离子液体[Emim]BF_4改性二氧化铅电极的制备与表征（英文）

采用电沉积法制备了离子液体[Emim]BF_4改性PbO_2电极。通过电化学氧化降解苯酚实验对电极催化性能进行了考察,发现苯酚模拟废水的COD去除率符合一级反应动力学,[Emim]BF_4改性PbO_2电极的速率常数为0.007 39 min~(-1),明显高于未改性PbO_2电极的速率常数0.003 83 min~(-1)。采用SEM、XRD、XPS对电极表面结构进行表征。结果显示,[Emim]BF_4改性钛基PbO_2涂层表面致密规整、结晶度高、晶格氧含量高。通过莫特-肖特基曲线、稳态极化和线性扫描伏安法考察了电极的电化学性质。结果表明,改性电极表面氧空位含量相比未改性电极大大降低,改性电极的析氧过电位相比未改性电极有明显提高。通过与未改性电极结构和电化学性质的对比研究,得出改性电极催化活性的提高主要是由于其氧空位含量较低,从而降低了氧化物电极表面羟基自由基(·OH)向晶格氧(O_(lat))转移的发生率。     

铝掺杂改性钛基PbO2电极性能研究

采用阳极电沉积技术制备了金属铝掺杂改性的Ti/PbO₂电极,通过表面粗糙度测量仪,扫描电镜,X射线衍射仪、线性极化扫描和交流阻抗谱电化学测试和加速寿命试验对铝掺杂引起PbO₂涂层电极的物理化学特性的影响进行分析,并对铝掺杂改性的Ti/PbO₂电极对苯酚模拟废水电催化氧化降解行为进行考察。结果表明,Al₃₊添加可使得Ti/PbO₂电极涂层结晶细化、沉积均匀致密,表面粗糙度明显降低,结瘤缺陷改善;铝掺杂改性的Ti/PbO₂析氧电位升高,电荷传递及催化性能提高,但呈非单调变化,其中添加3mM Al₃₊制备电极的析氧电位最高可达到2.09V,导电性优异,电催化性能最佳,电化学稳定性高,其强化寿命可达到460h,比未改性电极寿命提高了100h。铝掺杂改性的Ti/PbO₂电极对苯酚模拟废水具有良好的电化学氧化降解能力,180min处理后苯酚去除率最高可达到93.6%,COD去除率最大可达到73.6%。     

等离子喷涂致密La0.6Sr0.4Co0.2Fe0.8O3-δ透氧膜氧传输行为的研究

本文采用超音速等离子喷涂(SAPS)和等离子物理气相沉积方法(PS-PVD)制备了结构致密的钙钛矿型(ABO₃)La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ(LSCF)透氧膜。利用氧程序升温脱附(O₂-TPD)、XPS等手段,比较了两种膜在200-900℃间氧物种在表面及体相中的传递变化情况。O₂-TPD结果显示：SAPS膜的物理吸附氧脱附量、化学吸附氧脱附量和晶格氧脱附量分别超过PS-PVD膜的2倍、3倍和6倍;而XPS结果显示：SAPS膜表面吸附氧与晶格氧O1s峰面积比也高于PS-PVD膜。以上结果表明SAPS膜对氧具有更好的吸附及解离能力、更多的本征氧空位及更高的空位生成能力。     

丝网印刷氧化石墨烯对锂离子电池LiNi1/3Co1/3Mn1/3O2 三元正极的改性及性能影响

通过丝网印刷方法,在由LiNi_1/3Co_1/3Mn_1/3O₂、导电添加剂和聚偏氟乙烯制成的电极表面涂覆了一层薄薄的氧化石墨烯。在充电截止电压为4.3 V的条件下进行了循环性能和倍率性能测试。结果表明：未改性电极在恒电流充放电测试中容量下降且极化增加,而包覆改性后电极的容量衰减程度和极化增加速度降低。这是由于氧化石墨烯涂层抑制了LiNi_1/3Co_1/3Mn_1/3O₂电极和电解质之间的部分副反应,使得改性电极的循环稳定性和倍率性能显著提高,为提升LiNi_1/3Co_1/3Mn_1/3O₂电极性能提供了一种环境友好且非常有效的方法。     

