泡沫镍基三维空心球CoFe2O4@NF复合材料的制备与析氧性能研究

为降低电解水阳极的析氧反应过电位,采用一步水热法制备了泡沫镍基钴铁混合氧化物（CoFe₂O₄@NF）复合材料。采用XRD、SEM、TEM和XPS等方法对复合材料进行表征,并利用三电极体系对其电解水析氧催化性能进行了测试。结果显示：CoFe₂O₄以颗粒的形式聚集成空心球结构生长于泡沫镍基底上,其中空心球的直径大约4 μm,而CoFe₂O₄的粒径约为40 nm左右。在1 mol·L^-1 KOH溶液中,CoFe₂O₄@NF复合材料仅需293 mV的过电位即可达到20 mA·cm^-2的电流密度,Tafel斜率为51 mV·dec^-1。经过1 000次循环伏安扫描和10 h电流时间曲线测试后,其析氧性能依旧保持高稳定性,在析氧催化材料领域有着广阔的研究前景。     

Ti/IrO2-RuO2-SnO2阳极的制备与性能研究

采用热分解法制备了Ti/IrO₂-RuO₂-SnO₂阳极，并利用X射线衍射(XRD)、扫描电子显微镜(SEM)对Ti/IrO₂-RuO₂-SnO₂阳极涂层进行分析；在硫酸溶液中对Ti/IrO₂-RuO₂-SnO₂阳极性能进行循环伏安曲线(CV)、极化曲线(LSV)、电化学阻抗谱(EIS)测试。结果表明，添加Sn可细化涂层晶粒和改变涂层形貌，与Ti/IrO₂-RuO₂阳极相比，Ti/IrO₂-RuO₂-SnO₂阳极析氧电位更低、电催化活性更好。Sn质量为涂层氧化物总质量3%时所得Ti/IrO₂-RuO₂-SnO₂阳极综合性能最好，此时，阳极析氧电位为0.802 V(Vs.MSE),伏安电荷q=286.01 mC/cm,具...     

Co改性的Ti/IrO2-Co3O4-SnO2-Sb2O5析氧涂层电极性能研究

为提升析氧电极催化性能及使用寿命，通过热解法制备了Co改性的Ti/IrO₂-Co₃O₄-SnO₂-Sb₂O₅四元氧化物电极。采用极化曲线(LSV)、循环伏安曲线(CV)、交流阻抗图谱(EIS)及加速寿命实验研究了电极在硫酸溶液中的析氧催化活性及稳定性。结果表明，随着Co摩尔分数的增大，涂层表面的粗糙度先降低后升高，而电极的析氧活性及加速寿命均先升高后降低；当Co摩尔分数为50%时电极催化活性最佳，而当Co摩尔分数为30%时电极寿命最长，与Ti/IrO₂-SnO₂-Sb₂O₅电极相比寿命提高了约76.7%。电化学测试结果表明，Co改性电极催化活性的提高得益于反应控速步骤的改变、涂层表面反应位点数量的增大及电化学反应阻抗的降低。     

涂液浓度对Ti基IrO2–MnOx阳极涂层形貌及析氧性能的影响

采用溶胶凝胶法在TA1钛基体上制备了IrO₂–MnO_x涂层阳极，探析了涂液浓度对阳极涂层结构和电催化析氧性能的影响。结果表明，阳极涂层中的Ir会以金红石型IrO₂的形式存在，Mn则以非晶态Mn₃O₄的形式存在。阳极涂层表面呈现“类山脊状”形貌，涂液浓度的升高会提高涂层的结晶度和表面裂痕数量，但不会对涂层的表面粗糙度产生显著影响。阳极涂层的析氧催化活性表面积主要是易与电解液接触的外活性表面积，涂液浓度的变化对其影响较小。阳极的电催化析氧活性和稳定性随着涂液浓度的升高会呈现出先提高后降低的趋势。涂液浓度为0.3 mol/L时所得阳极的使用性能最优。在0.5 mol/L的硫酸溶液中，50 mA/cm²的电流密度下，其析氧过电位为280 mV，预计寿命长达3年。     

烧结时间对IrO2–Ta2O5/Ti电极寿命及电化学性能的影响

将氯铱酸和五氯化钽正丁醇溶液按Ir与Ta的物质的量比7∶3混合，采用热分解法在不同烧结时间下制备了IrO₂–Ta₂O₅/Ti阳极。通过扫描电子显微镜(SEM)和X射线衍射仪(XRD)分别分析了电极表面涂层的形貌及物相组成，通过循环伏安曲线(CV)、线性扫描伏安曲线(LSV)、电化学阻抗谱(EIS)、标准强化寿命试验(SALT)等方法考察了电极的电化学性能和稳定性。结果表明：随着烧结时间的延长，阳极的电催化活性表面积总体呈减小的趋势，阳极涂层的物相组成及析氧电位未发生明显变化。单层烧结5 min所制备的阳极具有最高的电催化活性，但电解寿命最短；烧结15 min的阳极具有最长的电解寿命，电化学综合性能最佳。     

