Facile method to prepare stable superhydrophobic Co3O4 surface

A facile and novel method was developed to fabricate rough Co₃O₄ surface with hierarchical micro- and nanostructures by the combination of simple solid state reactions and coating process. After modification with stearic acid, a superhydrophobic surface with water contact angle of 155 ± 1.8° and sliding angle of 2° was obtained. The superhydrophobic Co₃O₄ surface remained superhydrophobic property in a wide pH range from 3 to 14. The superhydrophobic Co₃O₄ surface also showed excellent self-cleaning property and high stability in ambient environments.     

Charge-discharge characteristics of nanocrystalline Co3O4 powders via aerosol flame synthesis

Nanocrystalline Co₃O₄ powders were synthesized by aerosol flame synthesis (AFS) method for the anode of lithium ion batteries and the basic electrochemical properties were investigated. The effects of synthesis conditions and heat-treatment temperature on the morphology, crystallite size and electrochemical properties were investigated. As-prepared soot contained Co₃O₄, CoO and Co(OH)₂, which were eventually converted into cubic spinel Co₃O₄ by post heat treatment. The as-prepared particle size was in the range of 10-30 nm and grew to 50-85 nm by the heat treatment. With growing particle size and improved crystallinity, charge-discharge capacity and cycle performance were improved and the discharge capacity of the powder heat-treated at 700 °C was 571 mAh/g after 30 cycles, which was better than Co₃O₄ powder reported in the previous literature.     

Interpretation of the optical absorption spectrum of Co3O4 with normal spinel structure from first principles calculations

First principles calculations based on density functional theory have been employed to study the electronic, magnetic and optical properties of Co₃O₄ in a cubic normal spinel structure. Exchange and correlation effects between electrons were treated by a B3PW91 hybrid functional, which produced better results than others scheme, such as GGA+U or PBE0 hybrid functionals or mBJ semilocal potential. The work focuses on clarifying the nature of the optical absorption bands, which have motivated various theoretical and experimental works in the literature. The calculated optical absorption spectrum was compared with available experimental data. On the basis of this calculated electronic and magnetic structure, the optical absorption peaks (theoretical and experimental) could be satisfactorily explained in terms of d3d   charge transfer transitions between both CO²⁺${\mathrm{CO}}^{2^{+}}$→CO²⁺${\mathrm{CO}}^{2^{+}}$ and CO³⁺${\mathrm{CO}}^{3^{+}}$→CO³⁺${\mathrm{CO}}^{3^{+}}$ ions. The calculations also predicted that the crystal field splittings at both octahedral and tetrahedral sites in the Co₃O₄ compound are of the same magnitude.     

Catalytic performance of Mn3O4 and Co3O4 nanocrystals prepared by sonochemical method in epoxidation of styrene and cyclooctene

A simple sonochemical method was developed to synthesis uniform sphere-like Co₃O₄ and Mn₃O₄ nanocrystals. Epoxidation of styrene and cyclooctene by anhydrous tert-butyl hydroperoxide over the prepared Co₃O₄ and Mn₃O₄ nanocatalysts was investigated. The results of conversion activity were compared with bulk Co₃O₄ and Mn₃O₄. Under optimized reaction conditions, the nanocatalysts showed a superior catalytic performance as compared to the bulk catalysts. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and BET surface area, were used to characterize and investigate the nanocatalysts.     

Synthesis of urchin-like Co3O4 hierarchical micro/nanostructures and their photocatalytic activity

Urchin-like Co₃O₄ hierarchical micro/nanostructures have been successfully synthesized by calcining urchin-like precursor CoCO₃, which are prepared by a facile hydrothermal route. The particle size of the urchin-like Co₃O₄ could be easily controlled by altering the calcination temperature. The morphology and structure of the as-prepared urchin-like products were characterized by XRD, FESEM and TEM. Photocatalytic measurement demonstrates that these urchin-like Co₃O₄ micro/nanostructures show good photocatalytic effect and their degradation efficiency is strongly dependent on their particle size. Furthermore, a plausible reaction mechanism is also proposed to illustrate the photocatalytic processes of Co₃O₄.     

径向生长的具有分级结构的四氧化三钴微晶及其在气体传感上的应用

通过在水热合成后追加退火处理,制备了径向生长的具有分级结构的树枝状三维Co₃O₄晶体,并用X射线衍射仪、扫描电子显微镜和透射电子显微镜对其结构和形貌进行了表征. 在110 oC对其气体探测性能的研究表明这种Co₃O₄分级结构对氨气有较高的探测灵敏度和响应速度(10 s),性能稳定并具有可重复性. 同时,还在较低的探测温度下对酒精、丙酮和苯进行了气敏探测.     

