Co3O4纳米催化剂催化CO的形貌效应：合成过程和催化活性

通过催化剂将CO转化为无毒气体仍然是目前减少CO污染的主要手段.随着纳米技术的快速发展,纳米催化剂因其在催化反应中呈现出的独特结构效应（如形貌效应、尺寸效应等）而受到人们的广泛关注.已有大量研究表明,纳米Co3O4作为一种非贵金属氧化物催化剂具有强烈的催化形貌效应,展现出优异的CO低温催化活性.因此,通过合理的设计来调控催化剂粒子的形貌,从而进一步改善催化剂的性能已成为近年来催化剂领域的重要研究方向.对于Co3O4纳米催化剂的可控制备,水热法具有反应温和、操作简便和产品形貌易控等特点.早期的研究主要围绕于Co3O4形貌的可控合成以及不同形貌Co3O4催化剂对其催化活性产生的影响,较少有对其形貌形成机制的报道.特别是在水热反应中,系统研究各反应参数对催化剂各异形貌的形成影响鲜有报道.
　　本文在前人的研究基础上,重点研究了水热反应过程中各主要反应参数对产品形貌控制的影响,绘制了一副不同形貌Co3O4材料的合成过程图,并研究了Co3O4纳米催化剂催化CO氧化的形貌效应.通过水热法先成功合成了三种不同形貌(纳米棒、纳米片和纳米立方)的碱式碳酸钴纳米粒子,然后将其焙烧得到了Co3O4纳米粒子.采用扫描电子显微镜(SEM),透射电子显微镜(TEM), X射线粉末衍射仪(XRD),程序升温还原(H2-TPR和CO-TPR),氮气吸附-脱附比表面积测试(BET),氧气程序升温脱附(O2-TPD), X射线光电子能谱(XPS)等表征手段研究了不同反应参数对纳米碱式碳酸钴前驱体形貌形成的作用和各异形貌Co3O4纳米粒子在催化CO氧化反应中催化性能的差异及原因.
　　结果表明, Co3O4较好地继承了碱式碳酸钴的形貌,在较低温度条件下(≤140°C),钴源(CoCl2或Co(NO3)2)是影响前驱体形貌的关键因素,反应时间只对粒子的尺寸产生较大影响.低温下, CoCl2作为钴源易诱导生产纳米棒状碱式碳酸钴,而Co(NO3)2则有利于纳米片状生成.当温度高于140°C后,无论何种钴源,最终均制得纳米立方体.表面活性剂CTAB对前驱体的均一性和粒子的分散性产生重要影响,加入CTAB后得到的产品尺寸更均一,形貌更加规整.对比于其他两种形貌的样品, Co3O4纳米片显示出更好的CO催化氧化活性.
　　 XPS结果表明,各形貌Co3O4纳米材料的表面组成存在明显差异,活性物种Co3+含量的不同是影响催化活性差异的重要原因. Co3O4纳米片具有更多的Co3+活性位,立方纳米Co3O4表面吸附氧含量较高, Co3O4纳米棒则暴露出相对更多的Co2+.因此,在三种形貌催化剂上CO氧化反应中, Co3O4纳米片表现出最优的催化活性,纳米立方次之,而纳米棒最差. H2-TPR, CO-TPR和O2-TPD等结果也表明, Co3O4纳米片拥有更强的还原性能和脱附氧能力,其次是纳米立方Co3O4.这与XPS结果一致,证实了不同形貌Co3O4纳米催化剂上暴露活性位的数量和表面氧物种的不同是造成彼此间催化CO氧化活性差异的重要原因.此外,通过稳定性测试发现Co3O4纳米片具有较高的催化稳定性,在水蒸气存在的情况下Co3O4纳米片逐渐失活,但随后在干燥条件下其催化活性又逐渐得到恢复.     

Ultrathin Co3O4 nanowires with high catalytic oxidation of CO

Ultrathin Co(3)O(4) nanostructures with high catalytic oxidation of CO were synthesized by heating cobalt foils under atmospheric conditions. The Co(3)O(4) nanostructures were selectively exposing (111) planes composed of plenty of Co(3+) cations. We observed ultrahigh catalytic oxidation of CO in Co(3)O(4) nanowires with about 3 nm diameter.     

