碳载体预处理对纳米Pt/C电催化性能影响

利用NaBH₄还原机制,采用经不同方法预处理的碳载体成功制备出Pt/C-HNO₃、Pt/C-H₂O₂和Pt/C 3种碳载铂纳米催化剂.通过扫描电镜(SEM)、透射电镜(HR-TEM)、循环伏安(CV)和CO_ad溶出技术进行表征.结果表明,所制备的催化剂大小分布较为均一,平均粒径约为4 nm;HR-TEM观察发现,Pt/C-HNO₃中铂纳米粒子的表面具有较高的台阶原子密度;在CO_ad溶出实验中Pt/C-HNO_3­表现出较强的抗一氧化碳毒化能力;所制备的3种催化剂及商业催化剂Pt/C JM对乙醇氧化的电催化活性顺序为:Pt/C-HNO₃ > Pt/C-H₂O₂ > Pt/C > Pt/C JM,其中Pt/C-HNO₃的电催化活性和稳定性分别为Pt/C JM的1.5倍和1.9倍.     

Effects of Carbonization Temperature and Time during Carbon Riveting Process on the Stability of Pt/C Catalyst

Effects of carbonization temperature and time during carbon riveting process on the stability of Pt/C catalysts have been investigated systematically. X‐ray diffraction, transmission electron microscopy, cyclic voltammograms, and accelerated potential cycling tests have been performed to characterize the catalysts. The experimental results show that the activity of the riveted Pt/C catalyst decreases with the increasing of the heat‐treated temperature and the extension of heat‐treated time due to sintering of Pt nanoparticles. The stability of the carbon riveted Pt/C catalysts exhibits the increasing trend with the increase of the carbonization time and temperature. Considering both of the activity and stability of the riveted Pt/C catalysts, the optimized carbonization temperature and time are 400 °C and 60 min for a Pt/VulcanXC‐72 catalyst with starting particle size before carbonization of 2.2 nm and 20 wt% platinum loading, respectively.     

Pt-CeO2/C anode catalyst for direct methanol fuel cells

In order to develop a cheaper and durable catalyst for methanol electrooxidation reaction, ceria (CeO₂) as a co-catalytic material with Pt on carbon was investigated with an aim of replacing Ru in PtRu/C which is considered as prominent anode catalyst till date. A series of Pt-CeO₂/C catalysts with various compositions of ceria, viz. 40 wt% Pt-3–12 wt% CeO₂/C and PtRu/C were synthesized by wet impregnation method. Electrocatalytic activities of these catalysts for methanol oxidation were examined by cyclic voltammetry and chronoamperometry techniques and it is found that 40 wt% Pt-9 wt% CeO₂/C catalyst exhibited a better activity and stability than did the unmodified Pt/C catalyst. Hence, we explore the possibility of employing Pt-CeO₂ as an electrocatalyst for methanol oxidation. The physicochemical characterizations of the catalysts were carried out by using Brunauer Emmett Teller (BET) surface area and pore size distribution (PSD) measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) techniques. A tentative mechanism is proposed for a possible role of ceria as a co-catalyst in Pt/C system for methanol electrooxidation.     

Pt-CeO2/C anode catalyst for direct methanol fuel cells

In order to develop a cheaper and durable catalyst for methanol electrooxidation reaction, ceria (CeO₂) as a co-catalytic material with Pt on carbon was investigated with an aim of replacing Ru in PtRu/C which is considered as prominent anode catalyst till date. A series of Pt-CeO₂/C catalysts with various compositions of ceria, viz. 40 wt% Pt-3–12 wt% CeO₂/C and PtRu/C were synthesized by wet impregnation method. Electrocatalytic activities of these catalysts for methanol oxidation were examined by cyclic voltammetry and chronoamperometry techniques and it is found that 40 wt% Pt-9 wt% CeO₂/C catalyst exhibited a better activity and stability than did the unmodified Pt/C catalyst. Hence, we explore the possibility of employing Pt-CeO₂ as an electrocatalyst for methanol oxidation. The physicochemical characterizations of the catalysts were carried out by using Brunauer Emmett Teller (BET) surface area and pore size distribution (PSD) measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) techniques. A tentative mechanism is proposed for a possible role of ceria as a co-catalyst in Pt/C system for methanol electrooxidation.     

