单原子分散的Ir-N-C燃料电池阳极抗中毒催化剂

燃料电池的阳极抗中毒研究是重要课题,探索具有超高质量活性和抗CO毒化的阳极催化剂具有显著的科学意义和应用价值。本文成功制备了Ir原子级别分散在N掺杂碳的载体上的新催化剂,并且发现该Ir-N-C对甲酸具有良好的电催化氧化性能,其质量比活性为商业Pd/C的48倍。组装了燃料电池单电池进行测试,结果显示,Ir-N-C催化剂在单电池中的质量比功率密度高达281 mW/mg,较商业Pd/C催化剂提升了3倍。同时,Ir-N-C对CO毒化的耐受性大大增强,经过14000 s的长期测试后,其活性仅衰减68%,优于商业Pd/C催化剂（衰减85%）。并且,该催化剂能够简单有效的大批量制备,为单原子催化剂的大批量制备提供了新思路。     

金属/非金属元素掺杂提升原子级分散碳基催化剂的氧还原性能

原子级别分散的过渡金属和氮共掺杂碳基催化剂(M-N_x-C)具有反应活性好、选择性高、制备容易等优点,被认为是最有可能取代价格昂贵的铂催化剂用作燃料电池阴极的一类非贵金属催化剂。然而,该类催化剂在阴极侧氧还原反应过程中存在活性位点密度较低、耐久性不足的问题制约了其在燃料电池中的实际应用。研究表明,通过多种金属/非金属元素的掺杂调控活性位点的电子结构与空间构型可显著提升M-N_x-C催化剂的氧还原活性和稳定性,已成为掺杂碳基催化剂领域的热门研究课题。本文综述了近年来国内外在多种金属/非金属元素掺杂提升M-N_x-C碳基催化剂性能方面的主要研究工作,包括金属元素掺杂、非金属元素掺杂等研究。文章进一步总结和指出了M-N_x-C碳基催化剂面临的问题及挑战,并对其发展前景和未来研究方向进行了展望。     

聚吡咯改性炭载Pd催化剂促进甲酸电氧化

直接甲酸燃料电池(DFAFC)阳极活性炭载Pd催化剂活性组分易聚集,分散差且存在炭载体的电腐蚀作用,造成催化活性低稳定性差。 为解决上述问题,本文通过调控炭载Pd催化剂的载体改善催化活性和稳定性。 采用低温化学氧化法制备了聚吡咯(PPy)与活性炭复合材料,在聚合过程中加入活性炭,经过高温热解聚吡咯形成复合碳载体负载Pd催化剂,并表征了热解聚吡咯碳修饰催化剂表面形貌,发现聚吡咯修饰后的催化剂载体表面氮元素以吡咯氮的形式存在,催化剂活性组分Pd纳米粒子可稳定在2.25 nm。 通过甲酸电催化氧化性能测试,结果表明,Pd单位质量比活性比Pd/C催化剂提高了2.5倍。     

燃料电池纳米催化剂的稳定化

低温燃料电池是理想的移动式电源,它所采用的电催化剂主要为Pt基贵金属纳米催化剂。提高纳米催化剂在电池内部环境中的稳定性、抑制其活性衰减,对于延长低温燃料电池的使用寿命和节约成本具有十分重要的意义。本文从三个方面综述了近年来在低温燃料电池纳米催化剂稳定化方面的研究进展。首先,通过载体效应实现催化剂的稳定化,包括碳载体的石墨化、碳载体的掺杂、表面功能化及其他载体的采用等。其次,通过空间效应实现催化剂的稳定化,包括催化剂粒子表面覆盖、催化剂粒子微孔嵌入、催化剂表面杂多酸单层自组装及聚合物电解质空间阻隔等。再其次,通过协同效应实现催化剂的稳定化,包括提升金属粒子的氧化电位、强化组分间的相互作用等。最后,对低温燃料电池纳米催化剂稳定化的发展前景进行了展望。     

炭载Pd-Ni合金纳米粒子对甲酸的电催化氧化

通过液相还原法制备了具有不同原子比例的Pd-Ni/C催化剂,并且使用X射线衍射（XRD）、透射电子显微镜(TEM)和X射线光电子能谱(XPS) 等表征手段对制备的催化剂进行了表征,总结了Ni的掺杂对Pd-Ni合金纳米粒子的尺寸及晶体结构的影响。电化学测试结果表明：适量的Ni的掺杂不但能够增强催化剂对甲酸催化氧化的活性,而且还能够提高催化剂的稳定性。因此,Pd-Ni/C催化剂是一类具有潜在应用前景的直接甲酸燃料电池阳极催化剂     

