Optical and physical properties of cobalt oxide films electrogenerated in bicarbonate aqueous media

For the first time, cobalt oxide films that are highly protective against localized corrosion and depicting a wide variety of bright and uniform colors due to light interference, have been successfully electrogenerated on polycrystalline cobalt disk electrodes under potentiostatic polarization in a mild aqueous bicarbonate medium. Open circuit potential measurements have shown the formation of a film with a bilayered structure, organized as a thin Co3O4 outer layer and a thick CoO inner layer. The existence of Co3O4 as a thin outer layer, previously postulated from galvanostatic reduction experiments, has been confirmed from XPS analysis. Raman spectroscopy, performed using a very low laser intensity, has shown that the films are mainly composed of CoO. The broadness of the Raman bands observed is associated to the amorphous character of the film, a result that has been confirmed by spectroscopic ellipsometry and X-ray diffraction analysis. Overall film thicknesses, well controlled by the anodization duration, were determined and correlated using mechanical (atomic force microscopy and profilometry) and spectroscopic (specular UV-vis-NIR reflectance and ellipsometry) techniques. Spectroscopic ellipsometry, using a simple amorphous dispersion model, has proved efficient for measuring thicknesses of films ranging from 31 to 290 nm with very low standard deviations. The real part of the complex refractive indices of these films, ranging from 1.8 to 2.2 (at lambda = 632.8 nm) depending on the anodization duration, is in good agreement with values reported in the literature for CoO. The film with the highest refractive index, and consequently the more densely packed structure, was obtained following a 30-minute anodization period.     

Metallic film formation using direct micropatterning with photoreactive metal complexes

Palladium, cobalt, and nickel in complex with photoacid-generating ligands, 4-(2-nitrobenzyloxycarbonyl)catechol and 4-(6-nitroveratryloxycarbonyl)catechol, were prepared in solution. Films formed from the metal complex solutions perform as positive-tone, directly photopatternable palladium, cobalt, nickel oxide, or composite film precursors. After exposure, acid-bearing selectively soluble complexes could be removed to give patterned films upon developing in aqueous base, which were transformable to the corresponding pattern-preserving metal/metal oxide film. The photodynamics of photoinduced solubility and direct micropatterning of palladium, cobalt, nickel, and palladium/nickel oxide composite films were investigated. Employing palladium as the initiator for autocatalytic chemical plating, selective direct copper plating on palladium film on polyethylene naphthalate and palladium/nickel oxide composite film on glass was accomplished.     

Approach to excellent superhydrophobicity and corrosion resistance of carbon-based films by graphene and cobalt synergism

A new series of carbon-based films doped with graphene oxide and cobalt (G-Co/a-C:H films) were successfully prepared on Si substrate via one-step electrochemical deposition of methanol as the carbon source and graphene oxide/cobalt as the dopant. G-Co/a-C:H films were fabricated at various graphene oxide concentration for comparative experiments. It can be found that the graphene oxide and cobalt were well embedded in amorphous carbon matrix to form superhydrophobic G-Co/a-C:H film at the doping GO concentration of 0.007 mg/mL, which was confirmed by transmission electron microscopy (TEM). It was noted that the superhydrophobicity of the resulting surface derives from its rough surface with hierarchical micro-nanostructures and the presence of the low-surface-energy GO components on it. The hierarchical micro-nanostructures are attributed to the corporate joint of GO and cobalt to form the multilevel nanoscale composite interface. Specially, the as-fabricated superhydrophobic G-Co/a-C:H film could exhibit excellent self-cleaning ability and corrosion resistance, revealed by the self-cleaning and corrosion tests.     

Nanostructured black cobalt coatings for solar absorbers

Nanocrystalline black cobalt electrically deposited onto a steel substrate from aqueous solution was investigated. The influence of electrolyte composition and operating parameters on the appearance and optical properties of the coat was studied. The deposition conditions that ensure the highest solar absorptance were optimized. The chemical composition of fabricated thin films before and after annealing at 400 °C was determined by energy dispersive X‐ray analysis (EDS) and XPS technique. The crystal structure analysis showed that the bulk composition of the films was mainly cobalt oxide. The surface analysis reveals that the topmost surface layers of the films are made of different cobalt compounds confirming the multivalence state of Co on the surface with an oxidation state of ≥ + 2. Scanning electron microscope (SEM) observation indicated that the surface morphology was changed from dendritic structure to lamellar at higher current density. The black cobalt film showed soft magnetic characteristicsand excellent optical properties to transform solar energy into thermal energy. Copyright © 2008 John Wiley & Sons, Ltd.     

