One-pot fabrication of single-crystalline octahedral Pd-Pt nanocrystals with enhanced electrocatalytic activity for methanol oxidation

This study reports the synthesis of octahedral Pd-Pt bimetallic alloy nanocrystals through a facile, one-pot, templateless, and seedless hydrothermal method in the presence of glucose and hexadecyl trimethyl ammonium bromide. The morphologies, compositions, and structures of the Pd-Pt nanocrystals were fully characterized by various physical techniques, thereby demonstrating their highly alloying octahedral nanostructures. The formation or growth mechanism of the Pd-Pt bimetallic alloy nanocrystals was explored and is discussed here based on the experimental observations. In addition, the synthesized Pd-Pt nanocrystals were applied to the methanol oxidation reaction (MOR) in alkaline media, which proved that the as-prepared catalysts exhibit enhanced electrocatalytic activity for MOR. Pd₁Pt₃ exhibited the best stability and durability, and its mass activity was 3.4 and 5.2 times greater than those of Pt black and Pd black catalysts, respectively. The facile synthetic process and excellent catalytic performance of the as-prepared catalysts demonstrate that they have the potential to be used in direct methanol fuel cell techniques.     

CO在Pd系双金属及其单金属催化剂上的吸脱附红外光谱

红外光谱表明吸附在担载于Al_2O_3上的Pd-Cu、Pd-Ag、Pd-Co和Pd-Pt 双组分催化剂上的CO仍保持其在单金属上的主要吸附物种,但其部分CO吸收带发生位移,吸附的CO易于脱附.CO在还原态Pd-Cu和Pd-Ag双金属催化剂上以吸附于Pd上者为主,其吸收带明显变弱而更易脱附.在Pd- Pt和Pd-Co氧化和还原态催化剂上CO桥式和线式吸收带强度比发生显著变化.似乎在这二类双金属催化剂上的几何结构效应比电子配位效应更为明显.     

Zr的添加对稀燃天然气汽车尾气净化催化剂Pd-Pt/Al2O3性能的影响

Pd-Pt双金属基甲烷氧化催化剂的催化活性、抗水热老化性和耐硫性在一个通有模拟稀燃天然气汽车尾气成分的固定床反应器中进行检测.研究发现Zr掺杂的Pd-Pt/Al₂O₃ (Pd-Pt/Zr_xAl_(1-x)O_(3+x)/2)提高了催化的催化活性、抗水热老化性和耐硫性.以共沉淀法制备Zr : Al的摩尔比分别为0 : 1、0.25 : 0.75、0.5 : 0.5、0.75 :0.25和1 : 0的材料为载体材料.双金属催化剂的活性组分分别为1.5% (w,质量分数)的Pd和0.3% (w)的Pt,活性组分Pd、Pt通过共浸渍的方法浸渍到以上载体材料上制备得到一系列整体式催化剂.分别采用低温N₂吸脱附、X射线衍射(XRD)、H₂程序升温还原(H₂-TPR)、O₂程序升温氧化(O₂-TPD)及X射线光电子能谱对制备的催化剂进行表征.结果显示Zr的加入使催化剂的载体材料结晶度提高,活性组分的分散度也得到了相应的提高.同时二价Pd物种与周围电子密度分别增加.相比于Pd-Pt/Al₂O₃和Pd-Pt/ZrO₂催化剂,在不同条件预处理后, Zr的添加对催化剂的性能有明显的提高,其中催化剂Pd-Pt/Zr_0.5Al_0.5O_1.75展现了最好的催化活性、抗水热老化性以及耐硫性.     

聚苯并噁嗪固载钯基纳米催化剂在芳香醇氧化反应中的应用

以球状聚苯并噁嗪为载体, 采用浸渍热解法合成了钯炭纳米催化剂. 通过透射电子显微镜观察发现, 钯纳米粒子几乎全部均匀分布在载体上, 且尺寸均一, 平均直径约为3.5 nm. 结果表明, 载体表面含有丰富的含氮含氧官能团, 氮和氧原子与钯之间存在相互作用, 从而使聚苯并噁嗪能够有效固载钯纳米粒子. 采用相同的方法进一步合成Pd-Au/C和Pd-Pt/C双金属催化剂, Pd-Au和Pd-Pt纳米粒子也展现出良好的分散性, 无明显团聚现象, 平均直径分别为4.3和4.2 nm, 进一步说明聚苯并噁嗪对金属活性组分的有效固载. 将催化剂应用于苯甲醇氧化反应, 其中Pd₁-Au₁/C在2 h的转化率为98%, 对产物苯甲醛的选择性大于99%, 该催化剂经过焙烧可恢复催化活性, 表现出良好的循环稳定性, 并能将不同取代基的芳香醇氧化为相应的醛, 是一种良好的醇氧化催化剂.     