Role of Pt in the Activity and Stability of PtNi/CeO2–Al2O3 Catalysts in Ethanol Steam Reforming for H2 Production

Hydrogen production from ethanol reforming was investigated on bimetallic PtNi catalysts supported on CeO₂/Al₂O₃. Pt content was varied from 0.5 to 2.5 %. Physico-chemical characterization of the as-prepared and H₂-reduced catalysts by TPR, XRD and XPS showed that Pt phase interacted with the Ni and Ce species present at the surface of the catalysts. This interaction leads to an enhancement of the reducibility of both Ni and Ce species. Loadings of Pt higher than 1.0 wt% improved the activity and stability of the Ni/CeO₂–Al₂O₃ catalyst in ethanol steam reforming, in terms of lower formation of coke, C₂ secondary products and a constant production of CO₂ and H₂. The amount and type of carbon deposited on the catalyst was analyzed by TG–TPO while the changes in crystalline phases after reaction were studied by XRD. It was found that for Pt contents higher than 1 wt% in the catalysts, a better contact between Pt and Ce species is achieved. This Pt–Ce interaction facilitates the dispersion of small particles of Pt and thereby improves the reducibility of both Ce and Ni components at low temperatures. In this type of catalysts, the cooperative effect between Pt⁰, Ni⁰ and reduced Ce phases leads to an improvement in the stability of the catalysts: Ni provides activity in C–C bond breakage, Pt particles enhance the hydrogenation of coke precursors (C_xH_y) formed in the reaction, and Ce increases the availability of oxygen at the surface and thereby further enhances the gasification of carbon precursors.     

炭载体前处理对Pt-Ru/C催化剂性能影响

为研究水蒸气处理后热处理对炭黑表面特性的影响,提高DMFC阳极催化剂的催化活性,利用先水蒸气处理后热处理的Vnlcan XC-72炭黑为载体制备Pt-Ru/C催化剂,与水蒸气处理的和未经处理的炭载体制备Pt-Ru/C催化剂的性能进行比较.采用XPS和BET测试了处理后的炭粉表面的含氧浓度和比表面,结果表明：水蒸气处理后,炭载体比表面积增大,含氧浓度降低;水蒸气处理后热处理,炭载体比表面积进一步减小,含氧浓度增加.用XRD对催化剂的结构进行了表征,结果表明：水蒸气处理后热处理的炭黑为载体制备Pt-Ru/C催化剂结晶状态良好,催化剂颗粒较小.在0.5mol/L CH3OH和0.5mol/L H2SO4混合溶液中,利用玻炭电极测试了循环伏安曲线和阶跃电位曲线,结果表明：用先水蒸气处理后热处理的炭粉为载体制备的催化剂比仅水蒸气处理和未经处理的炭粉为载体制备的催化剂的活性最高.     

A General Protocol for the Synthesis of Pt–Sn/C Catalysts for the Ethanol Electrooxidation Reaction

A general protocol for the synthesis of Pt–Sn/C catalysts for ethanol electrooxidation by the polyol method is developed after a systematic variation of the preparation variables. This protocol enables the complete transfer of all catalytic elements in the preparation solution to the catalyst support; thereby providing a convenient means of catalyst composition control. Water is a necessary co‐solvent for ethylene glycol in the polyol synthesis of Pt–Sn/C catalysts. The best preparation medium for controlling the particle size to small sizes is 0.1 M NaOH solution in a mixture of equal volumes of water and ethylene glycol. With this medium composition Pt–Sn/C catalysts with the optimized target Pt:Sn atomic ratio of 3:1 could be expeditiously prepared for ethanol electrooxidation.     

