纳米TiO2-Pt修饰电极的制备、性能及应用

采用电化学合成法和电沉积法制备高活性钛基纳米TiO₂-Pt(Ti/nano-TiO₂-Pt)修饰电极,通过循环伏安法研究并比较了钛基纳米TiO₂膜电极、纯Pt电极、Ti/nano-TiO₂-Pt电极在H₂SO₄溶液中的电化学行为以及Ti/nano-TiO₂-Pt电极对Mn²⁺氧化为Mn³⁺的电催化性能.结果表明纳米TiO₂-Pt修饰电极对Mn²⁺的电氧化有高催化活性.Mn²⁺氧化峰电位为1.28 V（vs SCE）,比纯Pt电极负移0.12 V;析氧电位为1.40 V,比纯Pt电极高0.08 V.Ti/nano-TiO₂-Pt修饰电极催化性能优于纯Pt电极和纳米TiO₂膜电极,非均相电解氧化效率可达90%以上.电解得到的Mn³⁺可一步氧化甘油为甘油醛,收率为96%.     

乙二醛在纳米TiO2-Pt电极上的电催化氧化

通过电沉积修饰铂微粒制备Ti基纳米TiO₂-Pt（Ti/nano-TiO₂-Pt）修饰电极,采用循环伏安法研究了乙二醛在Ti/nano-TiO₂-Pt上的电催化氧化。结果表明：Ti/nano-TiO₂-Pt修饰电极对乙二醛的氧化呈现较高的电催化活性,可作为乙二醛电氧化合成乙醛酸的高活性催化电极。     

乙醇在SnO2掺杂的TiO2-Pt复合纳米催化剂上的电催化氧化

通过溶胶凝胶和电沉积法制备了SnO₂掺杂的钛基纳米TiO₂-Pt（nano-TiO₂-Pt）复合纳米催化剂。XRD和SEM的研究结果表明,SnO₂的掺杂改变了TiO₂的结构。通过对它们的电化学性质的比较发现,SnO₂的掺杂使nano-TiO₂-Pt复合纳米催化剂的电化学活性表面积增加,常温常压下对乙醇的电化学氧化电位负移,氧化能力明显提高。     

反相微乳液法制备TiO2/ZrO2复合陶瓷膜

研究了采用反相微乳液法制备TiO₂/ ZrO₂复合微乳液,并以其作为前体制得TiO₂/ ZrO₂复合膜。通过对复合微乳液的透射电镜测试,结果表明TiO₂/ ZrO₂复合微粒在油相包裹的“水池”中生成。由扫描电子显微镜观察到TiO₂/ ZrO₂复合膜表面微粒以棒状形式分布,而且复合膜对大肠杆菌的灭菌率达98 %～99 %。     

水热法制备CdS/TiO2及其光活性

研究了CdS/TiO₂光催化的耦合效应.以TiO₂、CdCl₂和Na₂S为原料在200 ℃、6 h水热反应条件下一次合成CdS含量不同的CdS/TiO₂,通过XRD、SEM、EDS和IR对样品进行表征,并通过谢乐公式（Scherrer equation）估算出样品晶粒的粒径.XRD图表明CdS/TiO₂为锐钛矿型TiO₂、立方相和六方相CdS的混合相.SEM表明CdS粒径为20～50 nm,TiO₂粒径为50～100 nm.通过罗丹明B(rhodamine B)光降解脱色,表征了样品的光活性,结果表明当CdS∶TiO₂为1.0时,CdS/TiO₂开始出现耦合效应,当CdS∶TiO₂为1.5时,CdS/TiO₂的光活性最强,在30 min内紫外光降解4 mg•L^-1罗丹明B溶液的降解率达74.3%.     

