纳米Cu2O的制备及其对高氯酸铵热分解的催化性能

 以Cu(NO3)2和NaOH为原料,以水合肼为还原剂,通过沉淀法在室温下制备了纳米Cu2O. 采用X射线衍射、透射电镜和X射线光电子能谱等手段对产物进行了表征,并用热分析法考察了不同形貌的纳米Cu2O对高氯酸铵热分解的催化作用. 结果表明,通过改变NaOH溶液的加入量可分别得到长针形和多边形的纳米Cu2O. 通过调节反应物浓度可以将纳米Cu2O粒径控制在19～68 nm. 不同形貌的纳米Cu2O均能强烈催化高氯酸铵的热分解,其中分散性良好的多边形纳米Cu2O的催化活性较高,添加2%的多边形纳米Cu2O可使高氯酸铵的高温分解温度降低103 ℃,分解放热量由590 J/g增至1350 J/g.     

纳米Cu_2O材料的合成及其修饰电极安培法测定多巴胺

本文采用简单的一步化学还原方法合成了粒径均一的纳米Cu2O材料并采用扫描电子显微镜对其形貌进行了表征。研究发现,在p H 7.0的磷酸盐缓冲溶液中,采用纳米Cu2O和Nafion(全氟磺酸离子交换树脂)膜制备的复合修饰电极对多巴胺(DA)呈现出较强的电化学催化作用。优化实验条件后,建立了计时电流法直接测定多巴胺的痕量分析体系。在0.5~270μmol·L-1浓度范围内,多巴胺的阳极峰电流与浓度呈良好的线性关系(r=0.9980),检测限为0.17μmol·L-1,灵敏度为20.44μA m M-1且响应时间不超过3 s。该电极可有效屏蔽抗坏血酸(AA)的干扰,在20倍AA共存下仍能准确地测定DA。对含50μmol·L-1DA的溶液平行测定11次,相对标准偏差为3.3%,表明修饰电极的重现性和稳定性好。将该修饰电极用于模拟样品中DA的测定,结果令人满意。     

Recrystallization‐Induced Self‐Assembly for the Growth of Cu2O Superstructures

The assembly of inorganic nanoparticles (NPs) into 3D superstructures with defined morphologies is of particular interest. A novel strategy that is based on recrystallization‐induced self‐assembly (RISA) for the construction of 3D Cu₂O superstructures and employs Cu₂O mesoporous spheres with diameters of approximately 300 nm as the building blocks has now been developed. Balancing the hydrolysis and recrystallization rates of the CuCl precursors through precisely adjusting the experimental parameters was key to success. Furthermore, the geometry of the superstructures can be tuned to obtain either cubes or tetrahedra and was shown to be dependent on the growth behavior of bulk CuCl. The overall strategy extends the applicability of recrystallization‐based processes for the guided construction of assemblies and offers unique insights for assembling larger particles into complicated 3D superstructures.     

Highly Facet‐Dependent Photocatalytic Properties of Cu2O Crystals Established through the Formation of Au‐Decorated Cu2O Heterostructures

This work confirms the presence of a large facet‐dependent photocatalytic activity of Cu₂O crystals through sparse deposition of gold particles on Cu₂O cubes, octahedra, and rhombic dodecahedra. Au‐decorated Cu₂O rhombic dodecahedra and octahedra showed greatly enhanced photodegradation rates of methyl orange resulting from a better separation of the photogenerated electrons and holes, with the rhombic dodecahedra giving the best efficiency. Au–Cu₂O core–shell rhombic dodecahedra also displayed a better photocatalytic activity than pristine rhombic dodecahedra. However, Au‐deposited Cu₂O cubes, pristine cubes, and Au‐deposited small nanocubes bound by entirely {100} facets are all photocatalytically inactive. X‐ray photoelectron spectra (XPS) showed identical copper peak positions for these Au‐decorated crystals. Remarkably, electron paramagnetic resonance (EPR) measurements indicated a higher production of hydroxyl radicals for the photoirradiated Cu₂O rhombic dodecahedra than for the octahedra, but no radicals were produced from photoirradiated Cu₂O cubes. The Cu₂O {100} face may present a high energy barrier through its large band edge bending and/or electrostatic repulsion, preventing charge carriers from reaching to this surface. The conventional photocatalysis model fails in this case. The facet‐dependent photocatalytic differences should be observable in other semiconductor systems whenever a photoinduced charge‐transfer process occurs across an interface.     

ITO和ZnO基底对电化学沉积氧化亚铜薄膜的形貌、结构的影响及作用机制

采用电化学恒电位沉积方法在ITO导电玻璃上和在ZnO薄膜上沉积氧化亚铜(Cu₂O),并通过X射线衍射(XRD)和扫描电镜(SEM)对晶体的微观结构和表面形貌进行了分析.在ZnO基底上沉积得到了纳米级的Cu₂O粒子并且具有明显择优取向,而在ITO导电玻璃上仅得到粒径为2—5μm的Cu₂O粒子,没有明显的择优取向.对薄膜的生长机理进行了讨论.     

