碱性水电解镍基析氧催化材料最新进展

通过碱性水电解制氢技术,将可再生能源转化为绿氢,是实现能源储存和分布再平衡的最具应用前景的方法。开发低过电位的碱性水电解电催化剂是降低绿氢电耗和成本的必要条件。镍基材料是目前商业化碱性水电解制氢应用最广泛的电催化剂,但不断追求高电流密度和快速动力学的高效电催化剂是提高碱性水电解制氢设备性能的主要研究方向之一。综述碱性水电解制氢镍基析氧催化材料的研究进展,包括反应机理、评价指标和制备-结构-性能关系。同时,对目前存在的问题进行剖析,并对未来发展方向进行展望。     

一步电沉积制备高活性高稳定镍铁合金析氧电催化剂

以镍网为基底,通过一步电沉积方法成功制备出用于碱性水电解的多孔镍铁合金析氧反应(Oxygen Evolution Reaction,OER)电极.镍铁的沉积伴随强烈的析氢,此条件下构筑出的多级孔结构成为电极用于OER反应时液相中传质与气泡释放的适宜传递通道.在析氧反应中,电流密度为10 mA·cm-2时的过电位仅为21...     

Ni-Fe基析氧阳极材料的研究进展

寻找一种高效、稳定和低成本的析氧阳极材料对于在碱性环境中电解水的研究具有非常重要的实际意义。近年来,Ni-Fe基材料以其低成本及在碱性条件下具有高催化活性的特点成为析氧反应电极材料的研究热点。本文概述了近几年国内外学者对不同的Ni-Fe基析氧材料(包括Ni-Fe合金、Ni-Fe氧化物、Ni-Fe层状双金属氢氧化物及Ni-Fe基复合材料等)在合成方法、物理形态、化学结构和催化性能等方面所进行的研究,介绍了Ni-Fe基材料的析氧反应机理的进展,探究了析氧反应活性相以及Fe的掺入对Ni基氢氧化物的结构和活性的影响,最后指出了合成方法的改进及详细反应机理的探究将会成为未来Ni-Fe基析氧阳极材料的重点研究方向。     

过渡金属氧化物催化析氧反应研究进展

利用可再生能源电解水制氢,是实现绿色氢能经济的必由之路。现阶段,电解水过程的阳极析氧反应过电位较高,催化剂性能不稳定,制约着该技术的工业化应用。使用经济高效的催化剂,可显著降低析氧过电位,提高电解水制氢过程的经济性和电能转化效率。在各类析氧催化剂材料中,过渡金属氧化物(TMOs)由于晶体结构多样、储量丰富、环境友好、易于制备以及活性较高等优点,受到了越来越多的关注。本文从活性和稳定性出发,总结分析了近年来过渡金属氧化物催化析氧反应的研究进展,并对其未来的发展提出了建议与展望。     

Mn掺杂NiCo氧化物高效析氧催化剂的研究

采用水热法合成了一种高电化学性能、低成本的NiCo氧化物材料.通过在NiCo氧化物晶体结构中加入Mn,使用XRD、SEM、Mapping、XPS对样品结构和微观形貌进行了表征,对所制备材料的电化学析氧性能进行了测试和分析.结果 表明,Mn-NiCo-0.1 mmol只需要300 mV的低过电位即可实现10 mA·cm-...     

铁钴MOF的制备及电解水析氧性能研究

氢气是一种高能量密度的清洁型能源,具有高效率、低成本、产物无污染和来源丰富等优点,利用太阳能光伏、风力、水力等可再生清洁能源电催化分解水制氢是最具潜力的绿色制氢方式之一。其中电催化材料对能源转换效率起至关重要的作用,电催化优异的Pt、Ir等贵金属基材料价格高昂、储量稀缺,无法在工业上大规模应用。因此,非贵金属类电催化材料成为当前电催化领域研究的热点。而影响电解水效率的主要因素是动力学缓慢的析氧半反应(OER),本论文合成了一种新型有机双联配体,并利用该配体与钴、铁等配位,水热合成了一系列钴、铁单金属MOFs(Co_xMOFs、Fe_xMOFs)和钴铁双金属MOFs(Co_xFe_yMOFs)材料,表征其微观结构和形貌,并通过多种电化学手段测试其电催化分解水析氧性能,结果表明单金属MOF中有机配体与金属按物质的量比3∶1制备的MOF的析氧性能最好,而双金属MOF中铁和钴的相互作用提高了其电催化动力学、减小了电化学阻抗,Co₆FeMOF表现出最优的电催化析氧性能,且所有催化材料都具有较好的...     

复合氧化物La0.8Sr0.2CoO3的合成及其析氧电催化

通过有机酸辅助法在较低温度下合成了La0.8Sr0.2CoO3复合氧化物,XRD结果表明,用该方法合成的La0.8Sr0.2CoO3具有单相钙钛矿结构,从稳态物化曲线得出,在碱性溶液中,在La0.8Sr0.2CoO3表面的析氧Tafel斜率为65mV/dec,OH-的反应级数为1,在分析了反应机理后,得出了析氧反应的动力学方程,恒电流测试结果表明,用该方法制备的La0.8Sr0.2CoO3/Ni电极,在碱性溶液中具有良好的析氧催化活性.     

