Pt/C和Pt/CNTs电极的电化学稳定性研究

采用恒电位氧化法研究了Pt/C和Pt/CNTs电极的电化学稳定性. 相同条件下, Pt/C电极的氧化电流大约为Pt/CNTs电极的2倍; 120 h氧化后, Pt/C电极Pt的电化学表面积下降了21.3%, 而Pt/CNTs电极仅下降了7.6%, 表明Pt/CNTs电极性能衰减较慢. X射线光电子能谱(XPS)分析表明, Pt/C的载体碳黑表面氧增加量大于Pt/CNTs中碳纳米管(CNTs)表面氧的增加量, 说明碳黑的被氧化程度较高, 电化学稳定性差; Pt的表面化学状态没有发生变化; 碳纳米管本身的抗电化学氧化性也大于碳黑. 所以, 载体的被氧化程度不同是两种电极性能衰减不同的主要原因之一, 并且排除了Pt表面状态的影响.     

活性炭和石墨混合载体的Pt催化剂（Pt/CG）对乙醇氧化电催化活性的影响

用化学沉积法制备炭载Pt(Pt/C)和以活性炭与石墨作混合载体的Pt(Pt/CG)催化剂。实验结果表明，活性炭与石墨质量比影响Pt/CG催化剂对乙醇氧化的电催化活性。当活性炭与石墨的质量比为15∶1时，制得的Pt/CG催化剂对乙醇氧化的电催化活性最高。     

Electrochemical determination of the surface composition of Pd–Pt core–shell nanoparticles

Different amounts of Pt atoms were deposited onto the surface of Pd nanoparticles supported on carbon black by hydroquinone reduction method in anhydrous ethanol. Here, we surveyed electrochemical probing of surface compositions of Pd–Pt surface alloys. They were calculated from hydrogen desorption, carbon monoxide adlayer oxidation, and reduced carbon dioxide oxidation charges. The surface composition of Pt drastically increased up to Pt[0.3]/Pd/C (23.1 at.% of Pt) and then approached that of pure Pt with the moderate rate of increase.     

Controllable pt nanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells

We report a novel process to prepare well-dispersed Pt nanoparticles on CNTs. Pt nanoparticles, which were modified by the organic molecule triphenylphosphine, were deposited on multiwalled carbon nanotubes by the organic molecule, which acts as a cross linker. By manipulating the relative ratio of Pt nanoparticles and multiwalled carbon nanotubes in solution, Pt/CNT composites with different Pt content were achieved. The so-prepared Pt/CNT composite materials show higher electrocatalytic activity and better tolerance to poisoning species in methanol oxidation than the commercial E-TEK catalyst, which can be ascribed to the high dispersion of Pt nanoparticles on the multiwalled carbon nanotube surface.     

Supercritical,Freezing and Thermal Drying Process of Resorcinol‐Formaldehyde Polymer based Nano‐carbons and their Highly Loaded PtRu Anode Electrocatalyst for DMFC

The capillary condensation is affected by micropore and nanopore of catalyst layer on fuel cell. Due to limitation of sluggish mass transport and electrocatalytic activity, to retain the pore skeleton of carbon and metal nanoparticles are very significant for enhanced utilizations of pore structure in electrochemical reaction. Besides, thickness of electrocatalyst layer is very crucial due to one of the factor affected by cell performance of direct methanol fuel cell. Highly loaded four Pt?Ru anode catalysts supported on resorcinol‐formaldehyde (RF) polymer based on meso‐porous carbons (80 wt.% Pt?Ru/carbon cryogel, 80 wt.% Pt?Ru/carbon xerogel and 80 wt.% Pt?Ru/carbon aerogel) and conventional carbon (80 wt.% Pt?Ru/Vulcan XC‐72) were prepared by colloidal method for direct methanol fuel cell. These catalysts were characterized by X‐Ray diffraction (XRD), High resolution transmission electron microscopy (HR‐TEM) and X‐ray photoemission (XPS). The results of CO stripping voltammetry, cyclic voltammetry (CV) and single cell test performed on DMFC show that Pt?Ru/carbon cryogel and Pt?Ru/carbon aerogel exhibits better performances in comparison to Pt?Ru/carbon xerogel and Pt?Ru/Vulcan XC‐72. It is thus considered that particle size, oxidation state of metal and electrochemical active surface area of these catalysts are important role in electrocatalytic activity in DMFC.     