The Effects of Exposed Specific Facets and Sulfation on the Surface Acidity of Cu2O Solids

Cuprous oxide microcrystals with {111}, {111}/{100}, and {100} exposed facets were synthesized. ³¹P MAS NMR using trimethylphosphine as the probe molecule was employed to study the acidic properties of samples. It was found that the total acidic density of samples increases evidently after sulfation compared with the pristine cuprous oxide microcrystals. During sulfation, new {100} facets are formed at the expense of {111} facets and lead to the generation of two Lewis acid sites due to the different binding states of SO₄²⁻ on {111} and {100} facets. Moreover, DFT calculation was used to illustrate the binding models of SO₄²⁻ on {111} and {100} facets. Also, a Pechmann condensation reaction was applied to study the acidic catalytic activity of these samples. It was found that the sulfated {111} facet has better activity due to its higher Lewis acid density compared with the sulfated {100} facet.     

Amidation of Aryl Halides Catalyzed by the Efficient and Recyclable Cu2O Nanoparticles

Cu₂O nanoparticles/DMEDA (N,N′‐dimethylethylenediamine) was proved to be an efficient catalyst system for amidation of aryl halides under mild condition. This method displayed excellent selectivity and the catalyst was recyclable without loss of activity. The low cost, simple operation and excellent yields make this approach attractive for industrial applications.     

氧化亚铜单晶的声化学制备及表征(英)

So far,m any im portant sem iconductor m aterialssuch as ZnO,SnO2,Cu2O,In2O3have been synthesizedby using a variety of techniques including sol-gelm ethod[1],direct oxidation m ethod[2],m icrowave irradia-tion[3,4],sonochem ical m ethod[5],solution disper…     

Molecular dynamics simulation of the interaction between methyl benzotriazole and Cu2O crystal

In circulating water system , methyl benzotriazole (TTA) is one of the common corrosion inhibitors for copper. But the inhibition mechanisms have not been clearly understood so far. In different number of water molecules, the interaction between TTA and Cu₂O (copper surface) was investigated with molecular dynamics (MD) method. The results showed that the MD simulation result with water was more consistent with the experiment results. In different number of water molecules, the sequence of the interaction energies between TTA and Cu₂O (001) was ? E ₁ (150H₂O) > ? E ₁(200H₂O) > ? E ₁(100H₂O) > ? E ₁(50H₂O) > ? E ₁(0H₂O). The number of water molecules had an important influence on the interaction between corrosion inhibitors and Cu₂O crystal. From non‐bond energy and pair correlation functions, the interaction energies of the model system were mainly contributed by the non‐bond interaction. Strong adsorption could be raised by the Coulomb interaction between the negatively charged functional groups in TTA and the positive copper ions in the Cu₂O (001) face, and further interaction between aggressive media and copper could be restricted. So, copper corrosion could be avoided. Chemical bonds and non‐bond interactions were formed between TTA and Cu₂O (001) in different number of water molecules. Water molecules could not be ignored during the MD simulation, too. The results obtained here may provide theoretical supports for developing new corrosion inhibitors.     

Suppressed formation of CO2 and H2O in the oxidative coupling of methane over La2O3/MgO catalyst by surface modification

Oxidative coupling of methane (OCM) is a promising way to convert methane into C_2 hydrocarbons. However, CO_2 and H_2O are by-products of the reaction. To utilize the higher activity of lanthanum oxide and save its usage, MgO supported La_2O_3 catalyst was prepared. Surface modification of the catalyst with nitric acid was made to suppress the formation of the by-products. Experimental results indicated that the addition of nitric acid increased the surface oxygen species with binding energy of ca. 531.7 eV and at the same time reduced the pore volume of the catalyst. These effects of nitric acid finally led to the increase of C_2 selectivity and the decrease of the by-products formation. Hydrogen selectivity was found about 14%- 18% over the catalysts adopted in this work.     