Electrochemical characterization of Mn: Co3O4 thin films prepared by spray pyrolysis via aqueous route

Present investigation reports, spray pyrolytic deposition of Mn: Co₃O₄ thin films onto the stainless steel by spray pyrolysis, at the deposition temperature 573 ± 2 K via aqueous route. Prepared electrodes were characterized structurally and morphologically by means of XRD and SEM. Also optical and electrochemical characterizations were carried out in depth. Structural characterization confirms face centered cubic and tetragonal body centered crystal structures for Co₃O₄ and Mn₃O₄ respectively. The rough granular morphology is observed form SEM. Electrochemical study reveals the pseudo capacitive as well as double layer behavior with optimum specific capacitance 485.29 F/g at the scan rate 1 mV/s in 1 M KOH electrolyte. Specific energy, specific power and columbic efficiency were calculated using chronopotentiometric technique. Electrochemical impedance spectroscopy was carried out in the frequency range 1 mHz–1 MHz. Randles equivalent circuit parameters associated with the operative cell are reported.     

Neutron powder diffraction and magnetic studies of mesoporous Co3O4

Samples of mesoporous Co₃O₄, created by using mesoporous silicas KIT-6 and SBA-16 as hard templates to control the growth of Co₃O₄ have been investigated with SQUID magnetometry and neutron powder diffraction, to reveal the effects of high surface area on the magnetic and electronic properties. DC magnetic susceptibility measurements show lower Néel ordering temperatures and lower magnetic moments than in a “bulk” reference. A lower second transition temperature is also observed in the mesoporous samples, associated with the freezing of the surface (shell) magnetic moments. Measurements taken with increasing applied field at constant temperature show the materials to be antiferromagnetic as expected. Complementary parametric neutron powder diffraction studies show similar trends between the two mesoporous samples when looking at their Néel temperatures, and verify long range order within the samples.     

Comparison of magnetic properties in LixCoO2 and its decomposition products LiCo2O4 and Co3O4

Thermal stability of cathode material in the charged state is an important aspect for the safety of rechargeable batteries. It is well known that layered Li_xCoO₂ decomposes to a mixture of LiCoO₂ and Co₃O₄ at elevated temperatures. However, not many experimental evidences exist on intermediate phases those may form during the decomposition. Using magnetic measurements we show that it is possible to distinguish between the spinels LiCo₂O₄ and Co₃O₄ and thereby follow the decomposition of Li_xCoO₂. We characterize the magnetic behavior of thermally aged Li_xCoO₂ (x = 0.98, 0.76, 0.55) with increasing annealing time. Our results reveal the appearance of magnetic ordering in the thermally degraded products. The detailed analysis illustrates that the formation of Co₃O₄ is preceded by the formation of a meta stable LiCo₂O₄ phase.     

调控氧空位实现高比表面积Co3O4纳米片上的产氧反应

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we designed an efficient Co₃O₄ electrocatalyst using a pyrolysis strategy for oxygen evolution reaction (OER). Morphological characterization confirmed the ultra-thin structure of nanosheet. Further, the existence of oxygen vacancies was obviously evidenced by the X-ray photoelectron spectroscopy and electron spin resonance spectroscopy. The increased surface area of Co₃O₄ ensures more exposed sites, whereas generated oxygen vacancies on Co₃O₄ surface create more active defects. The two scenarios were beneficial for accelerating the OER across the interface between the anode and electrolyte. As expected, the optimized Co₃O₄ nanosheets can catalyze the OER efficiently with a low overpotential of 310 mV at current density of 10 mA/cm² and remarkable long-term stability in 1.0 mol/L KOH.     

Characterization and electrochemical performance of the spinel LiMn2O4 prepared from -MnO2

The preparation and characterization of the spinel LiMn₂O₄ obtained by solid state reaction from quasi-amorphous -MnO₂ is reported. A well-defined highly pure spinel was characterized from X-ray diffractograms. The average manganese valence of -MnO₂ and spinel samples was found to be 3.89±0.01 and 3.59±0.01, respectively. The electrochemical performance of the spinel was evaluated through cyclic voltammetry and chronopotentiometry. The voltammetric profiles obtained at 1 mV/s for the LiMn₂O₄ electrode in 1 M LiClO₄ dissolved in a 2:1 mixture of ethylene carbonate and dimethyl carbonate showed typical peaks for the lithium insertion/extraction reactions. The charge capacity of this electrode was found to be 110 mA h g⁻¹ for the first charge/discharge cycles.     

