Ho掺杂对Pt-Ru/C电催化氧化甲醇的性能影响

采用脉冲电沉积法制备了碳载的Pt-Ru-Ho电催化剂,循环伏安法(CV)和交流阻抗法(EIS)测定催化剂的甲醇电氧化活性,用XRD、EDS和XPS表征电催化剂的物性结构、表面元素组成和价态形式.结果表明,电催化剂中Pt,Ru,H0 3种元素以合金的形式存在,在合金表面有HoO存在,合金微粒粒径为3.5 nm,比表面积为73.3 m2.g-1;掺杂适量稀土金属Ho对Pt-Ru合金的活性有明显影响,其中原子比为npt:nRu:nHo=1:1:0.2时,Pt-Ru-Ho/C中Ho的含量较为适宜,电催剂的Tafel常数α减小,反应活化能低于Pt-Ru/C,为28.4 kJ·mol-1,催化活性明显高于Pt-Ru/C,但Ho含量过高Pt-Ru-Ho/C的活性低于Pt-Ru/C:Pt-Ru-Ho0 .2/C甲醇的反应级数为0.17级.     

Influence of the structure of TiO<Subscript>2</Subscript>, CeO<Subscript>2</Subscript>, and CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> supports on the activity of Ru catalysts in the catalytic wet air oxidation of acetic acid

Ru catalysts, supported on TiO₂, CeO₂, and CeO₂-TiO₂, were prepared by the impregnation method. The effect of the structure of the supports on the activity of Ru catalysts was investigated in the catalytic wet air oxidation (CWAO) of acetic acid under 230°C and 5 MPa in a batch reactor. Physical properties including the surface area, crystalline phase, and surface components of the Ru catalysts were characterized by N₂ adsorption, X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The CeO₂-based Ru catalysts had good activity, and the prepared RuO₂/CeO₂ catalyst showed markedly higher activity than the RuO₂/CeO₂-TiO₂ catalyst. The surface structure, the high amount of chemisorbed oxygen on the catalyst surface, and the suitable pH_pzc value of the supports played an important role in the activity of the Ru catalysts in CWAO of acetic acid.     

Effect of the thickness of the Ru-coating on a counter electrode on the performance of a dye-sensitized solar cell

A ruthenium (Ru) catalytic layer was assessed as the counter electrode (CE) in dye sensitized solar cells (DSSCs) by examining the effect of the Ru thickness on the DSSC performance. Ru films with different thicknesses (34, 46, 69 and 90 nm) were deposited on glass/fluorine-doped tin oxide (FTO) substrates as the CE by atomic layer deposition (ALD) at 250 °C using RuDi as the precursor and O₂ as the reaction gas. Finally, a 0.45 cm² DSSC of glass/FTO/TiO₂/dye(N719)/electrolyte(C6DMII, GSCN)/Ru CE structure was prepared. The properties of the DSSCs were examined by field emission scanning electron microscopy (FESEM), four-point-probe, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), current-voltage (I–V), incident photon-to-current conversion efficiency (IPCE), and dark current measurements. FESEM showed that the crystallized Ru films had been deposited quite uniformly and conformally on the glass/FTO surface. The sheet resistance of the Ru film decreased with increasing Ru thickness. CV profiling revealed an increase in catalytic activity with increasing film thickness. The charge transfer resistance at the interface between the Ru-coated CE and electrolyte decreased with increasing Ru thickness. I–V profiling showed that the energy conversion efficiency was increased up to 3.40 % by increasing the Ru thickness. Moreover, the IPCE and dark current results showed the efficiency of the Ru-coated CE was comparable to that of a conventional platinum (Pt) CE.     

Carbon formation on nickel and nickel-copper alloy catalysts

Equilibrium, kinetic and morphological studies of carbon forma- tion in CH₄ + H₂, CO, and CO + H₂ gases on silica supported nickel and nickel-copper catalysts are reviewed. The equilibrium deviates in all cases from graphite equilibrium and more so in CO + CO₂ than in CH₄ + H₂. A kinetic model based on information from surface science results with chemisorption of CH₄ and possibly also the first dehydrogenation step as rate controlling describes carbon formation on nickel catalyst in CH₄ + H₂ well. The kinetics of carbon formation in CO and CO + H₂ gases are in agreement with CO disproportionation as rate determining step. The presence of hydrogen influences strongly the chemisorption of CO. Carbon filaments are formed when hydrogen is present in the gas while encapsulating carbon dominates in pure CO. Small amounts of Cu alloying promotes while larger amounts (Cu : Ni ≥ 0.1) inhibits carbon formation and changes the morphology of the filaments (“octopus” carbon formation). Adsorption induced nickel segregation changes the kinetics of the alloy catalysts at high carbon activities. Modifications suggested in some very recent papers on the basis of new results are also briefly discussed.     

