Ultrahigh Durable PtPd/C Nanowire Networks Catalyst Synthesized by Modified Phase Transfer Method for Methanol Oxidation

A novel PtPd/C nanowire catalyst with interconnected network and fewer great grain boundaries has been successfully prepared by templateless and modified phase‐transfer method using cetyltrimethylammonium bromide as a capping in ethylene glycol solution by microwave‐assisted process. Its structure, composition, and morphology are characterized by X‐ray diffraction, energy dispersive analysis of X‐ray, and transmission electron microscopy, respectively. The electrochemical measurements demonstrate that the highly dispersed and uniform PtPd/C nanowire networks catalyst has a significantly higher electrocatalytic activity and durability for the methanol oxidation as compared to solid solution PtPd/C. The greatly improved durability of PtPd/C nanowire networks catalyst is mainly a consequence of the unique interconnected network structure with fewer grain boundaries, which provide more facile pathway for the electron transfer, and inhibit the particle growth and agglomeration, as well as prevent the particles embedded in the microporous of carbon support to enhance the Pt utilization.     

CO tolerance of PdPt/C and PdPtRu/C anodes for PEMFC

The performance of H₂/O₂ proton exchange membrane fuel cells (PEMFCs) fed with CO-contaminated hydrogen was investigated for anodes with PdPt/C and PdPtRu/C electrocatalysts. The physicochemical properties of the catalysts were characterized by energy dispersive X-ray (EDX) analyses, X-ray diffraction (XRD) and “in situ” X-ray absorption near edge structure (XANES). Experiments were conducted in electrochemical half and single cells by cyclic voltammetry (CV) and I-V polarization measurements, while DEMS was employed to verify the formation of CO₂ at the PEMFC anode outlet. A quite high performance was achieved for the PEMFC fed with H₂ + 100 ppm CO with the PdPt/C and PdPtRu/C anodes containing 0.4 mg metal cm⁻², with the cell presenting potential losses below 200 mV at 1 A cm⁻², with respect to the system fed with pure H₂. For the PdPt/C catalysts no CO₂ formation was seen at the PEMFC anode outlet, indicating that the CO tolerance is improved due to the existence of more free surface sites for H₂ electrooxidation, probably due to a lower Pd-CO interaction compared to pure Pd or Pt. For PdPtRu/C the CO tolerance may also have a contribution from the bifunctional mechanism, as shown by the presence of CO₂ in the PEMFC anode outlet.     

炭黑负载MnOx-Pt电催化剂的制备与初步研究

合适的电催化剂材料是质子交换膜燃料电池降低电极反应活化能、加快反应速度、提高电池能量转换效率的关键,尤其是用于阴极氧还原的电催化剂。Vuloan XC-72炭黑进行预处理后作为催化剂载体,采用分步化学沉积方法制备得到了炭黑负载的MnOx-Pt电催化剂。通过ICP、XRD、TEM、CV等物理和电化学手段测试和表征,结果表明;所得到电催化剂中锰氧化物的主要存在形式是隐钾锰矿型MnO2;三种催化剂样品中Mn的质量百分含量均为20％左右,而Pt的质量百分含量在5％左右。该催化剂具有较高的分散度,更高的氧还原起始电位和峰值电位,表现出良好的电催化氧还原性能,可作为质子交换膜燃料电池阴极氧还原的电催化剂;其电化学催化反应机理还有待于进一步深入的研究。     

Evaluation of the Performance of Carbon Supported Pt–Ru–Ni–P as Anode Catalyst for Methanol Electrooxidation

This research is aimed to improve the activity and stability of ternary alloy Pt–Ru–Ni/C catalyst. A novel anodic catalyst for direct methanol fuel cell (DMFC), carbon supported Pt–Ru–Ni–P nanoparticles, has been prepared by chemical reduction method by using NaH₂PO₂ as a reducing agent. One glassy carbon disc working electrode is used to test the catalytic performances of the homemade catalysts by cyclic voltammetric (CV), chronoamperometric (CA) and amperometric i–t measurements in a solution of 0.5 mol L^–1 H₂SO₄ and 0.5 mol L^–1 CH₃OH. The compositions, particle sizes and morphology of home‐made catalysts are evaluated by means of energy dispersive analysis of X‐ray (EDAX), X‐ray diffraction (XRD) and transmission electron micrographs (TEM), respectively. TEM images show that Pt–Ru–Ni–P nanoparticles have an even size distribution with an average diameter of less than 2 nm. The results of CV, CA and i–t curves indicate that the Pt–Ru–Ni–P/C catalyst shows significantly higher activity and stability for methanol electrooxidation due to the presence of non‐metal phosphorus in comparison to Pt–Ru–Ni/C one. All experimental results indicate that the addition of non‐metallic phosphorus into the Pt–Ru–Ni/C catalyst has definite value of research and practical application for enhancing the performance of DMFC.     

