离子溅射沉积法制备Pt-TiO2／Ti催化剂及其性能研究

为了提高TiO2催化剂的光催化活性，拟对其进行改性研究，以阳极氧化法制备的TiO2用催化剂为基体，用离子溅射法将贵金属Pt沉积到TiO2用催化剂，利用SEM、EDS、XRD等测试技术对样品的形貌、元素组成、晶型等进行表征，以腐殖酸作为目标物质，对其光催化活性进行研究。研究结果表明，离子溅射法制备的Pt-TiO2用催化剂膜表面的Pt微粒呈现均匀单分散状态，与膜的附着力强，物相组成以锐钛矿TiO2为主，含少量金红石TiO2，光催化活性优于TiO2／Ti催化剂。     

Pt／TiO2纳米粒子的制备及其光催化性能研究

采用溶胶-凝胶法制备了掺杂Pt的TiO2粉末，利用紫外可见光谱对粉末的光吸收性能进行了表征，并分别在模拟日光和可见光下考察了其光催化氧化对．硝基苯酚的活性。结果表明，掺杂Pt以后TiO2粉末的光谱吸收范围被拓展至可见光，光催化活性也明显提高。在模拟日光照射下，以光催化活性较好的Pt／TiO2粉末为催化剂降解对．硝基苯酚，4h后对-硝基苯酚的转化率为93．7％，其反应是一级反应。     

反胶束法制备PEMFC用Pt-Ru／C催化剂

采用反胶柬法制备质子交换膜燃料电池（PEMFC）用Pt-Ru／C催化剂．反胶柬体系由环己烷、水、表面活性剂和正辛醇组成．研究了反胶束体系中水与表面活性剂的物质的量之比（ω）、不同类型的表面活性剂和不同还原剂等因素对Pt-Ru／c催化剂性能的影响．研究表明,采用SDS为表面活性剂,控制ω值在适宜的范围内,采用强还原剂KHB4,在室温下反应,可得到粒径小、分布均匀的Pt-Ru／c催化剂．透射电镜（TEM）测试结果表明,Pt—Ru粒子的平均粒径为3．1nm;X射线衍射（XRD）分析表明,Pt—Ru／c催化剂合金化程度高,相对结晶度为3．1;能量散射能谱（EDS）分析表明,形成的Pt和Ru的含量接近实验设定值在0．5mol／L的H2SO4以及与0．5mol／L的CH3OH混合溶液中的循环伏安测试结果表明,自制Pt—Ru／C催化剂与Johnson公司商品Pt—Ru／C催化剂的电化学性能相近。     

PEMFC膜电极电催化层的制备和性能

膜电极催化层的组成和电催化剂的活性对质子交换膜燃料电池的性能有很大影响．采用浸渍还原法制备出了Pt平均粒径为3．1nm的Pt／C催化剂．催化剂中Pt的粒径和在碳黑载体（VulcanXC-72）表面的分散程度采用透射电镜（TEM）进行测试．用Pt／C催化剂、适量的Nation溶液和PrFE乳液制备出质子交换膜燃料电池（PEMFc）膜电极的催化剂层，并研究了该催化剂层中PTFE含量对其性能的影响．实验表明，PTFE强烈的疏水性可以迫使部分水分向阳极反扩散，催化层中加入适量的PTFE可以使膜电极具有一定的水管理能力，在去掉辅助增湿系统的条件下具有良好的极化性能．     

单壁碳纳米管负载Pt基二元金属催化剂对甲醇和乙醇氧化的电催化性能研究

用单壁碳纳米管（SWCNT）作为载体制备得到Pt,Pt—Fe,Pt—Co和Pt—Ni催化剂,并用循环伏安法和电化学阻抗谱法研究各催化剂对甲醇和乙醇氧化的电化学催化性能。对于甲醇和乙醇的氧化,Pt—Fe／SWCNT,Pt—Co／SWCNT和Pt—Ni／SWCNT电催化活性依次增强,抗中毒性能依次减弱。与Pt／SWCNT催...     