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 …     

Solidification behavior of Pt-containing 718Plus superalloy

Solidification behaviors of Pt-containing 718Plus superalloyswere studied by scanning electron microscopy (SEM), energy dispersive spectrum (EDS), differential scanning calorimetry (DSC) and simulation calculations. It is found that Pt increases solidification range and decreases solidus temperature of the alloy and precipitation temperature of Laves + γ eutectic phase since Pt enlarges the region of γ phase by increasing Nb solubility. In addition, Pt segregates to the interdendritic region and increases the segregation of Nb and Tiin the interdendriticregion due to the strong attractive interactions between Pt and Nb/Ti. As a result, Pt promotes the precipitation of the Laves + γ eutectic phase and η phase around eutectic phase. The increase of solidification range and segregation degrees of Nb and Al caused by Pt also promotes the precipitation and growth of γ’ + γ” phase around eutectic phase. These results provide experimental bases for understanding the mechanism of Pt in solidification behavior of superalloys.     

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.     

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.     

焙烧气氛对Pt/Al2O3 催化氧化CO和C3H6 性能的影响

使用Pt(NH₃)₂(NO₂)₂作为前驱体,通过过量浸渍法制备Pt/Al₂O₃催化剂,并将其在4种不同的气氛（H₂、O₂、NO或NH₃）中进行焙烧。利用N₂吸脱附、X射线衍射、程序升温还原（H₂-TPR）、CO脉冲吸附、CO原位漫反射傅里叶变换红外光谱（CO in situ DRIFTS）等手段对催化剂的物化性质进行了表征。结果表明：由于还原性焙烧气氛导致了众多小尺寸和高分散的Pt纳米颗粒的生成,经1%（体积分数）H₂/N₂焙烧的Pt/Al₂O₃表现出最佳的CO和C₃H₆催化氧化性能。     

Ru纳米颗粒包覆ITO纳米线热解纤维素性能研究

以阳极氧化铝(AAO)膜为模板,采用真空机械压注法制备铟锡(InSn)合金纳米线(NWs),然后采用“原位放电还原”方法在InSn NWs表面包覆Ru颗粒。随后,将复合材料在空气中进行热处理,合成RuO₂/ITO NWs。最后,在H₂气氛下还原RuO₂/ITO NWs获得Ru/ITO NWs。结果表明,InSn纳米线直径约为40 nm,2 ~ 5 nm的Ru纳米颗粒均匀地包覆在ITO NWs的表面。此外,检测了所得Ru/ITO NWs对纤维素的催化热解性能,所得产物为1,6-脱水吡喃葡萄糖、乙醇醛和羟基丙酮,对比无催化剂、ITO NWs,Ru/ITO NWs所得产物,可以发现Ru/ITO NWs催化剂减少了1,6-脱水吡喃葡萄糖的产生,表明Ru纳米颗粒加剧了热解过程中的氧桥的断裂,加速生成乙醇醛和羟基丙酮,提高纤维素热解效率。同时对存在醚键的壬基酚聚氧乙烯醚也进行了热解分析,结果表明Ru/ITO NWs对醚键的断裂起明显的催化作用。     

Properties of TiO2 support and the performance of Au/TiO2 Catalyst for CO oxidation reaction

Gold catalysts were prepared on TiO₂ supports of different phase structures (i.e., anatase, rutile and biphasic), TiO₂ crystal size (i.e., 9–23 nm), surface and textural properties (i.e., hydration and surface area). The CO oxidation on the gold catalysts was carried out in an operando-DRIFTS set-up equipped with DRIFTS reactor cell connected on-line to CO gas analyser and gas chromatograph enabling real time monitoring of surface reaction and simultaneous reaction rate measurements. Gold catalysts supported on pure anatase TiO₂ were more resistant to sintering compared to catalysts supported on rutile and bi-phasic TiO₂. Besides catalyst sintering, deposition of surface carbonates is an important cause of catalyst deactivation. The best gold catalyst was prepared on 13 nm anatase TiO₂. It displays both increased activity and stability for CO oxidation reaction at room temperature. Surface and textural properties of TiO₂ also play a role on the performance of the Au/TiO₂ catalyst.     

