核壳型铂基燃料电池催化剂制备方法与微结构控制综述

目前催化剂是制约燃料电池走向市场的关键,限制了燃料电池发展及大规模商业应用,寻求能够同时降低催化剂成本和提高催化剂性能的有效方法十分迫切。具有核壳结构的Pt-M催化剂不仅可以降低贵金属铂的用量,而且能显著提高催化活性。本文总结了近20年来核壳型Pt-M催化剂的主要制备方法,包括晶种法、去合金法、电化学沉积法等;重点分析非贵金属-铂核壳结构(M@Pt,M=Ni、Co、Cu、Fe等)的制备途径,总结了每种方法的特点。另外,还讨论了核壳结构在纳米层次上的精细控制和设计方案,这有助于理解核壳结构对电化学催化动力学的作用规律,更好地设计开发新型催化剂。     

燃料电池低Pt核壳结构催化剂的最新研究进展

传统的Pt/C催化剂,由于仅仅是处于纳米粒子表层的Pt原子参与电催化反应,而大多数位于粒子内层的Pt却未能得到有效利用,由此造成燃料电池成本高昂,阻碍了它的大规模商业化进程。核壳结构催化剂是近年来出现的一类极其重要的低Pt催化剂,这类催化剂是使用廉价贵金属、过渡金属、合金及导电化合物的纳米粒子作为核,在其表面覆盖一个原子层厚度或者几个原子层厚度的Pt为壳层而制得的新型高性能催化剂。核壳结构低Pt催化剂可大幅度降低燃料电池的贵金属Pt的使用量,进而降低燃料电池的成本,是实现质子交换膜燃料电池大规模商业化的希望所在。有关核壳结构低Pt催化剂的研究已成为燃料电池领域最热门的研究课题之一。综述了近年来低Pt核壳结构催化剂的研究进展,包括低Pt核壳结构催化剂制备技术的研究进展,以廉价贵金属、合金及导电化合物纳米粒子作为核的低Pt核壳结构催化剂的设计、制备及其相关研究情况。介绍了不同类型的核与Pt壳层之间的相互作用,讨论和总结了影响低Pt核壳结构催化剂电催化活性的相关因素,并对低Pt核壳结构催化剂的研究及其应用进行了展望。     

核-壳结构纳米复合材料在脱硝中的应用

核-壳结构纳米复合材料基于壳对核的有效保护和核壳之间的相互作用而表现出优异的脱硝活性和抗毒性。从核-壳催化剂的制备方法及核壳组成对脱硝活性的影响进行了总结和讨论。采用化学沉积法、自组装法和水热法等制备方法,以TiO_2、CeO_2和Fe-ZSM-5分子筛等为壳结构时,能有效阻止SO_2对活性中心原子的毒化作用,从而提高脱硝催化剂的抗硫性。通过优化成核的活性组分和成壳的物质,有望制备出具有高活性和高稳定性的核-壳脱硝催化剂。     

纳米二氧化铈制备和应用研究进展

目的 通过比较各类纳米二氧化铈制备方法的优缺点,总结纳米二氧化铈在食品生物化学检测、催化与燃料电池等领域的应用研究,以促进纳米CeO2的发展,并为其应用提供参考.方法 对比分析纳米二氧化铈的制备方法,包括水热合成法、沉淀法、溶剂热法、溶胶-凝胶法、微乳液法和电化学沉积法.阐述纳米CeO2在催化(催化甲苯、CO和NOx、光催化)、食品生物化学检测(抗坏血酸、葡萄糖、黄嘌呤检测等)、燃料电池、食品包装等领域中的应用.结果 通常采用水热合成法制备纳米CeO2.纳米CeO2负载贵金属可制备生物检测催化剂及燃料电池阳极催化剂;纳米CeO2复合金属氧化物可用于制备抗紫外功能的食品包装.结论 纳米CeO2在食品生物化学检测、催化与燃料电池等领域有广阔的研究空间.     