Pt／C催化剂的制备及其对甲醇电催化氧化的研究

首次报道了以乙二胺四乙酸（EDTA）作为螯合剂,采用硼氢化钠还原氯铂酸制备Pt／C（Pt的质量分数为20％）纳米催化剂,TEM分析表明,通过改变反应的pH值可以获得分散度与粒径不同的Pt粒子,当pH=12．5时,Pt的分散度最高,平均粒径最小（3．2nm）。催化剂的退火处理研究表明,经270℃氮气氛围内退火后,其电催化活性有了显著提高。使用循环伏安法在甲醇的溶液中电催化氧化研究结果表明,在pH=12．5时制备的催化剂对甲醇的电催化氧化活性最高。     

炭载体孔径对Pt2Sn1/蠕虫孔炭催化剂乙醇电氧化活性的影响

分别以孔径为8.5nm、4.4nm和3.1nm的3种蠕虫孔炭WMC-F7、WMC-F30和WMC-F0为载体,合成了纳米Pt2Sn1/WMC催化剂。XRD与透射电镜结果表明3种载体上的催化剂平均粒径均为3.0nm,其电化学性能却相差很大。研究发现蠕虫孔炭载体的孔径显著影响Pt2Sn1催化剂的电化学性能:当载体孔径(Dp)大于2倍催化剂平均粒径(dPt)时,催化剂(即Pt2Sn1/WMC-F7)的电化学活性面积(ESA)和乙醇电氧化(EOR)活性均为最高;当以另外两种孔径的蠕虫孔炭作载体时,Pt2Sn1催化剂活性很差。这主要归因于WMC-F7的大孔径有利于传质,提高了催化剂的利用率及乙醇电氧化活性。     

MWNTs/Fe_2O_3的光催化性能及机理分析

以多壁碳纳米管(MWNTs)、氨水(NH_3·H_2O)和九水合硝酸铁[Fe(NO_3)_3·9H_2O]为原料,采用共沉淀法得到前驱体,经高温煅烧制得MWNTs/Fe_2O_3,利用XRD、TEM、UV-Vis和FT-IR等对其结构特性进行分析。以偏二甲肼废水为目标降解物评价了MWNTs/Fe_2O_3的光催化活性,并对光催化机理进行了分析。结果表明,MWNTs的引入可以改变氧化铁(Fe_2O_3)的晶型,同时使Fe_2O_3的粒径减小,并增加催化剂的吸附能力。另外,Fe—O—C化学键的形成使Fe_2O_3和MWNTs之间形成联合电子系统,有利于电子转移,电子-空穴对复合率有效降低。羟基自由基在MWNTs/Fe_2O_3光催化降解偏二甲肼过程中起主要作用。当pH值为7,MWNTs/Fe_2O_3用量为1.0g/L,光催化降解120min,对20mg/L的偏二甲肼的降解率可达98.1%,比相同条件下二氧化钛(TiO_2)的降解率高39.2%。     

纳米Pt粒子的微乳液法制备研究

在十六烷基三甲基溴化铵／正辛醇／水（CTAB／C8H17OH／H2O）微乳液中，选择合适的微乳液配比，水合肼为还原剂，常温下制得了粒径为6－8nm的Pt粒子，研究了微乳液的形成条件和水含量对Pt粒子粒径大小的影响，在不同温度下，以He为保护气体，热处理Pt粒了后表明：100摄氏度时，XRD峰中有表面活性剂CTAB存在，200摄氏度时未见杂质成分；温度升高到300摄氏度时，Pt粒子XRD峰变尖变窄，这意味着Pt粒子开始出现晶粒长大，为避免Pt粒子长大，控制一定的热处理温度是必要的。     