Electrodeposition of cobalt oxide films from carbonate solutions containing Co(II)–tartrate complexes

An electrochemical procedure of anodic deposition of cobalt oxyhydroxide film on a glassy carbon substrate in an alkaline medium (i.e. pH 11.6) is described. The electrodeposited film was obtained either by voltage cycling or by potentiostatic conditions using non-deaerated 0.1 M Na₂CO₃ solutions containing 40 mM tartrate ions and 4 mM CoCl₂. The effects on the film formation and growth, such as tartrate–cobalt ratio, pH, applied potential, etc. were widely evaluated. The electrodeposition process, under anodic conditions and moderately alkaline solutions, most likely involves a redox transition Co(II)→Co(III)/Co(IV) with destruction of the tartrate complex and formation of insoluble oxide/hydroxide cobalt species on the glassy carbon surface. The resulting cobalt oxyhydroxide films were characterised by cyclic voltammetry (CV) in 0.1 M NaOH solutions and by scanning electron microscopy (SEM) analysis after different strategies of preparation and various electrochemical treatments. The electrochemical activity of the deposited films was checked using various organic molecules as model compounds.     

Soft‐Chemical Exfoliation Route to Layered Cobalt Oxide Monolayers and Its Application for Film Deposition and Nanoparticle Synthesis

A colloidal suspension of exfoliated, layered cobalt oxide nanosheets has been synthesized through the intercalation of quaternary tetramethylammonium ions into protonated lithium cobalt oxide. According to atomic force microscopy, exfoliated nanosheets of layered cobalt oxide show a plateau‐like height profile with nanometer‐level height, underscoring the formation of unilamellar 2D nanosheets. The exfoliation of layered cobalt oxide was cross‐confirmed by X‐ray diffraction, UV/Vis spectroscopy, and transmission electron microscopy. The maintenance of the hexagonal in‐plane structure of the cobalt oxide lattice after the exfoliation process was evidenced by selected‐area electron diffraction and Co K‐edge X‐ray absorption near‐edge structure analysis. The zeta‐potential measurements clearly demonstrated the negative surface charge of cobalt oxide nanosheets. Adopting the nanosheets of layered cobalt oxide as a precursor, we were able to prepare the monodisperse CoO nanocrystals with a particle size of ≈10 nm as well as the heterolayered film composed of cobalt oxide monolayer and polycation.     

基于三氯化铁催化作用制备大尺寸氧化石墨烯薄膜

本文用三氯化铁(FeCl₃)作催化剂制备了大面积的氧化石墨烯(L-GO)薄膜。 通过原子力显微镜(AFM)、偏光显微镜(POM)、红外光谱(FTIR)、X射线衍射(XRD)对FeCl₃催化剂存在下,不同温度和时间得到的L-GO薄膜进行形貌和结构研究。 结果表明,在 FeCl₃催化下L-GO薄膜片畴的面积为10 μm×10 μm,与无催化作用得到的GO薄膜相比增加了大约4倍。 从FTIR和XRD分析可以确定,大尺寸片畴的形成可以归因于催化作用促进了氧化石墨上的羟基、羧基、羰基等含氧官能团重新组合和连接。 据此,提出了FeCl₃催化下L-GO薄膜形成模型,为制备大面积石墨烯薄膜提供了新的途径。     

Optical CO gas sensor using a cobalt oxide thin film prepared by pulsed laser deposition under various argon pressures

An optical CO gas sensor was investigated using cobalt oxide thin films prepared by pulsed laser deposition. The cobalt oxide films were deposited on quartz glass and silicon wafer substrates in Ar at 0.07-133 Pa. The morphology and crystal phase of the films were changed by Ar pressure. Sensitivity was estimated as the transmittance change of the film in dry air and at 200 ppm of CO gas ambient at 350 degrees C. The morphology of the films greatly affected the sensing properties. The optimum Ar pressure for cobalt oxide film preparation for CO gas sensing was suggested to be 13.3 Pa, based on the relationship between the morphology and the optical sensor properties of the films.     

