Alcohol electrooxidation at Pt and Pt–Ru sputtered electrodes under elevated temperature and pressurized conditions

The electrooxidation properties of methanol and 2-propanol, which are both promising candidates for direct alcohol fuel cells (DAFCs), have been studied under elevated temperature and pressurized conditions. Sputter-deposited Pt and Pt–Ru electrodes were well-characterized and utilized for the electrochemical measurement of the alcohol oxidation at 25–100 °C. The Pt electrode prepared at 600 °C had a flat surface, and the Pt–Ru formed an alloy. The electrochemical measurements were carried out in a gas-tight cell under elevated temperature, which accompanies the pressurized condition. This is a representative example of the DAFC rising temperature operation. As a result, at 25 °C, the onset potential of the 2-propanol oxidation is about 400 mV more negative than that of the methanol oxidation, and current density of the 2-propanol oxidation exceeds that of the methanol oxidation. Conversely, at 100 °C, the methanol oxidation current density overcomes that of 2-propanol, and the onset potentials of the two are almost the same. The highest current density for the methanol oxidation is obtained at the Pt:Ru = 50:50 electrode, whereas at the Pt:Ru = 35:65 for the 2-propanol oxidation. A Tafel plot analysis was employed to investigate the reaction mechanism. For the methanol oxidation, the number of electrons transferred during the rate-determining process is estimated to be 1 at 25 °C and 2 at 100 °C. This suggests that the methanol reaction mechanism differs at 25 and 100 °C. In contrast, the rate-determining process of the 2-propanol oxidation at 25 and 100 °C was expected to be 1-electron transfer which accompanies the proton-elimination reaction to produce acetone. Consequently, it is deduced that methanol and 2-propanol have an advantage under the rising temperature and room temperature operation, respectively.     

Binary Pt–Pd and ternary Pt–Pd–Ru nanoelectrocatalysts for direct methanol fuel cells

Nano-sized binary and ternary alloys are synthesized by polyol process on Vulcan XC72-R support. Nanostructured binary Pt–Pd/C catalysts are prepared either by co-deposition or by depositing on each other. Ternary Pt–Pd–Ru/C catalysts are prepared by co-deposition. The structural characteristics of the nanocatalysts are examined by TEM and XRD. Their electrocatalytic activity toward methanol oxidation and CO stripping curves were measured by electrochemical measurements and compared with that of commercial Pt/C catalyst. The results show that the binary nanocatalyst prepared by depositing the Pt precursor colloids on Pd-Vulcan XC-72R are more active toward methanol oxidation than that of the co-deposited binary alloy nanocatalyst. The co-deposited ternary Pt–Pd–Ru/C nanocatalyst based membrane electrodes assembly shows higher power density compared to the binary nanocatalysts as well as commercial Pt/C catalyst in direct methanol fuel cell. Significantly higher catalytic activity of the nanocatalysts toward methanol oxidation compared to that of the commercial Pt/C is believed to be due to lower level of catalyst poisoning.     

Mechanically activated Pt–Ni and Pt–Co alloys as electrocatalysts in the oxygen reduction reaction

Mixtures of powders of platinum with nickel or cobalt to obtain Ni_0.75Pt_0.25 or Co_0.75Pt_0.25 were mechanical alloyed by high energy ball milling. The results of crystal structure, morphology and electrocatalytic performance are presented for mechanically activated powders after 3 and 9 h of ball milling. Total solid solutions of Ni and Co with platinum were analyzed by X-ray diffraction after 3 h of ball milling. After 9 h of ball milling, in both cases, the total solid solution was accompanied by the appearance of NiO or CoO and ZrO associated with a redox reaction with the milling media. The presence of zirconium monoxide was confirmed by energy dispersive spectroscopy analysis. In both cases, an amorphization was detected. X ray absorption spectroscopy measurements showed changes in atomic and electronic environment of platinum, a reduction of the distance to the first coordination sphere and increased d-band vacancy vs pure Pt and Pt nanoparticles were observed for both studied systems. The electrocatalytic activity was determined using cyclic and linear voltammetry. The Co_0.75Pt_0.25 alloy milled for 9 h showed a higher electrochemical activity for the oxygen reduction reaction (ORR) compared with the other samples, including Pt-Etek. The degree of the ORR electrochemical activity was correlated with the presence of ZrO, which could affect the oxygen adsorption and improve the catalytic activity for the oxygen reduction reaction.     

