Pt/CNTs催化剂的微波法制备及其对甲醇电氧化的催化性能

为快速制备高分散Pt催化剂,首先对氯铂酸乙二醇溶液微波加热制备了Pt颗粒,然后将Pt颗粒吸附在碳纳米管(CNTs)表面,得到了Pt/CNTs系列催化剂.用X射线衍射(XRD)和透射电镜(TEM)考察了NaOH对催化剂颗粒大小和分散的影响,结果表明,NaOH有助于降低Pt颗粒尺寸和增加Pt颗粒分散稳定性,从而得到CNTs表面均匀分布的Pt催化剂.并对催化剂进行循环伏安扫描,结果表明,Pt/CNTs对甲醇电氧化活性较好.     

乙二胺改性石墨烯载铂催化剂的制备及其电解水制氢的研究

采用乙二胺对氧化石墨烯(GO)进行功能化改性,利用傅里叶变换全反射红外光谱 (ATR FT-IR)、X射线光电子能谱 (XPS) 和透射电镜 (TEM)等测试手段对氧化石墨烯功能化前后的结构进行了定性和定量分析,结果表明功能化石墨烯(FG)中成功的引入了乙二胺。利用功能化石墨烯作为催化剂载体,制备了功能化石墨烯载铂催化剂(Pt/RFG),与商业碳载铂催化剂(Pt/C)进行对比,结果发现铂颗粒在RFG上具有良好的分散性,且平均粒径较小。将这两种催化剂样品分别与全氟磺酸树脂混合制成膜电极,应用于固体聚合物电解水制氢技术,测试其电解去离子水时的电流密度及产氢速率,其中含有Pt/RFG的膜电极电解效率较高,产氢速率可达到2.96 mL/(min·cm²)。     

光电催化中Pt／C阴极催化剂的制备与表征

采用浸渍法制备了阴极Pt/C催化剂,用XRD和TEM对催化剂中铂晶粒大小及分布进行了表征,并考察了载体的预处理、pH值、还原剂和稳定剂的用量对Pt/C催化剂活性的影响,又考察了不同载铂量的催化剂对苯酚降解效果的影响.结果表明:以未处理的导电碳黑作载体,较适宜的制备条件为70℃、0.3g稳定剂、9 mL甲醛和中性介质,铂质量分数为1.0%的Pt/C催化剂的催化活性最好,平均粒径约5.0 nm且分布均匀.     

含氧复合型Pt/C催化剂的制备、表征及其对甲醇电氧化催化性能的研究

利用亚锡酸对氯铂酸的弱的多步骤还原制备新型Pt/C催化剂. 用XRD、HRTEM、EDS、DSC以及氢吸附电化学对所制备的催化剂进行了表征,并用循环伏安和恒电位极化对其进行了甲醇电氧化催化活性测定. 实验结果表明,应用亚锡酸法合成的Pt/C催化剂具有很高的甲醇电氧化催化活性,在0.5V (SCE)电位下,其质量活性约为亚硫酸路线合成的Pt/C催化剂的2倍. 亚锡酸法可在纳米尺度范围内生成金属Pt和Pt氧化物共存的复合型碳载催化剂,这种含氧复合型催化剂可以促进Pt在甲醇电氧化过程中双功能作用的有效协调.     

燃料电池高活性Pt/C电催化剂的制备

实现低铂（Pt）载量高催化活性碳载铂（Pt/C）催化剂的制备，是达到降本增效的有效手段.实验研究了乙二醇溶液（EG）、甲醛溶液（HCHO）以及碱液（NaOH溶液）三者用量比例和后续热处理对水热法制备Pt/C催化剂电催化性能的影响.采用极化曲线（LSV）和循环伏安曲线（CV）表征催化剂的电催化性能，以及计算了Pt的电化学活性面积（ECA）.通过X射线衍射（XRD）、透射电子显微镜（TEM）以及热重分析（TG）对催化剂进行物化性能表征.实验发现：在一定范围内适当提高HCHO占比可有效提升催化剂电催化性能，当V（EG）∶V（HCHO）∶V（NaOH）溶液体积比为1∶2∶1时，所制备的Pt/C催化剂经过250℃的后续热处理后，电催化性能最优.以该方法制备的低载量Pt/C催化剂的ECA大于高载量的商业Pt/C催化剂的ECA.     