Pt基直接乙醇燃料电池阳极催化剂的性能研究

采用水热法制备了高分散碳载Pt/C和Pt-SnOJC电催化剂.采用XRD、SEM、TEM和激光粒度仪等方法对制得的纳米催化剂进行了表面微观结构分析.采用电化学工作站测试循环伏安曲线(CV)等表征Pt/C和Pt-SnO2/C纳米催化剂电催化活性.测试结果表明,Pt-SnO2/C纳米催化剂的峰电流密度(131.05 mA·cm-2)是Pt/C催化剂的峰电流密度(65.48 mA·cm-2)的2倍;Pt-SnO2/C催化的电化学表面积(108.4 m2·g-1)远高于Pt/C催化剂的电化学表面积(99.14 m2· g-1);Pt-SnO2/C纳米粒子比Pt/C纳米粒子具有更强的抗CO中毒能力和更高的电催化活性.     

高性能C/C复合材料制备工艺研究

对制备C/C复合材料的化学气相渗透工艺进行了系统的实验研究,着重分析了热解碳的沉积过程。研究表明,在化学气相渗透的初始阶段,热解碳主要在碳纤维表面沉积,并与碳纤维之间形成了界面结合;随后,热解碳的沉积继续填充碳纤维预制体内部的气孔。这一过程有助于缓解纤维与陶瓷基体之间的界面应力。研究表明,通过调节热解碳的沉积时间可以得到具有一定密度梯度的C/C复合材料。     

Effect of pH Value on Performance of PtRu/C Catalyst Prepared by Microwave‐Assisted Polyol Process for Methanol Electrooxidation

PtRu/C catalysts with different mean particle sizes have been synthesised by microwave‐assisted polyol process at various pH values and characterised by transmission electron microscopy (TEM), energy dispersive analysis of X‐ray (EDAX) and X‐ray diffraction (XRD). Their electrochemical performances have been tested by cyclic voltammetry, amperomeric i–t, and CO‐stripping techniques. The effects of pH values on performances of the PtRu/C catalysts have been mainly investigated. It has been found that the particle size, composition and catalytic activity of the PtRu/C catalyst are very sensitive to the pH value of reducing solution, and the PtRu/C catalyst prepared at the pH value of 8 exhibits the better performance for methanol electrooxidation than the other samples. The size of the nanoparticles decreases as the pH value increases from 0.2 to 10 with the largest size of 4.4 nm and the smallest one of 2.1 nm. The two metal elements distribute uniformly in the catalyst and their metal loadings are similar to the theoretical value.     

Synthesis of a highly active carbon-supported Ir–V/C catalyst for the hydrogen oxidation reaction in PEMFC

The active, carbon-supported Ir and Ir–V nanoclusters with well-controlled particle size, dispersity, and composition uniformity, have been synthesized via an ethylene glycol method using IrCl₃ and NH₄VO₃ as the Ir and V precursors. The nanostructured catalysts were characterized by X-ray diffraction and high-resolution transmission electron microscopy. The catalytic activities of these carbon-supported nanoclusters were screened by applying on-line cyclic voltammetry and electrochemical impedance spectroscopy techniques, which were used to characterize the electrochemical properties of fuel cells using several anode Ir/C and Ir–V/C catalysts. It was found that Ir/C and Ir–V/C catalysts affect the performance of electrocatalysts significantly based on the discharge characteristics of the fuel cell. The catalyst Ir–V/C at 40 wt.% displayed the highest catalytic activity to hydrogen oxidation reaction and, therefore, high cell performance is achieved which results in a maximum power density of 563 mW cm⁻² at 0.512 V and 70 °C in a real H₂/air fuel cell. This performance is 20% higher as compared to the commercial available Pt/C catalyst. Fuel cell life test at a constant current density of 1000 mA cm⁻² in a H₂/O₂ condition shows good stability of anode Ir–V/C after 100 h of continuous operation.     

