喷雾干燥法制备铂镍合金三维纳米骨架材料及增强甲醇氧化性能研究

本文以氯铂酸氨和氯化镍为原料,氯化铵作为造孔剂,通过雾化干燥法结合煅烧还原制备铂镍合金三维纳米骨架材料,该新型材料可增强催化甲醇氧化性能。重点研究了前驱体中加入氯化铵和不加入对铂镍合金三维纳米骨架形成的影响规律,研究不同结构的铂镍合金三维纳米骨架材料对催化氧化甲醇活性和稳定性的影响规律。研究结果表明,通过加入适量的氯化铵作为造孔剂,制备的铂镍合金为单项固溶体结构(面心立方结构),由弯曲纳米线交织组成三维纳米骨架材料,纳米线直径小于10 nm,纳米孔10 nm左右;与商用Pt黑和不加入氯化铵制备的铂镍合金纳米材料相比,PtNi合金三维纳米骨架材料具有更高的甲醇催化氧化活性(611.4 mA.mg_^-1Pt),分别是商用Pt黑的3.58倍(170.8 mA.mg_^-1Pt)和PtNi合金纳米材料(不加氯化铵)的1.36倍(448.8 mA.mg_^-1Pt);在催化甲醇氧化性能稳定性上,PtNi合金三维纳米骨架材料表现出最好的稳定性,稳定性顺序为：PtNi合金三维纳米骨架材料 > PtNi合金纳米材料(不加氯化铵)> 商用Pt黑。此外,本文对该方法进行了扩展,成功的制备了铂镍钴铜钌铱钯(PtNiCoCuRuIrPd)高熵合金三维纳米骨架材料。     

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。     

介孔碳载铂催化剂的制备、表征及催化性能评价

以介孔碳材料CMK-3为载体,采用乙二醇还原的方法进行金属铂负载,制备了不同铂含量(1.5%、2.0%和3%)的催化剂。XRD、BET、TEM的表征结果表明,催化剂保持了CMK-3高度有序的介孔结构,铂粒子的平均粒径在5 nm左右,均匀地分散在CMK-3孔道内。用萘的加氢反应对此催化剂的性能进行评价,获得的最优条件为:使用Pt(2%)/CMK催化剂,在280℃、氢气压力3 MPa、氢油比500、质量空速2 h-1的条件下,萘的转化率和生成十氢萘的选择性均大于98%。此催化剂对降低石油产品中芳烃具有潜在应用价值。     

碳载Pd-Co-Au合金纳米粒子的制备及其电催化性能

采用乙二醇还原法并进一步热处理制备碳载Pd-Co-Au(Pd-Co-Au/C)三元合金纳米电催化剂,通过旋转圆盘和环盘电极等技术评价催化剂对氧气还原反应的电催化活性,并分析氧气还原的机理.结果表明:合成Pd-Co-Au/C催化剂中Pd和Au两相面心立方(fcc)结构共存,且随着热处理温度的提高,对应于Au的衍射峰强度减弱,而Pd衍射峰强度增强:当温度高于800℃时,形成具有Pd单相fcc结构的三元合金纳米催化剂.氧气还原反应的动力学表明:氧气在Pd-Co-Au/C三元合金催化剂上按4e路径还原为水.电化学表征表明,在酸性介质中,经800℃热处理的Pd7Co<<2>Au1/C催化剂对氧气还原的电催化活性最高,接近于商业化Pt/C的性能;而在含甲醇的酸性介质中,Pd-Co-Au/C催化剂电催化氧气还原的活性显著高于Pt/C.因此,Pd-Co-Au/C是一种高抗甲醇的新型氧气还原反应电催化剂.     