Cobalt Hydroxide Nanosheets and Their Thermal Decomposition to Cobalt Oxide Nanorings

We demonstrate herein that single‐crystalline β‐cobalt hydroxide (β‐Co(OH)₂) nanosheets can be successfully synthesized in large quantities by a facile hydrothermal synthetic method with aqueous cobalt nitrate as the cobalt source and triethylamine as both an alkaline and a complexing reagent. This synthetic method has good prospects for the future large‐scale production of single‐crystalline β‐Co(OH)₂ nanosheets owing to its high yield, low cost, and simple reaction apparatus. Single‐crystalline porous nanosheets and nanorings of cobalt oxide (Co₃O₄) were obtained by a thermal‐decomposition method with single‐crystalline β‐Co(OH)₂ nanosheets as the precursor. A probable mechanism of formation of β‐Co(OH)₂ nanosheets, porous Co₃O₄ nanosheets, and Co₃O₄ nanorings was proposed on the basis of the experimental results.     

Morphology-controllable synthesis of cobalt oxalates and their conversion to mesoporous Co3O4 nanostructures for application in supercapacitors

In this work, one-dimensional and layered parallel folding of cobalt oxalate nanostructures have been selectively prepared by a one-step, template-free, water-controlled precipitation approach by simply altering the solvents used at ambient temperature and pressure. Encouragingly, the feeding order of solutions played an extraordinary role in the synthesis of nanorods and nanowires. After calcination in air, the as-prepared cobalt oxalate nanostructures were converted to mesoporous Co(3)O(4) nanostructures while their original frame structures were well maintained. The phase composition, morphology, and structure of the as-obtained products were studied in detail. Electrochemical properties of the Co(3)O(4) electrodes were carried out using cyclic voltammetry (CV) and galvanostatic charge-discharge measurements by a three-electrode system. The electrochemical experiments revealed that the layered parallel folding structure of mesoporous Co(3)O(4) exhibited higher capacitance compared to that of the nanorods and nanowires. A maximum specific capacitance of 202.5 F g (-1) has been obtained in 2 M KOH aqueous electrolyte at a current density of 1 A g(-1) with a voltage window from 0 to 0.40 V. Furthermore, the specific capacitance decay after 1000 continuous charge-discharge cycles was negligible, revealing the excellent stability of the electrode. These characteristics indicate that the mesoporous Co(3)O(4) nanostructures are promising electrode materials for supercapacitors.     

孔状Co_3O_4纳米片和纳米棒的选择性合成和表征(英文)

利用两步实验选择性合成孔状Co3O4纳米片和纳米棒:首先,以Co(NO3)2·6H2O,NaOH和不同量的NH4F为原料在120℃水热6h的条件下合成了Co(OH)2-Co3O4纳米片(S1)和Co(OH)F-Co3O4纳米棒(S2);然后将所得纳米片和纳米棒在400℃时加热2h即得到多孔的Co3O4纳米片和纳米棒。所得产物用X射线衍射(XRD)、场发射扫描电子显微镜(FE-SEM)和透射电子显微镜(TEM)进行了表征。此外电化学测试表明Co3O4纳米棒的电容量比Co3O4纳米片的更大。     

还原氧化石墨烯/碳纳米管/Co_3O_4三元复合材料的制备与电化学性能

将低温水热反应和低温热处理相结合,制备了含还原氧化石墨烯(RGO)、碳纳米管(CNTs)和Co3O4的三元纳米复合材料RGO-CNTs-Co3O4;利用X射线衍射仪、扫描电子显微镜、透射电子显微镜分析了合成产物的相组成和微观结构,分析了其形成过程;并利用电化学测试装置测定了其作为锂离子电池负极材料的电化学性能.结果表明,在合成反应过程中,氧化石墨烯被还原剂肼还原为石墨烯,同时在石墨烯和CNTs表面生成氢氧化钴;再经低温热处理得到RGO-CNTs-Co3O4三元复合材料.Co3O4纳米颗粒均匀分散在由RGO片层和CNTs组成的三维网络结构中;这种三维网络结构既有利于电子和离子的传输,又能够有效抑制Co3O4在脱嵌锂过程中因体积变化引起的结构破坏.总体而言,合成的新型三元复合材料具有高的比容量以及良好的循环性能与倍率性能.     

