PtRu/C电催化剂上甲醇吸附氧化过程的电化学原位红外光谱

采用调变的多元醇法制备了高分散的Pt/C, PtRu/C和Ru/C电催化剂. XRD计算结果表明, PtRu/C电催化剂的平均粒径和合金度分别为2.2 nm和71%. 采用电化学方法和原位傅里叶变换红外反射光谱方法(in situ FTIRS)研究了甲醇在3种电催化剂上的吸附氧化过程, 发现PtRu/C对甲醇的催化活性明显高于Pt/C, Ru的加入一方面影响了甲醇在Pt上的解离吸附性能, 另一方面提供了Ru-OH物种, 从而抑制了低电位下电催化剂中毒. 红外光谱研究结果表明, 线性吸附态CO(COL)是主要毒化物种, 反应产物主要是CO2, 还有少量的甲酸甲酯. 根据实验结果讨论了甲醇在PtRu/C电催化剂上的氧化机理.     

高分散PtRu/C催化剂的制备及对甲醇及吸附态CO的电催化氧化

采用化学还原浸渍法在两种不同条件下制备炭载PtRu催化剂,通过XRD和TEM技术对催化剂的晶体结构及微观形貌进行了分析,运用循环伏安法、线性扫描法来检测不同条件下制备的催化剂对甲醇及吸附态CO(COad)电催化氧化活性的影响.结果表明,不同条件下制备的催化剂Pt和Ru形成合金的程度不同,Pt-Ru合金原子的颗粒在载体炭上的粒径大小和分布不同,导致催化剂对甲醇及COad的电氧化催化活性不同.其中以甲醛为还原剂在乙二醇体系中制备的催化剂PtRu/C-2能形成较好的合金状态,粒径小,分布均匀,对甲醇及COad的氧化具有较高的电催化活性.     

PtRu catalysts supported on heteropolyacid and chitosan functionalized carbon nanotubes for methanol oxidation reaction of fuel cells

A simple self-assembly approach has been developed to functionalize carbon nanotubes (CNTs) with chitosan (CS) and heteropolyacids (HPAs) of phosphomolybdic acid (H(3)PMo(12)O(40), HPMo) and phosphotungstic acid (H(3)PW(12)O(40), HPW). The non-covalent functionalization method, which introduces homogenous surface functional groups with no detrimental effect on graphene structures of CNTs, can be carried out at room temperature without the use of corrosive acids. The PtRu nanoparticles supported on HPAs-CS-CNTs have a uniform distribution and much smaller size as compared to those of the PtRu nanoparticles supported on conventional acid treated CNTs (PtRu/AO-CNTs). The onset and peak potentials for CO(ad) oxidation on PtRu/HPAs-CS-CNTs catalysts are more negative than those on PtRu/AO-CNTs, indicating that HPAs facilitate the electro-oxidation of CO. The PtRu/HPMo-CS-CNTs catalyst has a higher electrocatalytic activity for methanol oxidation and higher tolerance toward CO poisoning than PtRu/HPW-CS-CNTs. The better electrocatalytic enhancement of HPMo on the PtRu/HPAs-CS-CNTs catalyst is most likely related to the fact that molybdenum-containing HPAs such as HPMo have more labile terminal oxygen to provide additional active oxygen sites while accelerating the CO and methanol oxidation in a similar way to that of Ru in the PtRu binary alloy system.     

On the influence of the metal loading on the structure of carbon-supported PtRu catalysts and their electrocatalytic activities in CO and methanol electrooxidation

PtRu (1:1) catalysts supported on low surface area carbon of the Sibunit family (S(BET) = 72 m(2) g(-1)) with a metal percentage ranging from 5 to 60% are prepared and tested in a CO monolayer and for methanol oxidation in H(2)SO(4) electrolyte. At low metal percentage small (<2 nm) alloy nanoparticles, uniformly distributed on the carbon surface, are formed. As the amount of metal per unit surface area of carbon increases, particles start coalescing and form first quasi two-dimensional, and then three-dimensional metal nanostructures. This results in a strong enhancement of specific catalytic activity in methanol oxidation and a decrease of the overpotential for CO monolayer oxidation. It is suggested that intergrain boundaries connecting crystalline domains in nanostructured PtRu catalysts produced at high metal-on-carbon loadings provide active sites for electrocatalytic processes.     