MoS2/CNTs电催化析氢性能探究

本文通过一步水热法成功实现了二硫化钼(Mo S₂)在碳纳米管(CNTs)内外壁的原位生长，形成了限域和非限域的Mo S₂/CNTs复合纳米材料，并探究了其对电化学析氢反应(HER)的催化活性。研究结果表明，在碳纳米管内外壁均原位生长出二维片状Mo S₂纳米材料，形成部分限域的Mo S₂/CNTs纳米材料。此外，电催化析氢性能测试显示，Mo S₂生长在适量的CNTs(～25mg)时，形成的Mo S₂/CNTs复合纳米材料表现出较强的HER活性和稳定性。在10mA·cm^-2时，HER的过电位为440mV。Tafel斜率为117mV·dec^-1。     

电沉积镍铁锰三元纳米片在析氧反应中的性能研究

电解水制氢技术作为当下最有效的制氢技术之一,低成本、高性能的电催化剂是提高电解水效率的理想选择。本文采用了一步电沉积法在泡沫镍上制备镍、铁、锰三元纳米片(NiFeMn)作为析氧反应(OER)电催化剂。当电流密度为20mA·cm^-2时,过电位达到297mV,Tafel斜率达到了143.2mV·dec^-1,经过了12小时的I-T测试后,其电流密度为86mV·cm^-2,表明该材料具有较好的稳定性和活性。NiFeMn纳米片良好的OER性能可能是由于其高的电化学活性表面积,为OER反应提供了更多的活性位点。     

质子交换膜水电解一体化析氧电极载体催化剂

以氯铱酸为前体,钛网为支撑体,二氧化钛为载体,采用浸渍-热分解法首次成功制备了一体化IrO₂-TiO₂/Ti析氧电极,进一步采用热压法制备膜电极(MEA)。综合扫描电镜(SEM)、循环伏安(CV)、交流阻抗(EIS)以及单池极化曲线测试,研究了载体对于析氧电极形貌以及性能的影响。结果表明:未加入载体二氧化钛的析氧电极表面以裂缝为主,孔隙率较低;而加入载体二氧化钛的析氧电极表面裂纹基本消失,取而代之的是大量的催化剂簇以及孔结构的生成,极大地提高了析氧电极的电催化活性。单池测试表明,电流密度为1000mA/cm²时,添加载体二氧化钛后制备的析氧电极的析氧电位大约是1.70V。     

泡沫镍上原位制备FeOOH/MoSey及电解水双催化性能研究

为设计同时具有优异电催化析氢和析氧性能的过渡金属基催化剂，以泡沫镍为载体和集流体，原位制备了硒化钼(MoSe_y)和羟基氧化铁(FeOOH),得到FeOOH/MoSe_y@Ni复合材料。表征结果表明，先通过电沉积法原位生长了MoSe_y层，再以该MoSe_y层为成核点，通过常温浸泡生长形成了由FeOOH纳米片组成的微米绒球。在三电极体系中，以1 mol·L^-1 KOH溶液为电解液，该FeOOH/MoSe_y@Ni复合材料表现出优异的电催化析氢和析氧性能，析氢电流密度在10 mA·cm^-2时的过电位(η₁₀)为128 mV,析氧电流密度在20 mA·cm^-2时的过电位(η₂₀)为306 mV,并具有较小的Tafel斜率、较大的双电层电容(C_dl)值和良好的稳定性。FeOOH/MoSe_y@Ni优异的电催化性能主要由于三维开放的泡沫镍骨架和原...     

Ti/IrO2+MnO2电极在酸性溶液中的电化学活性表面积

采用涂覆热分解法制备不同成分的Ti/IrO₂+MnO₂电极,利用恒电位循环伏安法研究Ti/IrO₂-MnO₂电极在硫酸溶液中的电化学表面行为,并用直线外推法定量地评价电极的电化学活性表面积。结果表明,Ti/(0.7)IrO₂+(0.3)MnO₂的伏安电荷达到最高,为电化学活性表面积最大;随着电位扫描速率增大,伏安电流密度不断增加,而伏安电荷容量逐渐减少,直到维持恒定;所有Ti/IrO₂+MnO₂电极的“内部”电化学活性表面积远大于“外部”电化学活性表面积,约为“外部”电化学活性表面积的2倍,说明电极内部存在丰富的多孔结构,真实表面积巨大,因此Ir⁴⁺/Ir³⁺转化反应多发生于内电化学活性表面区域。     