Porous ZnCo2O4 nanowires synthesis via sacrificial templates: high-performance anode materials of Li-ion batteries

A simple microemulsion-based method has been developed to synthesize ZnCo(2)(C(2)O(4))(3) nanowires that can be transformed to porous ZnCo(2)O(4) nanowires under annealing conditions. The morphology of porous ZnCo(2)O(4) nanowires can be tuned by the initial ZnCo(2)(C(2)O(4))(3) nanowires and the annealing temperatures. The as-synthesized porous ZnCo(2)O(4) nanowires have been applied as anode materials of Li-ion batteries, which show superior capacity and cycling performance. The porous one-dimensional (1D) nanostructures and large surface area are responsible for the superior performance. Moreover, it is indicated that porous ZnCo(2)O(4) nanowires synthesized at low annealing temperature (500 °C) show larger capacity and better cycling performance than that prepared at high annealing temperature (700 °C), because of their higher porosity and larger surface area.     

CoFe2O4纳米阵列催化剂的费托合成性能研究

通过可控的水热生长方法和钴铁碳酸根氢氧根水合物的焙烧在泡沫铁上制备了CoFe₂O₄纳米阵列催化剂。通过粉末X射线衍射,扫描电镜和电感耦合等离子体发射光谱表征了CoFe₂O₄纳米阵列的晶相,结构和组成。制备的催化剂被用于费托合成性能研究。CoFe₂O₄纳米阵列催化剂在5L/（g·h）的空速下具有69%的转化率,并且其性能优于粉体催化剂。     

High-yield preparation of uniform cobalt hydroxide and oxide nanoplatelets and their characterization

Cobalt hydroxide nanoplatelets with a uniform hexagonal shape were prepared in high yield ( approximately 95%) by a facile hydrothermal route in the presence of poly(vinylpyrrolidone). This method provides a simple, low-cost, and large-scale route to produce beta-cobalt hydroxide nanoplatelets with an average diameter of 280 nm and a thickness of ca. 26 nm which show a predominant well-crystalline hexagonal brucite-like phase. Their thermal decomposition produced anisotropic nanoplatelets of cobalt oxides (CoO and Co3O4) under designed temperatures. The products were characterized by transmission electronic microscopy, selected-area electron diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetric, and thermogravimetric analysis. The magnetic properties of the products were investigated by a superconducting quantum interference device magnetometer. Co3O4 nanoplatelets exhibit a superparamagnetic behavior, and they might be a promising material to study the magnetic tunneling effect as anisotropic nanostructures.     

三维花状Co3O4的低成本制备及其在催化CO氧化中的应用（英文）

采用一种快速、无模板、低成本的微波辅助水热法在2min内制备了三维花状Co3O4.所用原料均是无机盐.前驱体浓度和尿素的逐渐水解对Co3O4形貌影响很大.制得的花状Co3O4比表面积大,且暴露了(110)高活性指数面,对CO氧化具有较高的催化活性.     

Mesoporous nickel oxide nanowires: hydrothermal synthesis, characterisation and applications for lithium-ion batteries and supercapacitors with superior performance

Mesoporous nickel oxide nanowires were synthesized by a hydrothermal reaction and subsequent annealing at 400?°C. The porous one-dimensional nanostructures were analysed by field-emission SEM, high-resolution TEM and N(2) adsorption/desorption isotherm measurements. When applied as the anode material in lithium-ion batteries, the as-prepared mesoporous nickel oxide nanowires demonstrated outstanding electrochemical performance with high lithium storage capacity, satisfactory cyclability and an excellent rate capacity. They also exhibited a high specific capacitance of 348?F?g(-1) as electrodes in supercapacitors.     