用相转移法有机表面改性纳米TiO2

以正辛基三乙氧基硅烷（LM-N308）为有机表面改性剂,用相转移法对金红石相纳米TiO₂进行有机表面改性。采用了傅里叶变换红外光谱（FTIR）、热分析（TG-DTA）、X 射线光电子能谱（XPS）、高分辨透射电镜（HRTEM）、亲油化度实验等对所得的纳米TiO₂进行了表征。红外光谱和X射线光电子能谱表明LM-N308以化学键合的方式结合在纳米TiO₂表面。HRTEM结果显示,在纳米TiO₂的表面存在厚度均匀约2 nm的有机包覆层。TG和亲油化度实验数据表明,纳米TiO₂表面化学吸附的LM-N308的饱和质量分数为7.0%～9.7%。分散性实验表明,经LM-N308表面改性的纳米TiO₂由亲水性变成了疏水性。     

镍掺杂对二氧化钛光催化性能影响的研究

采用溶胶-凝胶法制备了纳米二氧化钛以及不同掺镍量的TiO₂纳米粒子(原料中Ni∶TiO₂的摩尔分数为1%、3%、5%、7%、9%)。用紫外光照射甲基橙溶液的光催化降解实验研究了掺镍对二氧化钛光催化剂催化效率的影响，试验结果表明,当用n（Ni）∶n（TiO₂）＝5%的Ni(NO₃)₂溶液进行镍掺杂时，制得的TiO₂催化剂光催化效率最高，但与纯TiO₂相比，镍掺杂会减弱TiO₂的光催化效率。X射线衍射分析表明，未掺杂的TiO₂以锐钛矿和金红石两种晶型混合存在，镍掺杂后TiO₂的晶型几乎全为锐钛矿。镍掺杂后会减小TiO₂粒子的尺寸，增大其比表面积。     

Fe3+和Ce3+掺杂对TiO2光催化剂性能的影响

采用溶胶-凝胶法在玻璃纤维上涂层TiO₂光催化剂,并掺杂Fe³⁺和Ce³⁺修饰TiO₂光催化剂,进行了间歇式光催化降解气相苯实验,结果表明掺杂Fe³⁺和Ce³⁺均可以提高TiO₂光催化剂的活性,其中0.2% Fe³⁺/TiO₂光催化剂活性最好.借助XRD、SEM和XPS等表征手段来分析修饰前后的催化剂表面的物理化学性质变化,研究表面性质的变化对于光催化性能的影响.表征结果显示载体玻璃纤维表面均匀分布了粒径为40～60 nm的锐钛型TiO₂微粒,0.2%Fe³⁺和Ce³⁺掺杂后催化剂表面Ti³⁺浓度增大,表面羟基浓度减小.催化剂表面的Ti³⁺会与被吸附氧气反应形成Ti⁴⁺并同时产生活性组分O^-₂,氧化剂O^-₂在光催化降解苯反应过程中起着重要作用.     

超增溶胶团自组装原位制备单分散纳米TiO2

以四氯化钛为原料，应用自制模板剂，采用超增溶胶团自组装原理制备TiO₂纳米微粒,利用XRD、TEM和BET吸附等分析测试手段对所得TiO₂微粒的晶相组成、粒径大小和形貌进行表征，表明制备的锐钛矿型TiO2纳米微粒具有较好的分散性，一次粒径大小为8～16 nm，二次粒径80～120 nm。     

碳纳米管/纳米TiO2-聚苯胺复合膜电极的制备及电化学性能

在含有0.2 mol·L^-1苯胺的0.5 mol·L^-1 H2SO4溶液中;采用循环伏安法（CV）;以扫描速度50 mV·s^-1;扫描电位为-0.1～0.9 V;在碳纳米管/纳米TiO₂（CNT/nanoTiO₂）膜电极上实现了苯胺的电化学聚合;通过CV法和电化学阻抗谱（EIS）并结合电子扫描显微镜和红外谱图对制备的碳纳米管/纳米TiO₂-聚苯胺（CNT/nanoTiO₂-PAn）复合膜电极的电化学性质和结构进行了表征;同时研究了复合膜电极对抗坏血酸（AH₂）的电催化性能;发现该复合膜电极对抗坏血酸的氧化具有较高的电催化活性。     