Development of carbon nanotube and carbon xerogel supported catalysts for the electro-oxidation of methanol in fuel cells

Multiwalled carbon nanotubes and high surface area mesoporous carbon xerogel were prepared and used as supports for monometallic Pt and bimetallic Pt-Ru catalysts. In order to assess the influence of the oxygen surface groups of the support, the mesoporous carbon xerogel was also oxidized with diluted oxygen before impregnation. Various reduction protocols were tested, the best results corresponding to reduction with sodium borohydride. High dispersion catalysts were obtained, which showed quite good performance in the electro-oxidation of methanol. In particular, a remarkable increase in the activity was observed when the Pt-Ru catalysts were supported on the oxidised xerogel. This effect was explained in terms of the metal oxidation state, as shown by XPS. It has been shown that the oxidised support helps to maintain the metals in the metallic state, as required for the electro-oxidation of methanol. This effect was negligible in the case of the Pt catalysts.     

Synthesis of very highly dispersed platinum catalysts supported on carbon xerogels by the strong electrostatic adsorption method

Highly dispersed Pt/carbon xerogel catalysts are obtained by applying the “strong electrostatic adsorption” (SEA) of hexachloroplatinic acid to carbon xerogels (PZC = 9.4) and platinum tetraammine chloride to oxidized carbon xerogels (PZC = 2.4). After the reduction step, all these Pt/carbon xerogel catalysts display a very high level of metal dispersion: very small platinum particles (1.1–1.3 nm) are observed by TEM. Pt particle sizes obtained by CO chemisorption are in good agreement with TEM micrographs, which shows that the metal is accessible to reactants. These Pt/carbon xerogel catalysts are very active for the hydrogenation of benzene into cyclohexane.     

Enhanced electrochemical activity of Pt nanowire network electrocatalysts for methanol oxidation reaction of fuel cells

In this work, Pt nanowire networks supported on high surface area carbon (Pt NWNs/C) are synthesized as electrocatalysts for direct methanol fuel cells (DMFCs). The electrocatalytic behavior of Pt NWNs/C catalysts for the methanol and adlayer CO oxidation reactions is investigated and the results are compared with the Pt nanoparticles (NPs) supported on carbon (Pt NPs/C). The results indicate that Pt NWNs are characterized by interconnected nanoparticles with large number of grain boundaries, downshifted d-band center and reduced oxophilicity, which results in the enhanced surface mobility of oxygen-containing species such as CO_ads and OH_ads. The enhanced surface mobility of CO_ads and OH_ads in turn facilitates the removal of intermediate CO species during the methanol oxidation. The activity of the Pt NWNs/C electrocatalyst for the methanol oxidation reaction and electrooxidation of adsorbed CO is also evaluated by cyclic voltammetry, CO stripping, and kinetic analysis. The results show that Pt NWNs/C catalysts have a significantly higher electrocatalytic activity for the methanol oxidation reaction as compared to Pt NPs/C catalysts. The enhanced electrocatalytic activity of Pt NWNs/C catalysts is mainly due to the existence of large number of the grain boundaries of the interconnected nanoparticles of the unique Pt NWN structure.     

Highly dispersed platinum nanoparticles on carbon nanocoils and their electrocatalytic performance for fuel cell reactions

Highly graphitic carbon nanocoils (GCNC) were synthesized through the catalytic graphitization of carbon microspheres obtained by the hydrothermal carbonization of different saccharides (sucrose, glucose and starch) and were used as a support for Pt nanoparticles. The Pt nanoparticles were deposited by means of a polymer mediated-polyol method. The Pt catalysts were characterized both physically (XRD, TEM, HRTEM and XPS) and electrochemically (electrooxidation of methanol in an acid medium). The electrocatalysts thus prepared show a high dispersion of Pt nanoparticles, with diameters in the 3.0-3.3 nm range and a very narrow particle size distribution. These catalytic systems possess high electroactive Pt surface areas (up to 85 m² g⁻¹ Pt) and they exhibit large catalytic activities towards methanol electrooxidation (up to 201 A g⁻¹ Pt). Moreover, they have a high resistance against oxidation, which is considerably greater than that of the Pt/Vulcan system.     