电沉积法制备碱性电解水镍基析氧电极的研究进展

在“碳达峰、碳中和”的目标下,绿氢成为极具前景的清洁能源。碱性电解水制取绿氢技术商业化程度最高,但由于析氧反应(OER)动力学过程缓慢且需要较高的过电位,成为制约电解水电极效率的主要瓶颈。商业电解槽中广泛使用的镍网或泡沫镍电极的OER性能仍有很大提升空间,在其上复合镍基催化功能层,开发新型高活性的析氧电极有利于提高电极效率,降低制氢成本。电沉积技术具有工艺简单、条件温和、利于放大生产自支撑电极的优势,成为工业化生产OER电极的理想工艺之一。本文综述了近年来利用电沉积技术制备的镍基析氧电极并用于碱性电解水的研究进展。采用电沉积技术在镍网或泡沫镍基底上制备镍(氢)氧化物、双金属及多元金属以及非金属掺杂的镍基催化剂作为催化功能层,通过增强催化功能层的电导率及金属间的协同作用、增加活性位点数量、减小扩散路径以及改变表面原子构型等方式提高镍基自支撑电极的OER性能。最后,展望了镍基自支撑电极在电解水领域的应用,同时指出了电沉积法制备电极材料存在的挑战。     

Ir-based oxide electrodes: oxygen evolution reaction from mixed solvents

The influence of 30% (v/v) organic cosolvent in 1.0 mol dm^–3 HClO₄ on the OER electrode kinetics, surface properties and electrode stability of IrO₂-based electrodes was investigated by cyclic voltammetry and polarization curves. The Tafel coefficients in the presence of cosolvent are explained in terms of the change of the rate-determining step (r.d.s.) of the OER electrode mechanism, coating dissolution and/or cosolvent oxidation. Of the several cosolvents investigated t-BuOH and PC show less effects on the OER and electrode properties making them the best choice for organic eletrosynthesis applications, in contrast to AN, which causes coating dissolution, and DMF and DMSO which show an anticipation of the voltammetric current.     

CIGS absorbing layers prepared by RF magnetron sputtering from a single quaternary target

Cu(In_1−xGa_x)Se₂ (CIGS) thin films were prepared by RF magnetron sputtering from a single quaternary target at multiple processing parameters. The structural, compositional, and electrical properties of the as-deposited films were systematically investigated by XRD, Raman, SEM, and Hall effects analysis. The results demonstrate that by adjusting the processing parameters, the CIGS thin films with a preferential orientation along the (112) direction which exhibited single chalcopyrite phase were obtained. The films deposited at relatively higher substrate temperature, sputtering power, and Ar pressure exhibited favorable stoichiometric ratio (Cu/(In+Ga):0.8–0.9 and Ga/(In+Ga):0.25–0.36) with grain size of about 1–1.5 µm, and desirable electrical properties with p-type carrier concentration of 10¹⁶−10¹⁷ cm⁻³ and carrier mobility of 10–60 cm²/Vs. The CIGS layers are expected to fabricate high efficiency thin film solar cells.     

Surface activation of manganese oxide electrode for oxygen evolution from seawater

Utilizing the fact that the equilibrium potential of oxygen evolution is lower than that of chlorine evolution, oxygen evolution in seawater electrolysis was enhanced by decreasing the polarization potential under galvanostatic conditions through increasing the effective surface area of manganese oxide electrodes. Electrodes were prepared by a thermal decomposition method. IrO2-coated titanium (IrO2/Ti electrode) was used as the substrate on which manganese oxide was coated (MnOX/IrO2/Ti electrode). Subsequently, oxide mixtures of manganese and zinc were coated (MnOX–ZnO/MnOX/IrO2/Ti electrode). The effective surface area of the MnOX–ZnO/MnOX/IrO2/Ti electrodes was increased by selective dissolution of zinc (leaching) into hot 6M KOH. The oxygen evolution efficiency of the MnOX/IrO2/Ti electrode was 68–70%. Leaching of zinc from the MnOX–ZnO/MnOX/IrO2/Ti electrodes with 25mol% or less zinc led to a significant increase in the oxygen evolution efficiency. The maximum efficiency attained was 86% after leaching of zinc from the MnOX–25mol%ZnO/MnOX/IrO2/Ti electrode. However, large amounts of zinc addition, such as 40mol% or more are detrimental because of a decrease in the oxygen evolution efficiency. This is due to the formation of a double oxide, ZnMnO3, which is hardly dissolved in hot 6M KOH.     