多壁碳纳米管填充丁苯橡胶复合材料的研究

采用浓硝酸(HNO3)氧化处理后的多壁碳纳米管(MWNTs)与丁苯橡胶(SBR)及其他配合剂在开炼机上进行混炼加工制备MWNTs／橡胶复合材料，并与炭黑补强橡胶体系进行对比，进而研究了MWNTs／橡胶复合材料的物理性能，并初步探讨了该材料微观结构与性能之间的关系。结果表明：随着MWNTs质量百分含量的增加，橡胶复合材料的力学性能也随之增高；MWNTs／橡胶复合材料的抗撕裂强度(25．9kN／m)、硬度(58)、磨耗(0．22mL/1．61km)性能较炭黑／橡胶体系要好。由MWNTs补强的橡胶对开发具有低滚动滞后性和抗疲劳损失的轮胎胎面胶将有很大的实用潜力。     

A novel multi-walled carbon nanotube (MWNT)-based nanocomposite for PEFC electrodes

A novel nanocomposite comprising MWNTs and mixed-conducting polymeric components (electronic and ionic) is prepared, characterized and investigated as a support for platinum (Pt). Nanocomposite of MWNTs and poly (3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT?CPSS) is prepared by in situ polymerization and characterized using Fourier?CTransform infrared spectroscopy (FT?CIR), thermogravimetric analysis (TGA) in conjunction with scanning electron microscopy (SEM). Atomic force microscopy (AFM) studies are also carried out to characterize the surface topography of MWNTs/PEDOT?CPSS nanocomposite. X-ray diffraction (XRD) studies reveal that MWNTs/PEDOT?CPSS nanocomposite provides better backbone for the improved dispersion of Pt as evidenced by the reduced Pt crystallite size over MWNTs/PEDOT?CPSS nanocomposite compared to MWNTs. Electrochemical characterization studies performed with Pt/nanocomposite and Pt/MWNTs demonstrate the superior catalytic activity of Pt/nanocomposite under reduced Nafion loadings in relation to Pt/MWNTs. It is observed that mixed conducting nanoporous network of MWNTs/PEDOT?CPSS composite structure promotes the catalytic activity of Pt by enhancing catalyst utilization.     

Design of an Assembly of Poly(benzimidazole), Carbon Nanotubes,and Pt Nanoparticles for a Fuel‐Cell Electrocatalyst with an Ideal Interfacial Nanostructure

A newly designed and fabricated novel nanocomposite composed of multiwalled carbon nanotubes (MWNTs), poly(benzimidazole) (PBI), and Pt nanoparticles. This composite is fabricated by the preparation of PBI‐wrapped MWNTs (MWNT/PBI), followed by Pt loading onto the MWNT/PBI. As a result of the PBI wrapping, the loading efficiency of the Pt nanoparticles onto the MWNTs is dramatically improved up to 58.8% compared to that of the pristine MWNTs (41.0%). The process also allows homogeneous Pt immobilization onto the surface of MWNTs without any strong oxidation process for the MWNTs that is typically used for metal supporting on carbon nanotubes. Far‐IR spectroscopy of the composite shows a peak from the Pt? N bonding, indicating that these improvements are derived from the coordination of the Pt ion with the PBI molecules. Cyclic voltammogram measurements reveal that the Pt nanoparticles deposited on the MWNT/PBI shows higher utilization efficiency (74%) for electrocatalysts compared to that on the pristine MWNT (39%).     