The construction of nitrogen-doped graphitized carbon–TiO2 composite to improve the electrocatalyst for methanol oxidation

The exploration of advanced catalyst supports is a promising route to obtain electrocatalysts with high activity and durability. Herein, the nitrogen-doped graphitized carbon/TiO₂ composite was fabricated and explored as support for the Pt catalyst. The composite support was constructed by carbonization of polypyrrole/TiO₂ using cobalt nitrate and nickel nitrate as graphitizing catalysts. The resulting catalyst shows enhanced electrocatalytic performance for methanol electrooxidation compared with the commercial Pt/C catalyst. The enhancement can be ascribed to combinatory effect of N-doped graphitized carbon and TiO₂, in which the tolerance to CO-poisoning and the intrinsic kinetics of methanol oxidation reaction were simultaneously improved by the bifunctional effect and the modification of the electronic structure. As a result, the as-developed nitrogen-doped graphitized carbon/TiO₂ composite present attractive advantages for the application in fuel cell electrocatalyst.     

A microwave-based method for the synthesis of carbon xerogel spheres

Carbon xerogel spheres with millimeter-scale diameters were synthesized by a simple process using microwave radiation as the heating source. Using this type of heating it is possible to establish the gelation point of different resorcinol–formaldehyde solutions and stop the gelation step of the material at the exact time of gelation. Organic gel spheres can then be directly obtained by stirring in a silicone bath at 80 °C. Finally, carbonization is performed to obtain carbon xerogels with a spherical shape. The size and porous texture of the spheres can be controlled by adjusting the synthesis conditions.     

Preparation of Pt/C electrocatalysts using an incipient precipitation method

Highly loaded and dispersed Pt/C catalysts, used as cathodic electrocatalysts in low temperature fuel cells, were prepared using a new method involving the slow addition of a Pt precursor to a solution containing dispersed carbon powder and a reducing agent. During this process, the added Pt precursor was reduced instantaneously into fine particles and adsorbed onto the carbon surface in the solution. A Pt loading of 55 wt% was obtained, which was close to the nominal amount of Pt, 60 wt%, added in the preparation step. The average particle size of Pt was about 4.2 nm, according to X-ray diffraction. The surface area of the Pt measured by cyclic voltammetry was about 61.4 m²/(g of Pt). The activity of the prepared Pt/C, as an electrode of polymer electrolyte membrane fuel cell, was increased by 34.8% and 15.0%, according to the half- and single-cell tests, respectively, compared to the activity of one prepared using a conventional precipitation method.     

乙二醇稳定的Pt/C催化剂的制备与表征

以乙二醇(EG)兼作溶剂和稳定剂,分别通过NaBH4和EG还原法制备了高度细化与分散的Pt/C催化剂,对其形貌、组成、结构和电化学活性比表面等进行了表征比较,并测试了它们对甲醇与乙醇电催化氧化的活性. 结果表明,2种催化剂中,Pt均为面心立方结构,粒径小且分布窄,在炭黑载体上分散均匀,单位质量Pt对甲醇与乙醇电催化氧化的活性相当;NaBH4还原法所制Pt/C催化剂中Pt0和Pt(220)晶面含量更高,Pt对甲醇与乙醇电催化氧化的峰电流密度分别为0.68与0.67 mA/cm2,分别是EG还原法所制Pt/C催化剂的1.2倍;2种催化剂对甲醇与乙醇电催化氧化的活性均与商品E-TEK催化剂相当.     

