氮修饰碳基ORR催化剂在BES系统中的应用进展

生物电化学系统(BES),利用产电微生物将废水中蕴含的丰富的化学能直接转换成电能,在净化废水的同时实现生物产电、污染物去除、生物传感等重要过程,为废水资源化利用提供了崭新的途径。目前BES性能主要受到阴极氧气还原反应(ORR)动力学的限制。设计和开发高性能的ORR催化剂对于提高BES性能至关重要。介绍了BES阴极氧还原反应的电催化机理,重点阐述BES中各种氮修饰碳基ORR催化剂(包括氮掺杂碳材料催化剂,氮掺杂碳载过渡金属催化剂,氮-杂原子共掺杂碳基催化剂)的发展现状,评价其在ORR效率、稳定性、经济性等方面的优越性和局限性。为实现BES更加高效、稳定的能源转换提供理论指导和实际参考。     

多孔碳材料的制备及其金属磷化物氧还原性能研究

多孔碳材料及其金属磷化物在电催化氧还原反应中具有广阔的应用前景。以三聚氰胺为碳源和氮源，磷酸氢二铵为磷源，制备具有超高比表面积的氮、磷共掺杂的中空碳纳米壳，通过调节磷源实现了多孔高比表面碳材料的制备。将三聚氰胺、磷酸氢二铵和铁前驱体复合，制备氮、磷共掺杂的石墨碳包裹的磷化铁纳米颗粒。石墨碳层和磷化铁之间存在电子相互作用，内部的磷化铁向外层石墨碳转移电子，这种界面相互作用大大提高了催化剂氧还原（ORR）活性，半波电位高达0.9 V。同时，包裹的碳层起到保护磷化铁（FeP）免受氧化和溶解的作用，催化剂表现出较好的稳定性。     

杂原子掺杂碳基氧还原反应电催化剂研究进展

氧还原反应（ORR）是质子交换膜燃料电池和金属空气电池等清洁能源转化技术中的关键步骤，但其反应能垒高，动力学缓慢。目前，氧还原性能最佳的催化剂仍然是已经商业化的碳载铂（Pt/C）催化剂，但其价格高、资源储量低，难以大规模应用。因此，近年来许多研究者致力于探寻低成本高性能非铂ORR催化剂，以期降低催化剂成本，推进质子交换膜燃料电池和金属空气电池的商业化进程。杂原子掺杂碳材料属于一种新型的非贵金属ORR催化剂，具有优异的电化学性能且成本低廉，显示了广阔的应用前景。以杂原子的不同作用原理为线索综述最近几年杂原子掺杂碳基ORR催化剂的研究进展，着重论述杂原子对于碳材料电子结构的影响，并讨论了杂原子掺杂碳材料催化剂面临的问题以及发展趋势。     

氢燃料电池阴极氧还原非金属催化剂研究进展

氧还原反应是制约氢燃料电池效率的重要因素,也是一直以来的研究热点和突破难点。非金属催化剂是近年来新兴的氧还原催化剂,对其的研究对推动燃料电池商业化具有重要意义,本文综述了近年来氧还原反应中非金属催化剂的研究进展,包括氮掺杂碳材料,硼、磷或硫掺杂碳材料,二元掺杂碳材料,最后展望了相关催化剂的未来研究趋势。     

异质结构碳材料的金属空气电池应用研究进展

金属空气电池在可穿戴电子产品和能源储存领域中具有巨大的应用潜力,然而稳定性差和能量效率低的问题限制其性能的进一步提高。电化学氧还原反应（ORR）和氧析出反应（OER）对于金属空气电池的性能起着至关重要的作用。发展催化活性高、稳定性好的空气电极催化剂是未来的研究趋势。碳材料因具有导电性优异、结构多样等优势已被广泛用作金属空气电池的导电骨架支撑材料和电催化材料,成为研究的热点。对非金属原子掺杂碳材料、过渡金属及其衍生物掺杂碳材料以及单原子催化剂作为单功能或双功能催化剂的研究进行综述,着重介绍了其在金属空气电池中的应用,对空气电极催化剂存在的问题进行总结,并对未来的发展方向进行展望。     