Carbon supported nano-sized Pt–Pd and Pt–Co electrocatalysts for proton exchange membrane fuel cells

Nano-sized Pt–Pd/C and Pt–Co/C electrocatalysts have been synthesized and characterized by an alcohol-reduction process using ethylene glycol as the solvent and Vulcan XC-72R as the supporting material. While the Pt–Pd/C electrodes were compared with Pt/C (20 wt.% E-TEK) in terms of electrocatalytic activity towards oxidation of H₂, CO and H₂–CO mixtures, the Pt–Co/C electrodes were evaluated towards oxygen reduction reaction (ORR) and compared with Pt/C (20 wt.% E-TEK) and Pt–Co/C (20 wt.% E-TEK) and Pt/C (46 wt.% TKK) in a single cell. In addition, the Pt–Pd/C and Pt–Co/C electrocatalyst samples were characterized by XRD, XPS, TEM and electroanalytical methods. The TEM images of the carbon supported platinum alloy electrocatalysts show homogenous catalyst distribution with a particle size of about 3–4 nm. It was found that while the Pt–Pd/C electrocatalyst has superior CO tolerance compared to commercial catalyst, Pt–Co/C synthesized by polyol method has shown better activity and stability up to 60 °C compared to commercial catalysts. Single cell tests using the alloy catalysts coated on Nafion-212 membranes with H₂ and O₂ gases showed that the fuel cell performance in the activation and the ohmic regions are almost similar comparing conventional electrodes to Pt–Pd anode electrodes. However, conventional electrodes give a better performance in the ohmic region comparing to Pt–Co cathode. It is worth mentioning that these catalysts are less expensive compared to the commercial catalysts if only the platinum contents were considered.     

Plasma-assisted Pt and Pt–Pd nano-particles deposition on carbon carriers for application in PEM electrochemical cells

Plasma-assisted deposition of platinum and platinum-palladium nano-particles at the surface of carbonaceous electronic carriers for application in proton-exchange membrane (PEM) electrochemical cells has been carried out using a conventional DC magnetron sputtering system. Different types of carrier have been used for that purpose: carbon powder (Vulcan XC-72), carbon nanotubes and carbon nano-fibers. The interest of initial chemical pretreatment or metallization of the electronic carrier to improve surface adhesion of catalyst nano-particles has been analyzed. Nanostructured catalytic powders thus obtained have been analyzed and characterized using TGA, SEM, TEM, XRD, XRF and cyclic voltammetry. The electrochemical performances of Pt/C and Pt–Pd/C electrodes have been measured in single-cell PEM fuel cell (PEMFC), water electrolyzer (PEMWE) and unitized regenerative fuel cell (URFC). Results show a high active surface area (up to 44 m² g⁻¹) and high electrochemical activity for a number of synthesized samples. A qualitative correlation has been established between sputtering parameters, type of carbon carrier and performances as electrocatalyst.     

Pt基催化剂二甲醚催化燃烧性能

利用二甲醚催化燃烧作为二甲醚重整制氢的热源可有效简化系统和提高效率,通过对比不同载体、不同Pt负载量以及不同助剂对Pt催化剂的性能影响,筛选出了最适合二甲醚低温起燃催化燃烧的催化剂.研究发现,HZSM-5型分子筛作为二甲醚催化燃烧载体具有较好的起燃特性,同时加入助剂Ce可以显著提高催化剂活性,起燃温度相对Pt/HZSM-5降低了58℃.Pt-Ce/HZSM-5催化剂的二甲醚起燃特性实验表明,在过量空气系数为1.1时具有最佳的起燃特性.对Pt-Ce/HZSM-5催化剂进行了稳定性实验,100h内催化剂性能稳定.     

低温燃料电池阴极Pt基催化剂的研究进展

Pt催化剂是低温燃料电池最常用的电极材料,其表面结构、电子特性与催化性能之间的内在联系和规律是设计和研制高活性、高稳定性、高选择性电催化剂的基础。以近年来国内外关于氧还原反应的研究成果,综述了制备高分散Pt基催化剂的新技术,并重点介绍了催化剂颗粒的大小、组成、合金性质、表面结构和性能调控方面的研究进展,最后对这一领域的发展趋势作了展望。     