Alumina incorporated with mesoporous carbon as a novel support of Pt catalyst for asymmetric hydrogenation

Mesoporous carbon incorporated with different alumina contents has been prepared by chelate-assisted co-assembly method. These composites were used as supports for Pt particles, and the as-prepared catalysts were reduced at 873 K in hydrogen atmosphere. Our current study by using N₂ sorption, X-ray diffraction and transmission electron microscopy revealed that carbon incorporated with 10–15 wt% alumina was favorable for the high Pt dispersion and retained the mesostructure of carbon. Moreover, 15 wt% alumina-carbon composite supported Pt particles modified by cinchonidine afforded the highest (84.8%) enantiomeric excess and could be reused at least five times for the asymmetric hydrogenation of ethyl 2-oxo-4-phenylbutyrate in acetic acid.     

Morphology-dependent activity of Pt nanocatalysts for ethanol oxidation in acidic media: Nanowires versus nanoparticles

The morphology of nanostructured Pt catalysts is known to affect significantly the kinetics of various reactions. Herein, we report on a pronounced morphology effect in the electrooxidation of ethanol and carbon monoxide (CO) on Pt nanowires and nanoparticles in an acidic solution. The high resolution transmission electron microscopy analysis showed the inherent morphology difference between these two nanostructured catalysts. Voltammetric and chronoamperometric studies of the ethanol electrooxidation revealed that these nanowires had a higher catalytic activity by a factor of two relative to these nanoparticles. The rate for CO monolayer oxidation exhibits similar morphology-dependent behavior with a markedly enhanced rate on the Pt nanowires. In situ infrared reflection–absorption spectroscopy measurements revealed a different trend for chemisorbed CO formation and CO₂-to-acetic acid reaction product ratios on these two nanostructures. The morphology-induced change in catalytic activity and selectivity in ethanol electrocatalysis is discussed in detail.     

Electrocatalytic activity of Pt/C catalysts for methanol electrooxidation promoted by molybdovanadophosphoric acid

A Pt/C catalyst modified by the Keggin-structure molybdovanadophosphoric acid (PMV) is prepared by cyclic voltammetry and the modified Pt/C catalyst is studied for methanol electrooxidation. The results show that the PMV modified Pt/C catalyst has increased the electron transfer coefficient of the rate-determining step and diminished the adsorption of CO on Pt/C catalysts. Significant improvements in the catalytic activity and stability for methanol electrooxidation are observed, and it indicates that the PMV combined with Pt/C catalyst can be considered as a good electrocatalyst material for potential application in direct methanol fuel cells.     

二甲醚在Pt系催化剂上的电氧化行为初探

本实验用化学浸渍-还原法,甲醛为还原剂制备直接二甲醚燃料电池阳极催化剂。用循环伏安法和稳态极化法,采用粉末微电极技术,研究二甲醚在自制Pt／C、PtSn／C和PtRu／C催化剂上的氧化行为。研究结果显示,二甲醚在PtRu／C上有较佳的反应活性。在PtRu／C催化剂上考察温度对于二甲醚电氧化的催化活性的影响,得出温度的升高有利于二甲醚电氧化的进行。     

Pt0．55Co0．45合金应用不同的碳基体作为质子交换膜燃料电池阴极催化剂的研究

分别选用VulcanXC-72和双壁碳纳米管（DWCNTs）作为碳基体,采用化学还原法制备了20％的Pt0.5Co0．45／C催化剂。合成的材料Pt055co0.45／C采用XRD和TEM手段进行表征,电化学性能通过循环伏安（CV）和稳态技术进行了检测。电化学测试结果表明,Pr0.55Co0.45／DWCNTs对氧还砸催化性能优于Pt055C0045／VulcanXC-72,并HDWCNTs具有比VulcanXC．72更好的稳定性。这说明DWCNTs是比VulcanXC－72更有效地催化剂载体。