Highly efficient photocatalytic dehalogenation of organic halides on TiO2 loaded with bimetallic Pd-Pt alloy nanoparticles

UV irradiation of TiO(2) loaded with bimetallic Pd-Pt alloy particles promotes highly efficient dehalogenation of organic halides with alcohol as a hydrogen source.     

柴油深度脱芳烃Pd-Pt/USY催化剂的EXAFS研究

为满足日趋严格的环保要求和适应汽车工业的快速发展,柴油深度脱芳烃已成为国内外普遍关注的课题．近年来的研究表明,Pd－Pt/USY催化剂具有较高的芳烃加氢活性和较强的耐硫中毒能力[’－     

贵金属催化p-叔丁基-α-甲基肉桂醛加氢

采用傅里叶变换红外光谱仪(FT-IR)、N₂吸脱附、X射线衍射(XRD)、透射电子显微镜(TEM)揭示了微波辅助-KOH处理对活性炭的物理化学性能的影响规律。 结果表明,活性炭表面的含氧基团的种类增加,微孔明显减少,中大孔的比例增大。 通过浸渍-原位还原方法制备了Pt、Pd、Ru、Rh负载微波辅助-KOH处理活性炭催化剂,并对其催化p-叔丁基-α-甲基肉桂醛选择性加氢性能进行了研究。 发现Pt具有优异的C=O加氢选择性,而Pd具有优良的C=C加氢选择性。 进一步研究了Pd-Pt双组分催化剂催化p-叔丁基-α-甲基肉桂醛加氢产物分布,随着Pt含量的增加, C=O选择性逐步提高, C=C选择性逐渐下降,且当m(Pd)∶m(Pt)=4∶1时,其催化剂的催化性能最佳。     

聚合物固载Ni-Ag双金属催化剂Ⅰ．XPS，XRD和磁测定表征

聚合物固载Ｎｉ┐Ａｇ双金属催化剂Ⅰ．ＸＰＳ，ＸＲＤ和磁测定表征吴世华朱常英王连邦张松祯（南开大学化学系，天津３０００７１）关键词溶剂化金属原子，镍，银，双金属催化剂，聚合物，负载型催化剂近年来，聚合物负载催化剂的研究受到重视，但由于一般聚合物载体的热...     

炭载Pd-Pt催化剂中Pd和Pt原子比对直接甲醇燃料电池阴极催化性能的影响

研究了不同Pd和Pt原子比的炭载Pd-Pt(Pd-Pt/C)催化剂对氧还原的电催化性能和抗甲醇性能。 发现当Pd和Pt原子比从20∶0增加至17∶3时,Pd-Pt/C催化剂对氧还原的电催化活性逐步增加,而对甲醇氧化均元电催化活性,表明有很好的抗甲醇能力。 但当Pd和Pt原子比增加至16∶4时,虽然对氧还原的电催化活性还在增加,但抗甲醇能力下降。 所以当Pd-Pt原子比为17∶3时,Pd-Pt/C有很好的对氧还原的电催化性能和抗甲醇能力,可以用作直接甲醇燃料电池(DMFC)的阴极催化剂。     

The onion-ring structure for Pd-Pt bimetallic clusters

The onion-ring structure is validated in the Pd-Pt bimetallic clusters of total atom numbers 147 and 309 through the Monte Carlo method by using the second-moment approximation of the tight-binding (TB-SMA) potentials, which is conceived in predicting the possible structures of the bimetallic clusters by He et al. [J. Am. Chem. Soc. 2003, 125, 11034] and Hwang et al. [J. Am. Chem. Soc. 2005, 127, 11140]. In the onion-ring structure, Pd atoms and Pt atoms occupy alternate layers of the clusters. The formation of the onion-ring structure can be associated with the fact that the single Pt impurity is favorable to stay in the subsurface layer and the central part of bimetallic clusters.     

Use of Pd-Pt loaded graphene aerogel on nickel foam in direct ethanol fuel cell

A size customized binder-free bimetallic Pd-Pt loaded graphene aerogel deposited on nickel foam plate (Pd-Pt/GA/NFP) was prepared and used as an electrode for an alkaline direct ethanol fuel cell (DEFC) under room temperature. The effect of fuel concentration and metal composition on the output power density of the DEFC was systematically investigated. Under the optimum fuel concentration, the cell could achieve a value of 3.6 mW cm⁻² at room temperature for the graphene electrode with Pd/Pt ratio approaching 1:1. Such results demonstrated the possibility of producing a size customized metal loaded GA/NFP electrode for fuel cell with high performance.     

