喷雾干燥法制备碳载铂钴镍合金催化剂及其甲醇催化氧化性能研究

本文以氯铂酸、氯化镍和硝酸钴为原料,XC-72炭黑为载体,通过雾化干燥法结合煅烧还原制备碳载铂基（PtCo Ni）分散性好的多元合金纳米粒子催化剂。重点研究表面经过改性的炭黑对合金纳米粒子形成和分散的影响规律,研究碳载PtCoNi（原子比为1:1:1）合金纳米粒子的甲醇催化氧化活性、抗CO中毒能力和耐久性,以及不同原子比对催化氧化甲醇活性和抗CO中毒能力的影响规律。研究结果表明,采用表面改性后的炭黑作为载体,制备的碳载铂基（PtCoNi）催化剂为合金纳米粒子,且纳米粒子在炭黑表面分散均匀,粒径分布在1-4nm,平均粒径为2.3nm;与商用的Pt/C催化剂相比,PtCoNi/C（原子比为1:1:1）催化剂具有更高的甲醇催化氧化活性、耐久性和抗CO中毒性;不同原子比铂基多元催化剂在催化氧化甲醇活性上的顺序为：PtCoNi/C>Pt3CoNi/C>Pt5CoNi/C,抗CO中毒性顺序为：PtCoNi/C>Pt3CoNi/C>Pt5CoNi/C。     

复合γ-Fe2O3/M（M=Pt/Pd）纳米磁敏催化剂超声制备与表征

采用焙烧法制备γ-Fe2O3之后,再利用3-氨丙基三乙氧基硅烷(APTES)对其表面进行功能化修饰,在其溶液体系中加入氯铂酸/氯化钯溶液,使游离的四价铂粒子/二价的钯离子吸附在磁性纳米粒子表面,与氨基化基团形成配位化合物,在超声化学作用下,利用水合肼将铂离子和钯离子还原为单质,制成γ-Fe2O3/M(M=Pt/Pd)复合磁敏催化剂纳米粒子。并采用Bruker Advanced-D8粉末衍射仪,带有选区电子衍射(SAED)的透射电子显微镜(TEM),高分辨透射电子显微镜(HRTEM)和带有超导量子干涉装置(SQUID)功能的磁性测量系统(MPMS)等对γ-Fe2O3粒子和γ-Fe2O3/M复合粒子磁性进行表征。结果表明:采用焙烧法制备的γ-Fe2O3磁性纳米粒子粒径在20 nm左右,制备的γ-Fe2O3/Pt和γ-Fe2O3/Pd复合粒子粒径分别在68和36 nm左右,室温下的磁化强度分别为29.4和31.2(A·m2)/kg,磁响应性能优越,可用于磁敏催化剂反应体系。这为贵金属Pt、Pd催化剂的回收与磁敏催化剂应用提供了新的思路。     

胶体法制备高活性Pt-Ni双金属纳米粒子及其甲醇催化性能研究

采用胶体法分别以乙酰丙酮铂(Pt(acac)_2)和乙酸镍(Ni(ac)_2·4H_2O)为前驱体制备了(1:3,1:1,3:1)不同摩尔比的Pt-Ni合金纳米粒子,将其负载在XC-72碳黑载体获得Pt-Ni/C双金属催化剂,其中Pt_3Ni/C催化剂催化活性最高,其正向扫描峰电流密度是42.5 m A·cm~(-2),分别是Pt Ni/C、Pt Ni3/C和Pt/C催化剂的3.2、5.3和1.2倍;而催化剂抗中毒能力则是Pt Ni_3/C最强(I f/I b值为23.5)。TEM和XRD分析表明Pt-Ni双金属纳米粒子单分散性好,粒径分布为2~4nm;同时XPS结果表明Ni的掺杂改变了Pt的外层电子层结构,减少了表面Pt原子对CO的吸附,释放出更多的Pt活性位,从而提高了Pt-Ni/C双金属催化剂的电催化活性和抗中毒能力。     

WxC/GC的离子交换-碳化制备及其载铂电化学性能

以离子交换树脂为碳源,偏钨酸铵(AMT)为钨源和亚铁氰化钾(K_4Fe(CN)_6·3H_2O)为催化剂,采用离子交换法制备树脂基前躯体,在氮气气氛下高温还原同步碳化制备碳化钨/石墨碳(WxC/GC)复合物。以WxC/GC为载体,采用微波加热乙二醇还原法负载纳米铂(Pt)颗粒制备了Pt/WxC/GC催化剂。通过XRD、TG和SEM等测试技术分析了WxC/GC的形成过程及其形貌。并在酸性介质中测试Pt/WxC/GC的电催化性能。实验结果表明:制备的WxC/GC复合物颗粒细小,分散均匀,WxC粒径为2~30 nm。载质量分数10%Pt的Pt/WxC/GC在酸性介质中具有较好的电催化活性和稳定性,对甲醇的氧化电流密度峰值为39 mA·cm~(-2)。     