Preparation of Multiwall Carbon Nanotubes-supported High Loading Platinum for Vehicular PEMFC Application

Multiwall carbon nanotube-supported Pt （Pt/MWNTs） catalysts with high dispersion and high loading of Pt were prepared by chemical reduction method and the loading of Pt got to 40 wt%. The average diameter of Pt nanoparticles on MWNTs was about 3.5 nm. When the hydrogen and air were used as reactant gases for PEMFC, Pt/MWNTs catalysts showed significantly higher performance than the Pt/XC-72 （carbon black） catalysts.     

原子层沉积制备掺氮碳膜修饰的 Pt/CNTs 实现甲醇高效电催化氧化

甲醇燃料电池作为一种清洁、高效的能源转化形式广受关注. 贵金属 Pt 是甲醇燃料电池阳极催化剂不可缺少的活性组分, 但 Pt 价格昂贵, 易与 CO 等中间体强相互作用而中毒失活, 从而限制了甲醇燃料电池的广泛应用. 因此, 如何提高Pt 的利用率成为一个关键问题. 研究表明, 在碳材料载体中掺杂氮元素, 改变了载体本身的表面结构和电子性质, 有利于Pt 颗粒的成核和生长, 可获得尺寸小、分布均匀的 Pt 纳米颗粒, 能显著提升催化反应活性和 Pt 利用率. 然而, 传统的氮掺杂方法需要在高温、高压及氨气条件下进行, 增加了催化剂制备难度和成本.原子层沉积技术是逐层超薄沉积技术, 能够在原子级别精确控制膜的厚度, 既可制备尺度均一、高度可控的纳米粒子,也能实现材料表面的可控超薄修饰. 本课题组利用原子层沉积技术优势, 首先在碳纳米管表面沉积了直径 2 nm 左右的 Pt纳米颗粒, 然后在 Pt 纳米颗粒外表面超薄修饰聚酰亚胺膜, 通过后处理得到多孔掺氮碳膜修饰的 Pt/CNTs 催化剂. 碳膜的厚度可简单通过调控聚酰亚胺膜的沉积厚度来控制. 结果表明, 适当厚度的碳膜修饰 Pt/CNTs 催化剂可显著提升其甲醇电氧化性能, 电流密度可达商业 20% Pt/C 的 2.7 倍, 催化剂稳定性也显著改善. 然而碳膜修饰过厚会导致催化剂活性降低.通过计算催化剂电化学活性表面积发现, 超薄修饰碳膜后催化剂活性表面积有所降低, 这是由于碳膜的覆盖导致表面 Pt原子数减少. 修饰前后催化剂颗粒尺度变化不大, 推测催化剂活性的提高与形成了有利于催化反应的 Pt-碳膜界面有关.然而, 当碳膜修饰层过厚时, 会导致反应物分子难以扩散到 Pt 颗粒表面, 使催化剂活性降低. 预吸附单层 CO 溶出实验结果表明, 多孔掺氮碳膜超薄修饰 Pt/CNTs 催化剂后, CO 氧化峰的起始电位和峰值电位都向低电位处偏移, 这表明 Pt 表面吸附的 CO 在较低电位下即可被氧化, CO 更容易从 Pt 表面移除, 从而提高了催化剂的抗 CO 毒化能力. X 射线光电子能谱实验结果进一步表明, 经多孔掺氮碳膜修饰后, Pt 的 4f 电子向高结合能处偏移, 表明 Pt 原子周围的电子密度减小, 从而弱化了 Pt 对 CO 吸附的σ-π键反馈作用, 即减弱了 Pt 原子对 CO 的吸附, 这是导致掺氮碳膜修饰后催化剂活性及稳定性都大幅提高的原因.     

