Corrosion stability of nanosize Pd/C,PdCo/C,and PdCoCr/C catalytic systems in acidic media for fuel cell cathodes

An express method for determining the corrosion stability of palladium-based cathodic catalytic systems was developed. The method consists of cycling the electrode potential with a thin catalyst layer in 0.5 M H₂SO₄ in the range of potentials of the fuel cell operation and a subsequent comparison of the characteristics of catalytic systems (specific surface area and activity in the oxygen reduction reaction) before and after the corrosion action. The suggested method was used to characterize the corrosion behavior of the Pd/C commercial catalyst, as well as the PdCo/C and PdCoCr/C catalysts synthesized at the Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences. According to the XRD data, they correspond to systems with a high level of alloy formation. It is shown that the PdCo/C and PdCoCr/C catalysts are considerably more stable towards corrosion action than 20% Pd/C (E-TEK). The results were compared with the stability data obtained using a chronoamperometric method.     

聚苯胺增强 Pt / C 催化剂活性和稳定性研究

目的制备一种具有高稳定性和高催化活性的Pt/C@PANI"核/壳"结构催化剂。方法利用原位化学氧化聚合法制备聚苯胺修饰Pt/C@PANI"核/壳"结构催化剂,采用循环伏安加速寿命实验,结合电化学活性表面积、氧还原活性、X-射线光电子能谱和透射电镜,考察所制备催化剂的活性和稳定性,通过密度泛函理论探究PANI增强Pt/C催化剂活性和稳定性的量子化学本质原因。结果电化学测试表明, Pt/C@PANI催化剂的催化活性与聚苯胺包覆层含量和厚度密切相关,Pt/C@PANI(30%)催化剂具有最好的催化活性,其质量比活性和比表面比活性分别为商业化Pt/C催化剂的1.6和1.8倍。加速寿命实验表明,Pt/C@PANI(30%)催化剂具有很好的稳定性,经过1500圈CV扫描后,其电化学活性表面积仅下降了30%,而商业化Pt/C催化剂降低了83%。理论计算表明,PANI将电子转移给载体C,导致自身空穴增加,PANI部分氧化,导电性增强;PANI的存在使Pt/C@PANI体系的HOMO能级升高,减小了与氧气分子LUMO能级的差异,有利于电子从催化剂HOMO转移到氧分子的LUMO轨道,使得氧容易得到电子;PANI吸附后,Pt原子d带中心显著降低,利于中间物种的脱附,催化活性更高。结论 PANI包覆层抑制了Pt纳米粒子在载体表面的迁移、团聚长大和溶解/再沉积,有效地解决了Pt/C催化剂的Ostwald肿大,催化剂的活性和稳定性得到显著提升。     

贵金属配比对催化剂活性的影响

以新开发的稀土基复合材料为负载涂层,不同比例的Pt、Pd、Rh为活性组分,平行制成贵金属总合量为0.5wt%的系列催化剂.并通过发动机台架测试系统研究了贵金属负载比例,尤其是Pt、Pd比例对催化剂活性的影响.结果表明:在Pt、Pd、Rh系列催化剂中,Pd比例的增加有利于提高催化剂的活性,但Pt、Pd比例相同时出现作用下降现象;相同比例的Pd/Rh催化剂明显优于Pt/Rh催化剂,且前者在系列催化剂中活性最高.作者建议,在研究贵金属比例变化对催化剂活性影响的同时,需充分考虑到不同贵金属组分间作用的相互促进和可能会出现的作用降低现象,从而以最佳的配比发挥最大的协同促进作用.     