Multiwalled carbon nanotube supported PtRu for the anode of direct methanol fuel cells

The activity of the methanol oxidation reaction of a multiwalled carbon nanotube (MWCNT)-supported PtRu catalyst was investigated and compared with the Vulcan XC-72 carbon-supported catalyst. The PtRu nanoparticles with 1:1 and 7:3 atomic ratios (with similar PtRu loadings and morphological structures) were deposited both on the MWCNTs and on the carbon. Cyclicvoltammetry results demonstrated that the MWCNT-supported PtRu catalyst exhibited a higher mass activity (mA mg(-1) of PtRu) for the methanol oxidation reaction than the carbon-supported PtRu under the condition that both catalysts possess more or less the same PtRu loadings, particle sizes, dispersions, and electrochemical surface area. The direct methanol fuel cell performance test data showed that MWCNT-supported PtRu catalysts yielded about 35-39% higher power densities than the carbon-supported PtRu.     

Temperature effects in carbon monoxide and methanol electrooxidation on platinum–ruthenium: influence of grain boundaries

The temperature dependence of methanol and CO monolayer oxidation is studied on carbon-supported PtRu (1:1 atomic ratio) electrodes with different metal percentages (5, 30, and 60 wt.%) in an aqueous H₂SO₄ electrolyte. High-resolution transmission microscopy confirms that at high (30 or 60 wt.%) metal percentage PtRu nanostructures with a high concentration of intercrystalline boundaries are formed. These nanostructures comprise multiple-twinned particles, particles with intersecting randomly oriented intergrain boundaries, or particles with parallel intergrain boundaries. Formation of such nanostructures leads to a decrease of the apparent activation energy of the methanol and CO monolayer oxidation, while the Tafel slope and the reaction order in methanol show minor dependence on the type of nanostructure. Materials with a high concentration of grain boundary regions may be of interest for practical applications in direct methanol or proton exchange fuel cells fed with reformate.     

甲醇电氧化催化剂Pt/CeO2-CNTs与PtRu/C的比较研究

为认识合成催化剂Pt/CeO2-CNTs与商用催化剂PtRu/C(E-TEK)的催化性能和结构特点, 用CO溶出法和恒电位氧化法比较了这两种催化剂对CO的电氧化活性, 运用循环伏安法和恒电位氧化法比较了这两种催化剂对甲醇的电氧化活性. CO电氧化实验结果表明, PtRu/C上CO的电氧化活性明显优于Pt/CeO2-CNTs; 甲醇电氧化实验结果却表明, Pt/CeO2-CNTs与PtRu/C上甲醇电氧化表观活性相当. 为从结构特点上解释PtRu/C上CO电氧化和甲醇电氧化活性的不一致, 对PtRu/C进行了循环伏安扫描和CO溶出实验. 结果表明, PtRu/C的甲醇电氧化电流之所以没有预期高, 一是由于Pt比表面积不够大, 同时Pt-Ru之间协同作用有待提高. 本研究结果表明, 尽管Ru对Pt上CO电氧化有显著助催化作用, 但要充分发挥其对Pt上甲醇电氧化的助催化作用, 需同时提高Pt表面积和Pt-Ru接触界面. 该结论对设计甲醇电氧化催化剂具有普适意义.     

Structures and catalytic properties of PtRu electrocatalysts prepared via the reduced RuO2 nanorods array

Structures and properties of PtRu electrocatalyts, derived from the aligned RuO2 nanorods (RuO2NR), are investigated using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and cyclic voltammetry toward COads and methanol oxidation. The catalytic activity of methanol oxidation and the CO tolerance are promoted significantly by reducing RuO2 into Ru metal before decorating with Pt. Reduction of RuO2NR was carried out by either thermal decomposition at 650 degrees C in vacuum or H2-reduction at 130 degrees C in low-pressure hydrogen. Reduction assisted by hydrogen allows infiltrating decomposition at low temperature and produces an array of nanorods with rugged walls featuring small Ru nuclei and larger surface area. Pt-RuNR, whose surface Pt:Ru ratio=0.58:0.42 was prepared by decorating with 0.1 mg cm(-2) Pt on the H2-reduced array containing 0.39 mg cm(-2) Ru, demonstrates a favorable combination of CO tolerance and high methanol oxidation activity superior to other RuO2NR-derived catalysts. When compared with a commercial electrocatalyst of PtRu (1:1) alloy (<4 nm), the activity of Pt-RuNR in methanol oxidation is shown to be somewhat lower at potential<0.48 V and higher at potential>or=0.48 V.     