Synthesis and characterization of bimetallic Pt–Fe/polypyrrole–carbon catalyst as DMFC anode catalyst

A novel synthesis route, concerning in situ interfacial polymerization of pyrrole on carbon black and following co-deposition of Pt and Fe on polypyrrole–carbon support, is developed to prepare the bimetallic Pt–Fe/polypyrrole–carbon catalyst. In this synthesis process, ferrous precursor simultaneously functions as an oxidant for the polymerization of pyrrole. The Pt–Fe/polypyrrole–carbon catalyst shows improved catalytic activity towards methanol oxidation compared to commercial Pt/C catalyst, which may be of great potential in direct methanol fuel cells.     

Ordered mesoporous platinum@graphitic carbon embedded nanophase as a highly active, stable, and methanol-tolerant oxygen reduction electrocatalyst

Highly ordered mesoporous platinum@graphitic carbon (Pt@GC) composites with well-graphitized carbon frameworks and uniformly dispersed Pt nanoparticles embedded within the carbon pore walls have been rationally designed and synthesized. In this facile method, ordered mesoporous silica impregnated with a variable amount of Pt precursor is adopted as the hard template, followed by carbon deposition through a chemical vapor deposition (CVD) process with methane as a carbon precursor. During the CVD process, in situ reduction of Pt precursor, deposition of carbon, and graphitization can be integrated into a single step. The mesostructure, porosity and Pt content in the final mesoporous Pt@GC composites can be conveniently adjusted over a wide range by controlling the initial loading amount of Pt precursor and the CVD temperature and duration. The integration of high surface area, regular mesopores, graphitic nature of the carbon walls as well as highly dispersed and spatially embedded Pt nanoparticles in the mesoporous Pt@GC composites make them excellent as highly active, extremely stable, and methanol-tolerant electrocatalysts toward the oxygen reduction reaction (ORR). A systematic study by comparing the ORR performance among several carbon supported Pt electrocatalysts suggests the overwhelmingly better performance of the mesoporous Pt@GC composites. The structural, textural, and framework properties of the mesoporous Pt@GC composites are extensively studied and strongly related to their excellent ORR performance. These materials are highly promising for fuel cell applications and the synthesis method is quite applicable for constructing mesoporous graphitized carbon materials with various embedded nanophases.     

碳材料中多层次孔对负载铂电催化活性的影响

分别以商用碳黑XC-72、介孔碳CMK-5和含多层次孔的碳气凝胶HCA为载体, 微波法负载Pt纳米粒子, 在硫酸和甲醇溶液中进行循环伏安测试, 考察碳材料中多层次孔对其电催化活性的影响. 结果显示, Pt/HCA电极表现出较高的峰电流(7.5 mA·cm-2)和电化学活性面积(128.0 m2·g-1). 这可能是因为碳气凝胶具有连续但非周期性的介孔结构, 有利于Pt纳米粒子的分散以及反应物质的传质.     

甲烷部分氧化催化剂抗积碳性能的DFT研究

采用基于密度泛函理论(DFT)的量子力学计算方法,研究比较了甲烷部分氧化反应制合成气过程中Ni(111),Pt(111),NiPt(111),NiIr(111)面上的积碳情况.计算了对积碳过程有影响的三个反应过程:CH的裂解,C的生长,CO的生成.研究发现Pt的掺杂对积碳的形成有一定的抑制作用;Pt的抗积碳性能很好,碳的产生和生长都比较困难;掺杂Ir后NiIr催化剂的抗积碳效果明显,CH容易活化解离,产生的C会及时生成CO,不易累积长大,从而更好地达到了抗积碳的目的.     