Pt/PPy-C电极催化剂的制备及其耐久性研究

为研究聚吡咯(PPy)–C复合担载Pt(Pt/PPy-C)质子交换膜燃料电池催化剂性能。采用循环伏安电化学法(CV)、单电池极化法、加速耐久性测试法、傅里叶变换红外光谱(FT-IR)、X线衍射仪(XRD)和扫描电子显微镜(SEM)表征催化剂的微观结构、导电性及电化学性能。结果表明:通过掺杂阴离子可显著改变PPy-C的电导率,亲核性较大的氟硼酸掺杂制备的PPy-C电导率(8.65 S/cm)明显高于草酸掺杂的PPy-C电导率(4.01 S/cm);以PPy-C为载体担载Pt催化剂的电化学活性面积高于Pt/C催化剂,可达57.8 m~2/g;Pt/PPy-C电化学活性表面积及电池性能的衰减率都低于传统Pt/C催化剂。     

质子交换膜燃料电池Pt/C电催化剂的制备研究

采用浸渍还原法 ,用H2 [PtCl6]制备了高分散的纳米级碳载铂 (Pt/C)电催化剂 .探讨了搅拌方式、H2 [PtCl6]浓度、反应温度、碳的热处理等因素对电催化剂性能的影响 .得到了较适宜的制备工艺 .     

Pt/C催化剂基底的制备及乙醇电催化氧化研究

采用超声波分散与化学还原法结合,以氯铂酸为前驱体,石墨为载体制备了Pt/C(含Pt质量分数为5%)催化剂基底,通过XRD和循环伏安法进行了表征,并以乙醇电化学氧化为探针反应,对所得Pt/C基底的催化性能进行评价,研究了不同焙烧、还原温度及分散介质中醇/水比等因素对Pt/C基底催化活性的影响.结果表明,采用乙二醇与水体积比为2∶1作为分散介质,于空气中400℃焙烧后得到的Pt/C基底具有铂多晶的特征伏安曲线,对乙醇的电化学氧化具有较好的催化活性,说明所制备的Pt/C基底与铂多晶表面相似,完全可以替代纯金属铂,从而可进一步制备成本较低、活性组分少、催化活性高的铂基双金属表面修饰电极催化剂(另文报道).     

固相反应制备的Pt/C对甲酸氧化的电催化活性

研究了用固相反应法制备的碳载Pt(Pt／C(s))催化剂对甲酸氧化的电催化活性．XRD和TEM的测量表明，Pt／C(s)催化剂中Pt的平均粒径和结晶度远小于用传统的液相反应法制备的碳载Pt(Pt／C(1))催化剂，因此，Pt／C(s)催化剂对甲酸氧化的电催化活性远高于Pt／C(1)催化剂．     

化学镀法制备Pt/Au-PAN催化电极及其催化氧化甲醇性能研究

利用静电纺丝和化学镀技术相结合的方法,制备出镀金聚丙烯腈杂化纤维膜Au-PAN,然后以此为载体,再利用化学镀法在该膜的表面镀上一层铂纳米粒子,从而构建出催化电极Pt/Au-PAN.为了比较,在相同条件下将商用Pt/C滴涂到Au-PAN基底上构建催化电极Pt/C/Au-PAN.采用SEM、TEM和XRD对催化电极结构表征,并研究其催化氧化甲醇的性能.结果表明:用化学镀法制备的Pt/Au-PAN电极对甲醇的电化学氧化活性和稳定性都明显优于商用铂碳催化剂.     

Pt/CeO2-CNTs和Pt/CNTs在H2SO4和NaOH中乙醇电氧化活性及循环稳定性研究

为考察pH和CeO2对Pt催化剂乙醇电氧化活性的影响,用循环伏安法比较了Pt/CNTs及Pt/CeO2-CNTs在NaOH和H2SO4介质中的电化学行为,表明催化剂在NaOH介质中活性高于在H2SO4中活性,Pt/CeO2-CNTs活性高于Pt/CNTs活性.因Pt催化剂上乙醇电氧化反应的tafel斜率接近,故活性不同可归于影响交换电流密度的OHad浓度的差别.NaOH中Pt表面OHad吸附起始电位和乙醇电氧化起始电位分别低于H2SO4中起始电位,表明OHad决定着Pt催化剂的乙醇电氧化活性.加速耐久性实验表明,CeO2可改善Pt/CNTs的循环稳定性,Pt/CeO2-CNTs和Pt/CNTs在H2SO4中稳定性优于在NaOH中稳定性.     