铂合金催化网及其在氨氧化法中的应用和研究进展

铂合金催化网具有化学稳定性好、催化活性和目标物选择性高、使用寿命长等优点,在氨氧化法制备硝酸和氢氰酸等化工原料中难以替代。本文概述了铂合金催化网从合金化到网面编织的制备加工技术,并分别介绍了氨氧化法合成硝酸和氢氰酸的反应机理和反应诱导催化网表面变化的研究进展,最后探讨了氨氧化法及铂合金催化网的未来发展趋势。     

碳载金铂双金属催化剂催化活性研究

采用KBH4做还原剂、PVP做保护剂,化学法一步合成Au-Pt合金纳米粒子,应用UV-Vis、TEM、XRD等手段对其进行了表征.将所合成的合金纳米粒子负载在碳黑上,获得Au-Pt双金属碳载催化剂,应用循环伏安法(CV)检测了催化剂对甲醇的电催化氧化活性.研究表明,Au-Pt/C催化剂的催化活性明显高于Pt/C的,说明...     

分散铂修饰聚苯胺电极的制备及其催化性能

利用扫描电子显微镜（SEM）、循环伏安（CV）方法,探讨了在合成分散铂修饰聚苯胺复合电极（Pt-PANi／pt）时能够影响聚苯胺表面形貌的质子酸种类以及铂微粒的电沉积方法。实验发现,采用循环伏安法制备聚苯胺时,在硝酸介质中制备的纳米聚苯胺纤维细小、膜层稳定、能够提高复合电极的催化活性,比在硫酸介质中制备的聚苯胺更适合作为Pt催化剂的载体;沉积分散铂所采用的电化学方法不同导致铂的生长方式不同,造成复合电极催化活性的差异。采用脉冲电位法,通过缩短脉冲沉积时间,能够使铂微粒数目增多、分布均匀,有效提高铂的比表面积,制备的Pt-PANi／pt复合电极显示出了较好的催化活性。     

钴镍合金纳米片分级结构及其双催化电解水性能

钴镍合金具有双功能电催化活性,可有效提高电解水效率、降低成本。利用电沉积的方法通过调节电流密度和沉积时间在耐蚀性钛箔上合成了具有分级结构的钴镍合金纳米片。参数优化后的结果表明,沉积电流密度为75mA·cm-2时,仅用5min即可获得规整有序的纳米片-纳米颗粒分级结构。XRD和HRTEM表征结果证实,在纳米片-纳米颗粒的分级结构中形成了具有双功能催化活性的钴镍合金,钴和镍的原子比随反应时间的变化而略有变化。纳米片-纳米颗粒分级结构的形成使得表面催化活性位点增加,其在碱性条件下表现出较优异的析氧和析氢双功能催化活性,在10mA·cm-2时HER和OER过电势分别为517与392mV,将来有望替代贵金属催化剂而成为新型的电解水催化剂。     

催化碳烟氧化用PtCexZr1-xO2催化剂的制备及性能研究

采用水热晶化法一步制备了铈锆摩尔比不同的PtCe_xZr_(1-x)O_2系列催化剂,测定其比表面积、储氧量、氢气还原温度等物化性能参数,并进行结构表征,研究催化剂组成中铈锆摩尔比(n_(Ce)/n_(Zr))对催化剂结构和性能的影响。结果表明,当n_(Ce)/n_(Zr)=5:5时,制备得到的PtCe_(0.5)Zr_(0.5)O_2催化剂晶粒尺寸最小,储氧量较高,氢气还原温度低,微观结构为四方相和立方相2种晶型结构并存的固溶体。与传统贵金属浸渍负载方法制备的Pt/Ce_(0.5)Zr_(0.5)O_2催化剂相比较,水热晶化法一步制备的PtCe_(0.5)Zr_(0.5)O_2催化剂对碳烟的低温氧化具有更优的催化活性。     

氧化镨纳米棒负载银纳米材料的制备及其催化性能

制备氧化镨纳米棒,利用浸渍法在纳米棒上负载金属银,得到稳定性较强的复合纳米材料。对合成的纳米样品进行XRD、TEM及HRTEM等表征。并以Pr6O11/Ag复合纳米材料催化烯烃环氧化反应,试验表明环己烯环氧化反应催化效果较好。     

Preparation and catalytic activity of CO-resistant catalyst core-shell Au@Pt/C for methanol oxidation