改性碳纳米材料在低温燃料电池中的应用

碳纳米材料(如炭黑、介孔碳、碳纳米管、石墨烯、碳纳米纤维、碳纳米角等)因其优异的电学性能和结构特性(良好的导电性能和超大的比表面积),被研究者广泛用作低温燃料电池贵金属催化剂的载体.然而,作为催化剂载体的这类碳纳米材料通常都存在电化学腐蚀的问题,碳载体的腐蚀通常会导致贵金属纳米催化剂的聚集,这将使催化剂的性能降低.为了改善碳载体的抗腐蚀性能,提高金属纳米粒子的活性和稳定性,许多研究工作致力于制备特殊结构的碳纳米材料,或对碳纳米材料进行表面修饰、掺杂等.与此同时,为了取代价格昂贵的贵金属催化剂,非贵金属催化剂的研究也成为一大热点,掺杂碳纳米材料就是研究热点之一.对近几年来围绕碳纳米材料制备、改性,以及这些改性碳纳米材料作为金属纳米粒子载体等的研究工作做了较为详细的综述,同时介绍了掺杂碳纳米材料作为氧还原催化剂的研究进展.     

氮硫共掺杂碳材料均匀担载核壳纳米颗粒Co@Co9S8作为氧还原催化剂的研究

开发高效、稳定的非贵金属氧还原(ORR)催化剂是促进燃料电池商业化进程的关键。通过树脂衍生N、S共掺杂碳材料负载原位生成的Co@Co₉S₈核壳结构纳米颗粒，制备出一种具有良好活性和稳定的非贵金属催化剂Co@Co₉S₈/NSC。电化学测试结果表明：Co@Co₉S₈/NSC催化剂的半波电位(E_1/2)和极限电流密度可与商业Pt/C催化剂相媲美。同时相较商业Pt/C催化剂，其还具有极好的抗甲醇活性。此外，计时电流测试表明：持续老化10000s后，Co@Co₉S₈/NSC的电流密度保持了初始值的97.5%,远低于商业Pt/C催化剂的23.3%。为构建高活性高稳定性核壳结构ORR催化剂提供了新的思路，同时其思路也可以应用于其他新能源电极材料如Li-空气电池、Li-S电池及超级电容器等。     

碳纳米管沉积铂和钌对PEMFC抗CO中毒能力的影响

通过催化裂解法制备了碳纳米管,对其进行氧化处理后,在其表面沉积了分布均匀、尺寸呈纳米级的铂和铂/钌颗粒.实验结果表明,当采用碳纳米管沉积铂为催化剂时,质子交换膜燃料电池的催化剂铂很容易受CO的毒化而失去活性,从而使电池的电压随电流密度的降低而迅速降低;当采用碳纳米管沉积铂/钌为催化剂时,钌能够使铂表面吸附的CO被氧化为CO₂,增加催化剂对CO的抵抗能力,使燃料电池的性能提高.     

美研制出新型氢燃料电池催化剂

美国研究人员日前开发出一种不需要使用贵金属铂的新型氢燃料电池催化剂,有望解决燃料电池推广过程中的一个主要障碍。据4月22日出版的美国新一期《科学》杂志报道,美国洛斯阿拉莫斯国家实验室和橡树岭国家实验室开发的催化剂通过加热聚苯胺、铁、钴盐生成,几乎与铂催化剂一样有效耐用。通常情况下,由非贵金属制备的类似催化剂     

Co修饰的碳载Pt纳米粒子催化剂的制备与表征

质子交换膜燃料电池阴极需要使用高活性的电催化剂来加速氧还原反应(ORR)速率,而提高活性成分贵金属铂(Pt)的功能反应利用率可解决其关键问题.本工作利用过渡金属钴Co(Ⅱ)?有机框架(Co?MOF)为前驱体合成ORR催化剂载体Co/C,并采取浸渍?液相还原法负载Pt纳米粒子制备了合金Pt?Co/C催化剂.通过对样品的孔隙结构、物相结构、微观形貌等表征,证实了载体Co/C具有较大的比表面积和相互连通的分级介孔结构,其独特的形貌、丰富的孔隙结构使负载的Pt纳米颗粒均匀分布、粒径范围窄,平均粒径约为6.8 nm.进一步对催化剂进行电化学性能评价,其电化学活性表面积(ECSA)接近于商用Pt/C催化剂的值,结果表明合金催化剂中活性成分Pt具有较高的利用率,同时还表现出载体独特的孔隙结构优势.     

