电催化氧气析出非贵金属催化剂的研究进展

电催化氧气析出反应是金属-空气电池充电过程和电催化分解水阳极的关键反应,对提高能量储存和转换效率、高效利用可再生清洁能源、缓解能源危机和环境污染具有重要作用。文章首先简要介绍了电催化氧气析出反应基本过程,随后综述了近年来用于电催化氧气析出反应的非贵金属催化剂的研究进展,重点讨论了过渡金属氧化物、过渡金属氢氧化物以及碳材料等非贵金属催化剂的研发情况。对这些催化剂的合成、结构及氧气析出催化性能进行了详细分析,也对这些催化剂的发展方向进行了简单分析。文章最后认为,新合成技术、新催化材料的发展以及氧气析出催化反应机理的阐明对发展高性能电催化氧气析出非贵金属催化剂将会起到极大的推动作用。     

In situ coupling of lignin-derived carbon-encapsulated CoFe-CoxN heterojunction for oxygen evolution reaction

Exploring highly active and stable electrocatalysts for oxygen evolution reaction (OER) is crucial for developing water splitting and rechargeable metal-air batteries. In this study, a hybrid electrocatalyst of CoFe alloy and Co_xN heterojunction encapsulated and anchored in N-doped carbon support (CoFe-Co_xN@NC) was in situ coupled via the pyrolysis of a novel coordination polymer derived from lignin biomacromolecule. CoFe-Co_xN@NC exhibited outstanding OER activity with a low overpotential of 270 mV at 10 mA cm⁻² and stability with an increment of 20 mV, comparable to commercial Ir/C. DFT calculations showed that Co_xN and N-doped graphitic encapsulation can reduce the binding strength between *O and CoFe alloy, limit metal leaching and agglomeration, and improve electron transfer efficiency, considerably enhancing the OER activity and stability. In situ coupling approach for preparing alloy and nitride heterojunctions on N-doped lignin-derived carbon offers a promising and universal catalyst design for developing renewable energy conversion technologies.     

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.     

Interface engineering for enhancing electrocatalytic oxygen evolution reaction of CoS/CeO2 heterostructures

To realize renewable energy conversion,it is important to develop low-cost and high-efficiency electrocatalyst for oxygen evolution reaction.In this communication,a novel bijunction CoS/CeO₂ electrocatalyst grown on carbon cloth is prepared by the interface engineering.The interface engineering of CoS and CeO₂ facilitates a rapid charge transfer from CeO₂ to CoS.Such an electrocatalyst exhibits outstanding electrocatalytic activity with a low overpotential of 311 mV at 10 mA·cm?2 and low Tafel slope of 76.2 mV·dec?1,and is superior to that of CoS(372 mV)and CeO₂(530 mV)counterparts.And it has long-term durability under alkaline media.     

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。     

Heterometallic cluster-based organic frameworks as highly active electrocatalysts for oxygen reduction and oxygen evolution reaction: a density functional theory study

Recently, metal–organic frameworks are one of the potential catalytic materials for electrocatalytic applications. The oxygen reduction reaction and oxygen evolution reaction catalytic activities of heterometallic cluster-based organic frameworks are investigated using density functional theory. Firstly, the catalytic activities of heterometallic clusters are investigated. Among all heterometallic clusters, Fe₂Mn–Mn has a minimum overpotential of 0.35 V for oxygen reduction reaction, and Fe₂Co–Co possesses the smallest overpotential of 0.32 V for oxygen evolution reaction, respectively 100 and 50 mV lower than those of Pt(111) and RuO₂(110) catalysts. The analysis of the potential gap of Fe₂M clusters indicates that Fe₂Mn, Fe₂Co, and Fe₂Ni clusters possess good bifunctional catalytic activity. Additionally, the catalytic activity of Fe₂Mn and Fe₂Co connected through 3,3′,5,5′-azobenzenetetracarboxylate linker to form Fe₂M–PCN–Fe₂M is explored. Compared with Fe₂Mn–PCN–Fe₂Mn, Fe₂Co–PCN–Fe₂Co, and isolated Fe₂M clusters, the mixed-metal Fe₂Co–PCN–Fe₂Mn possesses excellent bifunctional catalytic activity, and the values of potential gap on the Mn and Co sites of Fe₂Co–PCN–Fe₂Mn are 0.69 and 0.70 V, respectively. Furthermore, the analysis of the electron structure indicates that constructing a mixed-metal cluster can efficiently enhance the electronic properties of the catalyst. In conclusion, the mixed-metal cluster strategy provides a new approach to further design and synthesize high-efficiency bifunctional electrocatalysts.     

磁控溅射制备Cu1-xCoxO复合氧化物的催化析氧

采用直流反应磁控溅射法制备了Cu1-xCoxO(0.02≤x≤0.14)复合氧化物电极。利用XRD、EDS和SEM分析技术对沉积氧化物的晶体结构、化学组成及表面形貌进行了表征,并利用循环伏安、线性扫描及电化学交流阻抗对沉积氧化物电极的电化学性能进行了测试。XRD分析结果显示复合氧化物Cu1-xCoxO具有CuO单斜晶体结构,不存在氧化钴独立相。电化学测试结果表明Cu1-xCoxO复合氧化物电极对水氧化反应的催化活性远高于CuO和Co3O4电极,更好的催化活性、较低的电阻和高的表面粗糙度是Cu1-xCoxO复合氧化物电极催化活性提高的主要原因。生成最优Cu1-xCoxO(0.02≤x≤0.14)复合氧化物的溅射功率为45W(Co)、100W(Cu)。     