Synthesis of Pd/C Catalyst by Modified Polyol Process for Formic Acid Electrooxidation

Pd catalyst supported on Vulcan XC‐72 carbon black was prepared by a modified polyol process. Its performance was compared with that of Pd/C catalyst prepared by impregnation reduction method by using NaBH₄ as a reducing agent for formic acid electrooxidation. Their physical characterisations were tested by means of energy dispersive analysis of X‐ray, X‐ray diffraction and transmission electron micrographs. Their activities were presented by cyclic voltammetry and chronoamperometry. The results show that the particle sizes of Pd/C catalysts prepared by modified polyol process and impregnation reduction method are 3.9 and 7.9 nm, respectively. The size dispersion of the former is narrower and more homogeneous than that of the latter. However, both of Pd/C catalysts display the characteristic diffraction peaks of a Pd face‐centred cubic (f.c.c.) crystal structure. The results of electrochemical measurements present that the Pd/C catalyst prepared by modified polyol process has the higher electrocatalytic activity and stability for formic acid electrooxidation in comparison to the Pd/C one by impregnation reduction method due to the particle size effect, and its peak current density of CV and the current of chronoamperometric curve at 1,000 s reach 33.2 and 11.2 mA cm^–2, respectively.     

Platinum Nanoparticles Anchored on TiO2/C Nanowires as a High Performance Catalyst for Hydrogen Peroxide Eletroreduction

In this paper, we employed the as‐prepared TiO₂/C core/shell nanoarrays (TiO₂/C) obtained by a facile thermal evaporation method as a three‐dimensional (3D) architecture to support Pt nanoparticles through an optimized electrodeposition process. The morphology and structure of the as‐prepared electrode are characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Its catalytic performance towards H₂O₂ electroreduction in basic medium is evaluated by linear sweep voltammetry (LSV) and chronoamperometry (CV). Results revealed that the electrode exhibits significantly high catalytic activity. The current density reached –0.172 A cm⁻² in 1 mol dm⁻³ NaOH and 0.5 mol dm⁻³ H₂O₂ at –1.1 V (vs. Ag/AgCl). This high performance might be due to the 3D electrode architecture inheriting the high electronic conductivity from carbon shell and providing a short pathway for the ion diffusion, and the using of Pt owning an excellent catalytic activity.     

Investigation on Electrocatalytic Activity and Stability of Pt/C Catalyst Prepared by Facile Solvothermal Synthesis for Direct Methanol Fuel Cell

Pt nanoparticles supported on Vulcan XC‐72 carbon black have been synthesized by a facile solvothermal method. The obtained Pt/C catalysts are characterized by X‐ray diffraction (XRD), energy dispersive X‐ray analysis (EDAX), and transmission electron microscopy (TEM) analysis to identify Pt mean size and Pt content. The results of electrochemical measurements demonstrate that the Pt/C catalyst prepared at the reaction temperature of 140 °C and the reaction time of 2 h shows the biggest initial electrochemical area with an initial electrochemically active specific surface area (ESA) of 70.6 m²g_Pt⁻¹, the highest electrocatalytic stability with an ESA loss of 48.7% after 1,000 CV cycles, and the best electrocatalytic activity and stability toward methanol oxidation reaction (MOR) with a specific activity of 0.6 mA cm⁻² and a retention rate (the ratio of the final current density to the maximum current density) after 3,600 s of 42.8%. Moreover, the electrochemical performance of homemade Pt/C catalyst is superior to that of commercial Pt/C catalyst, suggesting that the solvothermal synthesis is a promising method for preparing Pt based catalyst.     

RuPd/C催化对苯二甲酸二甲酯加氢制备1,4-环己烷二甲酸二甲酯

采用纳米级Ru-Pd/C催化剂,在温和条件下将其应用于对苯二甲酸二甲酯(DMT)加氢制备1,4-环己烷二甲酸二甲酯(DMCD)的反应。考察了溶剂、反应温度、压力、催化剂用量对DMT加氢的影响。结果表明,在5 000mL高压反应釜中,最佳工艺条件为:温度140℃、压力4.0 MPa、溶剂异丙醇2 000 mL、DMT 1 300 g、催化剂65g,在该条件下,DMT转化率为99.8%,DMCD选择性为96.3%。保持反应条件不变,催化剂循环使用22次后,DMT转化率为99.0%,DMCD选择性为95.1%。     

硅/氧化硅/锡/碳锂离子电池负极复合材料制备及电化学性能

以一氧化硅、二氧化锡和导电碳(Super P)为原料,通过高能球磨,加入稀盐酸与糠醇发生聚合反应,再采用高温固相法制得硅/氧化硅/锡/碳复合材料作为锂离子电池负极材料.用 XRD、SEM 进行表征,并进行有关电化学性能测试,首次放电比容量高达 1503 mAh·g<'-1>,循环性能得到了较大改善.     