磁控溅射制备Pt-Cu双金属催化剂的性能研究

通过磁控溅射技术将Pt和Cu的纳米粒子共沉积于AlOx载体上,制备得到Pt-Cu双金属催化剂。催化剂的Pt/Cu原子比可以通过改变Pt的溅射功率轻松调控。通过扫描电镜、原子力显微镜和X射线光电子能谱对催化剂薄膜的组分、表面形貌和结合能进行表征。结果表明,非贵金属Cu替代Pt/AlOx中部分贵金属Pt可提高其催化活性并降低贵金属Pt的用量。当Pt/Cu原子比为3时,Pt-Cu双金属催化剂在100℃对甲醇燃烧的催化转化率达到95%,与相同条件下转化率为92%的Pt/AlOx催化剂相比,节省了约40%的贵金属Pt用量。催化活性的提升可以归结于Cu的掺杂降低了Pt~04f的结合能。     

CO在Pt-Fe催化剂的Pt/Fe/Pt(111)表面的吸附研究

低温(110~130 K)下,将次表层Fe结构的Pt-Fe模型催化剂(即Pt/Fe/Pt(111)结构)暴露于不同量CO气体,经不同温度退火后,采用高分辨电子能量损失谱(HREELS)研究催化剂表面CO分子的振动谱。结果表明,当CO的暴露量低于0.2 L (Langmuir)时,Pt/Fe/Pt(111)表面只存在顶位吸附;当暴露量大于0.4 L,除了顶位吸附外,桥位吸附开始出现;顶位吸附分子的C-O键振动峰随着暴露量的增加不断向高波数方向偏移。退火温度影响Pt/Fe/Pt(111)表面CO的吸附形式,低于255 K时,顶位吸附分子的脱附速率大于桥位吸附分子;高于255 K时,桥位吸附分子的脱附速率较大,并先于顶位吸附的CO从表面完全脱附,其完全脱附温度比Pt(111)表面低50 K。     

Pt/Co双金属纳米溶胶的制备及催化制氢性能

采用化学共还原法制备了聚乙烯吡咯烷酮(PVP)稳定的Pt/Co双金属纳米溶胶,利用UV-Vis、TEM等对所合成的Pt/Co双金属纳米溶胶进行了表征,并系统研究了PVP用量,还原剂用量,双金属比例对该溶胶型纳米双金属催化剂活性的影响。结果表明:所制备的Pt/Co双金属纳米溶胶的平均粒径在2~3 nm之间,大部分双金属纳米溶胶催化剂催化NaBH4制氢的活性都优于单金属Pt和Co纳米溶胶,Pt10Co90双金属纳米溶胶的催化活性最高,其催化NaBH4制取氢气的活性可以达到8800 mol-H2·mol-催化剂-1·h-1,该双金属纳米溶胶催化NaBH4水解反应的活化能为61.8 kJ/mol。所制备的Pt/Co双金属纳米溶胶催化剂具有很好的稳定性,即使在4次催化试验后该催化剂仍然保持着较高的催化活性。     

金核/铂壳纳米粒子的光化学合成及电催化活性

在含不同摩尔比的Au(Ⅲ)和Pt(Ⅳ)离子的PEG(聚乙二醇)-丙酮溶液中,采用光化学共还原法合成了一组Au@Pt复合纳米粒子,并以炭黑分别对其负载制成Au@Pt/C催化剂。借助于UV-Vis、TEM和HR-TEM的表征,证实复合纳米粒子为球形的核/壳结构;分别以XPS、EDS和电化学方法分析了复合粒子的化学状态、结构特点和Au@Pt/C催化剂的催化性质。结果表明,不同Au:Pt摩尔比的Au@Pt/C催化剂对甲醇氧化反应具有良好的催化活性和稳定性,其中Au:Pt=1:1时形成的Au@Pt/C催化剂电催化活性最高,约为商品Pt/C催化剂的4倍。简要讨论了核/壳结构产生高催化活性的主要原因。     

Co_(0.8)Zn_(0.2)Fe_2O_4及其磁电复合薄膜的制备与表征

采用溶胶-凝胶法制备Zn2+取代钴铁氧体Co0.8Zn0.2Fe2O4及Co0.8Zn0.2Fe2O4/(Ba0.85Ca0.15)(Zr0.1Ti0.9)O3磁电复合薄膜(CZFO/BCZT)。利用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM),拉曼光谱仪及振动样品磁强计(VSM)等对样品进行表征。研究表明,沉积在Pt(111)/Ti/SiO2/Si衬底上的CZFO薄膜为多晶结构,无明显择优取向,处于压应变状态。磁场平行于CZFO薄膜表面的饱和磁化强度和矫顽力分别为405emu/cm3和780×79.577A/m,其矫顽力高于CZFO粉体样品。制备的磁电复合薄膜结晶质量良好,多层纳米结构清晰完整。     