改性石墨烯用作燃料电池阴极催化剂

石墨烯材料以其独特的超薄片层结构、超高比表面积、良好的导电性等重要特性,而被认为在制备高性能燃料电池催化剂方面具有重要的潜在应用价值。最近的一些研究工作表明,通过选择合适的制备方法和前驱体制备的改性石墨烯,对于氧还原反应具有一定的活性,可用作燃料电池阴极催化剂。目前有关石墨烯应用于燃料电池阴极催化剂的研究工作主要集中在两个方面:一是通过表面改性后直接作为燃料电池非贵金属阴极催化剂;二是将改性石墨烯作阴极催化剂载体而制备活性组分高度分散的高性能催化剂。尽管有关改性石墨烯的氧还原活性中心的结构尚不明确,然而由于这类材料在酸性及碱性环境下对氧还原的良好的催化性能,对改性石墨烯的研究已成为探索燃料电池非铂催化剂的新途径。随着这类材料的催化性能的不断提高和对表面-活性关系认识的不断深入,改性石墨烯材料在燃料电池方面将具有广阔的应用前景。     

质子交换膜燃料电池非贵金属型Fe-N-C催化剂的研究进展

质子交换膜燃料电池具有绿色、可持续、效率高等优点,被认为是解决环境与能源问题最有前途的替代方案。燃料电池核心是催化剂,目前应用最成熟的是铂族贵金属,但其高昂的成本制约着燃料电池的快速推广,另外铂族金属对CO、NH₃等气体较为敏感,使得燃料纯度要求苛刻,因此开发高性能低成本的催化剂替代贵金属是推动燃料电池商业化的重要途径。本文总结了近年来燃料电池近年来Fe-N-C催化剂的研究成果,并对Cu、Co等金属掺杂影响进行了系统综述。文中从制备方法、载体、氮源、金属掺杂等对Fe-N-C催化剂氧还原活性及耐久性的影响进行了详细的对比分析,对催化剂的失活机理进行了一定的探讨。最后,本文展望了Fe-N-C催化剂未来的发展方向,提出催化剂活性、耐久性同步提升以及优化燃料电池催化剂层的方案。     

部分氧化碳化硅提高钯催化氧还原反应性能

燃料电池具有能量转换效率高的优点,是能量转换与储存的高效器件之一.目前,燃料电池阴极氧还原反应(ORR)动力学缓慢,并且催化ORR大量使用铂碳(Pt/C)催化剂,由于Pt储量少,价格高,载体碳材料易发生碳蚀导致催化剂稳定性降低,限制了其进一步商业化应用.钯(Pd)与Pt为同族元素,具有相似的电子结构和化学性质,其储量是Pt的50倍,同时,Pd具有良好的抗甲醇毒性和抗一氧化碳毒性,因此,被视为燃料电池中阴极Pt催化剂的潜在替代品.但商用Pd/C催化剂的ORR活性较Pt/C差,因此,大量的研究工作集中在提高Pd基ORR催化剂的活性方面:将Pd与具有3d轨道的金属形成合金或将Pd负载到不同的载体上.通过选择合适的载体影响Pd的电子结构,从而提高催化剂活性和稳定性,是一种较简单的、有利于规模化生产Pd基ORR催化剂的方法.碳化硅(SiC)具有良好的电化学稳定性、热稳定性、机械强度和较强的供电子能力,可被用作ORR的金属催化剂载体.然而,由于金属与SiC作用较弱,需要制备特殊形貌的SiC或将SiC表面改性;通常,这些SiC基载体的制备过程复杂并且成本高.而在有氧条件下制备、保存或使用SiC时,其表面不可避免地被氧化,这种在温和条件下生成的表面具有含氧官能团的SiC,由于制备过程简便,可以大规模生产,且与金属有强的相互作用,是一种很有前景的ORR的Pd基催化剂载体.对于用于替代Pt基催化剂的负载型Pd基ORR催化剂的开发和大规模制造来说,对载体表面改性的深入了解是一个重要并且具有挑战性的课题.目前尚未发现关于SiC表面的含氧基团对ORR性能影响的报道.因此,详细考察SiC载体上含氧基团在ORR中的作用对于理解、设计和开发具有优异ORR性能的SiC负载催化剂至关重要.本文采用沉积沉淀法在表面部分氧化的碳化硅(O-SiC)均匀负载了平均直径为5.2 nm的Pd纳米颗粒.与20 wt%商业Pt/C相比,制备的2.5 wt%Pd/O-SiC催化剂显示出较好的ORR活性(半波电位正向移动10 mV),较好的稳定性(10 h后,电流密度损失3.5%vs.34.9%),和较高的抗甲醇毒性.结构表征及密度泛函理论(DFT)计算结果表明,与Pd/C相比,Pd/O-SiC具有优异的ORR性能主要是由于O-SiC载体对Pd纳米颗粒具有电子调控作用,使Pd带负电.富电子Pd增强了ORR关键中间体OOH的吸附,降低了反应的吉布斯自由能,从而提高了ORR活性.另外,O-SiC载体对Pd纳米颗粒具有大的结合能和较好的SiC稳定性,增强了Pd/O-SiC催化剂的抗甲醇毒性及稳定性.DFT计算结果表明,SiC表面部分氧化后,仍保持对Pd的较高结合能,同时大幅增强了催化剂对中间体的吸附,降低了ORR关键电化学步骤吉布斯自由能,从而提高了氧还原性能.因此,本工作明确了SiC表面氧化的作用,同时提供了一种简易大规模制备高效负载型铂基替代ORR催化剂的策略.     