Polymer-mediated synthesis of highly dispersed Pt nanoparticles on carbon black

A new method was developed to prepare highly dispersed Pt nanoparticles on carbon black to use as proton exchange membrane (PEM) fuel cell catalysts. This method involves using a polymer, poly(vinylpyrrolidone) (PVP), to prevent particle aggregation and thereby reduce nanoparticle sizes to achieve high dispersion. It was found that Pt nanoparticles mediated by PVP are smaller than those obtained without PVP and have a narrower size distribution. Well-dispersed Pt nanoparticles with metal loadings from 5 to 35 wt % were obtained on carbon black (Vulcan XC-72R). It was found that well-dispersed Pt nanoparticles on carbon black could be synthesized at a PVP monomers-to-Pt atoms ratio of 0.1 under our experimental conditions. Larger amounts of PVP did not produce smaller nanoparticles, but rather reduced the Pt mass loading on carbon black. The morphology of the Pt nanoparticles that were supported on carbon black was characterized with transmission electron microscopy and X-ray diffraction. Their active surface areas were determined using cyclic voltammetry in a sulfuric acid solution. High Pt dispersion was obtained for the catalysts synthesized with PVP mediation, even at Pt loadings up to 35 wt %. The catalysts prepared with PVP mediation generally showed larger active specific areas than did those prepared without PVP.     

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.     

层级多孔碳载铂催化剂的制备及可达性

层级多孔碳作为氧还原铂基催化剂载体的选择之一, 简单的旋转圆盘电极(RDE)验证此类催化剂具有较高的氧还原活性, 但几乎都缺少膜电极(MEA)性能验证, 实用性无法保证. 本文设计制备了基于聚苯胺的层级多孔碳（NHPC）载铂催化剂（Pt/NHPC850）, 研究了其氧还原活性、 MEA质子传输和氧传输特性. RDE测试研究表明, Pt/NHPC850催化剂在低I/C（离聚物与碳载体质量比）时的面积活性低于实心碳载铂催化剂（Pt/XC-72）, 但当I/C增大到与膜电极中一致时, 由于Nafion树脂对Pt催化剂的毒化作用增强, 其面积活性反而优于 Pt/XC-72. Pt/NHPC850催化剂的高Pt分散性及其优异的抗Nafion毒化性能, 使其在I/C为0.8时的质量活性为Pt/XC-72催化剂的1.34倍. MEA质子传输研究表明, 即使在高加湿条件下, Pt/NHPC850质子电阻率仍高达72.6 mΩ·cm², 为Pt/XC-72的3倍. Pt/NHPC850制备的膜电极极化曲线在500 mA/cm²电流密度下性能迅速下降, Pt/NHPC850的氧增益电压达到144.4 mV, 比Pt/XC-72高56.7 mV. 表明Pt/NHPC850膜电极的质子传输和氧传输性能较差. 对比Pt/NHPC850催化剂的RDE和MEA的测试结果, 说明以层级多孔碳为载体的铂碳催化剂虽然耐Nafion毒化能力提高, 但是质子和氧气的氧传输性较差, 此类层级多孔碳还需进一步优化其结构, 才有可能满足低铂质子交换膜燃料电池（PEMFC）的应用需求.     

High dispersion Pt nanoparticles using mesoporous carbon support for enhancing conversion efficiency of dye-sensitized solar cells

<正>Mesoporous carbon(MC) with surface area of 380 m~2/g was prepared and employed as the carbon support of Pt catalyst for counter electrode of dye-sensitized solar cells.Pt/MC samples containing 1 wt%Pt were prepared by reducing chloroplatinic acid on MC using wet impregnation.It was found that Pt nanoparticles were uniform in size and highly dispersed on MC supports.The average size of Pt nanoparticles is about 3.4 nm.Pt/MC electrodes were fabricated by coating Pt/MC samples on fluorine-doped tin oxide glass.The overall conversion efficiency of dye-sensitized solar cells with Pt/MC counter electrode is 6.62%,which is higher than that of the cells with conventional Pt counter electrode in the same conditions.     