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。     

恒压电沉积 Pt-Ni 合金催化剂的形貌控制及其对催化剂性能的影响

目的通过对电沉积过程中基体亲水性及电解液温度参数的控制,实现对Pt-Ni催化剂的形貌及催化性能的控制。方法采用恒电压沉积技术制备Pt-Ni合金催化剂。利用5%(质量分数)Nafion对多孔碳布基体表面进行亲水修饰,并控制电解液温度,合成具有不同形貌的Pt-Ni合金催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、能量色散谱(EDS)、循环伏安(CV)、单电池极化性能等测试技术对制备的催化剂进行物理及电化学表征。结果碳布基体表面经适量的Nafion修饰后,电沉积制备的合金催化剂颗粒细小,分布均匀。当碳布基体表面修饰的Nafion含量达到0.8 mg/cm2时,催化剂单电池极化性能最佳。另外,较高电解液温度下制备得到的球状形貌具有更大的电化学活性表面积(ECSA),更高的催化活性,优于较低温下制备的"雪花"状催化剂的性能。其中,50℃下电沉积制备的Pt-Ni合金催化剂ECSA达到47.6 m2/(g Pt),单电池运行过程中最大功率密度达到77.8 m W/cm2,具有最高的催化活性。结论适量Nafion修饰后的亲水多孔碳布基体上电沉积Pt-Ni合金催化剂性能更加优越。电解液温度的控制对恒电压沉积的Pt-Ni合金表面形貌控制有重要意义。     

Selective dry oxidation of the ordered Pt-11.1 at.% V alloy surface evidenced by in situ temperature-controlled X-ray diffraction

A temperature-controlled X-ray diffraction study of the cold-rolled Pt-11.1 at.% V alloy was undertaken to gain better insight into the incomplete transformation of the metastable cubic disordered phase into the tetragonal ordered Pt₈V phase, earlier reported by Nxumalo and Lang [11]. This study has revealed a complex behaviour of the alloy when is annealed in primary vacuum. Upon heating above 450 °C, an ordering of vanadium atoms in the Pt-11.1 at.% V alloy leads to the appearance of a tetragonal Pt₈V phase. Concomitantly, vanadium atoms at the surface of the ordered alloy are slowly oxidized into V₂O₃ Corundum type phase by the low oxygen partial pressure existing in primary vacuum. This segregation of vanadium oxide onto the surface depleting the subsurface region in vanadium, an almost pure Pt cubic phase grows at the V₂O₃-ordered Pt₈V alloy interface with increasing the temperature. This investigation also shows that an external selective oxidation of the cold-rolled Pt-11.1 at.% V alloy takes place when is annealed in flowing argon atmosphere.     

Analysis of the electrochemical reaction behavior of alloy AZ91 by EIS technique in H3PO4/KOH buffered K2SO4 solutions

The EIS technique was used to analyze the electrochemical reaction behavior of Alloy AZ91 in H₃PO₄/KOH buffered K₂SO₄ solution at pH 7. The corrosion resistance of Alloy AZ91 was directly related with the stability of Al₂O₃ · xH₂O rich part of the composite oxide/hydroxide layer on the alloy surface. The break down of the oxide layer was estimated to occur mainly on the matrix solid solution phase in Alloy AZ91. The mf capacitive loop arose from the relaxation of mass transport in the solid oxide phase in the presence of Al₂O₃ · xH₂O rich part and from Mg⁺ ion concentration within the broken area in the absence of Al₂O₃ · xH₂O rich part in the composite oxide structure on the alloy surface. The lf inductive loop had tendency of disappear when the dissolution rate of the alloy decreased as a result of the formation of the protective oxide layer.     