Au@Pt core-shell nanoparticles were successfully synthesized by a successive reduction method and then assembled on Vulcan XC-72 carbon surface.Furthermore,its composition,morphology,structure,and activity towards methanol oxidation were characterized by UV-vis spectrometry,transmission electron microscopy (TEM),high-resolution TEM (HRTEM),X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS),and cyclic voltammetry (CV).Results reveal that Au@Pt/C catalyst has better activity towards methanol oxidation than the pure platinum prepared under the same conditions.When the atomic ratio of Au to Pt in the prepared Au@Pt/C catalyst is 1∶2,this catalyst exhibits best electrocatalytic activity towards methanol oxidation in acidic media,and the peak current density on this catalyst is ～2.0times higher than that on Pt/C catalyst.The better catalytic activity of Au@Pt/C results from its better resistance to toxic CO than Pt/C because the CO oxidation on Au@Pt/C is 60 mV more negative than the case on Pt/C.     

镁合金微弧氧化黑色膜的制备工艺和结构

用微弧氧化的方法,通过两种电解液体系在AZ91D镁合金基体上获得颜色均匀、致密性好的黑色陶瓷层,研究了在这两种体系中,着色盐成分、浓度,以及氧化电压和处理时间对氧化陶瓷层的影响。结果表明：试样在两种电解液体系中皆能得到黑色陶瓷层,不同的基础电解液所需加的着色盐不同,在硅酸盐体系中以CuSO4为主要着色盐,在磷酸盐体系中以CoSO4为主要着色盐。着色盐浓度和氧化电压对膜层颜色影响较大,在一定范围内,随着氧化电压的上升,膜层颜色有所加深,而相同条件下氧化时间的改变对颜色变化影响较为缓和。通过比较,发现在磷酸盐体系中膜层表面质量最好。     

Preparation of nano-platinum and its catalytic activity toward methanol oxidation and oxygen reduction

Nano-scale platinum catalysts were prepared on a glass carbon electrode by cyclic voltammetry. The surface morphology and active area of the catalysts, and their catalytic activity toward methanol oxidation and oxygen reduction were studied by SEM, linear and cyclic voltammetry. The result shows that the diameters of global Pt particles are affected by the scan rate of cyclic voltammetry： the faster the scan rate is, the smaller the diameters of Pt particles are. The size of the nano-scale platinum catalysts has different effects on their catalytic activity toward oxygen reduction and methanol oxidation： the catalyst with a size of 100 nm shows its best activity toward methanol oxidation, but the catalyst with a size of 65 nm shows its best activity toward oxygen reduction.     

Electrocatalytic oxidation of methanol on carbon-nanotubes/graphite electrode modified with platinum and molybdenum oxide nanoparticles

Electrochemical codeposition and electrocatalytic properties of platinum and molybdenum oxide nanoparticles(Pt-MoOx) on carbon-nanotubes/graphite electrode for methanol oxidation were investigated.The micrograph and elemental composition of the resulting Pt-MoOx/CNTs/graphite electrode were characterized by scanning electron microscopy(SEM)and energy dispersive X-ray spectroscopy(EDS).The results show that the Pt-MoOx particles with the average size of about 50 nm are highly dispersed on the CNTs surface.The Pt-MoOx/CNTs/graphite electrode delivers excellent electrocatalytic properties for methanol oxidation.The highest mass activity(Am)reaches 264.8 A/g at the loading mass of 159.3μg/cm2.This may be attributed to the small particle size and high dispersion of Pt-MoOx catalysts deposited on the CNTs surface.The kinetic analysis from electrochemical impedance spectroscopy(EIS)reveals that the existed MoOx phase can improve the chemisorptive and catalytic properties for methanol oxidation.     