纳米二氧化钒薄膜的制备及红外光学性能

采用双离子束溅射方法在Si3N4/SiO2/Si基底表面沉积氧化钒薄膜, 在氮气气氛下热处理获得二氧化钒薄膜. 利用X射线衍射(XRD)、扫描电子显微镜(SEM)和X射线光电子能谱(XPS)研究了热处理温度对氧化钒薄膜晶体结构、表面形貌和组分的影响, 利用傅里叶变换红外光谱(FT-IR)对二氧化钒薄膜的红外透射性能进行了测试分析. 结果表明, 所制备的氧化钒薄膜以非晶态V2O5和四方金红石结构VO2为主, 经400 ℃、2 h热处理后获得了(011)择优取向的单斜金红石结构纳米VO2薄膜, 提高热处理温度至450 ℃, 纳米结构VO2薄膜的晶粒尺寸减小. FT-IR结果显示,纳米VO2薄膜透射率对比因子超过0.99, 高温关闭状态下透射率接近0. 小晶粒尺寸纳米VO2薄膜更适合在热光开关器件领域应用.     

Cobalt alters the growth of a manganese oxide film

The mobility of dissolved heavy metals in natural waters is partially regulated by interactions with manganese oxide films. In the current work, the effects of aqueous cobalt(II) on manganese oxide film growth are studied by atomic force microscopy. The film is grown on the (104) surface of rhodochrosite (MnCO3). In the presence of O2(aq) and at circumneutral pH, film growth begins as manganese oxide islands that expand laterally across the surface. Addition of Co2+(aq) leads to the partial or complete dissolution of the manganese oxide film. Simultaneously, there is growth of new islands having multilayer structures that are unrestrained in the z-direction. The chemical composition of these new islands appears to include both Co and Mn ions. Empirical rules governing the growth of the two types of islands can be developed for the absence and the presence of Co2+(aq). In the absence of Co2+(aq), islands grow as flat two-dimensional rhombohedral islands of nearly uniform height (2.4 +/- 0.3 nm). These islands do not cross over steps on the substrate. The growth rules change markedly in the presence of Co2+(aq). The islands grow indefinitely in the z-direction as strata structures of polydisperse thickness and rounded tops. The islands readily grow over steps. Cobalt ions, therefore, relieve the two-dimensional restriction on layer formation and allow three-dimensional growth. Moreover, the shape of the dissolution pits on the surface of MnCO3 changes from rhombohedral in the absence of cobalt to partially rounded in the presence of cobalt. The rounding occurs for the obtuse edges of the pit. Direct microscopic observations of the interactions of cobalt with manganese oxide films provide new mechanistic insights that are important in the quantitative modeling of the mobility of heavy metals in the environment.     

多级孔ZSM-5负载的钴催化剂的费-托合成催化性能

采用水蒸气辅助转晶(SAC)法合成了粒径均一(180 nm)的纳米ZSM-5颗粒,颗粒间堆积形成大量的开放介孔,与ZSM-5的微孔共同形成多级孔结构。以该材料为载体采用满孔浸渍法制备了负载量为15%(质量分数)的钴催化剂。采用XRD、SEM、TEM、N_2物理吸附-脱附等表征技术对多级孔ZSM-5载体及其负载催化剂的形貌和结构进行了表征,并对催化剂的费-托合成催化性能进行了测试。结果表明,相比于大颗粒的ZSM-5和商业ZSM-5,多级孔ZSM-5负载的钴催化剂的费-托合成活性最高,CH_4选择性最低,C_(5-20)产物的选择性高达68.9%,这归因于多级孔ZSM-5的介孔孔道有效地促进反应过程中产物的传质扩散以及ZSM-5微孔骨架上的酸中心促进了长链烃产物的二次加氢裂解。     

Observation of the anisotropic photoinduced magnetization effect in Co-Fe Prussian blue thin films fabricated by using clay Langmuir-Blodgett films as a template

Thin films of cobalt-iron cyanide (Co-Fe Prussian blue) have been fabricated by means of the modified Langmuir-Blodgett (LB) method using a smectite clay mineral (montmorillonite). In this combined method, clay LB films play a template role in the formation of the Co-Fe Prussian blue thin layer. The films were revealed to possess a well-organized structure not only in perpendicular directions to the film surface but also in parallel directions to the film surface. The photoinduced electron transfer from the iron ion to the cobalt through the bridging cyanide in the films occurred at low temperature (8 K), similar to that in the bulk Co-Fe Prussian blue. The films clearly exhibited magnetic anisotropy with regards to the direction of the applied magnetic field. Moreover, the photoinduced magnetization effect in the films was also found to be anisotropic.     