N掺杂石墨烯负载AgPd纳米催化剂室温高效催化甲酸分解制氢

本文制备了一种AgPd纳米粒子负载在氮掺杂石墨烯上的催化剂(AgPd/N-G).通过一系列分析技术表征了样品的元素组成、微观结构、光电子能谱等,并测试了其对于甲酸分解制氢反应的催化活性.结果表明,由于氮的掺杂,该催化剂在保留石墨烯导电性、机械性能及高的比表面积等优异特性的同时,大大增加了其活性位点.同时,有效地加强了载体与AgPd金属纳米粒子的结合力,使得金属粒子分散性大大提高,显著增加了催化剂的催化活性和稳定性.     

核壳结构:燃料电池中实现低铂电催化剂的最佳途径

电催化剂是决定低温燃料电池性能、寿命和成本的关键材料之一,核壳结构电催化剂由于其在降低铂载量、提高催化剂活性方面表现出的良好性质,已成为燃料电池领域的研究热点。本文综述了低温燃料电池核壳结构电催化剂的最新研究进展。首先,在概述核壳结构电催化剂总体特征的基础上,详细介绍了核壳结构电催化剂的制备方法,主要包括胶体法、热分解法、置换法、电化学法等,其中胶体法是目前应用最为广泛的一种方法,具有合成过程简单易控等优点;置换法和电化学法则是在最近几年得到了迅速的发展,并有望用于核壳结构电催化剂的批量化生产。然后,分别从二元及其他多元催化剂组成方面阐述了核壳型电催化剂体系的研究进展,核壳结构电催化剂不仅可有效提高贵金属铂的质量比活性,同时,其他金属元素与铂之间存在的相互作用可对电催化剂的活性及稳定性产生十分重要的调变作用。最后,我们对低温燃料电池核壳结构电催化剂的发展趋势作了展望。     

Highly Efficient Oxygen Reduction Reaction Fe-N-C Cathode in Long-durable Direct Glycol Fuel Cells

The oxygen reduction reaction in direct glycol fuel cells heavily relies on noble metal-based electrocatalysts. In this work, novel Pt group metal-free catalysts based on porous Fe-N-C materials are successfully synthesized as catalysts with high activity and durability for the cathode oxygen reduction reaction (ORR). Through the encapsulation of NH₄SCN salt, the surface elements and pore structure of the catalyst are effectively changed, and the active sites of Fe effectively are increased. The half-wave potential of the best Fe-N-C catalyst was –0.02 V vs. Hg/HgO in an alkaline environment. The porous Fe-N-C catalyst possesses a large specific surface area(1158 m²/g) and shows good activity and tolerance to glycol. The direct glycol fuel cell with the Fe-N-C cathode achieved a maximum power density of 62.2 mW/cm² with 4 mol/L KOH and 4 mol/L glycol solution at 25 °C and maintained discharge for more than 250 h at a 50 A/cm² current density.     