Pt/a-Si肖特基太阳电池的退火效应

我们用射频溅射代替电子束蒸发制作(?)100mm的太阳电池,Pt的消耗量仅万分之一克左右。为了消除射频溅射造成a-Si表面的损伤和界面态的增加,在电池制成以后对它进行了适当的退火,使V_(oc)和j_(sc)分别提高40％和30％左右。经退火和加上减反射膜的单体电池,其性能如下:V_(oc)=595mV,I_(sc)=14.1mA/cm~2,FF=0.49,η=4.1％(电池面积为     

非Pt助燃剂在催化裂化装置的应用

随着环保要求的日益提高,尤其《石油炼制工业污染物排放标准(征求意见稿)》规定发布后,对催化裂化装置再生烟气中SOx、NOx排放标准更加严格。为满足新标准要求,在缺少脱硫、脱硝装置情况下,洛阳石化2号催化裂化装置试验使用庄信万丰公司生产的NOxGETTER-NP型助燃剂。使用过程中发现,与Pt基助燃剂相比,应用NOxGETTER-NP助燃剂,每天需增加成本3945.3元,但再生烧焦效果增强,助燃效果良好,未出现尾燃情况。应用NOxGETTER-NP助燃剂,在混合进料氮含量2896.39mg/kg条件下,三旋出口烟气中NOx平均含量由176.14mg/kg降至24mg/kg,脱硝率达到86.37%,且对主催化剂无影响,产品收率、产品质量、RON、平衡剂性质等参数基本无变化。NOxGETTER-NP助燃剂虽然可以降低NOx的产生,但洛阳2号催化裂化装置掺炼闪蒸塔底油,进料中的氮含量波动较大,单纯使用脱硝助剂时,若氮含量突然增大,有可能出现烟气硝排放不合格,因此,增上脱硝设施势在必行。     

Kinetics of hydrogen evolution reaction on stabilized Ni,Pt and Ni–Pt nanoparticles obtained by an organometallic approach

Both (Ni, Pt) and bimetallic (Ni_xPt; x = 1, 2, 3) nanoparticles have been synthesized by hydrogenation of Ni(cod)₂ ad Pt₂(dba)₃ in the presence of a weak coordinating ligand, hexadecylamine (CH₃(CH₂)₁₅NH_2, HDA). These nanostructures were characterized by different techniques (Fourier Transform-Infrared Spectroscopy (FT-IR), High-Resolution Transmission Electron Microscopy (HRTEM)), and were evaluated as Hydrogen Evolution Reaction electrocatalysts in 0.5 M sulfuric acid. The effects of varying the platinum amount during the synthesis were systematically studied by Cyclic Voltammetry (CV), polarization measurements and electrochemical impedance spectroscopy (EIS) techniques. HRTEM shows that the bimetallic nanostructures display a different morphology compared to that observed for pure Ni and Pt ones. The process of hydrogen adsorption–desorption in the as-prepared electrodes seems to occur in (110) and (100) facets. It was found that the increase in the activity for the HER is due to an increased electrochemical active surface area (ECSA) and/or stabilization in the case of elemental electrode materials; and to the effect of Pt amount in the case of the Ni–Pt nanostructures (synergistic effect leads to lower overpotential). It has been established that the main pathway for the HER is Volmer–Heyrovsky.     

Electrodeposition of Pt–Ru and Pt–Ru–Ni nanoclusters on multi-walled carbon nanotubes for direct methanol fuel cell

A full-electrochemical method is developed to deposit three dimension structure (3D) flowerlike platinum-ruthenium (PtRu) and platinum-ruthenium-nickel (PtRuNi) alloy nanoparticle clusters on multi-walled carbon nanotubes (MWCNTs) through a three-step process. The structure and elemental composition of the PtRu/MWCNTs and PtRuNi/MWCNTs catalysts are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray polycrystalline diffraction (XRD), IRIS advantage inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The presence of Pt(0), Ru(0), Ni(0), Ni(OH)₂, NiOOH, RuO₂ and NiO is deduced from XPS data. Electrocatalytic properties of the resulting PtRu/MWCNTs and PtRuNi/MWCNTs nanocomposites for oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) are investigated. Compared with the Pt/MWCNTs, PtNi/MWCNTs and PtRu/MWCNTs electrodes, an enhanced electrocatalytic activity and an appreciably improved resistance to CO poisoning are observed for the PtRuNi/MWCNTs electrode, which are attributed to the synergetic effect of bifunctional catalysis, three dimension structure, and oxygen functional groups which generated after electrochemical activation treatment on MWCNTs surface. The effect of electrodeposition conditions for the metal complexes on the composition and performance of the alloy nanoparticle clusters is also investigated. The optimized ratios for PtRu and PtRuNi alloy nanoparticle clusters are 8:2 and 8:1:1, respectively, in this experiment condition. The PtRuNi catalyst thus prepared exhibits excellent performance in the direct methanol fuel cells (DMFCs). The enhanced activity of the catalyst is surely throwing some light on the research and development of effective DMFCs catalysts.     