AlOOH纳米胶体制备及其在有机-无机纳米复合薄膜中的应用

采用胶体化学方法制备了不同形貌的纳米AlOOH胶体,并将其作为功能组分用于制备有机-无机纳米复合薄膜.采用的有机体系为有机硅烷单体,基底材料为有机玻璃(PMMA).研究发现纳米AlOOH粒子在薄膜体系中分散均匀,使薄膜具有透明、硬质等特点,赋予了PMMA表面优良的耐擦伤和耐磨损性能,而且可以利用纳米粒子形貌特征调控薄膜的性能.     

Fabrication, annealing, and electrocatalytic properties of platinum nanoparticles supported on self-organized TiO2 nanotubes

The platinum nanoparticles supported on self-organized TiO2 nanotubes （Pt-TiO2/Ti） were prepared using electrochemical anodic oxidation followed by cathodic reduction. The structure and chemical nature of the Pt-TiO2/Ti electrocatalyst were investigated by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. Both XRD and SEM results indicate the presence of platinum on nanotubular TiO2. The stability of the Pt deposits was also investigated in 0.5 mol/L H2SO4 solution by cyclic voltammetry. The electrocatalytic activity of the Pt-TiO2/Ti catalyst exhibits enhancement effect during electro-oxidation of methanol when annealed to anatase. Successive cyclic voltam- mograms of methanol oxidation on the Pt-TiO2/Ti electrocatalyst shows unique electrocatalytic characteristics when compared to methanol oxidation on the bulk Pt catalyst. This is because of further quick oxidation of adsorbed CO by Pt （111） facets of Pt particles on self-organized TiO2 nanotubes when the formation of an electroactive film onto the working catalyst surface occurs.     

Highly adhesive Pt-electrode films directly deposited on SiO2 by electron-cyclotron-resonance plasma sputtering

Pt films directly deposited on SiO₂ by electron-cyclotron-resonance (ECR) plasma sputtering and DC-magnetron sputtering have been compared in terms of their performance as electrodes. The DC-magnetron sputtered Pt film consisted of sharply (111) oriented crystallites, which was reflected in hexagonal crystallites observed in atomic force microscopy images. While ECR-sputtered Pt film was also (111) oriented, the X-ray diffraction rocking curve of the (111) peak was broader than that of the DC-magnetron sputtered film. The surface image revealed fine grains, thus having a flatter surface. A scratch test revealed that ECR-sputtered films had an adhesive strength about twice that of DC-magnetron-sputtered films, which was consistent with our tape-test results. Possible reasons for the different adhesion characteristics are discussed.     

Synthesis and study of λ-MnO_2 supported Pt nanocatalyst for methanol electro-oxidation

A λ-MnO2 supported Pt nanocatalyst(5 wt.% Pt/λ-MnO2) was synthesized using a facile approach.X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electronic microscope(SEM), transmission electron microscopy(TEM), and energy disperse spectroscopy(EDS) were used for catalyst structure and morphology characterization, which showed that the metallic Pt particles were attached on a λ-MnO2 surface through the interaction between Pt and λ-MnO2.Cyclic voltammetry(CV) was used to test the catalytic activity of Pt/λ-MnO2 toward methanol oxidation, which showed that Pt/λ-MnO2 catalyst has much higher catalytic activity than baseline Pt/C catalyst.     

Carbon nanotubes-supported PtAu-alloy nanoparticles for electro-oxidation of formic acid with remarkable activity

PtAu-alloy nanoparticles supported on multi-walled carbon nanotubes (MWCNTs) were successfully prepared by simultaneous reduction of H₂PtCl₆·6H₂O and HAuCl₄·3H₂O with sodium borohydride as a reducing reagent and sodium citrate as a stabilizing reagent. The morphology and composition of the composite catalyst were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The results show that the PtAu alloy nanoparticles with an average diameter of about 3.5 nm and narrow size distribution are supported on MWCNTs. Electrocatalytic oxidation of formic acid at the PtAu/MWCNTs nanocomposite electrode was investigated in a solution containing 0.50 M H₂SO₄ as a supporting electrolyte and 0.50 M formic acid by cyclic voltammogram and chronoamperometry. The results demonstrate that the PtAu/MWCNTs catalyst exhibits higher activity and stability for electro-oxidation of formic acid than the commercial Pt/C catalyst, reflecting by its lower onset potential (−0.05 V), oxidation mainly occurring in low potential range of −0.05 ± 0.65 V and higher peak current density of 3.12 mA cm⁻². The result of CO stripping voltammetry discloses that gold in the PtAu/MWCNTs nanocomposite enhances the catalytic activity and stability.     

