多壁纳米碳管空气电极的交流阻抗研究

研究了多壁纳米碳管、活性炭和石墨等空气电极的交流阻抗特性.结果表明,纳米碳管空气电极的阻抗谱由两个半圆组成,高频区半圆对应欧姆极化阻抗,低频区半圆对应电化学极化阻抗.催化剂Pt以纳米颗粒的形式沉积在碳管的外表面,明显减小了电极的欧姆阻抗和电化学极化阻抗,提高了氧还原反应的电催化活性.活性炭电极除存在电化学阻抗外,还存在薄液膜扩散阻抗(Nernst扩散),石墨电极形成的薄液膜反应区域较小,电极反应呈Warburg扩散阻抗特征,相应的电催化活性较低.采用交流阻抗等效电路分析方法,对拟合的动力学数据进行了解释.     

纳米碳管空气电极在氧还原反应中的电催化性能

电化学阻抗谱;纳米碳管空气电极在氧还原反应中的电催化性能     

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.     

氮/硫双杂化非贵金属碱性阴离子膜燃料电池阴极非铂催化剂

以吡咯和对甲苯磺酸(TsOH)作为碳载过渡金属催化剂的掺杂剂,经溶剂分散及600℃热处理制备了一种高效催化氧还原反应(ORR)的碳载双杂化过渡金属催化剂(Fe-N/C-TsOH-600).利用X射线衍射(XRD)和X射线光电子能谱(XPS)对催化剂的结构进行表征.运用旋转圆盘电极(RDE)技术研究了该催化剂在碱性介质中催化氧还原的电化学催化活性和稳定性,探讨了不同浓度甲醇溶液对Fe-N/C-TsOH-600催化剂催化氧还原活性的影响.结果表明,以Fe-N/C-TsOH-600制备的气体扩散电极在0.1 mol/L KOH电解质溶液中对氧具有很高的选择催化还原活性和稳定性.当电极经过4800圈循环伏安(CV)扫描测试后,催化剂催化氧还原的性能基本保持稳定,并以4电子途径将氧气催化还原.此外,研究还发现,Fe-N/C-TsOH-600在混有甲醇的碱性电解质溶液中对氧的催化还原选择性比商业Pt/C催化剂高.XPS结果表明,吡咯氮是催化剂高效催化氧还原的主要活性中心,提供氧还原的活性位,而TsOH作为供硫掺杂剂对提高催化剂的活性具有重要作用,其加入后形成的C—S—C有利于催化剂催化氧还原活性的提高,从而使该催化剂对氧还原表现出很好的电催化性能和选择性.     

耐甲醇碳载酞菁-铂纳米复合物催化电极

本文报导了一种H2Pc-Pt/C纳米复合物电化学催化剂,采用TEM、XRD、ICP对其组成与结构进行了表征. 在含有0.5 M甲醇的硫酸溶液中,H2Pc-Pt/C-Nafion?催化电极催化氧还原反应的起始电位比由商购Pt/C-JM与Nafion?制备的Pt/C-JM-Nafion?催化电极提高了200 mV,其催化氧还原反应的比活性是Pt/C-JM-Nafion?催化电极的7倍,表明其具有优良的耐醇性和对氧还原反应的高催化活性及良好的选择性. 不同于FePc,H2Pc与Nafion?在乙醇中不能形成可溶性配合物,H2Pc-Pt/C-Nafion?催化电极的耐醇性主要得益于H2Pc微晶的覆盖作用和H2Pc微晶/Pt边界上活性位点对氧还原反应的高催化活性及良好的选择性.     

碳载钴酞菁催化剂的一步法制备及其在碱性条件下对氧的电催化还原

通过固相加热,一步合成了以VulcanXC-72(碳黑)为载体的碳载钴酞菁(CoPc/C)复合催化剂,其可用作空气电极的氧还原催化剂。通过X射线衍射、红外光谱等测试技术对催化剂进行了表征。利用极化曲线和交流阻抗(EIS)方法测试了其在碱性介质(6mol/LKOH)中对氧还原的催化性能。结果显示,得到的产物为CoPc/C复合物,平均粒径30nm。以磷酸处理的碳黑为载体,在600℃下制备的CoPc/C复合催化剂表现出最佳的催化活性。以其制备的电极在空气气氛下-0.03V(Hg/HgO)电位时即可产生明显氧还原电流,-0.2V时电流密度达90×10-3A/cm2。     

石墨烯负载Pt催化剂的制备及催化氧还原性能

采用直接化学还原法, 以金属钠为还原剂, 四氯乙烯为碳源, 在石蜡油中不经氧化石墨(GO)和氧化石墨烯(GrO)而直接制备石墨烯(Gr), 然后将Pt纳米粒子担载在Gr基体上, 得到Pt/Gr催化剂, 并对其催化氧还原(OR)性能进行了研究. 通过X射线衍射(XRD), 透射电镜(TEM)和电化学测试对合成催化剂的结构、形貌和电化学性质进行了表征. 实验结果表明: 所制备的Pt/Gr催化剂具有较好的分散性, 平均粒径为3.1 nm; 氧还原起始电位比商业JM-Pt/C催化电极正移了24 mV; 交换电流密度达到1×10^-3 mA·cm^-2, 是商业JM-Pt/C催化电极的2.5倍.     

