化学还原法制备铂及铂合金催化剂及其性能

采用混合水溶液浸渍,硼氢化钠还原的方法制备了微型直接甲醇燃料电池用电催化剂,包括碳载铂、碳载铂基合金电催化剂.XRD、SEM、EDX测试结果表明催化剂的粒度达纳米级,且分散性好、原子摩尔配比合理.将Pt/C、Pt合金/C分别作为电池的阴极和阳极电催化剂,通过电池的极化曲线和功率密度曲线筛选出最佳的催化剂组成.在室温下,甲醇浓度为2mol/L时,阴极采用30wt%Pt的Pt/C,阳极采用n(Pt)∶n(Ru)∶n(Ir)∶n(Mo) = 2∶1∶2∶3的PtRuIrMo/C电催化剂,其电池的性能最好.     

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。     

质子交换膜燃料电池催化剂研究

质子交换膜燃料电池(PEMFC)的有效电催化剂仍以铂为主.由于铂价格昂贵,资源匮乏,使得PEMFC成本高,限制了其广泛应用,所以降低贵金属催化剂用量,寻找廉价催化剂,提高电极催化剂性能成为电极催化剂研究的主要目标.采用铂/碳催化剂,将铂催化剂担载在高活性碳材料上,可以将铂的担载量从4 mg/cm2降低到0.7 mg/cm2～1.0 mg/cm2,甚至到0.05 mg/cm2～0.2 mg/cm2,有效提高了铂的利用率.铂合金电催化剂以Pt-Ru为主,通过Pt和Ru的协同作用,大大减少了铂的用量(Pt与Ru的质量比为0.05:1),提高了催化剂抗CO性能.多元复合催化剂和非铂系催化剂也是目前的研究热点.     

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。     

碳载PtNi合金催化剂的制备、表征及氧还原催化性能研究

以乙酰丙酮铂(Pt(acac)₂)、乙酰丙酮镍(Ni(acac)₂)为前驱体,三正辛基氧膦(TOPO)为表面修饰剂,油胺(OAm)为还原剂,N,N-二甲基甲酰胺(DMF)为助剂,超导碳科琴黑ECP为载体,采用液相合成法制备了碳载PtNi合金纳米催化剂(Pt_2.7Ni/C)。通过TEM对其形貌进行表征,ICP-AES进行定性和定量分析,XRD对其结构进行表征,并进行电化学阴极氧还原催化性能研究。研究表明：所制备的Pt_2.7Ni/C纳米催化剂粒径分布在3～11 nm之间,平均粒径为6.25 nm;在酸性条件下,当电位在0.9 V(vs.RHE)时,Pt_2.7Ni/C纳米催化剂的质量比活性为796.08 mA·mg_Pt^-1,为商业Pt/C(JM)催化剂的约4.0倍,面积比活性为3.60 mA·cm^-2,为商业Pt/C(JM)催化剂的约11.3倍。同时在经过5000和10 000次的加速耐久性实验后,Pt_2.7...     

Pt/SiO2催化硝酸肼还原六价铀制备四价铀

以大孔二氧化硅为载体,采用浸渍法负载铂制备了3％Pt/SiO2催化剂,用于硝酸肼催化还原硝酸铀(Ⅵ)酰制备四价铀(U(Ⅳ)),考察了催化剂用量、硝酸浓度、硝酸肼浓度和反应温度对催化还原铀(Ⅵ)反应的影响.表征结果显示,催化剂中铂主要以1～3 nm的纳米粒子形态堆积在多孔SiO2载体表面;优化的催化反应条件为:反应液为1...     

不同改性的MWCNTs负载Au催化剂电催化甲醇的研究

通过光化学还原法,以HAuCl4溶液为前躯体,用312nm的紫外光辐照,在20 min内合成了红色Au纳米粒子溶胶.用苯硫酚溶液和5wt％ HF溶液分别改性管径为20～40nm的多壁碳纳米管(MWCNTs),并将合成的Au纳米粒子负载在改性的MWCNTs表面,制备了不同方法改性的Au/MWCNTs纳米催化剂.TEM显示,Au纳米颗粒平均粒径为4.3 nm,在MWCNTs表面的负载效果是HF的改性明显好于苯硫酚.在KOH溶液碱性介质中,电化学测试表明,苯硫酚和HF两种不同方法改性后,Au/MWCNTs纳米催化剂对甲醇具有一定的电催化活性,但后者具有更高的催化活性和更好的稳定性.     

热处理对Pt纳米线电催化性能的影响

采用阳极氧化铝(AAO)模板法电化学沉积制备了Pt纳米线催化剂,并进行了热处理。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学测试对热处理前后Pt纳米线催化剂的晶体结构、形貌和电催化性能进行了表征,并与商业碳载铂(Pt/C)做对比。SEM照片表明制备了表面粗糙的Pt纳米线。循环伏安法(CV)和计时电流曲线表明,Pt纳米线较Pt/C催化活性高,退火后Pt纳米线更利于甲醇氧化,且稳定性更好。旋转圆盘电极(RDE)测试研究发现,未经热处理的Pt纳米线催化剂氧还原反应(ORR)极化曲线的半波电势相对Pt/C有正移,有更大的极限扩散电流,利于氧还原反应的发生。     

