工程科学学报，第41卷，第2期：216-223,2019年2月 Chinese Joural of Engineering,Vol.41,No.2:216-223,February 2019 DOI:10.13374/j.issn2095-9389.2019.02.008;http://journals.ustb.edu.cn 吡咯/炭黑氧化物复合氧阴极材料的制备及催化性能 孙 珊，刘桎东，刁鹏四 北京航空航天大学材料科学与工程学院，北京100191 区通信作者，E-mail:buaa eclab@163.com 摘要氧还原反应(ORR)是碱性燃料电池和金属-空气电池的重要阴极反应.由于常见的铂基氧阴极材料存在价格昂贵、 稳定性较低等问题，因此，开发低成本、高效率的非贵金属基氧阴极材料具有重要的研究意义和应用价值.氨掺杂碳材料是目 前氧阴极材料研究的热点，炭黑中碳原子的排列方式类似于石墨，由于其价格低廉、来源广泛，在碳材料的研究中具有独特的 优势.本文基于炭黑，采用化学法制备了氨掺杂炭黑氧阴极材料，研究了其氧还原反应催化活性，并进行了相关表征.结果显 示炭黑-吡略复合材料具有极好的氧还原反应活性，700℃热处理后性能最优，在1mol·L1KOH中其起峰电位约为0.9V,极 限扩散电流密度为2.6mA·cm2,转移电子数高于3.5，这些特性使得这类材料具有广阔的应用前景. 关键词氧还原反应：阴极材料：氮参杂：碳材料 分类号0643.3 Preparation and catalytic studies of pyrrole-doped carbon black oxide cathode materials for oxygen reduction reactions SUN Shan,LIU Zhi-dong,DIAO Peng School of Materials Science and Engineering,Beihang University,Beijing 100191,China Corresponding author,E-mail:buaa_eclab@163.com ABSTRACT Oxygen reduction reaction(ORR)is an important cathode reaction for alkaline fuel and air-metal batteries.Because of the high cost and low stability of traditional Pt-based cathode materials for ORR,it is important to find an alternative cathode material of high performance and stability and low cost.Nitrogen-doped carbonaceous materials are currently of keen interest among those alter- native oxygen cathode materials.The arrangement of carbon atoms in carbon black (CB)is similar to that of graphite,and it is well- known that CB has a unique advantage over other carbon materials owing to its relatively low price and wide availability.Based on cheap carbon black,pyrrole-doped carbon black oxide (rCBO-Pyrrole)cathode materials were prepared using a facile synthesis meth- od for this article,and their catalytic performances toward ORR were studied.The characterization of the catalysts was explored using a scanning electron microscope (SEM),a transmission electron microscope (TEM),ultraviolet-visible spectroscopy (UV-Vis),and Brunauer-Emmett-Teller (BET)specific surface area and X-ray photoelectron spectroscopy (XPS).The results of these analyses in- dicate that nitrogen is successfully doped in the rCBO-Pyrrole composite.BET results show that both rCBO and rCBO-Pyrrole have large specific surface areas,which increase significantly after pyrrole doping of carbon black.Further,the results of catalytic perform- ances show that the rCBO-Pyrrole composite induces excellent catalytic activity toward ORR and exhibits the best performance after heat treatment at 700 C.In the electrolyte of KOH (1 mol.L),the onset potential of rCBO-Pyrrole is 0.9V es RHE,and the limit diffusion current density of this catalyst is 2.6mA.cm.Moreover,the electron transfer number of ORR on rCBO-Pyrrole is higher than 3.5,which indicates a preference for the four-electron reduction pathway.These characteristics and results demonstrate that this kind of material has broad potential applicability. KEY WORDS oxygen reduction reaction;cathode material;nitrogen doping;carbon material 收稿日期：2018-01-21工程科学学报,第 41 卷,第 2 期:216鄄鄄223,2019 年 2 月 Chinese Journal of Engineering, Vol. 41, No. 2: 216鄄鄄223, February 2019 DOI: 10. 