Influence of ph on the reduction of thick anodic oxide films on gold

The reduction of thick oxide films, produced anodically on gold under constant potential conditions in the oxygen gas evolution region, was examined as a function of sweep-rate in both acid and base. Although peak maxima potential values for the reduction reactions were not totally independent of sweep-rate, even at very low values of the latter, the earlier assumption that the film is composed of at least two (and in some cases, according to the present results, as many as five) different oxygold species was shown to be a reasonable one. The other assumption, namely that the hydrous film in the case of gold is anionic (due to excess hydroxide-ion incorporation) was also shown to be a reasonable one by comparison with recent work with hydrous nickel oxide films for which structural data is available. In these systems counterbalancing cations (H⁺, Na⁺, etc.) are assumed to be present in water contained in pores or layers in the structure. Furthermore, the unusual potential-pH dependence of the hydrous film reduction process can easily be explained in terms of the excess hydroxide incorporation model.     

Ligand field effect at oxide-metal interface on the chemical reactivity of ultrathin oxide film surface

Ultrathin oxide film is currently one of the paramount candidates for a heterogeneous catalyst because it provides an additional dimension, i.e., film thickness, to control chemical reactivity. Here, we demonstrate that the chemical reactivity of ultrathin MgO film grown on Ag(100) substrate for the dissociation of individual water molecules can be systematically controlled by interface dopants over the film thickness. Density functional theory calculations revealed that adhesion at the oxide-metal interface can be addressed by the ligand field effect and is linearly correlated with the chemical reactivity of the oxide film. In addition, our results indicate that the concentration of dopant at the interface can be controlled by tuning the drawing effect of oxide film. Our study provides not only profound insight into chemical reactivity control of ultrathin oxide film supported by a metal substrate but also an impetus for investigating ultrathin oxide films for a wider range of applications.     

Effects of oxidation pretreatment temperature on Kovar used as CO_2 reforming catalyst

The effect of oxidation pretreatment temperature(500 ~ 1 000 ℃) on the catalytic activity of Kovar applied on hydrocarbon CO2reforming was examined. Catalytic performance evaluation using tetradecane at 800 ℃ with 70 μmol/s CO2revealed 700 and 1 000 ℃ as the best pre-oxidation temperature in producing CO and H2,respectively. XRD and SEM-EDX analyses showed that a separate metal oxide layer composed of iron oxide(Fe2O3and F3O4),nickel,cobalt,and possibly their respective oxides started to form when oxidation was conducted at 700 ℃ or higher.The presence of iron enhanced the stability of nickel in the structure while the compact structure of Fe3O4resulted into the formation of a thick and rigid metal oxide layer on the surface of the Kovar tube. The strong physical bond between the metal oxide layer and Kovar tube provided the catalyst good mechanical strength and consequently good catalytic activity.     

Facile deposition of cobalt oxide based electrocatalyst on low-cost and tin-free electrode for water splitting

Facile deposition of a water-splitting catalyst on low-cost electrode materials could be attractive for hydrogen production from water and solar energy conversion. Herein we describe fast electrodeposition of cobalt-based water oxidation catalyst(Co-WOC) on simple graphite electrode for water splitting. The deposition process is quite fast, which reaches a plateau in less than 75 min and the final current density is～1.8 mA/cm2under the applied potential of 1.31 V at pH = 7.0. The scanning electron microscopy(SEM) study shows the formation of nanometer-sized particles(10-100 nm) on the surface of the electrode after only 2 min and micrometer-sized particles(2-5 μm) after 90 min of electrolysis. X-ray photoelectron spectroscopy(XPS) data demonstrate the as-synthesized ex-situ catalyst mainly contains Co2+and Co3+species incorporating a substantial amount of phosphate anions. These experiments suggest that cost-efficient cobalt oxide materials on graphite exhibit alluring ability for water splitting, which might provide a novel method to fabricate low-cost devices for electrochemical energy storage.     