非碱性条件下不同粒径的碳载体负载Pt催化剂上甘油的选择性氧化(英文)

采用浸渍法制备了不同粒径的活性炭负载的Pt催化剂,并运用扫描电镜、N2吸附-脱附、透射电镜和X射线衍射对催化剂进行了表征.结果表明,当活性炭载体的粒径从253.2?m下降至9.3?m时,其表面积或孔体积变化不大,Pt颗粒高度分散于载体表面,平均粒径为2.8～5.5nm.这些高度分散的Pt催化剂在非碱性条件下的甘油氧化反应中表现出较高的活性,且随着载体粒径的减小而明显提升.其中粒径为9.3?m的活性碳负载的Pt催化剂上,游离的甘油酸收率达到47.6%,且催化剂可以重复使用.     

Preparation and characterization of composite polyaniline materials for catalytic purposes

Composite film electrodes were prepared by open-circuit Pt deposition on polymeric PANI films that were electrosynthesized from aniline acid solutions with suspended carbon particles (CPs). Gold, nickel, and a Ni-based alloy, Nichrome, were used as substrates, and carbon particles, carbon nanotubes (CNT), and Vulcan XC-72R carbon black, suspended in the monomer acid solution, were incorporated into the film. Pt particles were dispersed on films grown on Ni-based substrates by deposition from a Pt(IV) acid solution at open circuit (OC). CNT trapped into the PANI films have a favorable influence on Pt dispersion. The novel composite electrodes showed significant catalytic activity for methanol oxidation.     

Remarkable support effect of SWNTs in Pt catalyst for methanol electrooxidation

Carbon nanotubes have been proposed as advanced metal catalyst support for electrocatalysis. In this work, different carbon support materials including single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs) and XC-72 carbon black, were compared in terms of their electrochemical properties using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The SWNTs is found to exhibit the highest accessible surface area in electrochemical reactions and the lowest charge transfer resistance at the SWNTs/electrolytes. These carbon materials are then loaded with varying amount of Pt by the electrodeposition technique to prepare carbon supported Pt catalysts. Electrochemical measurements of methanol oxidation reveal that the SWNTs supported Pt catalyst exhibits the highest mass activity (mA/mg-Pt). In comparison with Pt-XC-72 and Pt-MWNTs, the remarkably enhanced electrocatalytic activity of the Pt-SWNTs maybe attributed to a higher dispersion and utilization of the Pt particles, which are directly related to the electrochemical characteristics of SWNTs. The high concentration of oxygen-containing functional groups, high accessible surface area, low charge transfer resistance at the carbon/electrolyte interfaces can be important for the Pt dispersing and strong metal-support interaction in the Pt-SWNTs catalyst.     

A spontaneous combustion reaction for synthesizing Pt hollow capsules using colloidal carbon spheres as templates

Here we report a spontaneous combustion reaction in synthesizing Pt hollow capsules. In brief, Pt nanoparticles were loaded on the surface of colloidal carbon spheres by wet-chemical impregnation. When Pt-loaded carbon spheres were taken out of an argon-filled tube furnace at room temperature and exposed to air, they underwent spontaneous combustion. The internal carbon spheres templates were removed to leave nanostructured Pt hollow capsules. There are at least two critical conditions for the occurrence of the spontaneous combustion: the Pt particle size is below 5.8 nm, and the hydrogen content in the carbon spheres is above 2.570 wt %. Such a reaction is interesting for the preparation of metal hollow spheres and is also relevant with respect to removal of accumulated carbon on catalysts and for soot oxidation at room temperature.     

Preparation of Platinum Implanted Glassy Carbon Electrode and Electro-oxidation of Formic Acid and Formaldehyde

Electrocatalytic oxidation of small organic molecules has attracted considerable at-tentionin system of fuel celll-4. In this research field, Parsons4 pointed out that the electrodeswhich were prepared from non-noble substrates modified by excellent dispersal noblemetal particles and which still exhibited better catalytic activity should be studied. Ionimplantation is a technique with unique advantage and has been used in manyelectrochemical research fieldss'6. The present study is an at-tempt…