Pt/CeO2-CNTs和Pt/CNTs在H2SO4和NaOH中乙醇电氧化活性及循环稳定性研究

为考察pH和CeO2对Pt催化剂乙醇电氧化活性的影响,用循环伏安法比较了Pt/CNTs及Pt/CeO2-CNTs在NaOH和H2SO4介质中的电化学行为,表明催化剂在NaOH介质中活性高于在H2SO4中活性,Pt/CeO2-CNTs活性高于Pt/CNTs活性.因Pt催化剂上乙醇电氧化反应的tafel斜率接近,故活性不同可归于影响交换电流密度的OHad浓度的差别.NaOH中Pt表面OHad吸附起始电位和乙醇电氧化起始电位分别低于H2SO4中起始电位,表明OHad决定着Pt催化剂的乙醇电氧化活性.加速耐久性实验表明,CeO2可改善Pt/CNTs的循环稳定性,Pt/CeO2-CNTs和Pt/CNTs在H2SO4中稳定性优于在NaOH中稳定性.     

Chemically Synthesised Pt Particles on Surface Oxidized Carbon Nanotubes as an Effective Catalyst for Direct Methanol Fuel Cell

1 Results The synthesis, physical characterization and electrochemical analysis of Pt particles prepared using the surface oxidized carbon nanotubes prepared by chemically anchoring Pt onto the surface of the CNTs with 2.0 mol/L HNO3 by refluxing for 10 h to introduce surface functional groups.The particles of Pt are synthesized by reduction with sodium borohydride of H2PtCl6. The electro-oxidation of liquid methanol of this catalyst as a thin layer on glassy carbon electrode is investigated at room te...     

原位法制取碳纳米管/尼龙6复合材料

为改善尼龙 6 (PA6 )的力学性能 ,加入碳 nm管(CNTs)与之复合 ,制作 CNTs/ PA6复合材料 ,以提高基体PA6的力学性能 ,特别是抗拉强度。通过采用原位法复合CNTs与 PA6 ,获得了由 OC C化学键连接的、理想的CNTs/ PA6界面的、且 CNTs在基体 PA6中分散均匀的CNTs/ PA6复合材料 ,其抗拉强度有较大幅度的提高 ,同时还保持较高的冲击韧性和延伸率。经检测 ,CNTs/ PA6复合材料的断裂界面不象其它纤维增强 PA6复合材料那样在纤维 / PA6界面上 ,而是在 PA6包裹层与 PA6基体界面上。研究结果表明 ,采用原位复合法 ,CNTs能够对 PA6基体起到很好的增强作用     

Microst ructure andflexural properties of carbon/ca rbon composite with in-situ grown carbon nanotube as secondary reinforcement

Carbon nanotubes (CNTs) were in-situ grown in carbon felts using ferric chloride as catalyst and natural gas as carbon precursor via thermal gradient chemical vapor infiltration (TGCVI). Subsequently, the carbon felts were densified to obtain CNT reinforced carbon/carbon (C/C) composites in the same furnace. Effects of CNTs on the microstructure and flexural property of C/C composites were investigated by polarized light microscopy, Raman spectroscopy, scanning electron microscopy and universal mechanical testing machine. The results of PLM observation and Raman analysis showed that CNTs have two-sided effects on the microstructure of pyrocarbon: the pyrocarbons in the region without CNTs show medium texture; while, in the region full of CNTs, the microstructure was low-textured or even isotropic though the TGCVD conditions would lead to the deposition of pure low texture pyrocarbons. Analysis based on stress-strain curves demonstrated that the flexural strength increased first and then decreased with the CNT content increasing. When the CNT content was 5.23 wt%, the flexural strength was maximum and had a nearly 35% improvement compared with pure C/C composite. Besides, after adding CNTs, the flexural modulus of the composites decreased and the ductility increased obviously, indicating CNTs can toughen C/C composites.     