Chemistry,phase formation,and catalytic activity of thin palladium-containing oxide films synthesized by plasma-assisted physical vapor deposition

The chemistry, microstructure, and catalytic activity of thin films incorporating palladium were studied using scanning and transmission electron microscopies, X-ray diffraction, spectrophotometry, 4-point probe and catalytic tests. The films were synthesized using pulsed filtered cathodic arc and magnetron sputter deposition, i.e. techniques far from thermodynamic equilibrium. Catalytic particles were formed by thermally cycling thin films of the Pd–Pt–O system. The evolution and phase formation in such films as a function of temperature were discussed in terms of the stability of PdO and PtO₂ in air. The catalytic efficiency was found to be strongly affected by the chemical composition, with oxidized palladium definitely playing a major role in the combustion of methane. Reactive sputter deposition of thin films in the Pd–Zr–Y–O system allowed us forming microstructures ranging from nanocrystalline zirconia to palladium nanoparticles embedded in a (Zr,Y)₄Pd₂O matrix. The sequence of phase formation is put in relation to simple thermodynamic considerations.     

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.     

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。     

铂和钯的羟基四氨配合物的合成、表征及性能研究

合成了2种用作前驱体的新型水溶性的金属复合离子型化合物羟基四氨合铂二水合物([Pt(NH3)4](OH)2.2H2O)和羟基四氨合钯([Pd(NH3)4](OH)2)。采用元素分析、红外光谱以及¹H-NMR对产物进行了结构表征；用热重-差热(TG-TDA)测试其热分解特性，考察配合物的热稳定性能；对比评价制备DOC催化剂的性能。结果表明，TG-DTA测试显示这2种配合物分解温度均在200~400℃范围内，热稳定性能良好，制备得到的DOC催化剂具有较好的催化活性。     

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.     

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。     

性能优异的SrO改性Pd-Rh双金属催化剂的制备

在浸渍到Al₂O₃载体材料上之前,通过将Sr的前驱体引入到贵金属Pd和Rh的混合盐溶液中,即采用共浸渍法制备了一系列SrO改性的Pd-Rh/Al₂O₃催化剂。结果表明,由于SrO的扩散障碍效应,适量SrO（1%~2%,质量分数）的引入有利于促进Pd,Rh的分散,并且能提高催化剂的水热稳定性。水热老化之后,催化剂能保持更高的Pd,Rh分散度,并且Pd,Rh能稳定在活性更好的氧化态。因此,适量SrO改性的Pd-Rh/Al₂O₃催化剂具有更好的还原性能和三效催化活性。然而,当向催化剂中引入过量的SrO,由于SrO占据了过量的Al₂O₃的表面,而且老化后会出现新的物相SrAl₂O₄,反而会对催化剂的性能产生不利的影响。总的来说,2% SrO改性的催化剂具有最优异的三效催化活性,水热老化之后,相比于空白的Pd-Rh/Al₂O₃催化剂,2%SrO改性的催化剂使CO,HC和NO的起燃温度分别降低了23,15和27 ℃。     

Pd/TiO2/棉花纤维复合催化材料的制备与性能研究

先通过浸渍-提拉法将纳米TiO_2对棉花纤维表面进行修饰,再通过浸渍-NaBH4还原法将Pd纳米颗粒沉积在TiO_2/棉花纤维(TC)表面,制备得到Pd/TiO_2/棉花纤维复合催化材料(PTC)。所制备的复合催化材料用于室温氧化分解甲醛,研究了Pd负载量对催化性能的影响。结果表明,PTC催化材料具有远低于粉末状样品的气阻,此特点对催化材料的实际应用具有非常大的优势;该催化材料能有效室温分解甲醛成CO_2和H_2O。PTC催化材料的催化活性随Pd含量(0.25%～1.0%,质量分数)的增加而增加。鉴于PTC催化材料具有低气阻、轻质、使用灵活的属性和良好催化效率以及载体棉花原料来源广泛、成本低等优点,具有良好的实际应用于室内空气净化和相关催化过程的潜力。     

Fabrication of Pt nanoparticles decorated PPy–MWNTs composites and their electrocatalytic activity for methanol oxidation