复合储氢合金Mg1.8Zr0.2Ni- (1.2-x)Ni -xMgTi3结构和电化学性能研究

为改善Mg₂Ni储氢合金电化学性能,采用机械合金化法(Mechanical Alloying,MA),分别制备出改性合金Mg_1.8 Zr Ni以及MgTi₃,按一定比例和Ni混合球磨,制备出纳米晶或非晶化的Mg_1.8Zr_0.2Ni- (1.2-x)Ni -xMgTi₃复合储氢合金。研究结果表明,经部分取代改性和包覆修饰后的复合储氢合金,其表面和内部形成较多的纳米级褶皱、空隙层状和多相结构缺陷。随着MgTi₃含量增加,Mg_1.8Zr_0.2Ni- (1.2-x)Ni -xMgTi₃复合储氢合金初始放电比容量也逐渐增加,当MgTi₃含量为x=0.5时,合金初始放电比容量为973.3 mAh.g_-1。但MgTi3含量超过x=0.5时,其初始放电比容量又有所下降,研究表明添加MgTi₃却不利于复合储氢合金的循环稳定性和高倍率放电性能。通过对Mg_1.8Zr_0.2Ni- (1.0-x)Ni -xMgTi₃复合储氢合金进行线性极化、阳极极化和交流阻抗测试,进一步研究了系列合金电极的表面电化学反应、电荷转移过程、氢在合金中的扩散情况以及它们的电化学性能。     

简单一步法合成Co9S8氧还原反应电催化剂

采用低温回流技术,以Co₄(CO)₁₂和S粉为原料,在1, 6-己二醇溶剂中一步合成了钴硫化物催化剂。用X射线衍射仪和扫描电子显微镜对合成的化合物进行了表征。XRD分析表明合成样品为立方结构的Co₉S₈化合物,其SEM图片显示了花椰菜状的表面形貌。Co₉S₈化合物表现出良好的氧还原催化活性,开路电位为0.75 V(vs. NHE)。在电荷转移控制电位区,电极反应传递系数和塔菲尔斜率分别为0.50和119 mV。同时,将催化剂的催化活性和电化学稳定性与商业铂催化剂进行了比较。     

SiON/SiO2复合膜层对太阳能电池阵板间电缆的表面改性及其耐空间环境性能

在空间站工作的太阳电池阵板间电缆上下表面为聚酰亚胺薄膜,在低轨运行时会受到原子氧的强烈侵蚀,需要采取措施对其进行保护。采用射频磁控溅射法在电缆表面制备了颗粒尺寸均匀、排列致密的SiO₂膜层。通过表征空间环境试验前后样品发现由于电缆表面的凸起颗粒等缺陷无法完全被SiO₂膜层覆盖,导致原子氧会对缺陷位置产生侵蚀作用。采用全氢聚硅氮烷溶液对板间电缆基底进行表面改性处理,制备的聚硅氧氮烷涂层（SiON）可以有效地覆盖电缆基底表面的凸起颗粒等缺陷,使得其上溅射的SiO₂膜层表面光滑平整。经原子氧暴露试验,SiON/SiO₂层内部没有受到其侵蚀作用,可以防止原子氧对电缆基底的破坏。经多次冷热循环试验,SiON/SiO₂复合膜层仍然具备良好的结构特性与结合性能。     