石墨烯负载Pt催化剂的制备及催化氧还原性能

采用直接化学还原法, 以金属钠为还原剂, 四氯乙烯为碳源, 在石蜡油中不经氧化石墨(GO)和氧化石墨烯(GrO)而直接制备石墨烯(Gr), 然后将Pt纳米粒子担载在Gr基体上, 得到Pt/Gr催化剂, 并对其催化氧还原(OR)性能进行了研究. 通过X射线衍射(XRD), 透射电镜(TEM)和电化学测试对合成催化剂的结构、形貌和电化学性质进行了表征. 实验结果表明: 所制备的Pt/Gr催化剂具有较好的分散性, 平均粒径为3.1 nm; 氧还原起始电位比商业JM-Pt/C催化电极正移了24 mV; 交换电流密度达到1×10^-3 mA·cm^-2, 是商业JM-Pt/C催化电极的2.5倍.     

钯纳米粒子在电极表面的制备及其对氧的催化还原

纳米微粒的体积效应使其成为表面纳米工程及功能化纳米结构材料制备的理想研究对象 [1～ 3] .纳米粒子具有独特的电子、催化及光学特性[4 ] ,近年来关于纳米粒子的制备及其在材料科学领域中的应用受到研究者的极大关注 .而贵金属纳米粒子由于其在催化领域中的广泛应用而成为最重要的研究对象之一[5,6 ] .电催化氧还原是一直为化学家瞩目的研究领域[7～ 9] .研究主要目的之一是寻找合适的氧电极反应催化剂 ,并使之能够应用于燃料电池中 .其中催化氧电极材料研究得最多的是贵金属 Pt[10 ,11] .贵金属 Pd对氧催化还原的研究工作很少 .我们首次…     

三种碳材料上原位电沉积AuPt合金的催化性能

在碳纸(CP)及涂覆了碳粉科琴黑(KB)或石墨烯纳米片(GNs)的碳纸上,原位电沉积了Au Pt合金,制备成CP/Au Pt、CP/KB/Au Pt、CP/GNs/Au Pt三种空气电极。对比研究发现,以石墨烯纳米片为载体的CP/GNs/Au Pt空气电极上,Au Pt合金载量高,颗粒分散均匀,粒径约为100 nm,Au和Pt的含量分别为78.84%(n/n)和21.16%(n/n)。在0.1 mol·L-1 KOH溶液中氧还原反应的起峰电势为0.93 V,催化活性和稳定性优于其他两种空气电极。分析认为,石墨烯纳米片具有高导电性、高比表面积以及较多的缺陷活性位点,有利于Au Pt合金在其上均匀电沉积且沉积载量较高,同时GNs本身具有一定的催化活性,两者能够产生协同催化作用,提高了CP/GNs/Au Pt电极的催化性能。     

纳米碳管作为氧扩散电极催化层第二相碳载体的电极特性

A novel gas diffusion electrode using binary carbon supports (carbon nanotubes and active carbon) as the catalyst layer was prepared. The electrochemical properties for oxygen reduction reaction (ORR) in alkaline electrolyte were investigated by polarization curves and electrochemical impedance spectroscopy. The results show that the binary-support electrode exhibits higher electrocatalytic activity than the single-support electrode, and the best performance is obtained when the mass ratio of carbon nanotubes and activated carbon is 50 ∶50. The results from their electrode kinetic parameters indicate that the introduction of carbon nanotubes as a secondary support provides high accessible surface area, good electronic conductivity and fast ORR kinetics. The electrocatalytic activity of binary-support electrodes is obviously improved by the deposition of Pt nanoparticles on carbon nanotubes, even at very low Pt loading (45.7 μg/cm2). In addition, the EIS analysis results show that the process of ORR may be controlled by diffusion of oxygen in the thin film for binary-support electrodes with or without Pt catalyst.     