三维海胆状Co3O4的微纳结构制备及锂电池性能

水热法制备的合成海胆状Co₃O₄前驱物在空气中退火得到三维海胆状Co₃O₄的微纳结构. 采用FESEM、TEM、HRTEM以及XRD对产物进行形貌和结构的表征. 结果表明,合成的海胆状结构Co₃O₄由许多粒径约为15 nm的颗粒串接形成. 锂电池测试性能表明,制备的海胆状Co₃O₄首次放电容量达到1.369 Ah/g,经过20次循环     

Non-equilibrium effects in the magnetic behavior of Co3O4 nanoparticles

We report detailed studies of the non-equilibrium magnetic behavior of antiferromagnetic Co₃O₄ nanoparticles. The temperature and field dependence of magnetization, wait time dependence of magnetic relaxation (aging), memory effects, and temperature dependence of specific heat have been investigated to understand the magnetic behavior of these particles. We find that the system shows some features that are characteristic of nanoparticle magnetism such as bifurcation of field-cooled (FC) and zero-field-cooled (ZFC) susceptibilities and a slow relaxation of magnetization. However, strangely, the temperature at which the ZFC magnetization peaks coincides with the bifurcation temperature and does not shift on application of magnetic fields up to 1 kOe, unlike most other nanoparticle systems. Aging effects in these particles are negligible in both FC and ZFC protocols, and memory effects are present only in the FC protocol. We show that Co₃O₄ nanoparticles constitute a unique antiferromagnetic system which enters into a blocked state above the average Néel temperature.     

Al掺杂的尖晶石型LiMn2O4的结构和电子性质

采用基于密度泛函理论的第一性原理方法, 在广义梯度近似(GGA)和GGA+U方法下对尖晶石型LiMn₂O₄及其Al掺杂 的尖晶石型LiAl_0.125Mn_1.875O₄晶体的结构和电子性质进行了计算. 结果表明: 采用GGA方法得到尖晶石型LiMn₂O₄是立方晶系结构, 其中的Mn离子为+3.5价, 无法解释它的Jahn-Teller 畸变. 给出的LiMn₂O₄能带结构特征也与实验结果不符. 而采用GGA+U方法得到在低温下的LiMn₂O₄和其掺杂 体系LiAl_0.125Mn_1.875O₄的晶体都是正交结构, 与实验一致. 也能明确地确定Mn的两种价态Mn³⁺/Mn⁴⁺的分布并且能够说明Mn³⁺O₆的z方向有明显的Jahn-Teller 畸变, 而Mn⁴⁺O₆则没有畸变. LiMn₂O₄的能带结构与实验比较也能够符合. 采用GGA+U方法对Al掺杂体系的LiAl_0.125Mn_1.875O₄的研究表明, 用Al替换一个Mn不会明显地改变晶体的电子性质, 但可以有效地消除Al³⁺O₆ 八面体的Jahn-Teller畸变, 从而改善正极材料LiMn₂O₄的性能, 这与电化学实验的观察结果相一致.     

A density functional theory study of CH4 dehydrogenation on Co(1 1 1)

The dehydrogenation of CH₄ on the Co(1 1 1) surface is studied using density functional theory calculation (DFT). It is found that CH₄ is favored to dissociate to CH₃ and then transforms to CH₂ and CH by sequential dehydrogenation, and CH₄ activation into CH₃ and H is the rate-determining step on the Co(1 1 1) surface. CH₂ is quite unstable on Co(1 1 1) surface. CH dehydrogenation into C and H is difficult. CH₃ and H prefer to adsorb on 3-fold hollow hcp and fcc sites, and CH₂, CH and C prefer to adsorb on hcp sites.     

焙烧温度对SiO2负载的Co3O4纳米粒子表面氧缺陷浓度和CO氧化催化性能的影响

以传统的浸渍法,在不同焙烧温度下制备了用于CO氧化反应的Co₃O₄/SiO₂催化剂．通过激光拉曼光谱(Raman)、X射线光电子能谱(XPS)、X射线衍射(XRD)、程序升温还原(TPR)和X射线吸收精细结构谱(XAFS)表征了该系列催化剂的结构．在所有的催化剂中,XRD和Raman光谱都只检测到了Co₃O₄晶相的存在．与Co₃O₄体相相比,XPS结果表明在200 oC焙烧的(Co₃O₄(200)/SiO₂)催化剂中Co₃O₄表面上存在着过量的Co²⁺．与XPS的结果一致,TPR结果表明Co₃O₄(200)/SiO₂催化剂中Co₃O₄表面上存在氧缺陷, 并且XAFS结果也表明Co₃O₄(200)/SiO₂催化剂中Co₃O₄具有更多的Co²⁺．提高焙烧温度使得过量的Co²⁺进一步氧化为Co³⁺,同时降低了表面氧缺陷浓度,从而得到计量比的Co₃O₄4/SiO₂催化剂．在所有的负载催化剂中Co₃O₄(200)/SiO₂催化剂表现出了最好的CO氧化催化性能,表明过量Co²⁺和表面氧缺陷的存在能够促进Co₃O₄催化CO氧化反应的活性.     