Growth evolution of CaB6 thin films deposited by DC magnetron sputtering

CaB₆ films were deposited by a DC magnetron sputtering method to explore the growth evolution systematically through changing sputtering time. The crystalline structure was characterized by XRD and GIXRD respectively, which showed that the films were anisotropic with nanocrystalline structure. The grain sizes increased with the deposition time, and a weak (100) texture appeared when the deposition time reached to 120 min. HRTEM was employed to demonstrate the crystalline structure. The surface morphology evolution of CaB₆ films was analyzed by AFM and FESEM. The results showed that the films were initially formed by fine columnar grains. With the deposition time extended, the films exhibited a dense columnar structure with faceted surfaces. The grain size, film thickness and crystallization degree all increased with the sputtering time.     

The physical–chemical properties and electrocatalytic performance of iridium oxide in oxygen evolution

An IrO₂ anode catalyst was prepared by using the Adams method for the application of a solid polymer electrolyte (SPE) water electrolyzer. The effect of calcination temperature on the physical–chemical properties and the electrochemical performance of IrO₂ were examined to obtain a low loading and a high catalytic activity of oxygen evolution at the electrode. The physical–chemical properties were studied via thermogravimetry–differential scanning calorimetry (TG–DSC), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The electrochemical activity was investigated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronopotentiometry in 0.1 mol L⁻¹ H₂SO₄ at room temperature. The optimum condition was found to be at the calcination temperature of 500 °C, where the total polarization reached a minimum at high current densities (>200 mA cm⁻²). The optimized catalyst was also applied to a membrane electrode assembly (MEA) and stationary current–potential relationships were investigated. With an optimized catalytic IrO₂ loading of 1.5 mg cm⁻² and a 40% Pt/C loading of 0.5 mg cm⁻², the terminal applied potential difference was 1.72 V at 2 A cm⁻² and 80 °C in a SPE water electrolysis cell.     

Sulphur doped DLC films deposited by DC magnetron sputtering

Diamond‐like carbon (DLC) and sulphur doped diamond‐like carbon (S‐DLC) films were synthesised at different sulphur molar percentage of 0%, 2%, 5%, 8% and 10% by direct current (DC) magnetron sputtering process using novel compressed sulphur‐graphite targets at relatively low power density. Films were characterised for their morphologies, structural, electrical and optical properties. Scanning electron microscope images reveal changes in the quality of the obtained films shown by the denser packing of DLC grains at different sulphur percentage. The conductivities of S‐DLC films were found to be in the range of 6.0 × 10^?3–0.6/Ω cm. The optical band gap energies were found to be in the range of ～1.4–2.0 eV. Both electrical and optical measurements exhibit nonlinear responses with optimum at around 5% sulphur molar percentage (minimum for conductivity and maximum for optical band gap energy). These trends of change in both conductivity and optical band gap energy are consistent with the variation in bond characters of the films indicated by Raman spectroscopy. © 2011 Canadian Society for Chemical Engineering     

非晶态硼化物Ni-Fe-Co-B的合成及电催化析氧性能

电解水制氢是绿色氢能源研究中的热点课题。其中，析氧半反应较高的过电位是导致电解水动力学缓慢的主要原因。为了提高电解水制氢的效率，本文主要通过简单的液相合成方法，以硼氢化钠和过渡金属Ni，Fe，Co盐为原料，制备了非晶态的过渡金属硼化物Ni-Fe-Co-B，将其作为析氧半反应催化剂。对Ni-Fe-Co-B进行了SEM、TEM、XRD、XPS和电化学表征。结果表明，非晶态催化材料Ni-Fe-Co-B被成功合成，当n(Ni)∶n(Fe)∶n(Co)=1∶1∶1，电流密度为20 mA/cm2时，Ni-Fe-Co-B的过电位仅为299 mV，Tafel斜率为101 mV/dec。在0.47 V的恒电压测试下，Ni-Fe-Co-B具有12h以上的稳定性。     

超薄MOF纳米片前驱体高效电催化OER反应

金属-有机骨架材料作为前驱体制备特定形貌的纳米材料用于水氧化反应(OER)，成为新的研究热点。使用溶剂热法在泡沫镍基底上合成超薄的NiCoFe-MOF纳米片，在保留其纳米片形貌的基础上原位电化学转化为金属氢（羟基）氧化物。在1 M KOH电解液中，10 mA?cm-2电流密度时的过电位仅为189 mV，Tafel斜率为35 mV/dec，且长时间电解实验表明其具有较高稳定性。原位拉曼结果表明，反应的高活性来源于反应过程中的“活性氧物种”中间体。     

防磁控溅射镀银膜变色新工艺

利用RSFM-4直流磁控溅射机在纯铜片上制备了银膜。采用了电化学纯化、化学纯化、浸涂BTA、涂覆DJB-823以及复合处理等多种防银膜变色工艺方法进行处理。分别在二氧化硫气体、硫化氢气体和硫化钠溶液中进行了加速银膜变色试验。通过对试验结果进行综合评价，表明采用化学纯化 涂覆DJB-823的复合处理工艺处理的银膜在各种环境下都有良好的抗银膜变色能力。