B参杂对NiO/Ni(OH)2电极材料电容性能的影响

通过化学镀再电化学氧化的方法在铜片表面制备出带有微米微坑和微米微球的均一NiO/Ni(OH)₂和B参杂的NiO/Ni(OH)₂(B)两种电极材料,采用扫描电镜(SEM/EDX)、X射线衍射(XRD)、X射线光电子能谱(XPS)和电化学技术对所制备的两种电极材料进行表征和电化学性能测试。SEM、XRD和XPS的测试结果表明, 所制备的两种电极材料由Ni、NiO和Ni(OH)₂组成,并且NiO/Ni(OH)₂(B)中B的参杂量可达14.6wt%。循环伏安测量和恒电流充放电试验表明,两种电极材料均具有较高的电化学活性和可逆性;在1 A/g的充放电电流密度下, 两种NiO/Ni(OH)₂和NiO/Ni(OH)₂(B)电极材料经历10000次充放电循环后分别给出了1380 和1930F/g的比电容, 显示出较高的比电容特性和良好的电化学稳定性;电化学阻抗谱表明NiO/Ni(OH)₂(B)电极材料较NiO/Ni(OH)₂电化学反应电阻降低了约2个数量级;Ragone曲线揭示了所制备的两种电极材料具有较高的功率密度和较低的能量密度。B的参杂使得NiO/Ni(OH)₂(B)电极材料表面氧化物含量增大并且形成微米微球形貌,增大了电极表面积以及与电解液的接触和润湿作用,降低了电极材料表面能带带隙能,从而导致较小的电化学反应电阻和电导率的提高是其显示优异赝电容性能的主要原因。     

CeO2基储氧材料的制备和表征

用共沉淀法制备了四种CeO₂基储氧材料,并用X射线衍射(XRD),Raman,N₂吸附-脱附(BET方法),H₂程序升温还原(H₂-TPR),氧脉冲技术,X射线光电子能谱(XPS)和扫描电子显微镜(SEM)表征了其物理化学性质。XRD结果表明在CeO₂ 和CeO₂-Al₂O₃ (CA)中只能检测到宽的CeO₂ 的特征峰,而CeO₂-ZrO₂ (CZ) 和 CeO₂-ZrO₂-Al₂O₃ (CZA)中检测到了Ce_0.75Zr_0.25O₂ 相,在所有的CeO₂基储氧材料中都形成了均匀的固溶体。XPS结果表明三价铈和四价铈共存于CZ,CA和CZA的表面,而在纯CeO₂中几乎检测不到三价铈的存在。CZA表现出了最佳的织构性能,高的储氧量(OSC)和优异的热稳定性。另外,为了阐释四个样品的差异,本文提出了一种新的观点：Al₃₊可能插入了萤石结构的间隙或者高度分散在固溶体中。CZA固溶体可能是由间隙型固溶体和置换型固溶体混合组成的,这一点由CA和CZA中存在两种不同的氧物种或者两种类型的氧通道可以证明。然而,关于这个观点的详细证据还不够充分,需要继续进行深入的研究。     

Ni-B-C对La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20储氢合金电化学性能的影响研究

为提高新型AB₃型储氢合金La_0.94Mg_0.06Ni_3.49Co_0.73Mn_0.12Al_0.20的电化学性能,将球磨法制备的Ni-B-C粉末按不同重量比添加到合金中。采用X-射线粉末衍射仪(XRD)和扫描电子显微镜(SEM)分析合金的相结构和表面形貌,添加Ni-B-C粉末后,合金相结构没有变化,仍由LaNi₅相和La₂Ni₇相两个相组成,但合金表面出现了细小颗粒。添加Ni-B-C粉末后,合金电极的最大放电容量和放电容量保持率均提高。当添加重量百分比为10%的Ni-B-C粉末后,电极的最大放电容量从346 mAh/g增加到363 mAh/g,50个循环后的放电容量保持率从70%提高到77%,交换电流密度I₀与极限电流密度I_L分别为106 mA/g和987 mA/g。动电位极化测试表明,电极的抗腐蚀能力也有所增强。研究结果表明,Ni-B-C可以提高AB₃型储氢合金的综合电化学性能。     

Quantum chemical aided molecular design of ionic liquids as green electrolytes for electrodeposition of active metals

Quantum chemical calculation was used to estimate the reduction potentials of 25 organic cations and the oxidation potentials of 11 anions. This information was used to select promising cations and anions for the preparation of ionic liquids as green electrolytes for electrodeposition of active metals. The reasonable linear correlations between the lowest unoccupied molecular orbital (LUMO) energies and the reduction potentials of cations, and the linear relationships between the oxidation potentials and the highest occupied molecular orbital (HOMO) energies of anions were obtained. The orders of electrochemical stability for cations and anions being obtained agree well with the experimental measurements. The suitable ionic liquids with sufficiently wide electrochemical windows for electrodeposition of active metals are suggested to be [Emim]NTf₂, [Bmim]NTf₂, [Bmim]BF₄, [Bmim]PF₆, [Bmim]CTf₃, [Emim]BF₄, [Emim]PF₆, [Emim]CTf_3..     