掺杂碳材料用于氧还原反应中的研究进展

燃料电池具有高效和洁净等突出优点,是最有发展前途的一种动力电池,可广泛用于移动电源和便携式电源。近年来,非铂催化剂成为燃料电池领域研究的热点,掺杂碳材料因其价格低廉,环境友好,具有良好的耐腐蚀性,高电导性以及在氧还原反应过程表现出良好的催化活性,被认为是燃料电池阴极氧还原反应的理想催化剂。本文主要介绍了氮,硫,硼,磷掺杂碳材料以及用于燃料电池氧还原反应催化剂的研究进展。     

杂原子掺杂碳基氧还原反应电催化剂研究进展

氧还原反应(ORR)是质子交换膜燃料电池和金属空气电池等清洁能源转化技术中的关键步骤,但其反应能垒高,动力学缓慢。目前,氧还原性能最佳的催化剂仍然是已经商业化的碳载铂(Pt/C)催化剂,但其价格高、资源储量低,难以大规模应用。因此,近年来许多研究者致力于探寻低成本高性能非铂ORR催化剂,以期降低催化剂成本,推进质子交换膜燃料电池和金属空气电池的商业化进程。杂原子掺杂碳材料属于一种新型的非贵金属ORR催化剂,具有优异的电化学性能且成本低廉,显示了广阔的应用前景。以杂原子的不同作用原理为线索综述最近几年杂原子掺杂碳基ORR催化剂的研究进展,着重论述杂原子对于碳材料电子结构的影响,并讨论了杂原子掺杂碳材料催化剂面临的问题以及发展趋势。     

质子交换膜燃料电池非铂电催化剂研究进展

质子交换膜燃料电池(PEMFCs)目前主要催化剂为贵金属Pt基催化剂。然而,Pt价格高、储量低等问题严重阻碍了PEMFCs的商业化进程。发展低成本、高性能的氧还原催化剂是解决铂资源短缺、降低燃料电池成本、实现燃料电池商业化的关键。结合本课题组的研究工作,综述了最近几年非铂催化剂在燃料电池阴极氧还原方面的研究进展,着重探讨了新型氮掺杂碳基纳米材料的设计与制备,并概述了非铂催化剂面临的困难以及未来发展方向。     

锌空气电池双功能阴极催化剂研究进展

可充电锌空气电池(ZAB)被认为是具有前景的储能设备之一.阴极氧还原反应和氧析出反应(ORR和OER)动力学缓慢,限制ZAB的实际应用,开发出高活性催化ORR/OER双功能阴极电催化剂尤为重要.综述了非贵金属双功能阴极电催化剂,包括无金属碳材料催化剂、过渡金属催化剂和过渡金属-氮掺杂碳材料组合催化剂,讨论几种催化剂催化...     

金属大环化合物基氧还原电催化剂的研究进展

作为燃料电池的关键反应,阴极电极上的氧还原反应（ORR）的反应动力学缓慢,需要大量昂贵的铂基电催化剂提高反应动力学。然而,铂的价格昂贵、稀缺和耐久性差等问题严重阻碍了燃料电池系统在实际中的广泛应用。因此,发展廉价高活性的非贵金属氧还原反应催化剂是实现燃料电池商业应用关键途径之一。大环化合物基催化剂以其独特的配位结构和高共轭化学性质发展迅速,被认为是铂基材料的潜在替代品。本文总结了近年来金属大环化合物基氧还原催化剂的发展和研究成果,着重探讨了金属大环化合物基氧还原催化剂的设计和制备,并概述了金属大环化合物基氧还原催化剂面临的挑战和未来的发展方向。     

Highly active nitrogen-doped few-layer graphene/carbon nanotube composite electrocatalyst for oxygen reduction reaction in alkaline media