Cobalt Phenanthroline–Indole Macrocycles as Highly Active Electrocatalysts for Oxygen Reduction

The replacement of scarce and expensive platinum species poses a challenge in fuel‐cell development. The design and synthesis of a novel type of Co^II–N₄ macrocyclic complex, [CoN₄], based on the phenanthroline–indole macrocyclic ligand (PIM) is reported. This unique ligand allows the formation of mono‐ and dinuclear complexes with defined active sites that facilitate the direct four‐electron reduction of oxygen. Electrochemical measurements revealed that the [CoN₄]/C (20 wt %) catalysts have a high activity and long‐term stability for the oxygen‐reduction reaction (ORR) under alkaline conditions, similar to the Pt/C catalyst. These structurally well‐defined complexes represent a nonprecious alternative to platinum species for future fuel‐cell applications.     

Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts

Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low‐temperature fuel cells. A novel type of catalysts prepared by high‐pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting of uniform iron carbide (Fe₃C) nanoparticles encased by graphitic layers, with little surface nitrogen or metallic functionalities. In acidic media the outer graphitic layers stabilize the carbide nanoparticles without depriving them of their catalytic activity towards the oxygen reduction reaction (ORR). As a result the catalyst is highly active and stable in both acid and alkaline electrolytes. The synthetic approach, the carbide‐based catalyst, the structure of the catalysts, and the proposed mechanism open new avenues for the development of ORR catalysts.     

Mesopore‐controllable Carbon Aerogel and their Highly Loaded PtRu Anode Electrocatalyst for DMFC Applications

Catalyst loading and layer thickness are crucial factors to enhance the cell performance and to reduce cost of membrane electrode assemblies (MEAs). Outstanding properties, such as large surface area to disperse metal nanoparticles and sufficient pore volume and size, is needed in utilization of fuel cell. Carbon aerogels are one of the good candidates that meets the above conditions. Those are synthesized by polycondensation reaction of resorcinol and formaldehyde (RF) polymer, supercritical drying to keep pore skeleton structure caused by capillary force and calcination of RF polymer in nitrogen atmosphere to be controllable meso pore (2～43 nm) as role of support for electric conductor and dispersion of metal nanoparticles. In order to utilization of anode catalyst in direct methanol fuel cell, highly loaded (80 weight percent) platinum and ruthenium onto carbon aerogel are synthesized by Bönnemann colloid method. The single cell test of carbon aerogel supported PtRu anode catalyst is performed and over 40 nm pore sized‐catalysts are the best performance due to sufficient surface area to anchor uniform and small metal nanoparticles and good pathway to drive fuel and outgas even though PtRu nanoparticles are anchored on the outer surface of carbons.     

Highly active iridium/iridium-tin/tin oxide heterogeneous nanoparticles as alternative electrocatalysts for the ethanol oxidation reaction

Ethanol is a promising fuel for low-temperature direct fuel cell reactions due to its low toxicity, ease of storage and transportation, high-energy density, and availability from biomass. However, the implementation of ethanol fuel cell technology has been hindered by the lack of low-cost, highly active anode catalysts. In this paper, we have studied Iridium (Ir)-based binary catalysts as low-cost alternative electrocatalysts replacing platinum (Pt)-based catalysts for the direct ethanol fuel cell (DEFC) reaction. We report the synthesis of carbon supported Ir(71)Sn(29) catalysts with an average diameter of 2.7 ± 0.6 nm through a "surfactant-free" wet chemistry approach. The complementary characterization techniques, including aberration-corrected scanning transmission electron microscopy equipped with electron energy loss spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy, are used to identify the "real" heterogeneous structure of Ir(71)Sn(29)/C particles as Ir/Ir-Sn/SnO(2), which consists of an Ir-rich core and an Ir-Sn alloy shell with SnO(2) present on the surface. The Ir(71)Sn(29)/C heterogeneous catalyst exhibited high electrochemical activity toward the ethanol oxidation reaction compared to the commercial Pt/C (ETEK), PtRu/C (Johnson Matthey) as well as PtSn/C catalysts. Electrochemical measurements and density functional theory calculations demonstrate that the superior electro-activity is directly related to the high degree of Ir-Sn alloy formation as well as the existence of nonalloyed SnO(2) on surface. Our cross-disciplinary work, from novel "surfactant-free" synthesis of Ir-Sn catalysts, theoretical simulations, and catalytic measurements to the characterizations of "real" heterogeneous nanostructures, will not only highlight the intriguing structure-property correlations in nanosized catalysts but also have a transformative impact on the commercialization of DEFC technology by replacing Pt with low-cost, highly active Ir-based catalysts.     

