocatalyst, was successfully used for hydrazine and hydroxylamine electrocatalytic oxidation. The results show that, at the present bifunctional modified electrode, two different redox couples of ruthenium oxides serve as electrocatalysts for simultaneous electrocatalytic oxidation of hydrazine and hydroxylamine. At the modified electrode surface, the peaks of differential pulse voltammetry (DPV) for hydrazine and hydroxylamine oxidation were clearly separated from each other when they co-exited in solution. Thus, it was possible to simultaneously determine hydrazine and hydroxylamine in the samples at a ruthenium oxide nanoparticles modified glassy carbon electrode (RuON-GCE). Linear calibration curves were obtained for 2.0-268.3 μM and 268.3-417.3 μM of hydrazine and for 4.0-33.8 μM and 33.8-78.3 μM of hydroxylamine at the modified electrode surface using an amperometric method. The amperometric method also exhibited the detection limits of 0.15 μM and 0.45 μM for hydrazine and hydroxylamine respectively. RuON-GCE was satisfactorily used for determination of spiked hydrazine in two water samples. Moreover, the studied bifunctional modified electrode exhibited high sensitivity, good repeatability, wide linear range and long-term stability.     

LSDA+U方法研究Ni掺杂CuO和Cu掺杂NiO的电子结构和反铁磁学性质

光催化分解水制H2和光催化还原CO2是解决能源危机和全球变暖的有效途径.但是,由于粉末光催化剂存在回收效率低的问题,因而光催化成本很高.而磁性光催化剂便于回收和重复利用,因此人们把目光转向具有磁性的非光催化剂材料,试图通过改性使得磁性材料具有合适的水分解或者还原CO2的氧化还原电位.同时,对具有光催化活性但是没有磁性的材料进行磁化改性可以得到新型的磁性光催化剂.本文通过对本身具有磁性的NiO材料进行Cu掺杂能带调整,使调整后的NiO具有合适的氧化还原电位;对本身具有良好光催化氧化还原电位的CuO材料进行Ni掺杂磁化调整,使磁化后的CuO既有良好的氧化还原电位又有磁性.最终两种材料经过掺杂变成磁性光催化材料,既有较好的光催化性能,又可高效回收,因此有望在光催化领域具有潜在的应用前景.LSDA(局域自旋密度近似)+U(有效库仑相关能)计算方法能够很好地给出磁矩和禁带宽度等电子结构性质.本文通过LSDA+U计算方法对具有磁性的宽禁带半导体材料NiO进行电子结构改性研究,希望通过降低其禁带宽度、调整其氧化还原电位使之对太阳光有响应.因其同时具有磁性便于回收,使得光催化分解水制H2和光催化还原CO2成本高的问题得到解决.对NiO的磁胞进行了Cu掺杂计算,结果发现Cu的掺杂几乎没有引起NiO空间结构的变化,这是因为Cu和Ni的离子半径相近.通过对电子结构的计算发现掺杂体系的禁带变窄,并且在禁带中间出现了两条杂质能级,该杂质能级是由掺杂原子Cu 3d态组成.杂质能级的出现能够降低光生载流子在带隙中的复合,从而提高光催化效率.计算结果同时表明,Cu掺杂的NiO系统具有一个1μB的净磁矩,即Cu的掺杂使得NiO显示出磁性,而Ni的磁矩在掺杂前后几乎保持不变,由纯相的1.67μB增加到掺杂体系中的1.70μB.由于CuO本身低指数(111)面和(011)面具有合适的分解水制H2和还原CO2的氧化还原电位,如果对CuO进行磁化改性,可以使光催化剂CuO同时带有磁性,便于回收再利用.本文对CuO磁胞进行了Ni的掺杂计算.结果表明,由于离子半径相近,Ni掺杂几乎没有引起CuO空间结构的变化.掺杂后的体系具有一个1.66μB的净磁矩,同时Ni的掺杂引起多个杂质能级出现,靠近价带的杂质能级由Cu 3d态组成,而在导带底位置出现的杂质能级主要由Ni 3d态组成.整个能带向高能级方向平移.     

Highly dispersed Cu supported on mesoporous Al-KIT-6 for oxidative carbonylation of methanol to dimethyl carbonate

Microporous NaY zeolite is a common support of Cu catalysts for oxidative carbonylation of methanol, but the dispersion of Cu species on NaY is usually subjected to its micropore size. Here, ordered mesoporous KIT-6 was employed as the support for Cu catalyst and Al was incorporated into its framework to increase the surface acidity, which eventually improves the surface exchange capacity and Cu dispersion. The evolution of the state of Cu species on KIT-6 was analyzed combined with control of Cu loading. The physicochemical properties of the supports and corresponding catalysts were characterized by N₂ adsorption–desorption, X-ray diffraction, ammonia temperature programmed desorption, Fourier transform infrared spectra, transmission electron microscopy, hydrogen temperature programmed reduction, and X-ray photoelectron spectroscopy. It was found that mesoporous KIT-6 showed better Cu dispersion than microporous NaY zeolite. Agglomerated CuO, dispersed CuO, and Cu²⁺ are the major Cu species observed on the catalyst surface. The increased surface acidic sites of KIT-6 by Al incorporation promoted the formation of Cu²⁺ and dispersion of CuO. With the increase in Cu loading, the Cu²⁺ content in the catalyst was decreased gradually along with increase in the bulk CuO. It was speculated that some exchanged Cu²⁺ could be transformed into highly dispersed CuO and even bulk CuO after calcination at a high Cu loading. Combined with the catalyst evaluation results, it was deduced that highly dispersed Cu²⁺ and CuO particles play significant roles in catalytic activity. The catalyst Cu/Al-K-10 achieved the highest space time yield of dimethyl carbonate of 135.4 mg/(g·h), which is 2.7 times the Cu/K-10 owing to its more dispersed Cu species. This laid the basis for preparing highly dispersed Cu species on mesoporous silica supports.