Influence of nano-CeO2 on coating structure and properties of electrodeposited Al/α-PbO2/β-PbO2

Al/α-PbO₂/β-PbO₂ composite electrodes doped with rare earth oxide (CeO₂) were prepared by anodic oxidation method investigate the influence of nano-CeO₂ dopants on the properties of Al/α-PbO₂/β-PbO₂-CeO₂electrodes and the impact of α-PbO₂ as the intermediate layer. The results show that using α-PbO₂ as the intermediate layer will benefit the crystallization of β-PbO₂ and β-PbO₂ is more suitable as the surface layer than α-PbO₂. CeO₂ dopants change the crystallite size and crystal structure, enhance the catalytic activity, and even change the deposition mechanism of PbO₂. The doping of CeO₂ in the PbO₂ electrodes can enhance the electro-catalytic activity, which is helpful for oxygen evolution, and therefore reduce the cell voltage.     

Electrocatalytic Processes on PbO<Subscript>2</Subscript> Electrodes at High Anodic Potentials

The determination of the electrocatalytic activity and selectivity of electrodes with respect to the target process is considered to be of interest both in the theoretical aspect for the development of electrocatalysis theory and in application for efficient electrocatalysts which can be used in electrochemical systems for wastewater treatment. The purpose of the given work was to identify the relationship between the chemical and phase composition of materials based on lead dioxide, their physicochemical properties, and their electrocatalytic activity. The main research methods were quasi-stationary polarization and impedance spectroscopy, photocolorimetry, fluorescent and spectrophotometry in the UV and visible regions, atomic absorption spectroscopy, and high performance liquid chromatography (analysis of the solutions). It was shown that the modification of lead dioxide by ionic additives results in significant changes in the electrocatalytic activity of the system in respect to the oxygen evolution reaction and electrochemical oxidation reactions of organic compounds. It was found that, at low polarizations, the oxygen evolution reaction is limited by the electrochemical desorption step (the second electron transfer), and its overpotential at PbO₂-modified electrodes increases in the order that coincides with the dependence in which the number of oxygen-containing particles strongly bound to the electrode surface increases. It was found that the rate of oxidation of organic substances on the anode materials involved is directly proportional to the amount of oxygen-containing radicals formed on the electrode during the water oxidation.     

十二烷基硫酸钠对IrO2-Ta2O5/SnO2- Sb-Mn/Ti电极电催化性能影响

采用涂刷-热分解法制备不同浓度阴离子表面活性剂十二烷基硫酸钠（SDS）的IrO2-Ta2O5/SnO2- Sb-MnO2/Ti电极,通过扫描电子显微镜（SEM）和X射线衍射仪（XRD）对其微观形貌及物相组成进行分析;应用循环伏安、极化等测试手段,表征制备电极的电催化活性.结果表明,适量添加十二烷基硫酸钠能够改善IrO2-Ta2O5/SnO2-Sb-Mn/Ti电极的微观形貌,提高电催化活性.在本实验条件下,SDS最佳添加量是1.6 g/L,结晶化度高达99.83%.利用苯酚电催化降解实验和强化寿命测试进一步考察所制电极的电催化活性与稳定性,结果显示,在电流密度15 mA/cm2条件下电解180 min,SDS的加入使苯酚去除率由原来的68.5%提高到79.2%.COD去除率由60.1%提高到 67.5%,电催化性能得到提升,电极强化寿命由52 h延长至68 h.     