In-situ X-ray absorption spectroscopy study of Pt and Ru chemistry during methanol electrooxidation

Methanol electrooxidation in a 0.5 M sulfuric acid electrolyte containing 1.0 M CH3OH was studied on 30% Pt/carbon and 30% PtRu/carbon (Pt/Ru = 1:1) catalysts using X-ray absorption spectroscopy (XAS). Absorption by Pt and Ru was measured at constant photon energy in the near edge region during linear potential sweeps of 10-50 mV/s between 0.01 and 1.36 V vs rhe. The absorption results were used to follow Pt and Ru oxidation and reduction under transient conditions as well as to monitor Ru dissolution. Both catalysts exhibited higher activity for methanol oxidation at high potential following multiple potential cycles. Correlation of XAS data with the potential sweeps indicates that Pt catalysts lose activity at high potentials due to Pt oxidation. The addition of Ru to Pt accelerates the rate of methanol oxidation at all potentials. Ru is more readily oxidized than Pt, but unlike Pt, its oxidation does not result in a decrease in catalytic activity. PtRu/carbon catalysts underwent significant changes during potential cycling due to Ru loss. Similar current density vs potential results were obtained using the same PtRu/carbon catalyst at the same loading in a membrane electrode assembly half cell with only a Nafion (DuPont) solid electrolyte. The results are interpreted in terms of a bifunctional catalyst mechanism in which Pt surface sites serve to chemisorb and dissociate methanol to protons and carbon monoxide, while Ru surface sites activate water and accelerate the oxidation of the chemisorbed CO intermediate. PtRu/carbon catalysts maintain their activity at very high potentials, which is attributed to the ability of the added Ru to keep Pt present in a reduced state, a necessary requirement for methanol chemisorption and dissociation.     

直接甲醇燃料电池阳极催化剂PtRu/MWCNTs的水热合成及其电催化行为

采用水热法合成了PtRu/MWCNTs阳极催化剂,并以循环伏安、线性扫描、计时电流和交流阻抗等电化学测试研究了其对甲醇的电催化氧化,结果表明,水热合成的PtRu/MWCNTs较之同样条件下合成的PtRu/Vu lcan XC-72有更好的对甲醇氧化的催化活性和更强的抗毒化能力。     

Improving electrochemical activity of PtRu/SnO_2/C catalyst by reduction treatment and alkaline etching

PtRu/SnO_2/C catalyst was prepared in a polyol process, followed by reduction treatment and alkaline etching. X-ray diffraction, transmission electron microscope with energy dispersive spectrometer and Xray photoelectron spectroscopy were used to characterize the morphology, structure and composition of the catalysts. CO and methanol electro-oxidation activities of the catalysts were evaluated by CO stripping voltammetry, cyclic voltammetry and chronoamperometry measurements. Reduction treatment of the prepared PtRuSnO_2/C catalyst in a polyol process induced the enrichment of Sn on the surface, inhibiting methanol dissolution and CO adsorption on Pt. Alkaline etching removed Sn or SnO_x and thus exposed PtRu on the surface, resulting in enhanced activities for CO and methanol electro-oxidation due to the synergy effects of PtRu on the surface and Sn species beneath.     