Evaluation of Pt–Ru–Ni and Pt–Sn–Ni catalysts as anodes in direct ethanol fuel cells

In this study, the electrooxidation of ethanol on carbon supported Pt–Ru–Ni and Pt–Sn–Ni catalysts is electrochemically studied through cyclic voltammetry at 50 °C in direct ethanol fuel cells. All electrocatalysts are prepared using the ethylene glycol-reduction process and are chemically characterized by energy-dispersive X-ray analysis (EDX). For fuel cell evaluation, electrodes are prepared by the transfer-decal method. Nickel addition to the anode improves DEFC performance. When Pt₇₅Ru₁₅Ni₁₀/C is used as an anode catalyst, the current density obtained in the fuel cell is greater than that of all other investigated catalysts. Tri-metallic catalytic mixtures have a higher performance relative to bi-metallic catalysts. These results are in agreement with CV results that display greater activity for PtRuNi at higher potentials.     

Evaluation of the stability and durability of Pt and Pt–Co/C catalysts for polymer electrolyte membrane fuel cells

Carbon supported Pt and Pt–Co nanoparticles were prepared by reduction of the metal precursors with NaBH₄. The activity for the oxygen reduction reaction (ORR) of the as-prepared Co-containing catalyst was higher than that of pure Pt. 30 h of constant potential operation at 0.8 V, repetitive potential cycling in the range 0.5–1.0 V and thermal treatments were carried out to evaluate their electrochemical stability. Loss of non-alloyed and, to a less extent, alloyed cobalt was observed after the durability tests with the Pt–Co/C catalyst. The loss in ORR activity following durability tests was higher in Pt–Co/C than in Pt/C, i.e. pure Pt showed higher electrochemical stability than the binary catalyst. The lower stability of the Pt–Co catalyst during repetitive potential cycling was not ascribed to Co loss, but to the dissolution–re-deposition of Pt, forming a surface layer of non-alloyed pure Pt. The lower activity of the Pt–Co catalyst than Pt following the thermal treatment, instead, was due to the presence of non-alloyed Co and its oxides on the catalyst surface, hindering the molecular oxygen to reach the Pt sites.     

Performance studies of Pd–Pt and Pt–Pd–Au catalyst for electro-oxidation of glucose in direct glucose fuel cell

Platinum is employed as anode catalyst for low temperature electro-oxidation of glucose in direct glucose fuel cell (DGFC), but it suffers from poisoning by intermediate oxidation products. In the present investigation, palladium and gold precursors are added with platinum precursor to form low metal loading (∼15–20% by wt.) carbon supported catalyst by NaBH₄ reduction technique. The prepared PtPdAu/C (metal ratio 1:1:1) and PdPt/C (metal ratio 4:1) catalysts are tested in DGFC. The Physical characterization of electro-catalysts by scanning electron microscope, transmission electron microscope, energy dispersive X-ray, X-ray diffraction and thermo-gravimetric analysis confirms the formation of nano-sized metal particles on carbon substrate with two prominent homogeneous bi- or tri-metallic crystal phases for PtPdAu/C. The cyclic voltammetry studies carried out for glucose (0.05 M) oxidation in (0.5 M KOH) alkaline medium shows the metal catalysts can efficiently electro-oxidize glucose. The catalysts tested as anode in a batch type DGFC using commercial activated charcoal as cathode produced peak power density of 0.52 mW cm⁻² for both PdPt/C and PtPdAu/C in 0.3 M glucose in 1 M KOH solution.     

碘化氢分解用Pt／活性碳催化剂制备与表征

为了提高碘化氢的分解效率,采用化学镀法制备了系列活性碳(记为AC)负载铂催化剂,利用XRD、BET、ICP和TEM等分析技术对不同铂负载量催化剂的结构、比表面积、组成和金属铂颗粒的大小进行了表征.在固定床反应装置上考察了催化剂的碘化氢分解催化活性,研究了铂负载量和反应温度对催化剂活性的影响.研究结果表明,采用化学镀法成功实现了纳米金属铂粒子在活性碳表面的负载,当负载量为5%时,催化剂的活性最好,500℃时,碘化氢的转化率可达21.4%,接近该条件下的平衡转化率(约23%).     