热碱对MmNi_(3.5)Mn_(0.4)Co_(0.7)Al_(0.4)贮氢电极放电性能的影响

比较研究了采取热碱预处理(方法A)和热碱充电处理(方法B)对贮氢电极MmNi3.5Mn0.4Co0.7Al0.4(Mm为混合稀土)活化过程和放电性能的作用。结果表明,两种处理方法均可使电极的活化次数减少,初次放电容量增大,放电电位提高,放电过电位降低,快速放电能力增强,其中方法B比方法A的效果明显。同时,用同一种方法处理8 h电极的性能优于处理5 h电极的性能。     

Cr_2O_3掺杂对混合稀土贮氢电极性能影响的研究

研究了金属氧化物Cr2O3掺杂对MmNi3.5Mn0.4Co0.7A l0.4(Mm:混合稀土)贮氢电极的活化、放电容量、快速放电能力等性能的影响。实验表明,掺杂15%Cr2O3使电极的放电容量增大3.0%,充电效率提高2.7%,快速放电能力提高8.1%;同时,掺杂Cr2O3使电极循环充放性能有所提高,并对电极的活化次数、放电电位和过电位有不同程度的影响。     

铷掺杂三元正极材料Li1-xRbxNi0.4Co0.2Mn0.4O2的制备及其电化学性能

采用共沉淀法制备了三元材料LiNi0.4Co0.2Mn0.4O2,掺杂不同比例铷进行改性,对其进行了结构表征,考察了其电化学性能. 结果表明,Li0.97Rb0.03Ni0.4Co0.2Mn0.4O2样品的结晶度较好,铷掺杂起到了稳定三元材料晶体结构的作用,有效改善了材料的电化学性能,5C倍率下放电比容量达130 mA?h/g.     

Electrochemical and crystallographic characterization of Co-free hydrogen storage alloys for use in nickel–metal hydride batteries

Electrochemical and crystallographic characterization of Co-free hydrogen storage alloys containing Si and/or Fe was carried out. In the charge–discharge cycle test, the maximum discharge capacity of a Co-free MmNi_4.3Mn_0.4Al_0.3 (Mm=misch metal) alloy electrode was decreased by the partial substitution of Si and/or Fe for Ni, but the cycle performance was improved. The MmNi_3.6Mn_0.4Al_0.3Si_0.1Fe_0.6 electrode showed the most excellent cycle durability in this study. It was found by SEM, EPMA and XRD that Fe and Si contained in these alloys more or less suppressed the dissolution of Al and the lattice expansion with hydrogen absorption, leading to the long cycle life. This effect was strengthened by the simultaneous partial substitution of Si and Fe for Ni in the Co-free alloy.     

固相法合成高电压正极材料镍铬锰酸锂

5 V尖晶石型LiNi_0.5Mn_1.5O₄以其高能量密度、价格低廉、无环境污染等特点被视为最具发展潜力的锂离子电池正极材料之一。分别采用蔗糖、葡萄糖、柠檬酸3种不同碳源,通过固相混合、掺铬、球磨、高温煅烧制备出镍铬锰酸锂。通过XRD、SEM、粒度测量和电池充放电性能测试,对样品的结构、形貌、粒径、粒径分布及电性能等进行了分析。结果表明,加柠檬酸可制得粒径更细、粒径分布更窄的亚微米级的尖晶石型LiCr_0.2Ni_0.4Mn_1.4O₄,且其具有更好的电化学性能,在3.4～5.2 V、1 C下放电比容量可达149 mA·h/g,循环100次后容量保持率为98.0%。     