Enhanced CO photocatalytic oxidation in the presence of humidity by tuning composition of Pd-Pt bimetallic nanoparticles supported on TiO2

Here we put forward for the first time that the negative effect of humidity on CO photooxidation at room temperature can be overcome by adjusting the composition of Pd-Pt bimetallic particles supported on TiO(2). Consequently, optimized Pd(x)Pt(1-x)/TiO(2) materials can be considered as common and efficient photocatalysts for simultaneous elimination of CO and VOCs in the presence of humidity, i.e. for real indoor air treatment.     

聚合物固载Ni－Ag双金属催化剂Ⅱ．催化剂的催化性质

聚合物固载Ｎｉ┐Ａｇ双金属催化剂Ⅱ．催化剂的催化性质吴世华朱常英王连邦张松桢（南开大学化学系，天津３０００７１）关键词镍，银，聚合物固载金属催化剂，加氢，燃料电池电极溶剂化金属原子浸渍（ＳＭＡＩ）技术是制备聚合物负载零价金属催化剂的一个非常有用的方法...     

碳纳米纤维负载Pd-Pt催化剂的萘加氢耐硫性能

Catalytically-grown carbon nanofibers of two different conformations,fishbone and parallel types of the arrangement of carbon layers,were employed as the support of Pd-Pt metal catalysts for the hydrogenation of naphthalene to tetralin. The sulfur tolerance of the catalyst system was investigated with the addition of 0. 05% thiophene to the reactant of naphthalene in the process. The dispersion of Pd-Pt metal particles on the support was observed with a HREM and a pulsed hydrogen chemisorption method. The hydrogenation reaction of naphthalene was carried out in a CSTR at 250℃ and with the hydrogen pressure of 6 MPa. The results showed that the Pd-Pt catalyst supported on the carbon nanofibers was active in the process. The Pd-Pt metal catalyst supported on the parallel carbon nanofibers showed a higher sulfur tolerance than that on the fishbone carbon nanofibers. The reason may be attributed to their different conformations of the carbon layers,which leads to the different interaction of carbon layers with the supported metal particles.     

Dehydrocyclization of Diphenylamine to Carbazole over Platinum-Based Bimetallic Catalysts

 Gas phase dehydrocyclization of diphenylamine (DPA) to carbazole over monometallic and bimetallic 0.4 wt% Pt-based catalysts in a fixed bed reactor was studied in the presence of hydrogen at a temperature of 550 ^oC. Alumina and carbon supported Pt catalysts showed very high initial activity (> 95%). The selectivity for carbazole over carbon supported Pt catalysts was slightly lower. Doping of the catalyst with potassium led to an increase in the selectivity for carbazole by 15%. Bimetallic Pt-Sn catalysts prepared by co-impregnation were less selective than catalysts prepared by successive impregnation. The selectivity for carbazole over bimetallic Pt-Sn catalysts prepared by successive impregnation was 75%, but their activity decreased with increased Sn loading. Highly active and reasonably selective catalysts were Ir-doped bimetallic Pt-based catalysts. The conversion of diphenylamine over Pt-Ir catalysts was above 98% and the selectivity for carbazole was nearly 55%, while the lifetime was much longer.     

Characterization of carbon-supported AuPt nanoparticles for electrocatalytic methanol oxidation reaction

In view of the recent finding that the bimetallic AuPt nanoparticles prepared by molecular-capping-based colloidal synthesis and subsequent assembly on carbon black support and thermal activation treatment exhibit alloy properties, which is in sharp contrast to the bimetallic miscibility gap known for the bulk counterparts in a wide composition range, there is a clear need to assess the electrocatalytic properties of the catalysts prepared with different bimetallic composition and different thermal treatment temperatures. This paper reports recent results of such an investigation of the electrocatalytic methanol oxidation reaction (MOR) activities of the carbon-supported AuPt nanoparticle catalysts with different bimetallic composition and thermal treatment temperatures. Au(m)Pt(100)(-)(m) nanoparticles of 2-3 nm core sizes with different atomic compositions ranging from 10% to 90% Au (m = 10 approximately 90) have been synthesized by controlling the feeding of the metal precursors used in the synthesis. The electrocatalytic MOR activities of the carbon-supported AuPt bimetallic catalysts were characterized in alkaline electrolytes. The catalysts with 65% to 85% Au and treated at 500 degrees C were found to exhibit maximum electrocatalytic activities in the alkaline electrolytes. The findings, together with a comparison with some well-documented catalysts as well as recent experimental and theoretical modeling results, have revealed important insights into the participation of CO(ad) and OH(ad) on Au sites in the catalytic reaction of Pt in the AuPt alloys with approximately 75% Au. The insights are useful for understanding the correlation of the bifunctional electrocatalytic activity of the bimetallic nanoparticle catalysts with the bimetallic composition and the thermal treatment temperatures.     