Synthesis of Cobalt Ion‐Based Coordination Polymer Nanowires and Their Conversion into Porous Co3O4 Nanowires with Good Lithium Storage Properties

Cobalt ion‐based coordination polymer nanowires were synthesized by using nitrilotriacetic acid (NA) as a chelating agent by a one‐step hydrothermal approach. In the synthesis, cobalt ions were bonded with amino or carboxyl groups of NA to form one‐dimension polymer nanowires, which can be confirmed by FTIR and TGA results. Our experimental results show that the morphologies of polymer nanowires greatly depend on the precursor salts, ratios between deionized water and isopropyl alcohol. The probable molecular formula and growth mechanism have been proposed. After heat treatment, the cobalt ion‐based coordination polymer nanowires can be converted into porous Co₃O₄ nanowires, which completely preserved the nanowire‐like morphology. When used as anodes in lithium‐ion batteries, the obtained porous Co₃O₄ nanowires exhibited a high reversible capacity of 810 mA h g^?1 and stable cyclic retention at 30th cycle. The good electrochemical performance could be attributed to the porous nanostructure of Co₃O₄, which provides pathways for easy accessibility of electrolytes and fast transportation of lithium ions.     

Hierachically porous nanocrystalline cobalt oxide monoliths through nanocasting

Nanocrystalline cobalt oxide, Co(3)O(4), monoliths exhibiting hierarchical bimoidal porosity have been prepared by nanocasting of porous silica monoliths.     

Solution decomposition of the layered double hydroxide of Co with Fe: phase segregation of normal and inverse spinels

The nitrate-intercalated layered double hydroxide of Co with Fe decomposes on hydrothermal treatment to yield an oxide residue at a temperature as low as 180 degrees C. The oxide product is phase segregated into a Co(3)O(4)-type normal spinel and a CoFe(2)O(4)-type inverse spinel. Phase segregation is facilitated as decomposition in a solution medium takes place by dissolution of the precursor hydroxide followed by reprecipitation of the oxide phases. In contrast, thermal decomposition takes place at 400 degrees C. This temperature is inadequate to induce diffusion in the solid state whereby phase segregation into the thermodynamically stable individual spinels is suppressed. The result is a single-phase metastable mixed spinel oxide. This is rather uncommon in that a hydrothermal treatment yields thermodynamically stable products where as thermal decomposition yields a metastable product.     

Mesoporous Nickel Oxide Nanowires: Hydrothermal Synthesis,Characterisation and Applications for Lithium‐Ion Batteries and Supercapacitors with Superior Performance

Mesoporous nickel oxide nanowires were synthesized by a hydrothermal reaction and subsequent annealing at 400 °C. The porous one‐dimensional nanostructures were analysed by field‐emission SEM, high‐resolution TEM and N₂ adsorption/desorption isotherm measurements. When applied as the anode material in lithium‐ion batteries, the as‐prepared mesoporous nickel oxide nanowires demonstrated outstanding electrochemical performance with high lithium storage capacity, satisfactory cyclability and an excellent rate capacity. They also exhibited a high specific capacitance of 348 F g^?1 as electrodes in supercapacitors.     

Synthesis, characterization, and electrochemical properties of Ag2V4O11 and AgVO3 1-D nano/microstructures

We report on the synthesis, characterization, and electrochemical properties of Ag(2)V(4)O(11) nanowires, alpha-AgVO(3) microrods, and beta-AgVO(3) nanowires that were synthesized through a simple and facile low-temperature hydrothermal approach without any template or catalyst. It was found that by simply controlling the hydrothermal reaction parameters such as pH and dwell time, the transformation of alpha-AgVO(3) microrods to beta-AgVO(3) nanowires were readily achieved through a "ripening-splitting model" mechanism. Electrochemical measurements revealed that the as-prepared Ag(2)V(4)O(11) nanowires, alpha-AgVO(3) microrods, and beta-AgVO(3) nanowires exhibited high discharge capacities and excellent high-rate dischargeability. In particular, the beta-AgVO(3) nanowires have much higher capacity above 3 V than that of alpha-AgVO(3) microrods, Ag(2)V(4)O(11) nanowires, and commercial Ag(2)V(4)O(11) bulk. The mechanisms for electrochemical lithium intercalation of the AgVO(3) nanostructures were also discussed. It is anticipated that the novel Ag(2)V(4)O(11) and AgVO(3) one-dimensional nano/microstructures are promising cathode candidates in the application of primary lithium ion batteries for implantable cardioverter defibrillators (ICDs).     