Preparation and characterization of polyvinylchloride membrane embedded with Cu nanoparticles for electrochemical oxidation in direct methanol fuel cell

Copper nanoparticles were prepared by the chemical reduction method. These copper particles were embedded into the polyvinylchloride (PVC) matrix as support and used as an electrode (PVC/Cu) for the oxidation of methanol fuel for improving the current response. The PVC/Cu electrodes were characterized by thermal gravimetric analysis (TGA) for thermal stability of the electrode, X-ray diffraction (XRD) for identification of copper nanoparticles in the electrode, Fourier transform infrared spectroscopy (FTIR) to identify the interaction between PVC and Cu and scan electron microscopy (SEM) with EDAX for the morphology of the electrode. The electrocatalytic activity of the electrode was characterized by the cyclic voltammetry, linear sweep voltammetry, and chronoamperometry techniques. An increase in the electrode activity was observed with the increase of copper quantity from 0.18 g (PVC/Cu-0.18 g) to 0.24 g (PVC/Cu-0.24 g) and the maximum was found at 0.24 g of copper in the electrode. Also, it was observed that the electrode achieved the maximum catalytic current in 0.5 mol/L CH₃OH + 1 mol/L NaOH solution. FTIR identified that water molecules, C—H group, copper nanoparticle and its oxide were available in the electrode. SEM images with EDAX showed that copper particles were properly embedded in the polyvinylchloride matrix.     

Facile synthesis of 3D nanoporous Pd/Co2O3 composites with enhanced catalytic performance for methanol oxidation

To simultaneously reduce noble metal Pd usage and enhance electrocatalytic performance for methanol oxidation, Pd/Co₂O₃ composites with ultrafine three-dimensional (3D) nanoporous structures were designed and synthesized by simple one-step dealloying of a melt-spun Al-Pd-Co alloy with an alkaline solution. Their electrocatalytic activity in alkaline media was determined by a Versa-STAT MC workstation. The results indicate that the typical sizes of the ligaments and pores of the composites were approximately 8–9 nm. The Co₂O₃ was uniformly distributed on the Pd ligament surface. Among the as-prepared samples, the nanoporous Pd/Co₂O₃ composite generated from dealloying of the Al_84.5Pd₁₅Co_0.5 alloy had the best electrocatalytic activity, and its activity was enhanced by approximately 230% compared with the nanoporous Pd from dealloying of Al₈₅Pd₁₅. The improvement of the electrocatalytic performance was mainly attributed to the electronic modification effect between Pd and Co as well as the bifunctional mechanism between Pd and Co₂O₃.     

Preparation of heat-resistant aluminum alloy pipe blanks by multi-layer spray deposition

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Salt spray corrosion test of micro-plasma oxidation ceramic coatings on Ti alloy

Ceramic coatings were prepared on Ti-6Al-4V alloy in NaAlO2 solution by micro-plasma oxidation (MPO). The salt spray teste of tne coated samples and the substrates were carried out in a salt spray test machine. The phase composition and surface morphology of the coatings were investigated by XRD and SEM. Severe corrosion occurred on the substrate surface, while there were no obvious corrosion phenomena on the coated samples. The coatings were composed of Al2TiO5 and a little α-Al2O3 and rutile TiO2, and the salt spray test did not change the composition of the coatings. The weight loss rate of the coatings decreased with increasing MPO time because of the increase in density and thickness of the coatings. The surface morphology of the coatings was influenced by salt spray corrosion test Among the coated samples, the coating prepared for 2 h has the best corrosion resistance under salt spray test.     

喷雾干燥结合微波煅烧法制备微米级球形钼粉的研究

本文以仲钼酸铵(优级纯)为原料,通过结合气流式雾化干燥法和微波煅烧氢还原法制备出球形、微米级、比表面积大、分散性好的钼粉。重点研究雾化造粒过程和微波煅烧氢还原阶段的升温速率对最终Mo粉的形貌、粒度以及比表面积的影响及规律。研究结果表明,控制一定的参数可以制备出球形、微米级、分散性好的钼酸铵前驱体粉末;最终Mo粉的微观形貌受升温速率的影响,升温速率越低制备的Mo粉破碎越严重,且有少量团聚现象,升温速率越高制备的Mo粉球形度越高,分散性越好;升温速率也直接影响平均粒度和比表面积,升温速率越低,平均粒度越小,而比表面积越大,升温速率越高,平均粒度相应增大,比表面减小。