氧化亚铜微米结构的可控合成及其光催化性能

采用溶液法,以五水硫酸铜为铜源,葡萄糖为还原剂,通过调节碱溶液用量,制备了多种形貌的微米Cu₂O材料,实现了正方体、球形和二十四面体形貌Cu₂O微米结构的可控合成,其结构、形貌和性能经UV-Vis, SEM,TEM和XRD表征。研究了三种不同形貌的微米Cu₂O对亚甲基蓝在可见光下降解反应的光催化性能。结果表明：二十四面体微米Cu₂O的光催化活性优于正方体和球形,降解率为97.72 %。     

Stable Aqueous Photoelectrochemical CO2 Reduction by a Cu2O Dark Cathode with Improved Selectivity for Carbonaceous Products

Photocatalytic reduction of CO₂ to produce fuels is a promising way to reduce CO₂ emission and address the energy crisis. However, the H₂ evolution reaction competes with CO₂ photoreduction, which would lower the overall selectivity for carbonaceous products. Cu₂O has emerged as a promising material for suppressing the H₂ evolution. However, it suffers from poor stability, which is commonly regarded as the result of the electron‐induced reduction of Cu₂O. This paper describes a simple strategy using Cu₂O as a dark cathode and TiO₂ as a photoanode to achieve stable aqueous CO₂ reduction with a high Faradaic efficiency of 87.4 % and a selectivity of 92.6 % for carbonaceous products. We have shown that the photogenerated holes, instead of the electrons, primarily account for the instability of Cu₂O. Therefore, Cu₂O was used as a dark cathode to minimize the adverse effects of holes, by which an improved stability was achieved compared to the Cu₂O photocathode under illumination. Additionally, direct exposure of the Cu₂O surface to the electrolyte was identified as a critical factor for the high selectivity for carbonaceous products.     

Photoelectrochemical Hydrogen Production in Alkaline Solutions Using Cu2O Coated with Earth‐Abundant Hydrogen Evolution Catalysts

The splitting of water into hydrogen and oxygen molecules using sunlight is an attractive method for solar energy storage. Until now, photoelectrochemical hydrogen evolution is mostly studied in acidic solutions, in which the hydrogen evolution is more facile than in alkaline solutions. Herein, we report photoelectrochemical hydrogen production in alkaline solutions, which are more favorable than acidic solutions for the complementary oxygen evolution half‐reaction. We show for the first time that amorphous molybdenum sulfide is a highly active hydrogen evolution catalyst in basic medium. The amorphous molybdenum sulfide catalyst and a Ni–Mo catalyst are then deposited on surface‐protected cuprous oxide photocathodes to catalyze sunlight‐driven hydrogen production in 1 M KOH. The photocathodes give photocurrents of ?6.3 mA cm^?2 at the reversible hydrogen evolution potential, the highest yet reported for a metal oxide photocathode using an earth‐abundant hydrogen evolution reaction catalyst.     

MgO负载Cu2O催化剂的制备及其催化环己醇脱氢

 以MgO为载体,水合肼为还原剂,采用浸渍还原法制备了Cu2O/MgO催化剂,考察了不同制备条件对其催化环己醇脱氢性能的影响,并采用N2物理吸附、 X射线衍射、透射电镜、 X射线光电子能谱、俄歇电子能谱和程序升温还原等手段对催化剂进行了表征. 实验结果表明,当Cu2+∶N2H4·H2O∶NaOH摩尔比为1∶1∶2时催化剂的活性最高. 与传统的Cu/MgO催化剂相比, Cu2O/MgO催化剂对环己醇脱氢反应具有很高的催化活性.     

Interaction of O2, CO and CO2 with Co films

Metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS(HeI)) and x‐ray photoelectron spectroscopy (XPS) were applied to study the interaction of O₂, CO and CO₂ with Co films at room temperature. The films were produced on Si(100) surfaces under the in situ control of MIES, UPS and scanning tunnelling microscopy (STM). For O₂, dissociative adsorption takes place initially and then incorporation of oxygen starts at exposures of ～5 L. Comparison of the MIES and UPS spectra with those published for CoO shows that near‐stoichiometric CoO films can be obtained by co‐deposition of Co and O₂. The CO is adsorbed molecularly up to a maximum coverage of ～0.6 monolayer, with the C‐end pointing towards the surface. The CO₂ adsorption is dissociative, resulting in the formation of Co–CO bonds at the surface. The resulting oxygen atoms are mostly incorporated into the Co layer. For all studied molecules the interaction with Co is similar to that with Ni. Copyright © 2005 John Wiley & Sons, Ltd.     

Synergetic Effect of Dual Co‐catalysts on the Activity of p‐Type Cu2O Crystals with Anisotropic Facets

Spatial separation of reduction sites and oxidation sites to inhibit the recombination of photogenerated electrons and holes plays a vital role in improving the efficiency of photocatalyst systems. It is very challenging to rationally deposit cocatalysts on the right facets (sites), namely, the reduction cocatalyst on the reduction facets (sites) and the oxidation cocatalyst on the oxidation facets (sites). Herein, we report that the reduction and oxidation cocatalysts can be selectively constructed on the different facets of p‐type Cu₂O crystals with anisotropic facets, but not on the Cu₂O crystal with isotropic facets. The deposition of dual cocatalysts on the different facets resulted in a remarkable synergetic effect in the photocatalytic performance, which could be attributed to the spatial separation of the photogenerated charges between facets. Our work reports an instructive strategy for constructing high‐efficiency photocatalyst systems for solar energy conversion.     