Synthesis of Truncated‐Octahedral Pt–Pd Nanocrystals Supported on Carbon Black as a Highly Efficient Catalyst for Methanol Oxidation

A novel PtPd/C nanocrystals catalyst with truncated‐octahedral structure has been successfully prepared by ethylene glycol reduction to induce anisotropic growth in an isotropic medium by adding a small amount of Fe³⁺ species. Its structure, composition, and morphology are characterized by X‐ray diffraction, transmission electron microscopy, and scanning transmission electron microscopy‐energy dispersive spectroscopy elemental maps, respectively. The electrochemical measurements demonstrate that the highly dispersed and uniform PtPd/C nanocrystals have excellent poisoning tolerance, significantly higher electrocatalytic activity and durability for the methanol oxidation, as compared to solid solution PtPd/C and Pt/C catalysts. This may be ascribed to the stepped atoms and dangling bonds, which served as active sites for breaking chemical bonds during oxidation–reduction reaction; the high density of preferred crystal planes of (111) facets greatly enhanced the oxidation of poisonous residues during reaction.     

锂离子电池锡/碳复合负极材料的制备及电化学性能研究

以二氧化锡和导电碳(Super P)为原料,通过高能球磨,采用高温固相法制得锡/碳复合材料作为锂离子电池负极材料。用XRD、SEM进行表征,并进行有关电化学性能测试,首次放电比容量高达566.4 mAh.g-1,循环性能得到了较大改善。     

Co改性的Pd/C催化剂在转移加氢中的应用研究

通过调整Co和Pd的浸渍顺序制备了不同的钴改性的Pd/C催化剂,考察了催化剂在3,5-二羟基苯甲酸转移加氢制备3,5-二氧代环己烷羧酸反应中的活性。确认先浸渍钴后浸渍钯、并在300℃以氢气还原得到的Co-Pd/C催化剂具有最佳活性,反应转化率和选择性分别达到94.6%和99.5%。对该催化剂以BET、TPR、XRD、SEM、TEM、XPS等手段进行了表征。结果表明,先浸渍的钴占据了活性炭的微孔使最可几孔径由2.72nm增大为3.32nm,并且与一些对反应不利的官能团作用,使后浸渍的钯主要分布在催化剂的大孔中,避免了过多深度加氢副产物的生成。催化剂活性组分为零价的钯,其平均粒径约10nm,以有利于转移加氢的聚集态存在,使催化剂获得了较高的活性和选择性。     

工艺条件对碳二前加氢催化剂性能的影响

以α-Al2O3为载体,钯为活性组分,银为助剂制备了前加氢催化剂,并在750 mL工业侧线装置上与进口催化剂进行了对比评价。考察了入口温度、空速和CO含量三个工艺参数对碳二前加氢催化剂性能的影响,结果表明:提高入口温度,催化剂乙炔转化率、MAPD转化率升高,乙烯增量先增加后降低;和入口温度相比,空速对催化剂性能的影响稍小;CO含量对催化剂性能影响较大。     

副产C4和C5转化成丙烯及乙烯的技术进展

文中介绍了国外采用乙烯装置副产的C4／C5转化成丙烯和乙烯的新技术，并从我国乙烯行业的实际出发提出了相应的建议。     

固相反应制备Pt/C催化剂

利用固相反应法制得具有较高催化活性的Pt/C催化剂,探讨了制备条件对催化剂性能的影响。结果显示:用水作浸渍介质、n(NaOH)/n(H2PtCl6)=6 4、固相还原剂为聚甲醛时,制得的Pt/C催化剂中Pt粒子的平均粒径为3 8nm。线性扫描伏安结果表明:在30℃、扫速为50mV/s时,制得的Pt/C催化剂在c(CH3OH)=0 5mol/L和c(H2SO4)=0 5mol/L混合溶液中,甲醇氧化的峰电流密度为11 3mA/cm2;而同样条件下,E TEK公司商品化的Pt/C催化剂为9 2mA/cm2。     

Suppression of Potential Oscillations in PEFCs by Using Anode Catalyst Prepared by Polygonal Barrel‐Sputtering Method

In this study, we investigated the suppression of potential oscillations that occur while feeding H₂ gas including a large amount of CO to polymer electrolyte fuel cells. A carbon‐supported Pt–Ru alloy (Pt–Ru/C) sample was prepared by the polygonal barrel‐sputtering method. Electrochemical measurement was conducted in 1 N H₂SO₄ electrolyte solution saturated with H₂ gas including CO of 1,000 ppm. From the measurement, it was found that the prepared Pt–Ru/C sample showed higher CO tolerance than a commercially available sample, and therefore, potential oscillations in the case of the prepared sample occurred for slightly longer intervals. Additional samples were prepared by sputtering different amounts of Ru on the prepared Pt–Ru/C sample, and it was observed that the average interval of potential oscillations increased with the amount of Ru. This result suggests that in the case of the polygonal barrel‐sputtering method, Ru plays an important role in suppressing potential oscillations and influences the CO tolerance of Pt–Ru/C.