Physical and electrochemical characterizations of microwave-assisted polyol preparation of carbon-supported PtRu nanoparticles

PtRu nanoparticles supported on Vulcan XC-72 carbon and carbon nanotubes were prepared by a microwave-assisted polyol process. The catalysts were characterized by transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). The PtRu nanoparticles, which were uniformly dispersed on carbon, were 2-6 nm in diameter. All PtRu/C catalysts prepared as such displayed the characteristic diffraction peaks of a Pt face-centered cubic structure, excepting that the 2theta values were shifted to slightly higher values. XPS analysis revealed that the catalysts contained mostly Pt(0) and Ru(0), with traces of Pt(II), Pt(IV), and Ru(IV). The electro-oxidation of methanol was studied by cyclic voltammetry, linear sweep voltammetry, and chronoamperometry. It was found that both PtRu/C catalysts had high and more durable electrocatalytic activities for methanol oxidation than a comparative Pt/C catalyst. Preliminary data from a direct methanol fuel cell single stack test cell using the Vulcan-carbon-supported PtRu alloy as the anode catalyst showed high power density.     

热处理对甲醇电氧化催化剂PtRu/C性能的影响

采用非离子表面活性剂Triton X-100作为稳定剂制备了催化甲醇电氧化反应的PtRu/C催化剂, 研究了热处理温度对催化剂的组成、结构、形貌和活性的影响. 利用循环伏安法研究了PtRu/C催化剂催化甲醇电氧化的活性, 用热重和差热分析(TG-DTA)、X射线能量色散谱(EDX)、X射线衍射(XRD)、X射线光电子能谱(XPS)和透射电子显微镜(TEM)对PtRu/C催化剂进行了表征. 研究结果表明, 热处理对PtRu/C催化剂粒子的大小、分布和Pt的氧化态有重要的作用. 在350 ℃下热处理的催化剂显示了最好的催化甲醇电氧化的性能, 由Triton X-100作为稳定剂制备的PtRu/C催化剂最适宜的热处理温度是350 ℃.     

A strategy for the high dispersion of PtRu nanoparticles onto carbon nanotubes and their electrocatalytic oxidation of methanol

Carbon nanotubes (CNTs) were non-covalently functionalized by 1-pyrenecarboxaldehyde (PCA) via π-π stacking interactions. PCA not only acts as the reductant for the deposition of PtRu nanoparticles, but the oxidation product of PCA can also effectively anchor and stabilize the in-situ-produced PtRu?NPs on the surface of CNTs. Transmission electron microscopy demonstrates that PtRu?NPs are uniformly dispersed on the surface of CNTs with small particles sizes of about 1.7 nm. The obtained PtRu-NP/CNT composites have higher electrochemical surface areas, electrocatalytic activities, and better stability towards methanol oxidation compared to PtRu?NPs supported on pristine CNTs.     

Facile synthesis of PtRu/C electrocatalyst with high activity and high loading for passive direct methanol fuel cell by synergetic effect of ultrasonic radiation and mechanical stirring

The PtRu/C electrocatalyst with high loading (PtRu of 60 wt%) was prepared by synergetic effect of ultrasonic radiation and mechanical stirring. Physicochemical characterizations show that the size of PtRu particles of as-prepared PtRu/C catalyst is only several nanometers (2–4 nm), and the PtRu nanoparticles were homogeneously dispersed on carbon surface. Electrochemistry and single passive direct methanol fuel cell (DMFC) tests indicate that the as-prepared PtRu/C electrocatalyst possessed larger electrochemical active surface (EAS) area and enhanced electrocatalytic activity for methanol oxidation reaction (MOR). The enhancement could be attributed to the synergetic effect of ultrasound radiation and mechanical stirring, which can avoid excess concentration of partial solution and provide a uniform environment for the nucleation and growth of metal particles simultaneously hindering the agglomeration of PtRu particles on carbon surface.     

PtRu/carbon nanotube nanocomposite synthesized in supercritical fluid: a novel electrocatalyst for direct methanol fuel cells

Platinum/ruthenium nanoparticles were decorated on carbon nanotubes (CNT) in supercritical carbon dioxide, and the nanocomposites were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). TEM images show that the particles size is in the range of 5-10 nm, and XRD patterns show a face-centered cubic crystal structure. Methanol electrooxidation in 1 M sulfuric acid electrolyte containing 2 M methanol were studied onPtRu/CNT (Pt, 4.1 wt%; Ru, 2.3 wt%; molar ratio approximately Pt/Ru = 45:55) catalysts using cyclic voltammetry, linear sweep voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. All the electrochemical results show that PtRu/CNT catalysts exhibit high activity for methanol oxidation which resulted from the high surface area of carbon nanotubes and the nanostructure of platinum/ruthenium particles. Compared with Pt/CNT, the onset potential is much lower and the ratio of forward anodic peak current to reverse anodic peak current is much higher for methanol oxidation, which indicates the higher catalytic activity of PtRu/CNT. The presence of Ru with Pt accelerates the rate of methanol oxidation. The results demonstrated the feasibility of processing bimetallic catalysts in supercritical carbon dioxide for fuel cell applications.     