Deactivation resistant PdSb/C catalysts for direct formic acid fuel cells

Formic acid oxidation at novel carbon supported PdSb alloy catalysts has been studied in a multi-anode direct formic acid fuel cell with supporting mechanistic studies in a conventional electrochemical cell. The optimized PdSb/C catalysts show better high voltage and long term performances than a comparable commercial Pd/C catalyst and much better resistance to poisoning (deactivation). Electrochemical stripping voltammograms show that the presence of Sb lowers the potential required for CO oxidation, and greatly decreases the accumulation of CO on the catalyst surface during formic acid oxidation.     

燃料电池中Pt基催化剂对CO的催化氧化

燃料电池具有燃料多样性、噪声低、对环境污染小等优势,近年来备受研究者关注。然而,电池中的贵金属催化剂极易被少量的CO毒化,成为制约其商业化的一大障碍。因此,设计出高性能的催化剂对于推动燃料电池的发展十分关键。本文综述了燃料电池中铂(Pt)基催化剂对CO催化氧化的研究现状,首先探讨了CO催化氧化机理以及CO在Pt金属表面化学吸附的机理,其次详细介绍了Pt负载型催化剂、双金属催化剂以及助催化剂在催化反应中的不同作用,然后简单分析了影响Pt基催化剂性能的其他因素。最后,对燃料电池中Pt基催化剂的研究方向作了进一步的展望,旨在为燃料电池中CO催化氧化的发展开拓新思路。     

高活性和耐久性非铂氧还原催化剂的研究进展（英文）

质子交换膜燃料电池(PEMFCs)阴极氧还原反应(ORR)动力学迟缓,需要消耗大量的贵金属催化剂,这限制了其商业化应用。目前,原子级分散的M-N-C (M=Fe,Co,Mn等)催化剂受到人们青睐,有望替代铂催化剂。在过去的几十年里,M-N-C催化剂取得了很大的进步,具有优异的ORR活性,而且燃料电池初始性能有希望接近传统的Pt/C催化剂。然而,这些高活性的Fe-N-C催化剂在燃料电池实际工作条件下的稳定性比较差。这篇综述总结了在高效氧还原M-N-C催化剂方面的最近进展,主要概述了作者课题组在限域策略和自旋调控方面的贡献。此外,我们还总结了几种提高活性的有效方法以及近期的关于揭示M-N-C催化剂的降解机制的认识,如金属浸出、碳腐蚀、质子化和微孔淹没都会造成催化剂降解。为改善M-N-C催化剂的寿命,我们概括了文献中的缓解策略,包括控制催化剂中S1/S2位点、使用非铁基催化剂、增强金属氮键、改善碳载体的耐腐蚀性和使用质子缓冲液等。最后,提出了目前原子级分散的M-N-C催化剂的存在的挑战和可能的解决方案。     

The problem of Ru dissolution from Pt–Ru catalysts during fuel cell operation: analysis and solutions

Platinum–ruthenium catalysts are widely used as anode materials in polymer electrolyte fuel cells (PEMFCs) operating with reformate gas and in direct methanol fuel cells (DMFCs). Ruthenium dissolution from the Pt–Ru anode catalyst at potentials higher than 0.5?V vs. DHE, followed by migration and deposition to the Pt cathode can give rise to a decrease of the activity of both anode and cathode catalysts and to a worsening of cell performance. A major challenge for a suitable application of Pt–Ru catalysts in PEMFC and DMFC is to improve their stability against Ru dissolution. The purpose of this paper is to provide a better knowledge of the problem of Ru dissolution from Pt–Ru catalysts and its effect on fuel cell performance. The different ways to resolve this problem are discussed.