Monochromatic blue-green and red emission of rare-earth ions in MgGa2O4 spinel

Pr³⁺-activated blue-green phosphor and Eu³⁺-activated red phosphor hosted in MgGa₂O₄ spinel have been prepared by a gel-assisted high-temperature calcination process, respectively. Both anion and cation vacancies in the host were formed by decreasing the Mg concentration in the reaction source. The induced vacancies provide possibility of the accommodation of the doped rare-earth ions with larger atomic size in the highly symmetrical spinel structure. Due to the efficient energy transfer from the spinel host to the sole 4f sub-level of the doped rare earths, monochromatic emissions with high efficiency can be obtained to allow the phosphors to find applications in solid-state laser device and other phosphors excited under low energy. The corresponding spectroscopic transition mechanism has been proposed in this work.     

Biosynthesis and magnetic properties of mesoporous Fe3O4 composites

Magnetic Fe₃O₄ materials with mesoporous structure are synthesized by co-precipitation method using yeast cells as a template. The X-ray diffraction (XRD) pattern indicates that the as-synthesized mesoporous hybrid Fe₃O₄ is well crystallized. The Barrett-Joyner-Halenda (BJH) models reveal the existence of mesostructure in the dried sample which has a specific surface area of 96.31 m²/g and a pore size distribution of 8-14 nm. Transmission electron microscopy (TEM) measurements confirm the wormhole-like structure of the resulting samples. The composition and chemical bonds of the Fe₃O₄/cells composites are studied by Fourier transform infrared (FT-IR) spectroscopy. Preliminary magnetic properties of the mesoporous hybrid Fe₃O₄ are characterized by a vibrating sample magnetometer (VSM). The magnetic Fe₃O₄/cells composites with mesoporous structure have potential applications in biomedical areas, such as drug delivery.     

Silane treatment of Fe3O4 and its effect on the magnetic and wear properties of Fe3O4/epoxy nanocomposites

In this study, the effect of silane treatment of Fe₃O₄ on the magnetic and wear properties of Fe₃O₄/epoxy nanocomposites was investigated. Fe₃O₄ nanopowders were prepared by coprecipitation of iron(II) chloride tetrahydrate with iron(III) chloride hexahydrate, and the surfaces of Fe₃O₄ were modified with 3-aminopropyltriethoxysilane. The magnetic properties of the powders were measured on unmodified and surface-modified Fe₃O₄/epoxy nanocomposites using SQUID magnetometer. Wear tests were performed on unmodified and surface-modified Fe₃O₄/epoxy nanocomposites under the same conditions (sliding speed: 0.18 m/s, load: 20 N).The results showed that the saturation magnetization (M_s) of surface-modified Fe₃O₄/epoxy nanocomposites was approximately 110% greater than that of unmodified Fe₃O₄/epoxy nanocomposites. This showed that the specific wear rate of surface-modified Fe₃O₄/epoxy nanocomposites was lower than that of unmodified Fe₃O₄/epoxy nanocomposites. The decrease in wear rate and the increase in magnetic properties of surface-modified Fe₃O₄/epoxy nanocomposites occurred due to the improved dispersion of Fe₃O₄ into the epoxy matrix.     

Synthesis and properties of Au-Fe3O4 and Ag-Fe3O4 heterodimeric nanoparticles

Monodisperse Au-Fe 3 O 4 heterodimeric nanoparticles (NPs) were prepared by injecting precursors into a hot reaction solution.The size of Au and Fe 3 O 4 particles can be controlled by changing the injection temperature.UV-Vis spectra show that the surface plasma resonance band of Au-Fe 3 O 4 heterodimeric NPs was evidently red-shifted compared with the resonance band of Au NPs of similar size.The as-prepared heterodimeric Au-Fe 3 O 4 NPs exhibited superparamagnetic properties at room temperature.The Ag-Fe 3 O 4 heterodimeric NPs were also prepared by this synthetic method simply using AgNO 3 as precursor instead of HAuCl 4.It is indicated that the reported method can be readily extended to the synthesis of other noble metal conjugated heterodimeric NPs.