In this work the electrocatalysis of oxygen reduction on nitrogen-doped few-layer graphene/multi-walled carbon nanotube (FLG/MWCNT) composite catalyst has been investigated. These composite materials were prepared from different nitrogen precursors, acid-treated MWCNTs and graphene oxide (GO), which was synthesised from graphite by the modified Hummers’ method. Urea and dicyandiamide were used as nitrogen precursors and the doping was achieved by pyrolysing the mixture of GO and MWCNTs in the presence of these nitrogen-containing compounds at 800 °C. The N-doped composite catalyst samples were characterised by scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy, the latter method revealed successful nitrogen doping. The oxygen reduction reaction (ORR) was studied in 0.1 M KOH on glassy carbon electrodes modified with N-doped FLG/MWCNT electrocatalysts employing the rotating disk electrode (RDE) method. The RDE results indicated that these metal-free nitrogen-doped nanocarbon catalysts possess remarkable electrocatalytic activity towards the ORR in alkaline media similar to that of commercial Pt/C catalyst. The results obtained in this work are particularly important for the development of non-Pt cathode catalysts for alkaline membrane fuel cells.     

非贵金属氧还原电极催化剂研究进展

质子交换膜燃料电池(PEMFC)中普遍使用Pt作为阴极电催化剂,但由于Pt价格昂贵、储量稀少,PEMFC中使用大量的Pt,必然导致PEMFC制造成本的上升。因此,寻找一种能够部分或者完全达到Pt催化效果的非贵金属催化剂,成为一种可行的方法。本文对近年来非贵金属氧还原电极催化剂的研究进行了总结,特别是不同催化剂的制备方法、反应机理及活性中心进行了梳理,并对非贵金属氧还原电极催化剂的发展进行了展望。     

Improved carbon nanostructures as a novel catalyst support in the cathode side of PEMFC: a critical review

Carbon supported platinum nanoparticles are extensively used as electrocatalysts in proton exchange membrane fuel cells (PEMFCs). The stability and performance of the electrocatalyst strongly depends on the deposition method and properties of the carbon support. Carbon black is commonly used as support for platinum (Pt–C) due to its low cost and high availability, good electrical performance, and relatively high surface area. However, carbon corrosion, Ostwald ripening, and Pt dissolution have been recognized as the main cause for low durability of this electrocatalyst under high potential conditions. As a result, the necessity for promising supports with higher stability is inevitable. It has been reported that carbon nanomaterials with higher mesoporosity, surface area, electrical conductivity, stability and suitable anchoring site are promising supports under harsh oxidizing condition of PEMFCs. This review is devoted to the development of recent advances in novel carbon nanomaterials as catalyst support, such as carbon nanotubes, carbon nanofibers, graphene, mesoporous carbon, and etc., for the oxygen reduction reaction (ORR) in PEMFCs. Moreover, the main challenges such as low activity, poor durability, and high cost, are addressed and discussed. The performance and obstacles of these carbons associated with different metal catalyst deposition methods are highlighted.     

热处理温度对Fe-N-C-t催化ORR性能的影响及动力学研究

选用天然高分子化合物壳聚糖（CS）与水杨醛（salicylaldehyde）反应生成壳聚糖水杨醛席夫碱（CS-Sal）,CS-Sal又与过渡金属Fe盐发生螯合反应,得到壳聚糖水杨醛席夫碱Fe配合物（Fe-CS-Sal）。将Fe-CS-Sal负载于活化的高纯石墨上,在N2氛围中进行不同温度的热处理,得到系列催化剂Fe-N-C-t（t=200℃,400℃,600℃,800℃,1000℃）。运用循环伏安法（CV）、计时库仑法（CC）研究了Fe-N-C-t催化剂电催化氧还原反应（ORR）的催化性能,并结合FT-IR、XRD结构表征,探索了Fe-N-C-t催化剂电催化ORR的催化活性位。结果表明,催化剂Fe-N-C-1000对ORR的电催化活性最好。同时根据循环伏安法和计时电流法计算得出ORR的动力学参数,提出了在此催化剂上可能发生的ORR的催化机理。     