Monte Carlo simulation on layered polymeric films

Thin films of polymer blends composed of alternating copolymer, diblock copolymer and/or homopolymer are studied using Monte Carlo simulation. A multilayer morphology is observed in the film, that is, the blended polymers assemble into individual domains arranged from interior to the surfaces of the film. The coexisting components residing throughout the neighboring domains in the film make no distinguishable interface between any neighboring domains. By this means, it forms a vertical composition gradient in the polymeric film. Being different from layer-by-layer deposition of polyelectrolyte or hydrogen bonding approach etc., the layered structure in this study is formed by polymer blending in one step. Alternating copolymers are found to be essential components to form vertical composition gradient （layered structure） in thin films.     

Effect of catalyst confinement and pore size on Fischer-Tropsch synthesis over cobalt supported on carbon nanotubes

This paper studies the impact of structure of cobalt catalysts supported on carbon nanotubes(CNT) on the activity and product selectivity of Fischer-Tropsch synthesis(FTS) reaction.Three types of CNT with average pore sizes of 5,11,and 17 nm were used as the supports.The catalysts were prepared by selectively impregnating cobalt nanoparticles either inside or outside CNT.The TPR results indicated that the catalyst with Co particles inside CNT was easier to be reduced than those outside CNT,and the reducibility of cobalt oxide particles inside the CNT decreased with the cobalt oxide particle size increasing.The activity of the catalyst with Co inside CNT was higher than that of catalysts with Co particles outside CNT.Smaller CNT pore size also appears to enhance the catalyst reduction and FTS activity due to the little interaction between cobalt oxide with carbon and the enhanced electron shift on the non-planar carbon tube surface.     

The in situ characterization and structuring of electrografted polyphenylene films on silicon surfaces. An AFM and XPS study

An atomic force microscope was used so as to structure by nanofriction films of polynitrophenylene electrografted on substrates of n-type silicon (100) with the native oxide on the top of the surface. AFM measurements of thin films thickness have been carried out in the electrolytic solution for different applied potentials during the electrografting. This investigation allows (i) to determine the relationship between the applied potential and the final thickness of electrografted polyphenylene films and (ii) to specify how the thin layers grow. XPS analysis confirmed the AFM observations on (i) the effective shaving of the grafted polymer chains under mechanical stress and (ii) the existence of a potential threshold for electrografting a polyphenylene film on silicon oxide surfaces. The presence of a residual film in the rubbed zone was attributed to stronger interactions between the first electrografted layer and the native oxide of silicon (through Si-C or/and Si-O-C bonds) than those insuring the cohesion of the multilayer (C-C and C-N bonds).     

Creation of high-refractive-index amorphous titanium oxide thin films from low-fractal-dimension polymeric precursors synthesized by a sol-gel technique with a hydrazine monohydrochloride catalyst

Amorphous titanium dioxide (TiO(2)) thin films exhibiting high refractive indices (n ≈ 2.1) and high transparency were fabricated by spin-coating titanium oxide liquid precursors having a weakly branched polymeric structure. The precursor solution was prepared from titanium tetra-n-butoxide (TTBO) via the catalytic sol-gel process with hydrazine monohydrochloride used as a salt catalyst, which serves as a conjugate acid-base pair catalyst. Our unique catalytic sol-gel technique accelerated the overall polycondensation reaction of partially hydrolyzed alkoxides, which facilitated the formation of liner polymer-like titanium oxide aggregates having a low fractal dimension of ca. (5)/(3), known as a characteristic of the so-called "expanded polymer chain". Such linear polymeric features are essential to the production of highly dense amorphous TiO(2) thin films; mutual interpenetration of the linear polymeric aggregates avoided the creation of void space that is often generated by the densification of high-fractal-dimension (particle-like) aggregates produced in a conventional sol-gel process. The mesh size of the titanium oxide polymers can be tuned either by water concentration or the reaction time, and the smaller mesh size in the liquid precursor led to a higher n value of the solid thin film, thanks to its higher local electron density. The reaction that required no addition of organic ligand to stabilize titanium alkoxides was advantageous to overcoming issues from organic residues such as coloration. The dense amorphous film structure suppressed light scattering loss owing to its extremely smooth surface and the absence of inhomogeneous grains or particles. Furthermore, the fabrication can be accomplished at a low heating temperature of <80 °C. Indeed, we successfully obtained a transparent film with a high refractive index of n = 2.064 (at λ = 633 nm) on a low-heat-resistance plastic, poly(methyl methacrylate), at 60 °C. The result offers an efficient route to high-refractive-index amorphous TiO(2) films as well as base materials for a wider range of applications.