PbO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> composite electrodes

Electrodeposition of composite PbO₂-based materials containing titanium dioxide particles was studied. The TiO₂ content of the composite depends on the bath composition and the deposition conditions. Inclusion of TiO₂ particles in PbO₂ substantially changes the morphology and structure of the deposit. The oxygen overpotential at composite materials increased but the rate of the conversion of 4-chlorophenol into nontoxic compounds remained virtually unchanged. The lifetime of the electrodes containing the inert TiO₂ phase was found to be twice as long as that of traditional PbO₂ anodes.     

Mesoporous silica doped with a chemosensor based on phosphorescent copper(I) complex: Synthesis,characterization, photophysical property,and sensing behavior towards molecular oxygen

In this paper, we report the synthesis, crystal structure, photophysical properties, and electronic nature of a phosphorescent Cu(I) complex of [Cu(OP)(PPh₃)₂]BF₄, where OP and PPh₃ stand for 2-(5-phenyl-[1,3,4]oxadiazol-2-yl)-pyridine and triphenylphosphine, respectively. [Cu(OP)(PPh₃)₂]BF₄ is a yellow-emitting complex with a phosphorescence peaking at 552 nm and a long excited state lifetime of 83.5 μs under N₂ atmosphere. Density functional calculation reveals that the emission comes from a triplet metal-to-ligand-charge-transfer excited state. We dope [Cu(OP)(PPh₃)₂]BF₄ into a mesoporous silica matrix of MCM-41, hoping to explore the possibility of using the doped silica as an oxygen sensing material. The resulted samples exhibit a maximum sensitivity of 4.48 towards oxygen with short response time due to the large surface-area-to-volume ratio of MCM-41 matrix, and no photobleaching is detected in these samples.     

氯和氢对新型超高强度Cr12Ni4Mo2Co14钢在酸性环境中电化学腐蚀行为的影响

采用极化曲线、电化学阻抗和Mott-Schottky等电化学试验研究了酸性环境中Cl~-和氢对一种新型超高强度Cr12Ni4Mo2Co14钢电化学腐蚀行为的影响。结果表明:Cl-和氢均对Cr12Ni4Mo2Co14钢的阳极钝化区产生影响,随着Cl~-含量和氢含量的增加,点蚀电位负向移动,钝化区间缩短;Cl-通过占据氧空位促进钝化膜中形成Schottky空位对,而金属离子空位聚集会引起钝化膜的破坏;与未充氢Cr12Ni4Mo2Co14钢相比,充氢Cr12Ni4Mo2Co14钢中的施主和受主密度均有所提高,导致阳离子空位浓度提高,局部阳离子空位的聚集可诱导钝化膜的击穿。     

锡锑中间层的铕掺杂量对 Ti / PbO2电极性能的影响

采用涂层热解法在Ti基体表面制备不同掺杂量的铕掺杂锡锑中间层,并在锡锑中间层的表面电镀上PbO2。对所制备的电极作LSV曲线,研究了电极的电化学性能;以对硝基苯酚为目标有机物,考察了电极的电催化活性;采用SEM,XRD等分析方法表征了电极中间层的形态、元素组成和结构组成,据此分析了电极的性质。结果表明,铕掺杂量对电极的各项性能有较大影响,制备电极时以n(Sn)∶n(Sb)∶n(Eu)=1∶0.1∶0.01为佳,该掺杂量下得到的电极析氧电位和电催化能力较高,表面涂层结构和覆盖度较好,电化学寿命达78.6 h。     

Effect of SnO2 intermediate layer on performance of Ti/SnO2/MnO2 electrode during electrolytic-manganese process

SnO₂ intermediate layers were coated on the titanium (Ti) substrate by thermal decomposition. Scanning electron microscope (SEM) and X-ray diffraction (XRD) results show that uniform SnO₂ intermediate layers with rutile crystal structure were successfully achieved. According to the results of linear sweep voltammetry (LSV), oxygen evolution potential (OEP) of the Ti/SnO₂/MnO₂ electrodes decreases with increasing SnO₂ content, indicating that the electro-catalytic oxidation activity of the electrode increases. Accelerated service life tests results demonstrate that SnO₂ intermediate layer can improve the service life of the Ti/SnO₂/MnO₂ electrode. As the content of SnO₂ intermediate layer increases, the cell voltage and the energy consumption decrease apparently.