掺杂炭黑电催化剂氧还原性能研究

碳纳米材料由于其良好的结构和功能特性,常做为氧还原反应中电催化剂的载体或直接做为氧还原反应的电催化剂。本文从具有良好导电性和高比表面积的炭黑(BP2000)出发,在对其进行表面氧化的基础上分别通过高温氨化和Fe(NO3)3溶液浸渍/高温煅烧进行了掺氮(N-BP2000)和掺铁(Fe-BP2000),对比考察了掺氮和掺铁对所得催化剂氧还原性能的影响。结果表明,所制备的掺氮炭黑(N-BP2000)和掺铁炭黑(Fe-BP2000)电催化剂的氧还原活性均较BP2000电催化剂提高显著。其中,Fe-BP2000电催化剂,表现出了最佳的氧还原活性,其半波电位为0.774 V,分别比N-BP2000与BP2000电催化剂正22、108 mV,同时其也表现出最佳的长程稳定性。     

Progress in non-precious metal oxide-based cathode for polymer electrolyte fuel cells

The cathode catalysts for polymer electrolyte fuel cells should have high stability as well as excellent catalytic activity for oxygen reduction reaction (ORR). Group 4 and 5 metal oxide-based compounds have been evaluated as a cathode from the viewpoint of their high catalytic activity and high stability. Although group 4 and 5 metal oxides have high stability even in acidic and oxidative atmosphere, they are almost insulator and have poor ORR activity because they have a large band-gap. It is necessary to modify the surface of the oxides to improve the ORR activity. We have tried the surface modification methods of oxides into four methods: (1) formation of complex oxide layer containing active sites, (2) substitutional doping of nitrogen, (3) introduction of surface oxygen defect and (4) partial oxidation of carbonitrides. These modifications were effective to improve the ORR activity of the oxides. The solubility of the oxide-based catalysts in 0.1 mol dm⁻³ at 30 °C under atmospheric condition was mostly smaller than that of platinum black, indicating that the oxide-based catalysts had sufficient stability compare to the platinum. The onset potential of various oxide-based cathodes for the ORR in 0.1 mol dm⁻³ at 30 °C achieved over 0.9 V vs. a reversible hydrogen electrode.     

Highly efficient metal-free phosphorus-doped platelet ordered mesoporous carbon for electrocatalytic oxygen reduction

Platinum-free electrocatalysts especially, various heteroatom-doped carbon nanostructures have attracted particular attraction as plausible solution for commercializing fuel cell technology. In this direction, novel phosphorus-doped platelet ordered mesoporous carbon (P-pOMC) is developed for the first time as metal-free electrocatalyst for alkaline oxygen reduction reaction. The P-pOMC is synthesized by nanocasting method using platelet ordered mesoporous silica as template. Various characterizations reveal that the P-pOMC materials have covalently bound P atoms with carbon framework for facilitation of oxygen reduction reaction (ORR) and also have very high surface area with uniform distribution of short mesoporous channels for unhindered mass transfer. Combination of P doping and excellent surface properties empowers the newly-developed P-pOMC catalyst to show high ORR activity nearly equal to that of state of the art Pt catalyst along with superior long-term stability and excellent methanol tolerance.     

非铂燃料电池电催化剂研究进展

商业铂碳催化剂价格高昂,开发非铂材料是推进燃料电池商业化的关键一步。本文首先介绍了燃料电池氧还原反应电催化剂的研究背景,接着分别介绍了非贵金属、非金属以及复合材料的催化剂,并对各类催化剂的活性位点和催化机理进行了简要的评述。其中,过渡金属的氮碳化物成本低廉,具有较高的催化活性以及优异的稳定性,是最有望替代贵金属Pt的一类催化剂。杂原子的掺杂能够改变碳材料的表面电荷分布,提升碳材料的催化活性。将过渡金属的氮碳化物和特殊结构的碳材料有效结合,可以设计出具有双功能的复合材料。最后,针对非铂催化剂存在的问题进行了分析并提出了今后工作的几个方向,为今后非铂电催化剂的研究提供参考。高活性高稳定性的非铂催化剂是未来该领域的重点研究方向。