Inter-granular exchange coupling and magnetic anisotropy of Ta/Ru/Co-23 at%Pt perpendicular thin films with different Ru underlayer thicknesses

In the present work, a series of Ta/Ru/Co-23 at%Pt thin films with varied Ru underlayer thicknesses were fabricated by magnetron sputtering. All of the films show c-axis preferred orientation perpendicular to the film surface. The drop of c/a ratio and lattice expansion of Co–Pt layer with the increase in Ru underlayer thickness was revealed by X-ray diffraction(XRD). The coercivity of the Ta/Ru/Co–Pt thin films increases drastically with Ru underlayer thickness increasing, due to the enhancement of effective magneto-crystalline anisotropy constant and exchange decoupling of magnetic nano-grains. The enhancement of effective magneto-crystalline anisotropy constant is ascribed to the lattice deformation of Co–Pt layer by mismatching the Ru layer and Co–Pt surface.Moreover, the exchange decoupling of magnetic nanograins is attributed to the further isolation of magnetic nano-grains.     

Osteoblast growth behavior on micro-arc oxidized β-titanium alloy

β-titanium (β-Ti) alloys are known for their excellent physical properties and biocompatibility, and are therefore considered as next-generation metals for orthopedics and dental implants. To improve the osseous integration between β-Ti alloys and bone, this study develops a titanium dioxide (TiO₂) coating on the surface of β-Ti alloys by using micro-arc oxidation (MAO) technique. The anatase (A) rich and rutile (R) rich TiO₂ layer, were formed on β-Ti, respectively. In vitro tests were carried out using pre-osteoblast cell (MC3T3-E1) to determine biocompatibility and bone formation performance. Biocompatibility includes cell adhesion, cell proliferation, and alkaline phosphatase (ALP) activity, while the bone formation performance contains osteopontin (OPN), osteocalcin (OCN) and calcium content. Cell morphology was also observed. In addition, raw β-Ti, A rich TiO₂ and R rich TiO₂ were implanted into the distal femora of Japanese white rabbits for 4, 8, and 12 weeks to evaluate its in vivo performance.Experimental results show that TiO₂ coating can be grown on and well-adhered to β-Ti. The anatase phase formed under a low applied voltage (350 V), while the rutile phase formed under a high applied voltage (450 V), indicating that crystal structure is strongly influenced by applied voltage. A porous morphology was obtained in the TiO₂ coating regardless of the crystal structure and exhibited superior bone formation performance than β-Ti. In vivo analysis and in vitro test show similar trends. It is also noticeable that the R rich TiO₂ coating achieved better biocompatibility, osteogenesis performance. Therefore, a MAO-treated R rich TiO₂ coating can serve as a novel surface modification technique for β-Ti alloy implants.     

CO2对Pd8Y0.23Ru合金膜氢渗透性能的影响

在300~450℃范围内,研究氢中加入CO2对Pd8Y0.23Ru合金膜氢渗透性能的影响。结果表明,CO2的加入会大大降低膜的氢渗透率,CO2浓度越高,氢渗透率降低越多;CO2对Pd8Y0.23Ru合金膜存在一定的毒化作用,使氢渗透率下降,450℃下的毒化作用明显强于300℃,但随着时间的延长,渗透率降低速率趋缓。CO2降低氢渗透率还有另外2个因素:当CO2浓度较高(>3%,摩尔分数)时,聚集在膜表面附近的CO2对氢气传质的阻塞作用是氢渗透率降低的主要因素;当CO2浓度较低(<1%)时,CO2在膜表面吸附,占据氢的活性点位,是氢渗透率降低的主要因素。     

Effect of Y addition on microstructure and mechanical properties of Mg–Zn–Mn alloy

The effects of Y on the microstructure and mechanical properties of Mg–6Zn–1Mn alloy were investigated. The results show that the addition of Y has significant effect on the phase composition, microstructure and mechanical properties of Mg–6Zn–1Mn alloy. Varied phases compositions, including Mg₇Zn₃, I-phase (Mg₃YZn₆), W-phase (Mg₃Y₂Zn₃) and X-phase (Mg₁₂YZn), are obtained by adjusting the Zn to Y mass ratio. Mn element exists as the fine Mn particles, which are well distributed in the alloy. Thermal analysis and microstructure observation reveal that the phase stability follows the trend of X>W>I>Mg₇Zn₃. In addition, Y can improve the mechanical properties of Mg–Zn–Mn alloy significantly, and the alloy with Y content of 6.09% has the best mechanical properties. The high strength is mainly due to the strengthening by the grain size refinement, dispersion strengthening by fine Mn particles, and introduction of the Mg–Zn–Y ternary phases.     

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...