Here we report the synthesis and characterization of a catalyst material constituted of Pt, polypyrrole (PPy) and multi-walled carbon nanotubes (MWNTs). The catalyst supports (PPy–MWNTs nanocomposites) were synthesized via in situ chemical polymerization in advance, in which MWNTs were regarded as the matrix material. The supports were characterized by SEM & TEM, elemental analysis, XRD, FTIR and conductivity measurements. Then the catalysts were synthesized by a chemical reduction using sodium borohydride (NaBH₄) as reducing agent and acetic acid buffer (pH = 4) containing trace K₂C₂O₄ as reaction media. FTIR spectra showed that there existed relations between PPy and MWNTs during in situ polymerization. SEM and TEM micrographs of the catalyst samples exhibited that the existence of PPy layer which was evenly wrapped on the surface of MWNTs resulted in significant improvement in helping Pt particles well dispersed. XRD results showed that higher Pt(1 1 1) content in the catalyst deposited on PPy–MWNTs supports than that on MWNTs. The cyclic voltammetry (CV) tests of methanol electrocatalytic oxidation demonstrated that the electrode modified by Pt/PPy–MWNTs ternary composite catalyst showed higher catalytic stability than Pt/MWNTs binary catalyst, due to the synergic interaction between Pt and the carrier.     

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。     

负载型纳米Pd/C的尺寸可控制备及其2,3,6-三氯吡啶加氢性能

在催化剂制备过程中引入氨羧络合剂(氨三乙酸三钠,NTA),通过配位作用稳定并保护Pd粒子,得到纳米Pd/C催化剂,研究了氨三乙酸三钠引入量对Pd/C催化剂结构的影响。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电镜(TEM)及化学吸附(H_2-TPR)表征发现,与常规浸渍法制备的Pd/C催化剂相比,氨三乙酸三钠的引入能够有效减小Pd的平均粒径,并且通过调变氨三乙酸三钠的量可以获得Pd粒子不同大小的负载型Pd/C催化剂,随着氨三乙酸三钠引入量的增多(Pd摩尔含量的0.5、1、2倍),Pd粒径由5.7 nm减小至2.1 nm,但是继续增加氨三乙酸三钠的量(Pd摩尔含量的4倍),Pd粒径不再继续减小。当氨三乙酸三钠:Pd=1:1时,即Pd粒子大小约为4 nm时,催化剂获得了最佳催化反应性能,反应6 h原料全部转化,2,3-二氯吡啶的选择性可达76.86%。     

Microfibrous entrapment of small catalyst particulates for high contacting efficiency removal of trace CO from practical reformates for PEM H2-O2 fuel cells

Preferential oxidation (PROX) of CO in H₂ is the most efficient way to remove CO from a practical reformate stream for PEM H₂-O₂ fuel cells. Pt/Al₂O₃ has long been known as a suitable catalyst for this purpose. Over the conventional Pt/Al₂O₃ catalyst, however, PROX of CO in H₂ has been known to occur at temperatures above 150°C, and the maximum CO conversion usually takes place at about 200°C. In this study, the promotion of Pt/Al₂O₃ with a transition metal results in significantly enhanced catalytic performance in the temperature range of 25 to 150°C. The active reaction temperature window is enlarged to 25 to 200°C compared with a narrow window at about 200°C over the conventional Pt/Al₂O₃. A high void and a tailorable sintered microfibrous carrier consisting of 5 vol.% of 4 and 8 μm diameter Ni fibers is used to entrap 15 vol.% 150 to 250 μm diameter Al₂O₃ particulates. The alumina support particulates are uniformly entrapped into a sinter-locked, three-dimensional network of 4 and 8 μm Ni fibers. Promoter and Pt are then dispersed onto the microfibrous entrapped alumina support particles by the incipient-wetness impregnation method. The composite catalysts possess 80 vol.% voidage. At equivalent bed volumes, microfibrous entrapped catalysts achieve complete CO reduction (GC detection limit ∼40 ppm CO) at five times the higher gas hourly space velocity value compared with packed beds of 1 to 2 mm catalyst particles demonstrating ultrahigh contacting efficiency provided by the microfibrous entrapped catalysts. This paper was presented at the ASM Materials Solutions Conference & Show held October 18–21, 2004 in Columbus, OH.     