磁响应性贵金属核/壳纳米复合粒子制备研究进展

磁响应的贵金属核/壳结构复合纳米粒子具有不同于单组分纳米粒子更优越的多重功能,在催化剂、光学材料、生物传感器及生物医学领域具有重要前景。从核/壳结构类型出发,综述了具有磁响应的贵金属核/壳结构纳米复合粒子的化学制备与结构特征,并简要对其应用研究进展做了讨论。     

Selective catalysts for the hydrogen oxidation and oxygen reduction reactions by patterning of platinum with calix[4]arene molecules

The design of new catalysts for polymer electrolyte membrane fuel cells must be guided by two equally important fundamental principles: optimization of their catalytic behaviour as well as the long-term stability of the metal catalysts and supports in hostile electrochemical environments. The methods used to improve catalytic activity are diverse, ranging from the alloying and de-alloying of platinum to the synthesis of platinum core-shell catalysts. However, methods to improve the stability of the carbon supports and catalyst nanoparticles are limited, especially during shutdown (when hydrogen is purged from the anode by air) and startup (when air is purged from the anode by hydrogen) conditions when the cathode potential can be pushed up to 1.5 V (ref. 11). Under the latter conditions, stability of the cathode materials is strongly affected (carbon oxidation reaction) by the undesired oxygen reduction reaction (ORR) on the anode side. This emphasizes the importance of designing selective anode catalysts that can efficiently suppress the ORR while fully preserving the Pt-like activity for the hydrogen oxidation reaction. Here, we demonstrate that chemically modified platinum with a self-assembled monolayer of calix[4]arene molecules meets this challenging requirement.     

Adhesion enhancement for liquid silicone rubber and different surface by organosilane and Pt catalyst at room temperature

Surface modification of aluminum, glass, epoxy resin, polypropylene and polyethylene via corona discharge pretreatment and platinum catalyst addition to promote their adhesion with liquid silicone rubber is reported. The corona-pretreated substrate surface was silanized with vinyltrimethoxysilane to generate vinyl groups on the surface, which could be initiated by platinum catalyst to form vinyl radicals. Then, the vinyltrimethoxysilane modified substrate was dipped into platinum catalyst solution to introduce platinum on the vinyltrimethoxysilane surface. The modified aluminum surface was characterized by X-ray photoelectron spectroscopy (XPS). The strong adhesion property between liquid silicone rubber and different surface was achieved by introducing a small amount of vinyltrimethoxysilane and platinum catalyst, followed by curing at low temperature. XPS result indicated the formation of vinyltrimethoxysilane coating on aluminum surface. Peel strength for liquid silicone rubber/vinyltrimethoxysilane–platinum surface was over 3·2 kN/m compared to only 1·1 kN/m for liquid silicone rubber/vinyltrimethoxysilane–aluminum. The cohesive failure in the bulk of liquid silicone rubber was observed for liquid silicone rubber/vinyltrimethoxysilane–platinum surface. It is assumed that the cross-linking reactions between vinyl groups in the vinyltrimethoxysilane coating and unsaturated terminal group of liquid silicone rubber occur due to the existence of platinum catalyst.     

A novel non-catalytic approach for fabrication of bamboo-like carbon nanotubes

Bamboo-like carbon nanotubes (BCNTs) were synthesized via pyrolysis of PMMA@PDVB core-shell spheres in argon atmosphere at 900 °C without any metallic catalyst. TEM and HRTEM observations show the carbon nanotubes with bamboo-like structure. The content of polymerized divinylbenzene (PDVB) in the core-shell nanostructures plays a very important role for the formation of BCNTs. The possible growth mechanism for BCNTs is proposed.     

Formation, microstructural characteristics and stability of carbon supported platinum catalysts for low temperature fuel cells

Supported platinum electrocatalysts are generally used in low temperature fuel cells to enhance the rates of the hydrogen oxidation and oxygen reduction reactions. In such catalysts, the high surface to volume ratios of the platinum particles maximize the area of the surfaces available for reaction. It is the structure and proper dispersal of these platinum particles that make low-loading catalysts feasible for fuel cell operation, lowering the cost of the system. If the platinum particles cannot maintain their structure over the lifetime of the fuel cell, change in the morphology of the catalyst layer from the initial state will result in a loss of electrochemical activity. This loss of activity in the platinum/carbon catalysts due to the agglomeration of platinum particles is considered to be a major cause of the decrease in cell performance, especially in the case of the cathode. In the light of the latest advances on this field, this paper reviews the preparation methods of these catalysts, their microstructural characteristic and their effect on both thermal and in cell conditions stability.     