改进多元醇法制备Pt/C催化剂及其性能表征

采用多元醇法和一种新的改进多元醇法制备了用于质子交换膜燃料电池的Pt/C催化剂,并对2种方法制备的催化剂进行了比较。后者是将Pt前驱体先负载至碳黑上,再加入多元醇还原,制备出了粒度分布均匀,分散性好的Pt/C催化剂。利用透射电镜(TEM)、X射线衍射(XRD)以及动态伏安法(CV)表征催化剂的微观组织形貌、物相组成以及电化学性能。研究结果表明,先还原后负载方式的多元醇法制备的Pt/C催化剂容易团聚。而先负载后还原方式制备的Pt/C催化剂则粒度分布均匀,分散性好,粒径大小在1.2～3.2 nm,电化学测试也表明,该Pt/C催化剂的质量电流密度为23.42 A/g,具有更高的催化活性。     

钯/多壁碳纳米管作为直接甲醇燃料电池阳极材料

将Pd纳米颗粒负载在功能化的多壁碳纳米管(MWCNTs)上制备出Pd/MWCNTs催化剂.应用TEM、XRD对其进行表征,并利用循环伏安(CVs)、时间电流法检测其对碱性溶液中甲醇的催化活性.结果表明,Pd纳米颗粒高分散在功能化的多壁碳纳米管上,在碱性溶液中Pd/MWCNTs催化剂对甲醇显出了高的催化活性和稳定性.     

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.     

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.     

PtPb/ C 催化剂的制备及其对甲酸电氧化的催化性能

目的通过Pb元素的添加来提高Pt/C催化剂电催化氧化甲酸的性能。方法通过乙二醇协助硼氢化钠还原法,以氯铂酸为Pt源和硝酸铅为Pb源制备不同原子比的PtxPb/C催化剂。采用X射线衍射光谱法(XRD)和透射电子显微镜技术(TEM)表征样品的晶体结构和颗粒形貌;采用循环伏安法表征样品催化氧化甲酸的性能。结果利用乙二醇协助硼氢化钠还原法成功制得了Pt和Pb原子比不同的PtxPb/C催化剂,XRD和TEM测试结果表明这些样品均为Pt的面心立方结构,且颗粒大小均一、分散均匀,其平均粒径为4 nm左右。循环伏安测试结果表明PtxPb/C催化剂催化氧化甲酸的性能优于商业Pt/C催化剂的催化性能,且受Pt和Pb原子比的影响,当原子比为5∶1时,其对氧化甲酸的催化性能最好,峰电位对应的Pt的比质量活性达到2000 m A/(mg Pt),远远高于商业Pt/C,同时计时电流曲线表明其具备良好的稳定性。结论 Pb原子的加入影响了Pt原子的电子结构,与Pb对Pt的协同作用共同促进了CO等中间产物在Pt表面的快速氧化,降低了催化氧化甲酸的初始电位,促使甲酸在低电位直接氧化为CO2和H2O,提高了其催化氧化甲酸的峰电流,有效减轻了Pt中毒,提高了其催化活性。     

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 …     

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.     

FeO薄膜担载的Pt纳米粒子

研究了FeO/Pt(111)体系中FeO薄膜及其担载的Pt纳米粒子的制备和热稳定性。在Pt(111)表面制备出完整的单层FeO薄膜,并作为载体制备2~3 nm粒径均一且分散均匀的纳米Pt粒子,形成 Pt/FeO/Pt(111)模型催化剂。氧气气氛(1.1×10-6 mbar)以及不同温度的退火处理并不能有效地促进Pt粒子在FeO薄膜表面的分散,也不利于形成全同有恅的Pt纳米粒子阵列。单层FeO表面担载的Pt纳米粒子已能够符合相关模型催化剂研究工作的总要,将成为下一步的工作基础。     

微波合成WCx/MWCNTs及其电催化性能研究

目的制备多壁碳纳米管负载碳化钨的纳米复合材料(WC_x/MWCNTs),探索微波加热温度对WC_x/MWCNTs合成的影响规律。方法利用分子自组装技术与微波加热技术相结合,以钨酸钠为W源,制备了WC_x/MWCNTs纳米复合材料。采用X射线衍射(XRD)和透射电子显微镜技术(TEM)对不同条件下制得样品的物相组成、结构及微观形貌进行了表征;采用循环伏安法在酸性环境下测试了WC_x/MWCNTs对氢和CH3OH的电催化性能。结果当微波加热温度为1000℃时,制备的WC_x/MWCNTs纳米复合材料由WC、WC2和C组成,碳纳米管的多壁结构保留较好,碳化钨颗粒均匀地分布在碳纳米管外表面,粒径为20~50 nm。循环伏安测试结果表明,制备的WC_x/MWCNTs在酸性环境下对氢具有一定的催化作用,但对甲醇没有明显的电催化作用。结论通过控制合理的微波加热温度,可制备出碳化钨粒径小、分布均匀、碳纳米管多壁结构完好的WC_x/MWCNTs纳米复合材料。制备的WC_x/MWCNTs在酸性环境下对氢具有一定的催化作用,可作为催化剂载体来负载其他金属制备复合催化剂。     

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。     

Porous carbon nanotube electrodes supported by natural polymeric membranes for PEMFC

A new type of porous multiwalled carbon nanotube (MWCNT) electrode with a macroporous networking inner-structure was prepared. First, the MWCNTs were homogeneously introduced inside and outside of a bacterial cellulose membrane with a 3D inter-connected network structure using ultrasound treatment and vacuum filtration in order to form the GDL. Second, the CL was formed on the surface of the GDL through vacuum filtration of the Pt incorporated MWCNTs (Pt/MWCNTs). Finally, the electrode was created through freeze-drying. The final electrode had a sheet resistance of 80 Ω/□ and an electro-chemical active surface area (ECSA) of 10.1 m²/g. Although the ECSA of the electrode did not have the efficiency (14.3 m²/g) of a typical electrode (carbon cloth/Pt/carbon black), these results suggested that the new type of electrode has potential as a proton exchange membrane fuel cell.