New degradation mechanism of Ti/IrO2 + MnO2 anode for oxygen evolution in 0.5 M H2SO4 solution

Degradation mechanism of Ti/IrO₂(0.7) + MnO₂(0.3) anode for oxygen evolution was studied in 0.5 M H₂SO₄ solution by field emission scanning electron microscopes (FESEM), Tafel slope, X-ray diffraction (XRD) and electrochemical impedance spectroscopic (EIS). The whole surface of the non-electrolyzed Ti/IrO₂(0.7) + MnO₂(0.3) anode consisted of nano-IrO₂ poles array. The anode surface had hardly discovered cracks and had compact morphology that can prevent the electrolyte from entering the Ti/oxide interface and an insulating TiO₂ film from growing on the Ti-based surface. An insulating TiO₂ phase had not been generated on the Ti/oxide interface during the process of O₂ evolution and the inactive anode surface still remained mass of the IrO₂ and MnO₂ oxides. The chemical dissolution of Ti/IrO₂(0.7) + MnO₂(0.3) anode coating was not the main reason for electrode degradation in 0.5 M H₂SO₄ solution. The degradation mechanism of Ti/IrO₂(0.7) + MnO₂(0.3) anode differed from other conventional oxide electrodes for O₂ evolution in acid medium. The platforms of Tafel slope and anode potential (900–1050 h) indicated that the change of the oxygen evolution reaction (OER) mechanism was the main reason for degradation of Ti/IrO₂(0.7) + MnO₂(0.3) anode due to the change of adsorption intermediate.     

DFT studies of interaction of Ir cluster with O2, CO and NO

Hybrid DFT calculations have been carried out for IrCO, IrNO, IrO₂, Ir₁₃CO, Ir₁₃NO, and Ir₁₃O₂ clusters in order to investigate the electronic state and the catalytic activity of Ir catalyst. The results of Ir model clusters show that the surface atoms of the Ir₁₃ cluster have small negative charges and the clusters have strong interactions with adsorbates.     

Chlorine-free emission disposal of spent acid etchant in a three-compartment ceramic membrane reactor

Electrochemical technologies for the on-site treatment of spent acid etchant have received great attention due their ease of operation and economic benefits. On the other hand, a large amount of Cl₂ is generated during the electrolysis process, which leads to potential environmental risks. In the present work, a novel threecompartment ceramic membrane flow reactor, including a cathode chamber, an anode chamber, and a gas absorption chamber was developed. The three chambers were divided by an Al₂O₃ ceramic membrane and a breathable hydrophobic anode diffusion electrode (ADE). The Cl₂ evolution onset potential of the ADE was increased to 1.19 V from 1.05 V of the graphite felt, effectively inhibiting the chlorine evolution reaction (CER). The anode-generated Cl₂ diffused into the gas absorption chamber through the ADE and was eventually consumed by the H₂O₂ adsorbent. Cu could be recovered without emitting chlorine due to the special structure of reactor. The current efficiency of copper precipitation and cathode reduction from Cu²⁺ to Cu⁺ reached 97.7% at a working current of 150 mA. These results indicated that the novel membrane reactor had high potential for application in the copper recovery industry.     

Facile synthesis of spinel LiNi0.5Mn1.5O4 as 5.0 V-class high-voltage cathode materials for Li-ion batteries

LiNi_0.5Mn_1.5O₄ and LiMn₂O₄ with novel spinel morphology were synthesized by a hydrothermal and post-calcination process. The synthesized LiMn₂O₄ particles (5-10 μm) are uniform hexahedron, while the LiNi_0.5Mn_1.5O₄ has spindle-like morphology with the long axis 10-15 μm, short axis 5-8 μm. Both LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ show high capacity when used as cathode materials for Li-ion batteries. In the voltage range of 2.5-5.5 V at room temperature, the LiNi_0.5Mn_1.5O₄ has a high discharge capacity of 135.04 mA·h·g^-1 at 20 mA·g^-1, which is close to 147 mA·h·g^-1 (theoretical capacity of LiNi_0.5Mn_1.5O₄). The discharge capacity of LiMn₂O₄ is 131.08 mA·h·g^-1 at 20 mA·g^-1. Moreover, the LiNi_0.5Mn_1.5O₄ shows a higher capacity retention (76%) compared to that of LiMn₂O₄ (61%) after 50 cycles. The morphology and structure of LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ are well kept even after cycling as demonstrated by SEM and XRD on cycled LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ electrodes.     