Pt/C催化剂制备及CO催化氧化性能研究

采用大气压介质阻挡放电辅助氢气热还原方法和氢气热还原方法制备Pt/C催化剂,考察了制备方法及Pt负载量对Pt/C催化性能的影响。采用X-射线衍射(XRD)、循环伏安法、CO催化氧化反应研究Pt/C催化剂的晶相结构、电催化性能和CO催化氧化活性。结果表明:大气压介质阻挡放电辅助氢气热还原所制备的样品具有更高的电化学活性和CO催化氧化活性。当Pt负载量在2%到10%之间变化时,Pt/C-PC催化活性随负载量增加而增加。XRD测试结果显示当Pt负载量为2%,5%和10%时,Pt粒径分别为:10.6 nm,9.1 nm和6.4 nm,说明采用等离子体辅助氢气热还原方法制备的Pt/C-PC催化剂,Pt负载量越大,Pt粒径越小,CO催化氧化活性更高。     

Electrochemical fabrication of polyaniline/multi-walled carbon nanotube composite films for electrooxidation of methanol

Polyaniline (PANI)/multi-walled carbon nanotubes (MWNTs) composite films were fabricated by electropolymerization of aniline containing well-dissolved MWNTs. The films can be used as catalyst supports for electro-oxidation of methanol. Cyclic voltammogram and Chronoamperogram results show that platinum particles deposited on PANI/MWNT composite films exhibit higher electrocatalytic activity towards methanol oxidation than that deposited on pure PANI films. The porous structure and electrical conductivity of PANI films has been significantly changed by introduction of MWNTs, higher surface areas of PANI/MWNT composites has been achieved therefore. It favors for platinum particles to be highly dispersed on the PANI/MWNT composite films and the better electrocatalytic activity of Pt/PANI/MWNT electrode is induced consequently.     

镁钼氧化物催化剂制备多壁纳米碳管的初步研究

采用溶胶-凝胶法合成了可用来催化裂解甲烷大量制备高质量和较高纯度的多壁纳米碳管的镁钼氧化物催化剂. 实验表明该催化剂具有较高的活性和催化效率, 反应2h后, 制备的多壁纳米碳管的量接近原始催化剂量的30倍. 并用透射电镜、高分辨透射电镜、激光拉曼和热重分析对制得的粗产品进行了表征, 结果表明: 碳管的直径在10～22nm之间, 且随着反应时间的延长, 制备的纳米碳管石墨化程度增加, 反应1h后, 粗产品中碳管含量达95%, 同时, 对催化剂的特殊催化生长机理作了讨论, 生长过程中多层Mo颗粒析出在MgO载体表面是碳管成束的主要原因.     

羟基锡酸盐载铂复合催化剂Pt/(Co,Zn)Sn(OH)6的合成及其甲醇电催化氧化性能

以羟基锡酸盐CoSn（OH）₆和ZnSn（OH）₆纳米空心立方体为前体,采用抗坏血酸作为弱还原剂,经过超声过程分别合成了羟基锡酸钴载Pt/CoSn（OH）₆和羟基锡酸锌载Pt/ZnSn（OH）₆复合催化剂,并在甲醇氧化反应（MOR）中表现出良好的性能。Pt/CoSn（OH）₆和Pt/ZnSn（OH）₆催化剂的单位质量活性分别为1 095.6 mA/mg和699.5 mA/mg,高于C载Pt（Pt/C）的594.6 mA/mg。利用XRD、SEM、TEM、XPS和电化学测试对催化剂晶体结构和性能间的关系进行了探索。CO溶出实验结果表明,羟基锡酸盐载体有利于Pt表面CO的去除,载体与Pt间的强相互作用和载体表面的大量羟基基团增强了催化剂的催化活性和CO抗毒性。此外,Pt/（Co,Zn）Sn（OH）₆催化剂中单质Pt高的相对含量也有利于提高MOR活性。通过研究载铂羟基锡酸盐电催化氧化甲醇性能,能够揭示载体结构对催化性能的影响,有助于羟基锡酸盐载铂复合催化剂在直接甲醇燃料电池（DMFCs）领域的应用。     