镀液中氨基磺酸镍质量浓度对电镀镍层析氢催化活性的影响

采用由10 g/L NiCl₂·6H₂O、30 g/L NH₄Cl和310～390 g/L Ni(NH₂SO₃)2·4H₂O(氨基磺酸镍)组成的镀液(pH=3.8),在温度35°C和电流密度3 A/dm²的条件下电镀30 min,获得镍电极。研究了镀液中氨基磺酸镍质量浓度对镍镀层表面形貌和析氢催化活性的影响。结果表明,镀液中氨基磺酸镍质量浓度为350 g/L时,镍镀层结晶最细致,析氢催化活性和稳定性最佳。     

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。     

电沉积制备镍-铁-钨合金析氢电极的工艺研究

以紫铜片为基体电沉积制备了Ni–Fe–W合金电极。研究了镀液中不同组分的浓度和工艺条件对Ni–Fe–W合金析氢性能的影响,得到最佳镀液配方和工艺条件为:NiSO4·6H2O80g/L,FeSO4·7H2O20g/L,Na2WO4·2H2O0.020mol/L,Na3C6H5O7·2H2O 0.5 mol/L,H3BO3 0.65 mol/L,Na2SO4 0.1 mol/L,十二烷基硫酸钠0.1 g/L,pH 5~6,温度30°C,电流密度4 A/dm2,磁力搅拌800 r/min,时间30 min。在该条件下所得Ni–Fe–W合金电极表面Ni、Fe和W的原子分数为63.79%、34.35%和1.86%,具有较大的比表面积,在30%KOH溶液中的析氢催化活性较好。     

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。     

析氢对电沉积镍枝晶生长的影响

采用点电极电沉积的方法,在环形电解池中用自行设计的试验装置研究了不同电压和NiSO4质量浓度时,析氢对电沉积金属镍枝晶二维生长行为的影响。研究发现,析氢对沉积产物的形貌影响显著,氢气的大量析出有利于枝晶产生分枝,使沉积物的形貌趋于致密。     

Electrocatalysis of oxygen evolution at stainless steel anodes by electrosynthesized cobalt hydroxide coatings

Controlled growth of cobalt hydroxide coatings (1–2 m thick) on stainless steel electrodes was achieved by electrogeneration of base by cathodic reduction of aqueous cobalt nitrate solutions. These coatings catalyse the oxygen evolution reaction in alkaline medium (1 M KOH) by as much as 100 mV, making cobalt hydroxide a candidate catalyst for these applications.     

Recent advance in transition metal oxide-based materials for oxygen evolution reaction electrocatalysts

Using renewable energy to electrolyze water to produce hydrogen is the only way to realize a green hydrogen economy. At present, the large-scale application of this technology is encumbered by the relatively low activity and stability of oxygen evolution reaction (OER) electrocatalysts. The use of cost-effective catalysts can significantly reduce the overpotential of oxygen evolution and improve the economics and power conversion efficiency of the hydrogen production process from electrolysis of water. Among the various candidates, the transition metal oxide-based (TMOs) materials show great prospects and receive ever-increasing research interests because of their diversified surface/bulk structures, natural enrichment, easy accessibility and environmental friendliness. In this review, the latest tactics aiming at enhancing activity via increasing the accessible active sites and promoting intrinsic activity have been summarized. In addition, with special emphasis on the long-term stability, the up-to-data strategies for elevating the stability are introduced. Finally, conclusions and perspectives are also presented.     

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。     

Electrodeposition of Ni-transition alloys for the oxygen evolution reaction

The oxygen evolution reaction (OER) is the anodic reaction in several industrial electrolytic processes. The objective of this work was to develop a new electrocatalytic material for long-lasting and economical high performance electrodes. New electrodes were prepared by electrodeposition of nickel, nickel-ruthenium and nickel-iridium alloys. They were then activated by anodic polarization at 100 mA cm^–2 to form an oxide layer. The electrocatalytic activity was characterized for the OER in 5M KOH solution. The results show that nickel-iridium alloys provide greater electrocatalytic activity for the OER and better corrosion resistance than nickel-ruthenium in alkaline solution. The effects of transition elements on improving the performance of the nickel electrode are then discussed.Notation b Tafel slope - i _ex exchange current density - i _dp electrodeposition current density - i _OER oxygen evolution reaction current density - C _dl double-layer capacity - o₂ oxygen overpotential     

快速界面法制备FeOOH@CoNi-LDH@NF用于高效析氧

以六水合硝酸钴、六水合硝酸镍、尿素和氟化铵为原料,采用水热法在镍网上原位构筑层状双金属氢氧化物(LDH)(CoNi-LDH@NF),然后采用快速界面法在硝酸钠和六水合氯化铁的100℃溶液中对其进行刻蚀制备了FeOOH@CoNi-LDH@NF.利用XRD、SEM、XPS和TEM对FeOOH@CoNi-LDH@NF进行了形...     

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.     

电沉积法制备高活性析氢电极

高活性阴极材料在电化学工业中具有重大的应用价值。介绍了电沉积积法制备高活性析氢电极的发展,现状及应用前景。     

Electrodeposition of nickel in the presence of Al<Superscript>3+</Superscript> from sulfate baths

The effect of Al³⁺ on the cathodic current efficiency, deposit morphology, crystallographic orientations and polarisation behaviour of the cathode during electrodeposition of nickel from acidic sulfate solutions was investigated. Higher concentration of Al³⁺ (>10 mg dm^–3) significantly deteriorated the surface quality of the nickel deposit as well as the current efficiency. X-ray diffraction studies revealed that the (200) plane was the most preferred crystal plane and was not affected by the presence of varying concentration of Al³⁺ in the electrolytic bath. The presence of Al³⁺ caused polarisation of the cathode, which increased with increasing Al³⁺ concentration. The effect of Al³⁺ on the electrokinetic parameters: Tafel slope (b), transfer coefficient () and exchange current density (i₀) were also investigated.