Photochemical synthesis of a water oxidation catalyst based on cobalt nanostructures

New cobalt-based nanocomposites have been prepared by photoreduction of Co(2+) salts to generate cobalt nanoparticles deposited on carbon-based materials such as nanocyrstalline diamond and carbon felt. Spontaneous air oxidation converts the metal to Co(2)O(3) which has been tested as a water oxidation catalyst. This work demonstrates that the cobalt oxide nanostructures can be deposited on various carbon surfaces and can catalyze the four-electron oxidation of water to oxygen under anodic bias.     

Effect of Various Synthesis methods on the Electrochemical Properties of LiNi1/3Co1/3Mn1/3O2

Layered LiNi1/3Co1/3Mn1/3O2 has the isostructure of α-NaFeO2 and shows high rate capacity with stable cycleability. Furthermore, the thermal behavior of this material is milder than that of lithium nickel oxide and lithium cobalt oxide. In addition, it is expected to be stable at elevated temperatures. Therefore LiNi1/3Co1/3Mn1/3O2 may be the most promising cathode materials of lithium-ion secondary battery.In this research, LiNi1/3Co1/3Mn1/3O2 was prepared by solid-state reaction, sol-gel method and mixed hydroxide method. The influences of synthesis method on the physical and electrochemical properties of LiNi1/3Co1/3Mn1/3O2 were characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), charge/discharge cycling cyclic voltammetry and differential scanning calorimetry (DSC). XPS studies show that the predominant oxidation states of Ni, Co and Mn in the LiNi1/3Co1/3Mn1/3O2 compound are 2+, 3+ and 4+. From the voltage profile and cyclic voltammetry, the redox processes occurring at ～3.8V and ～4.5V are assigned to the Ni2+/Ni3+ and Co3+/Co4+ couples, respectively. Different preparation methods result in the difference in morphology (shape, particle size and specific surface area) and electrochemical behaviors. A sample prepared by solid-state reaction has the worst electrochemical performance among these three methods. Sample synthesized by mixed hydroxide method displays the better rate capacity than that prepared by sol-gel method, while the capacity retention of sample prepared by sol-gel method is superior to that synthesized by mixed hydroxide method.     

A Molecular Approach to Self‐Supported Cobalt‐Substituted ZnO Materials as Remarkably Stable Electrocatalysts for Water Oxidation

In regard to earth‐abundant cobalt water oxidation catalysts, very recent findings show the reorganization of the materials to amorphous active phases under catalytic conditions. To further understand this concept, a unique cobalt‐substituted crystalline zinc oxide (Co:ZnO) precatalyst has been synthesized by low‐temperature solvolysis of molecular heterobimetallic Co_4?xZn_xO₄ (x=1–3) precursors in benzylamine. Its electrophoretic deposition onto fluorinated tin oxide electrodes leads after oxidative conditioning to an amorphous self‐supported water‐oxidation electrocatalyst, which was observed by HR‐TEM on FIB lamellas of the EPD layers. The Co‐rich hydroxide‐oxidic electrocatalyst performs at very low overpotentials (512 mV at pH 7; 330 mV at pH 12), while chronoamperometry shows a stable catalytic current over several hours.     

Shape-controlled synthesis and characterization of cobalt oxides hollow spheres and octahedra

We demonstrated that single-crystalline cobalt monoxide (CoO) hollow spheres and octahedra could be selectively synthesized via thermal decomposition of cobalt(II) acetylacetonate in 1-octadecene solvent in the presence of oleic acid and oleylamine. The morphologies and sizes of as-prepared CoO nanocrystals could be controlled by adjusting the reaction parameters. Cobalt oxide (Co(3)O(4)) hollow spheres and octahedra could also be selectively obtained via calcination method using corresponding CoO hollow spheres and octahedra as precursors. The morphology, size and structure of the final products were investigated in detail by XRD, SEM, TEM, HRTEM, DSC, TG, and XPS. The results revealed that the electrochemical performance of cobalt oxide hollow spheres is much better than that of cobalt oxide octahedra, which may be related to the degree of crystallinity, size, and morphology of cobalt oxides.