Platinum‐Based Nanowires as Active Catalysts toward Oxygen Reduction Reaction: In Situ Observation of Surface‐Diffusion‐Assisted,Solid‐State Oriented Attachment

Facile fabrication of advanced catalysts toward oxygen reduction reaction with improving activity and stability is significant for proton‐exchange membrane fuel cells. Based on a generic solid‐state reaction, this study reports a modified hydrogen‐assisted, gas‐phase synthesis for facile, scalable production of surfactant‐free, thin, platinum‐based nanowire‐network electrocatalysts. The free‐standing platinum and platinum–nickel alloy nanowires show improvements of up to 5.1 times and 10.9 times for mass activity with a minimum 2.6% loss after an accelerated durability test for 10k cycles; 8.5 times and 13.8 times for specific activity, respectively, compared to commercial Pt/C catalyst. In addition, combined with a wet impregnation method, different substrate‐materials‐supported platinum‐based nanowires are obtained, which paves the way to practical application as a next‐generation supported catalyst to replace Pt/C. The growth stages and formation mechanism are investigated by an in situ transmission electron microscopy study. It reveals that the free‐standing platinum nanowires form in the solid state via metal‐surface‐diffusion‐assisted oriented attachment of individual nanoparticles, and the interaction with gas molecules plays a critical role, which may represent a gas‐molecular‐adsorbate‐modified growth in catalyst preparation.     

The growth and characterization of ZnO/ZnTe core-shell nanowires and the electrical properties of ZnO/ZnTe core-shell nanowire field effect transistor

Vertically aligned ZnO/ZnTe core-shell nanowires were grown on a-plane sapphire substrate by using chemical vapor deposition with gold as catalyst for the growth of ZnO core and then followed by growing ZnTe shell using metal-organic chemical vapor deposition (MOCVD). Transmission electron microscope (TEM) and Raman scattering indicate that the core-shell nanostructures have good crystalline quality. Three-dimensional fluorescence images obtained by using laser scanning confocal microscope demonstrate that the nanowires have good optical properties. The core-shell nanowire was then fabricated into single nanowire field effect transistor by standard e-beam photolithography. Electrical measurements reveals that the p-type ZnO/ZnTe FET device has a turn on voltage of -1.65 V and the hole mobility is 13.3 cm2/V s.     

Deposition of platinum nanoparticles on carbon nanotubes by supercritical fluid method

Carbon nanotube-supported platinum nanoparticles with a 5-15 nm diameter size range can be synthesized by hydrogen reduction of platinum(ll) acetylacetonate in methanol modified supercritical carbon dioxide. X-ray photoelectron spectroscopy and X-ray diffraction spectra indicate that the carbon nanotubes contain zero-valent platinum metal and high-resolution transmission electron microscopy images show that the visible lattice fringes of platinum nanoparticles are crystallites. Carbon nanotubes synthesized with 25% by weight of platinum nanoparticles exhibit a higher activity for hydrogenation of benzene compared with a commercial carbon black platinum catalyst. The carbon nanotube-supported platinum nanocatalyst can be reused at least six times for the hydrogenation reaction without losing activity. The carbon nanotube-supported platinum nanoparticles are also highly active for electrochemical oxidation of methanol and for reduction of oxygen suggesting their potential use as a new electrocatalyst for proton exchange membrane fuel cell applications.     

Magnetic Fe3O4@chitosan nanoparticle: synthesis, characterization and application as catalyst carrier

A novel method was developed to prepare Fe3O4@CS beads with core-shell structure using a double-crosslinking process. Before the coating process, an unique crosslinking agent, glutaraldehyde (GA), was adsorbed onto the surface of Fe3O4 in advance, so the subsequent CS can uniformly coat around the magnetic core processed from the strong interaction between GA and CS, forming a perfect core-shell structure. The obtained Fe3O4@CS beads were followed by the Pd deposition through in-situ reduction method, and the prepared composite catalyst was applied exemplarily in synthesizing nabumetone to check its reusing property. The nanoparticles were characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and the magnetic hysteresis loop determination method. This novel composite catalyst showed admirable potential in reusable catalysis.     

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.