硼高效掺杂LiNi0.5Co0.2Mn0.3O2正极材料及其性能提升机制

高键能异质原子的高效掺杂是稳定高电压LiNi_0.5Co_0.2Mn_0.3O₂（NCM）三元正极材料并提升其电化学性能的有效策略。借助含硼前体在二次颗粒表面富集及随后高温煅烧强化B³⁺体相扩散的策略,构建了硼离子高效掺杂NCM正极材料（NCM-B）。引入B—O键（键能：809 kJ·mol^-1）抑制了电化学反应过程中晶格氧析出,进而稳定材料的氧离子框架;此外,表面残余的高锂离子导体Li₂O-B₂O₃包覆层可以在一定程度上稳定电极-电解液界面。与改性前NCM相比,改性后的NCM-B正极材料在3.0~4.5 V电压区间的可逆比电容量可以达到193.7 mA·h·g^-1,在10 C大功率下,比电容量仍保持120 mA·h·g^-1（NCM仅为78.2 mA·h·g^-1）。1 C下连续循环100圈后,比电容量保持率从73%提升到90%。表面富集和扩散强化的思想也有望实现其他正极材料的高效掺杂。     

Influence of the pre-treatment on the structure and reactivity of Ir/γ-Al2O3 catalysts in the selective reduction of nitric oxide by propene

The selective catalytic reduction (SCR) of nitric oxide by propene over Ir/Al₂O₃ under lean-burn conditions (1000 vpm NO, 2000 vpm C₃H₆, 500 vpm CO, 10 vol.% O₂) was studied. The activity was shown to be strongly enhanced after exposure of the catalyst at 600°C under the reaction mixture, irrespective of the oxidising or reducing pre-treatment. Simultaneously, the Ir dispersion decreased from 78 to 10%. The influence of each component of the reaction mixture on the activation process was examined. The presence of both CO and O₂ was found to be necessary to activate Ir/Al₂O₃ while NO would not be. In situ FT-IR results revealed that initially fully oxidised Ir particles partially reduced in the feed to form Ir⁰ reduced surface sites (νCO at 2060 cm⁻¹) which adsorbed CO up to 350–400°C. The activation under reactants was related to the formation of these sites. The presence of reduced (or partially reduced) Ir sites, possibly siting at the surface of IrO₂ particles and stabilised by CO adsorption, was proposed to be responsible for the SCR activity.     

Electrocatalysis of chlorine evolution on different materials and its influence on the performance of an electrochemical reactor for indirect oxidation of pollutants

Two different Ti/Pt–Ir materials (commercial and home made) and Ti/PdO + Co₃O₄ were investigated for their electrocatalytic properties versus Cl₂ evolution reaction. The materials were used in a batch electrochemical reactor to treat biologically recalcitrant di-azo compound. An electrochemically driven oxidation, mediated by a Cl₂/Cl⁻ couple, proved efficient for destruction of this complex organic molecule, causing cleavage of the conjugated double bonds and destruction of unsatured bonds. Both Ti/Pt–Ir materials performed well; lower kinetics obtained with the Ti/PdO + Co₃O₄ anode was caused by adsorption of the model compound, evidenced in preliminary voltammetric measurements. The dye oxidation reaction followed the second order kinetics with partial orders in the model compound and (time varying) chlorine concentrations equal to one. Specific energy consumption of 3.12 kWh m⁻³ proved the process more economic than the homogeneous phase oxidation.     

镍锰酸锂正极材料及其适配性电解液研究最新进展

随着新能源汽车产业的蓬勃发展,对高能量密度动力电池的需求日益迫切。开发高电压正极材料及其适配性电解液,成为下一代高能量密度动力电池的主要研究方向。镍锰酸锂（LiNi_0.5Mn_1.5O₄）材料以其高电压（4.7 V,vs.Li/Li ⁺）、高能量密度（达650 W·h/kg）、资源丰富且价格低廉而受到广泛关注。然而,镍锰酸锂材料在长期的充放电循环过程中,锰从电极材料中溶解,破坏了电极材料的结构,导致电池性能恶化。介绍了镍锰酸锂正极材料及其适配性电解液研究最新进展。指出离子掺杂、表面包覆、复合方法是改善镍锰酸锂电化学性能的有效途径。同时,通过引入成膜添加剂、改变锂盐的种类及浓度、调整主溶剂的种类及比例等方法,可以提高电解液的耐高压性能,提高镍锰酸锂电极与电解液的界面稳定性,也是提升镍锰酸锂电池性能的重要方法。最后提出,适用于锂离子电池的5 V高电压电解液的研发相对滞后,其是制约高电压电池体系应用的主要问题。