导电高分子聚苯胺载铂电极的交流阻抗测定

利用循环伏安方法电聚合导电高分子聚苯胺.用于在直接甲醇燃料电池电极中负载催化剂Pt.聚苯胺载Pt电极(Pt/PAni/C)的制备,提高了Pt的分散度,增加了Pt在电催化体系中的利用率.交流阻抗测试结果表明:Pt/PAni/C与直接碳载Pt电极(Pt/C)相比,电化学反应电阻减小,催化活性增高.通过比较Pt/PAni/C与Pt/C对甲醇的电催化氧化活性可知,Pt/PAni/C电极催化氧化甲醇的最大电流为50.7mA/cm2,是Pt/C电极最大氧化电流(7.6mA/cm2)的6.67倍.     

硫辅助填充高压Fe5C2/Fe7C3单晶相的碳纳米管研究

硫可以用作生长促进剂制备具有不同形态的碳纳米结构, 例如: Y型和海胆状结构, 单壁碳纳米管(SWCNTs), 双壁碳纳米管薄膜等. 此外, 研究表明低浓度的硫和低气体流量可实现碳纳米管中高压Fe7C3和Fe5C2相晶体的填充. 然而, 碳纳米管中高压相的填充条件以及连续垂直取向的碳纳米管薄膜的合成和形貌控制的条件尚需进一步研究. 本文采用化学气相沉积(CVD),使用硫和二茂铁的混合物作为生长促进剂和碳源, 在氩(Ar)气环境中将Si/SiO2基底作为局部生长区域, 实现了在碳纳米管内填充碳化铁相, 并通过对所得碳结构进行详细表征, 揭示填充的碳化物相(Fe5C2和Fe7C3)之间可能存在结合, 这些结果在磁数据存储方面将有潜在应用.     

Synthesis of carbon nanotube arrays using ethanol in porous anodic aluminum oxide template

Carbon nanotube (CNT) arrays confined by porous anodic aluminum oxide (AAO) template were synthesized using ethanol as reactant carbon source at low pressure. Images by scanning electron microscope (SEM) and low magnification transmission electron microscopy (TEM) show that these CNTs have highly uniform outer diameter and length, absolutely controlled by the diameter and depth of nano-channel arrays of the AAO. High resolution transmission electron microscopy (HRTEM) imaging indicates that the graphitization of the CNT walls is better than the results reported on this kind of template-based CNT arrays, although it is not so good as that of multiwalled carbon nanotubes (MWCNTs) synthesized by catalysis. CNTs synthesized using acetylene as reactant gas show much less graphitization than those prepared using ethanol by comparing the results of HRTEM and Raman spectroscopy. The etchingeffects of decomposed OH radicals on the amorphous carbon and the roughness of AAO nano-channel arrays on the CNTs growth were employed to explain the graphitization and growth of the CNTs.     

Pyrolysis of Iron(III) porphyrin coated Pt/C toward oxygen reduction reaction in acidic medium

Design and synthesis of highly active and durable electrocatalysts toward oxygen reduction reaction (ORR) is of particular importance for proton exchange membrane fuel cells (PEMFCs), yet remains a grand challenge. Herein, we report the deposition of iron (III) porphyrin (FeP) on house-made Pt/C by rotary evaporation of the mixture of FeP and house-made Pt/C dispersed in chloroform, followed by pyrolysis at 650 °C in argon atmosphere. This approach led to the synthesis of new non-precious metal electrocatalyst (NPME)-Pt/C composites (Pt/C–FeP) with an average nanoparticle diameter of 3.1 ± 1.5 nm without aggregation. According to X-ray photoelectron spectroscopy (XPS), the binding energy of Pt 4f_7/2 became larger due to the presence of pyrolyzed FeP. In addition, the electrochemically active surface area (ECSA) of Pt/C–FeP-650 is 65 m²/g less than that of house-made Pt/C (80.2 m²/g). This implies that the pyrolyzed FeP may have partially covered the surface of Pt nanoparticles and thus lowering the ECSA. Interestingly, the mass activity (MA) of Pt/C–FeP turns out to be 349.0 mA/mg_Pt @0.9 V vs. RHE, which is 2.6 times and 1.5 times of house-made Pt/C and commercial Pt/C, respectively. It is speculated that the electronic interaction and possible synergy between Pt and pyrolyzed FeP as NPME might have contributed to the ORR activity improvement despite of partial loss of ECSA. During accelerated durability tests (ADTs), the MA of Pt/C–FeP-650 degrades 64.3% inferior to commercial Pt/C (52.2%). The main reason likely arises from the degradation of pyrolyzed FeP, which is a bottleneck problem confronting NPMEs.