Enhanced activity of Pt(HY) and Pt–Ru(HY) zeolite catalysts for electrooxidation of methanol in fuel cells

The investigation describes the synthesis of Pt and Pt–Ru catalysts by a new method using a HY zeolite support. The catalysts are used to study the anodic oxidation of methanol in an acidic medium to investigate their suitability for use in direct methanol fuel cells (DMFCs). The catalysts prepared in a HY zeolite support display significantly enhanced electrocatalytic activity in the order: HY<Pt/C<Pt(HY)<Pt–Ru/C<Pt–Ru(HY). The enhanced electrocatalytic activity is explained on the basis of the formation of specific CO clusters in zeolite cages.     

Facile synthesis of supported Pt–Cu nanoparticles with surface enriched Pt as highly active cathode catalyst for proton exchange membrane fuel cells

Carbon supported Pt–Cu catalyst (PtCu/C) with surface enriched Pt was synthesized by annealing the Pt-deposited Cu particles. X-ray diffraction (XRD) results indicate the formation of disordered Pt–Cu alloy phase with a high level of Cu/Pt atomic ratio. X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) analysis confirm the surface enrichment of Pt. Electrochemical measurements show that PtCu/C has 3.7 times higher Pt mass activity toward the oxygen reduction reaction (ORR) than commercial Pt/C. The enhanced ORR activity of PtCu/C is attributed to the modified electronic properties of surface Pt atoms, which reduces the surface blocking of the ORR oxygenated species.     

Tailoring a Pt–Ru catalyst for enhanced methanol electro-oxidation

A carbon-supported (1:1) Pt–Ru (Pt–Ru/C) alloy catalyst has been prepared in-house by the sulfito-complex route, and has been tailored to achieve enhanced activity towards methanol electro-oxidation by annealing it at varying temperatures in air. The catalyst samples annealed between 250 and 300 °C in air for 30 min exhibit superior catalytic activity towards methanol electro-oxidation in a solid-polymer-electrolyte direct methanol fuel cell (SPE-DMFCs) operating at 90 °C. Both the as-prepared and annealed Pt–Ru/C catalysts have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS), and cyclic voltammetry. It is conjectured that while annealing the Pt–Ru/C catalysts, both PtPt and PtRu bonds increase whereas the PtO bond shrinks. This is accompanied with a positive variation in Ru/Pt metal ratio suggesting the diffusion of Ru metal from the bulk catalyst to surface with an increase in oxidic ruthenium content. Such a treatment appears seminal for enhancing the electrochemical activity of Pt–Ru catalysts towards methanol oxidation.     

In-situ investigation on the CO tolerance of carbon supported Pd–Pt electrocatalysts with low Pt content by electrochemical impedance spectroscopy

Carbon supported Pd–Pt electrocatalysts (Pd–Pt/C) with low Pt content were investigated in proton exchange membrane fuel cells (PEMFCs) with pure H₂ and CO/H₂ as the feeding fuels, respectively. The Pd–Pt/C catalysts showed high activity for hydrogen oxidation reaction (HOR) and improved CO tolerance. Electrochemical impedance spectroscopy (EIS) was employed to probe the in-situ information of the improved CO tolerance. The dependence of Nyquist plots and Bode plots on current density and feeding gas was investigated in low polarization region. The results of EIS analysis indicated that the improved CO tolerance of Pd–Pt/C catalysts can be attributed to the lower coverage of CO on the Pd–Pt bimetal than that on the pure Pt.     

Pt/C催化剂催化微晶纤维素加氢的研究

通过对Pt/C催化剂催化转化微晶纤维素的研究,探讨了纤维素催化转化的反应机理及反应温度、H2压力、反应时间对纤维素转化率和乙二醇选择性的影响,同时考察了超声波预处理微晶纤维素,讨论了超声时间对微晶纤维素催化加氢转化率的影响。试验结果表明,随着反应温度、H2压力的增大和反应时间的延长,纤维素转化率逐渐增加,在250℃,H2压力为4 MPa,反应2 h时,微晶纤维素的转化率可达到80.08%,乙二醇的选择性为70.02%。随着超声时间的延长,微晶纤维素的转化率逐渐增大,超声20 min后变化不明显。