Carbon nanotubes as a secondary support of a catalyst layer in a gas diffusion electrode for metal air batteries

In this paper, we report the use of binary carbon supports (carbon nanotubes (CNTs) and active carbon) as a catalyst layer for fabricating gas diffusion electrodes. The electrocatalytic properties for the oxygen reduction reaction (ORR) were evaluated by polarization curves and electrochemical impedance spectroscopy (EIS) in an alkaline electrolyte. The binary-support electrode exhibits better performance than the single-support electrode, and the best performance is obtained when the mass ratio of carbon nanotubes and active carbon is 50:50. The results from the electrode kinetic parameters indicate that the introduction of carbon nanotubes as a secondary support provides high accessible surface area, good electronic conductivity, and fast ORR kinetics. Furthermore, the effect of CNT support on the electrocatalytic properties of Pt nanoparticles for binary-support electrodes was also investigated by different loading-reduction methods. The electrocatalytic activity of the binary-support electrodes is improved dramatically by Pt loading on CNT carbon support, even at very low Pt loading. Additionally, the EIS analysis results indicate that the process of ORR may be controlled by diffusion of oxygen in the electrode thin film for binary-support electrodes with or without Pt catalyst.     

Electrochemical impedance analysis of methanol oxidation on carbon nanotube-supported Pt and Pt-Ru nanoparticles

Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are employed to investigate methanol oxidation reactions on single-walled carbon nanotube-supported platinum (Pt) and platinum–ruthenium (Pt-Ru) nanoparticles. EIS and CV measurements show consistent results: Pt catalyst supported on single-walled carbon nanotubes possesses higher catalytic activity for methanol oxidation than that on carbon black. Additionally, semicircles in the second quadrant of the Nyquist diagrams are observed for methanol oxidation on all types of catalytic nanoparticles when applying an electrical potential of 600 mV, which indicates the occurrence of negative resistance during electrocatalytic methanol oxidations. However, all impedance spectra show positive resistance at other electrode potentials (e.g., 300, 400, and 800 mV). Electrocatalytic characteristics of all catalysts are further analyzed by equivalent circuit simulations. We propose that intermediate coverage on the catalyst surface and subsequently the oscillation of nonlinear electrochemical methanol oxidations lead to the occurrence of negative resistance at 600 mV.     

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.     

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.     

高分散的介孔碳载Pt纳米粒子的制备及其对乙二醇的电催化氧化性能

以二氧化硅溶胶为硬模板,嵌段聚合物F127为软模板,通过双模板法合成了高介孔比例、窄孔径分布的介孔碳(MC).进而经乙二醇还原法制备了高分散的MC载铂催化剂(Pt/MC).采用循环伏安、计时电流、线性扫描伏安和电化学阻抗谱法研究了硫酸溶液中乙二醇在Pt/MC催化剂电极上的电化学氧化行为.实验结果表明,Pt/MC催化剂对乙二醇的电催化氧化性能显著高于商业化炭黑XC72R载Pt(Pt/XC72R)催化剂.电化学阻抗谱分析进一步揭示,乙二醇在Pt/MC催化剂电极上的电氧化反应具有较低的电荷传递电阻.Pt/MC催化剂高的电催化活性可以归结于MC大的孔径和均一的介孔结构对电子传输和传质的促进作用.     

反应pH值对微波法合成的Mo修饰的Pt/C催化剂结构和乙醇电氧化催化性能的影响

通过调节微波反应溶液的pH值合成了一系列Mo修饰的Pt/C催化剂并用于乙醇的电氧化催化反应.利用X射线衍射(XRD)、透射电子显微镜(TEM)及X射线光电子能谱(XPS)对催化剂的晶型结构、微观形貌、粒径尺寸和表面电子结构进行了表征,并采用循环伏安法(CV)、计时电流法(CA)和电化学阻抗谱(EIS)对催化剂的乙醇电氧化催化性能进行了测试.结果表明,碱性环境有利于催化剂组分在碳载体上的均匀分布,pH值为14时制得的催化剂组分颗粒尺寸最小,且分布最均匀.该催化剂不仅表现出了最大的有效电化学比表面积和最高的乙醇电氧化催化活性,而且具有最稳定的乙醇氧化催化性能.     

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。     

Porous phosphorus-rich CoP3/CoSnO2 hybrid nanocubes for high-performance Zn-air batteries

Porous metal phosphide cubes with exposed vertices and edges containing abundant catalytically active sites are promising electrocatalysts. Herein, by integrating the advantages of the phosphorus-rich cobalt phosphides and bimetallic oxides to form hybrid architectures, we prepared CoP_3/CoSnO_2 via phosphating CoSn(OH)_6 nanocubes, which has unique porous nanocubic structure. The optimized CoP_3/CoSnO_2 porous nanaocubes showed excellent electrocatalytic activity for OER/ORR. What's more, the electrochemical performances of CoP_3/CoSnO_2 porous nanaocubes as air cathode catalyst for zinc air batteries were better than that of commercial RuO_2 and 20 wt% Pt/C with a mass ratio of 1:1 as the air cathode catalyst. This work offers a new strategy to fabricate metal phosphide with porous nanocubic structures.