Platinum colloid catalyzed etchingless gold electroless plating with strong adhesion to polymers

Echingless electroless plating (ELP) process that can produce gold thin film with strong adhesion to various polymer films has been developed. We have found that platinum (Pt) colloidal nanoparticles have excellent catalytic activity for ELP. The Pt colloidal nanoparticles can be immobilized via electrostatic interactions on a substrate simply by dipping it into a Pt colloid. Owing to the excellent catalytic property of the Pt nanoparticles, continuous gold thin films can be produced at room temperature using a simple cyanide-free gold electroless plating solution composed of chloroauric acid and hydrogen peroxide. The process requires no surface modifications for the immobilization of the catalyst, and by simple post-annealing the adhesion of the plated films to various polymer films can be improved by three orders of magnitude in comparison to that of “as-deposited” film. The process developed in this work is expected to be an environment-friendly thin metal film deposition process without the use of toxic and hazardous substances.     

碳载铂纳米微粒修饰的玻碳电极对甲醇的电催化氧化

利用X射线粉末衍射、透射电镜和扫描电镜对商用Pt/C催化剂反应前后的变化进行了物化表征，同时应用电化学方法研究了甲醇在碳载铂纳米微粒修饰的玻碳电极上的电催化氧化性能。结果表明，修饰电极对甲醇氧化呈现较高的电催化活性。铂氧化物的电化学还原在Pt/c催化剂中受到了抑制，该现象可能是由于Pt与载体碳间的强烈作用所引起的。通过扫描电镜和循环伏安研究表明，该催化剂对甲醇的氧化可能存在着表面结构敏感效应。     

Effect of annealing temperature on ferroelectric properties of （Bi, Nd）4（Ti, V）3O12 thin films

Thin films of Nd^3＋/V^5＋-cosubstituted bismuth titanate, （Bi3.sNd0.5）（ Ti2.96V0.04）O12 （BNTV）, were fabricated on the Pt（111）/Ti/SiO2/Si（100） substrates by a chemical solution deposition technique and annealed at different temperatures of 650, 700, 750 and 800 ℃. The surface morphology and ferroelectric properties of the samples were studied in detail. The result shows that the film annealed at 800 ℃ indicates excellent ferroelectricity with a remanent polarization of 2Pr=40.9 i.tC/cm^2, a coercive field （Ec） of 114 kV/cm at an applied electrical field of 375 kV/cm. The substitution of Ti-site ion by V^5＋ ions could improve the upper limit of the optimal annealing temperature by decreasing the space charge density in BNT thin film. Additionally, the mechanism concerning the dependence of ferroelectric properties of BNTV thin films on the annealing temperature was discussed.     

Effects of post-annealing on Schottky contacts of Pt/ZnO films toward UV photodetector

The Schottky contact of Pt/ZnO was formed by depositing ZnO films oriented along c-axis by pulsed-laser deposition on Pt/Ti buffer layer supported by SiO₂/Si substrate. Effects of the post-annealing on the crystallinity, uniformity and native defects of ZnO film as well as Schottky contacts of Pt/ZnO films were investigated. Results show that the annealing can improve the crystallinity of ZnO film, suppress the native defects, and enhance the performance of Pt/ZnO Schottky contacts dramatically. The best Schottky diode shows the largest barrier height of 0.8 eV with reverse leakage current of 1.5 × 10⁻⁵ A/cm². The zero-biased photodetector based on the best Schottky diode possesses responsivity of 0.265 A/W at 378 nm, fast photo-response component with rise time of 10 ns and fall time of 17 ns. This report demonstrates possibility of ZnO films/Pt hetero-junction with large area Schottky contact, and establishes the potential of this material for use in UV photodetector devices.     

Comparative studies of adsorbed CO and methanol electrooxidation on carbon supported Pt and PtRu catalysts in acid solution

1. Introduction Direct methanol fuel cells (DMFCs) have con-siderable advantages compared to gas feed (H2/air) polymer electrolyte membrane (PEM) fuel cells [1-2]. The hydrogen PEM fuel cells use gaseous hy-drogen as fuel. But there is no source and infra-structure established yet for hydrogen distribution and storage, neither as a liquid nor as a gas. How-ever, the DMFC, similar to a proton exchange membrane fuel cell (PEMFC), uses methanol fuel directly for electric power generation …