新型IT-SOFC阴极材料的合成和表征

以La（NO3）3·6142O、Ni（N03）2·6H2O和Co（NO3）2·6H2O为原料,尿素为燃料,采用凝胶低温燃烧技术合成L％Ni0．7C00．304粉体,利用各种分析方法粉体进行研究。X射线衍射分析表明：适当提高尿索在凝胶中的含量,燃烧后得到的粉体晶粒尺寸显著减小,未经燃烧的粉体中除含有La2Ni0.7Co0．3O4外,还有h2O3、CoO、La2cO5等杂质相。扫描电镜观察发现,随着锻烧温度的提高,La2NiO．7C00．304粉体的粒径有所增大,且远小于在相同锻烧条件下用固相反应法制备的La2Ni0.7Co0．304。采用低温燃烧法能够合成具有单一相结构的La2Ni0．7Co0．3O4粉体。     

Co~(3+)掺杂对La_(0.7)Sr_(0.3)Mn_(1-x)Co_xO_3的结构及光催化性能的影响

本文采用溶胶-凝胶法制备了钙钛矿型复合氧化物La0.7Sr0.3Mn1-xCoxO3。利用XRD,SEM对纳米颗粒的结构、形貌进行了表征。结果表明,合成的样品为钙钛矿型,呈立方颗粒状,粒径均匀,边长约为1μm。根据甲基橙的降解情况对其光催化活性进行了研究。结果表明,经过B位Co3+离子掺杂的La0.7Sr0.3Mn1-xCoxO3样品,光催化活性明显提高。     

Investigation of hydrogen transport through Mm(Ni3.6Co0.7Mn0.4Al0.3)1.12 and Zr0.65Ti0.35Ni1.2V0.4Mn0.4 hydride electrodes by analysis of anodic current transient

Hydrogen transport through such metal-hydride electrodes as Mm(Ni_3.6Co_0.7Mn_0.4Al_0.3)_1.12 and Zr_0.65Ti_0.35Ni_1.2V_0.4Mn_0.4 was investigated in 6 M KOH solution by using potentiostatic current transient technique. From the shape of the anodic current transient and the dependence of the initial current density on the discharging potential, the boundary conditions at the electrode surface were established during hydrogen extraction from the as-annealed and as-surface-treated electrodes. Especially, it was experimentally confirmed that the diffusion-limited boundary condition is no longer valid at the electrode surface during hydrogen transport in case hydrogen diffusion is coupled with either the interfacial charge transfer reaction or the hydrogen transfer reaction between adsorbed state on the electrode surface and absorbed state at the electrode sub-surface. From the transition behaviour of the boundary condition, it was further recognised that the boundary condition at the electrode surface during hydrogen transport is not fixed at the specific electrode/electrolyte system by itself, but it is rather simultaneously determined even at any electrode/electrolyte system by the potential step and the nature of the electrode surface, depending upon e.g. the presence or absence of the surface oxide scales.     

Visible-light-induced photoelectrochemical behaviors of Fe-modified TiO2 nanotube arrays

Fe-modified TiO(2) nanotube arrays (TiO(2) NTs) were prepared by annealing amorphous TiO(2) NTs whose surface was covered with Fe(3+) by a dip-coating procedure, and characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and UV-visible reflectance spectroscopy. The photoelectrochemical properties were evaluated by the photocurrent response and photoelectrocatalytic (PEC) degradation of methylene orange (MO) and 4-chlorophenol in water under visible-light irradiation (λ > 420 nm). The results showed that a Fe-modified TiO(2) NTs electrode exhibited a larger photocurrent response and higher PEC activity for the degradation of organic pollutants than a pure TiO(2) NTs electrode. At a bias potential of 0.4 V, the photocurrent response of a 0.5 M Fe-modified TiO(2) NTs electrode exceeded that of a pure TiO(2) NTs electrode by a factor of about 10, and the PEC degradation rates of MO and 4-chlorophenol on a 0.5 M Fe-modified TiO(2) NTs electrode exceeded those on a pure TiO(2) NTs electrode by a factor of about 2.5. The larger photocurrent response and higher PEC activity of Fe-modified TiO(2) NTs could be attributed to the enhancement of separation of charge-carriers at the external electric field and the extension of the light response range of TiO(2) to the visible-light region with the narrowing of the band gap.