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。     

Self-propagating high-temperature synthesis with post-heat treatment of La1−xSrxFeO3 (x = 0–1) perovskite as catalyst for soot combustion

La_1−xSr_xFeO₃ (x = 0–1) perovskite, Sr-substituted LaFeO₃, was prepared by Self-propagating high-temperature synthesis (SHS) and its catalytic activity for soot combustion was experimentally examined in comparison with that of a conventional Pt/Al₂O₃ catalyst. The products were also characterized by XRD, FE-SEM, and BET specific surface area. The XRD analysis revealed that all the products had a perovskite phase as the major compound, together with intermediate phases with higher x values (x = 0.7–1). The BET specific surface area of the products increased with x. Moreover, the catalytic activity for soot combustion also increased with x, wherein the BET specific surface area appeared an appropriate index for explaining the observed activity. The sample with x = 0.8 exhibited the highest activity for soot combustion among all the SHS products. The soot combustion temperature of this product was as much as 100 °C lower than that of non-catalytic soot combustion. In other words, it had the same activity as that at only 20 °C higher, in comparison to conventional Pt/Al₂O₃ catalyst. More significantly, average apparent activation energy of sample with x = 0.8 calculated by Friedman method using TG/DTA was approximately 15 kJ/mol lower than that of Pt/Al₂O₃ catalyst. This result suggested that La_1−xSr_xFeO₃ has the possibility to be an alternative catalyst to Pt/Al₂O₃ catalyst.     

Gold based bimetallic catalysts for liquid phase applications

The liquid phase oxidation of D-Sorbitol has been carried out in water using oxygen as the oxidant in the presence of gold based catalyst. Au/C, Pt/C and Pd/C monometallic systems were compared to bimetallic Au/Pd and Au/Pt on carbon. A strong synergistic effect was observed producing a significant increase of reaction rate. Moreover, the addition of gold to Pd or Pt catalyst produced a system more resistant to oxygen poisoning allowing it to work also under a moderate pressure. The effect of varying the molar ratio of the metals has also been studied.     

载体中ZrO2/Al2O3比对Pt/ZrO2-Al2O3催化剂性能的影响

相比汽油车而言,柴油车具有高效、低油耗的优势已得到广泛应用。本实验以ZrO₂作为改性剂,探究了ZrO₂与Al₂O₃的质量比对催化剂的影响。研究结果表明：随着ZrO₂的加入,Pt粒子先减小后增大;Pt粒子与载体的交互作用先增大后减小。活性实验数据分析表明,ZrO₂的最佳添加量为40 wt%,CO和C₃H₆完全氧化温度分别降低20 _oC 、25 _oC。贵金属在催化剂的分散度以及贵金属与载体的相互作用随着ZrO₂与Al₂O₃质量比的变化而变化。Pt粒子越小,其与载体的交互作用越强,这表明催化剂性能越强。     

The formation of interstitial solid solutions based on solvents showing the fcc structure: elastic versus chemical interaction

Unit cell parameters and densities were measured for the terminal solid solutions of the late transition metals showing the fcc structure (α-Co, Rh, Ir, Ni, Pd, Pt) with boron and partly with carbon. Especially the solid solutions Pd(B) and Pd(C) were investigated because of the large homogeneity range up to the atomic fractions x^f_B=0.186 and x^f_C≃0.05, respectively. The unit cell parameter increases and the density decreases with increasing boron and carbon content. Comparison of the calculated and measured number of atoms in the Pd(B) and Pd(C) unit cells confirms the interstitial nature of both solid solutions. The difference between the measured dependence of the Pd–B shortest interatomic distances on the solute content and those calculated according to the hard sphere model indicates a distinct negative deviation from additivity of the pure form volumes. The chemical (electronic) interaction plays a more important role than the elastic interaction (characterized by a size factor) in the formation of solid solutions of metals with the interstitially dissolved metalloids H, B, C, N and O.