负载型双金属催化剂的制备及其等离子体催化氨分解制氢性能

利用等体积浸渍法制备了Fe-Co、Fe-Ni、Mo-Co、Mo-Ni双金属催化剂(总金属含量均为10%(w,质量分数),双金属摩尔比均为1:1),考察了其在等离子体条件下氨分解活性,结果表明Fe-Ni双金属催化剂表现出较好的协同作用。在此基础上,进一步考察了Fe/Ni摩尔比对其活性的影响。结果表明:当Fe/Ni摩尔比为6/4时,氨分解活性最好,而且该双金属催化剂稳定性良好。采用N_2物理吸附、X射线衍射(XRD)、H_2-程序升温还原(H_2-TPR)和高分辨透射电子显微镜(HRTEM)对催化剂的物化性质、还原性能、微观形貌等进行了研究。结果表明:活性较好的Fe-Ni双金属催化剂中,Fe与Ni形成尖晶石结构NiFe_2O_4,该结构有利于Fe和Ni的还原,即活性组分易恢复金属态,这可能是其活性较高的原因。     

Surface properties of Ni-Pt/SiO2 catalysts for N2O decomposition and reduction by H2

The surface properties of bimetallic Ni-Pt/SiO2 catalysts with variable Ni/Ni + Pt atomic ratio (0.75, 0.50, and 0.25) were studied using N2O decomposition and N2O reduction by hydrogen reactions as probes. Catalysts were prepared by incipient wetness impregnation of the silica support with aqueous solutions of the metal precursors to a total metal loading of 2 wt %. For both model reactions, Pt/SiO2 catalyst was substantially more active than Ni/SiO2 catalyst. Mean particle size by TEM was about the same (in the range 6-8 nm) for all catalysts and truly bimetallic particles (more than 95%) were evidenced by EDS in the Ni-Pt/SiO2 catalysts. CO adsorption on the bimetallic catalysts showed differences in the linear CO absorption band as a function of the Ni/Pt atomic ratio. Bimetallic Ni-Pt/SiO2 catalysts showed, for the N2O decomposition, a catalytic behavior that points out an ensemble-size sensitive behavior for Ni-rich compositions. For the N2O + H2 reaction, the bimetallic catalysts were very active at low temperature. The following activity order at 300 K was observed: Ni75Pt25 > Ni25Pt75 approximately Ni50Pt50 > Pt. TOF values for these catalysts increased 2-5 times compared to the most active reference catalyst (Pt/SiO2). The enhancement of the activity in the Ni75Pt25 bimetallic catalysts is explained in terms of the presence of mixed Ni-Pt ensembles.     

Enhancement of catalytic activity in dehydrogenation ofn-dodecane over nano-structured Pt-Sn/SBA-16 catalysts by microwave drying

In the present investigation, experimental results from a study of cubic SBA-16-supported Pt-Sn bimetallic catalysts used to investigate dehydrogenation ofn-dodecane to 1-dodecene are presented. Pt (1 wt%)-Sn (1 wt%)/SBA-16 catalyst is synthesized using a simple co-impregnation (CI) method. Further, the impregnated catalysts are dried separately using microwave drying (MW-D) and conventional electrical drying (CE-D) techniques. The microwave-mediated drying of Pt (1%)-Sn (1%)/SBA-16 shows a better catalytic performance and time-on-stream activity for the target reaction.     

Titania-supported PdAu bimetallic catalysts prepared from dendrimer-encapsulated nanoparticle precursors

We report the synthesis, characterization, and catalytic activity of titania-supported bimetallic PdAu particles prepared using dendrimer-encapsulated nanoparticle (DEN) precursors. Single-particle energy-dispersive spectroscopy indicates a homogeneous distribution of bimetallic nanoparticles having compositions closely related to the metal-ion ratios used to prepare the DEN precursors. The catalytic activity of the supported PdAu catalysts was compared to that of supported Pd-only and Au-only catalysts; the enhanced CO oxidation activity of the PdAu catalysts is indicative of a synergetic bimetallic interaction.