Development of stable PtRu catalyst coated with manganese dioxide for electrocatalytic oxidation of methanol

Manganese dioxide was coated on multiwall carbon nanotubes-supported PtRu particles to prepare the MnO₂/PtRu/CNT catalyst by a facile oxidation–reduction method. The prepared catalyst showed a high stability for electrocatalytic oxidation of methanol. After 2000 potential cycles, 55% activity still remained for MnO₂/PtRu/CNT catalyst, while only 30% activity remained for PtRu/CNT, which indicated that the electrochemical stability of MnO₂/PtRu/CNTs was improved significantly. MnO₂ in MnO₂/PtRu/CNTs prevented the dissolution of PtRu particles as well as the corrosion of the CNT supports, resulting in the improvement of the stability and activity.     

碳载Pt和PtRu催化剂的甲醇电氧化比较

利用电化学方法对商用Pt/C和PtRu/C催化剂在酸性介质中的甲醇电氧化进行了比较研究.动电位和恒电位氧化实验结果皆表明PtRu/C比Pt/C对甲醇电催化活性高.PtRu合金的形成不仅改变了催化剂表面对氢的吸附性质,而且使氧化物还原峰电位向阴极方向移动.Ru与甲醇的相互作用为温度活化过程,需要较高的温度.     

Methanol electrooxidation on a colloidal PtRu-alloy fuel-cell catalyst

The electrooxidation of methanol on a novel carbon supported PtRu electrocatalyst produced via colloidal PtRu precursors was investigated by thin-film-electrode (TFE) measurements and compared with commercially available Pt and PtRu catalysts. The PtRu-colloid-based catalyst shows similiar activity towards methanol oxidation as other conventional PtRu catalysts. A comparison with literature data from half-cell measurements at similiar mass-specific current densities clearly demonstrates the high potential of the colloid-based PtRu catalyst for fuel-cell applications.     

Simple replacement reaction for the preparation of ternary Fe(1-x)PtRu(x) nanocrystals with superior catalytic activity in methanol oxidation reaction

The finding of new metal alloyed nanocrystals (NCs) with high catalytic activity and low cost to replace PtRu NCs is a critical step toward the commercialization of fuel cells. In this work, a simple cation replacement reaction was utilized to synthesize a new type of ternary Fe(1-x)PtRu(x) NCs from binary FePt NCs. The detailed structural transformation from binary FePt NCs to ternary Fe(1-x)PtRu(x) NCs was analyzed by X-ray absorption spectroscopy (XAS). Ternary Fe(35)Pt(40)Ru(25), Fe(31)Pt(40)Ru(29), and Fe(17)Pt(40)Ru(43) NCs exhibit superior catalytic ability to withstand CO poisoning in methanol oxidation reaction (MOR) than do binary NCs (FePt and J-M PtRu). Also, the Fe(31)Pt(40)Ru(29) NCs had the highest alloying extent and the lowest onset potential among the ternary NCs. Furthermore, the origin for the superior CO resistance of ternary Fe(1-x)PtRu(x) NCs was investigated by determining the adsorption energy of CO on the NCs' surfaces and the charge transfer from Fe/Ru to Pt using a simulation based on density functional theory. The simulation results suggested that by introducing a new metal into binary PtRu/PtFe NCs, the anti-CO poisoning ability of ternary Fe(1-x)PtRu(x) NCs was greatly enhanced because the bonding of CO-Pt on the NCs' surface was weakened. Overall, our experimental and simulation results have indicated a simple route for the discovery of new metal alloyed catalysts with superior anti-CO poisoning ability and low usage of Pt and Ru for fuel cell applications.