氧还原电催化剂Pt/WO3-C的制备及稳定性研究

采用化学沉淀法由HCl-Na₂WO₄制备WO₃-C复合载体, 通过微波辅助乙二醇还原法制备Pt/WO₃-C复合载体催化剂。研究了WO₃含量以及热处理温度对Pt/WO₃-C催化剂性能的影响, 采用X射线衍射、透射电子显微镜和能量散射光谱对Pt/WO₃-C的物化结构和组成进行了表征。结果表明, WO₃的最佳含量为10wt%, N₂气氛中热处理适宜温度为250℃。所制备的Pt/WO₃-C催化剂中WO₃以单斜晶型存在, Pt颗粒的平均粒径为2.77 nm。通过循环伏安法和单体质子交换膜燃料电池极化曲线测试了Pt/WO₃-C催化剂的电化学性能, 证实了Pt与WO₃之间存在协同催化作用, 与Pt/C催化剂相比, Pt/WO₃-C的催化活性和稳定性都有明显改善。     

Effect of Pt/alumina catalyst preparation method on sensing performance of thermoelectric hydrogen sensor

We fabricated three different Pt/alumina catalysts for micro-thermoelectric hydrogen sensor (micro-THS). In the three Pt/alumina catalysts, two were prepared by impregnation of a commercial alumina with an aqueous solution of platinum (IV) chloride pentahydrate, and the third was prepared by impregnation of commercial alumina and nano-Pt with isobornyl acetate solution. To fabricate the micro-THS, the three Pt/alumina catalysts were integrated on thin membrane of the micro-THS, and its hydrogen sensing properties were investigated. The micro-THS with nano-Pt loaded alumina catalyst showed better sensing performance than those with Pt/alumina catalysts prepared by an aqueous solution of platinum (IV) chloride pentahydrate, because of effectively dispersed nano-Pt metal grain on the surface alumina grain observed by TEM. Its voltage signal was 15.7 mV for hydrogen concentration of 1% in dry air at catalyst temperature of 100°C.     

Highly dense and uniformly dispersed platinum nanoparticles on poly(acrylic acid) modified multi-walled carbon nanotubes for methanol oxidation

Poly(acrylic acid) modified multi-walled carbon nanotubes (PAA-MWNTs) were synthesized through in situ radical polymerization in acetone and the PAA-MWNTs were used as supporting material for platinum nanoparticles. Platinum nanoparticles were deposited on the surface of PAA-MWNTs with high loading and high dispersion through ethylene glycol reduction. The size of Pt nanoparticles on PAA-MWNTs can be tuned by the water content in the reaction system and the loading amount can be adjusted by the mass ratio of H₂PtCl₆ to PAA-MWNTs. The electrocatalytic properties of the Pt/PAA-MWNTs catalyst were evaluated by methanol oxidation. The results of cyclic voltammetry show that the Pt/PAA-MWNTs composite possesses high electrocatalytic activity, good long-term stability and storage property, which can be attributed to the small particle size and high dispersion of Pt nanoparticles as well as the nature of MWNTs.     

Aged nano-structured platinum based catalyst: effect of chemical treatment on adsorption and catalytic activity

To examine the effect of chemical treatment on the adsorption and catalytic activity of nanostructured platinum based catalyst, the aged commercial Pt/AC catalyst was pretreated with sulfuric acid (H2SO4) and a cleaning agent (Hexane). Several reliable methods such as nitrogen adsorption, X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and inductively coupled plasma (ICP) were employed to characterize the aged Pt/AC catalyst and its chemically pretreated Pt/AC catalysts. The catalytic and adsorption activities of nano-structured heterogeneous Pt/AC catalyst were investigated on the basis of toluene oxidation and adsorption isotherm data. In addition, the adsorption isotherms of toluene were used to calculate the adsorption energy distribution functions for the parent catalyst and its pre-treated nano-structured Pt/AC catalysts. It was found that sulfuric acid aqueous treatment can enhance the catalytic performance of aged Pt/AC catalyst toward catalytic oxidation of toluene. It was also shown that a comparative analysis of the energy distribution functions for nano-structured Pt/AC catalysts as well as the pore size distribution provides valuable information about their structural and energetic heterogeneity.