以SDS-PVP项链状软团簇为模板简易一锅法合成Cu2O中空亚微球

在SDS-PVP水溶液中采用N2H4•H2O还原CuSO4, 在pH (10±0.5), (40±1.0) ℃条件下反应55 min得到橙色Cu2O溶胶, 离心分离产物经XRD鉴定为Cu2O立方晶系晶体; SEM和TEM表明该法获得的晶体为形状规整、粒径分布窄的Cu2O中空亚微球, 并证实系由大量10 nm量级的原级Cu2O纳米晶粒组装而成. 根据实验事实推断, SDS-PVP项链状软团簇提供了“双重软模板”功能, 借助独特的“模板诱导两级组装”作用一锅法合成了Cu2O中空亚微球. Cu2O中空亚微球生长的可能途径为: 首先, 项链状软团簇中的SDS束缚胶束作为第一重软模板, 诱导一级组装10 nm量级的原级Cu2O纳米晶粒; 然后, 软团簇中立体桥联SDS束缚胶束的PVP链节作为第二重软模板, 诱导一定空间范围内的原级Cu2O纳米晶粒长大并进一步聚集/二级组装, 经一锅法合成得到次级Cu2O中空亚微球. 实验结果证明该一锅法温和、简便、快捷, Cu2O中空亚微球的粒径分布窄.     

Synthesis,analytical characterization and bioactivity of Ag and Cu nanoparticles embedded in poly-vinyl-methyl-ketone films

The electrosynthesis of copper and silver core-shell nanoparticles (NPs) by the sacrificial anode technique, employing tetraoctylammonium (TOA) salts as base electrolyte for the first time, is described. These surfactants were selected because they combine high NP stabilizing power with useful disinfecting properties. The resulting colloids were mixed with a solution of an inert dispersing polymer and used to prepare nanostructured composite thin films. The morphologies and chemical compositions of the nanomaterials were characterized by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The TEM reveals that the average core diameter of the metal NPs ranges between 1.7 and 6.3 nm, as a function of the nature of the metal and of the electrosynthesis conditions, and does not change significantly upon inclusion in the polymer matrix. An appreciable concentration of the metal is detected on the nanoparticle surface by XPS. High-resolution XP spectra indicate that both copper and silver are present at zero oxidation state in all of the materials (colloids and composite films). This demonstrates the high efficiency of the surfactant at controlling the morphology and the chemical composition of the nanodispersed metal in both the as-synthesized colloid and in the polymeric dispersion. The nanocoatings are shown to exert a marked inhibitory effect on the growth of eukaryote and prokaryote target microrganisms, and experimental evidence of a synergic disinfecting effect due to the surfactant and the nanodispersed metal is provided. On the basis of these stability and bioactivity results, it is clear that Cu-NPs and Ag-NPs are suitable for application in disinfecting or antifouling paint and coating formulations.Electronic Supplementary Material Supplementary material is available for this article at Dedicated to the memory of Wilhelm Fresenius     

Thin films of vanadium oxide grown on vanadium metal: oxidation conditions to produce V2O5 films for Li‐intercalation applications and characterisation by XPS,AFM, RBS/NRA

Thin films of vanadium oxide were grown on vanadium metal surfaces (i) in air at ambient conditions, (ii) in 5 mM H₂SO₄ (aq), pH 3, (iii) by thermal oxidation at low oxygen pressure (10^?5 mbar) at temperatures between 350 and 550 °C and (iv) at near‐atmospheric oxygen pressure (750 mbar) at 500 °C. The oxide films were investigated by atomic force microscopy (AFM), X‐ray photoelectron spectroscopy (XPS), X‐Ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA). The lithium intercalation properties were studied by cyclic voltammetry (CV). The results show that the oxide films formed in air at room temperature (RT), in acidic aqueous solution, and at low oxygen pressure at elevated temperatures are composed of V₂O₃. In air and in aqueous solution at RT, the oxide films are ultra‐thin and hydroxylated. At 500 °C, nearly atmospheric oxygen pressure is required to form crystalline V₂O₅ films. The oxide films grown at pO₂ = 750 mbar for 5 min are about 260‐nm thick, and consist of a 115‐nm outer layer of crystalline V₂O₅. The inner oxide is mainly composed of VO₂. For all high temperature oxidations, the oxygen diffusion from the oxide film into the metal matrix was considerable. The oxygen saturation of the metal at 450 °C was found, by XPS, to be 27 at.% at the oxide/metal interface. The well‐crystallized V₂O₅ film, formed by oxidation for 5 min at 500 °C and 750 mbar O₂, was shown to have good lithium intercalation properties and is a promising candidate as electrode material in lithium batteries. Copyright © 2005 John Wiley & Sons, Ltd.