13374 / j. issn2095鄄鄄9389. 2019. 02. 008; http: / / journals. ustb. edu. cn 吡咯 / 炭黑氧化物复合氧阴极材料的制备及催化性能 孙 珊, 刘桎东, 刁 鹏苣 北京航空航天大学材料科学与工程学院, 北京 100191 苣通信作者, E鄄mail: buaa_eclab@ 163. com 摘 要 氧还原反应(ORR)是碱性燃料电池和金属鄄鄄空气电池的重要阴极反应. 由于常见的铂基氧阴极材料存在价格昂贵、 稳定性较低等问题,因此,开发低成本、高效率的非贵金属基氧阴极材料具有重要的研究意义和应用价值. 氮掺杂碳材料是目 前氧阴极材料研究的热点,炭黑中碳原子的排列方式类似于石墨,由于其价格低廉、来源广泛,在碳材料的研究中具有独特的 优势. 本文基于炭黑,采用化学法制备了氮掺杂炭黑氧阴极材料,研究了其氧还原反应催化活性,并进行了相关表征. 结果显 示炭黑鄄鄄吡咯复合材料具有极好的氧还原反应活性,700 益热处理后性能最优,在 1 mol·L - 1 KOH 中其起峰电位约为 0郾 9 V,极 限扩散电流密度为 2郾 6 mA·cm - 2 ,转移电子数高于 3郾 5,这些特性使得这类材料具有广阔的应用前景. 关键词 氧还原反应; 阴极材料; 氮掺杂; 碳材料 分类号 O643郾 3 收稿日期: 2018鄄鄄01鄄鄄21 Preparation and catalytic studies of pyrrole鄄doped carbon black oxide cathode materials for oxygen reduction reactions SUN Shan, LIU Zhi鄄dong, DIAO Peng 苣 School of Materials Science and Engineering, Beihang University, Beijing 100191, China 苣Corresponding author, E鄄mail: buaa_eclab@ 163. com ABSTRACT Oxygen reduction reaction (ORR) is an important cathode reaction for alkaline fuel and air鄄metal batteries. Because of the high cost and low stability of traditional Pt鄄based cathode materials for ORR, it is important to find an alternative cathode material of high performance and stability and low cost. Nitrogen鄄doped carbonaceous materials are currently of keen interest among those alter鄄 native oxygen cathode materials. The arrangement of carbon atoms in carbon black (CB) is similar to that of graphite, and it is well鄄 known that CB has a unique advantage over other carbon materials owing to its relatively low price and wide availability. Based on cheap carbon black, pyrrole鄄doped carbon black oxide (rCBO鄄鄄Pyrrole) cathode materials were prepared using a facile synthesis meth鄄 od for this article, and their catalytic performances toward ORR were studied. The characterization of the catalysts was explored using a scanning electron microscope (SEM), a transmission electron microscope (TEM), ultraviolet鄄visible spectroscopy (UV鄄鄄Vis), and Brunauer鄄鄄Emmett鄄鄄Teller (BET) specific surface area and X鄄ray photoelectron spectroscopy (XPS). The results of these analyses in鄄 dicate that nitrogen is successfully doped in the rCBO鄄鄄 Pyrrole composite. BET results show that both rCBO and rCBO鄄鄄 Pyrrole have large specific surface areas, which increase significantly after pyrrole doping of carbon black. Further, the results of catalytic perform鄄 ances show that the rCBO鄄鄄 Pyrrole composite induces excellent catalytic activity toward ORR and exhibits the best performance after heat treatment at 700 益 . In the electrolyte of KOH (1 mol·L - 1 ), the onset potential of rCBO鄄鄄Pyrrole is 0郾 9 V vs RHE, and the limit diffusion current density of this catalyst is 2郾 6 mA·cm - 2 . Moreover, the electron transfer number of ORR on rCBO鄄鄄 Pyrrole is higher than 3郾 5, which indicates a preference for the four鄄electron reduction pathway. These characteristics and results demonstrate that this kind of material has broad potential applicability. KEY WORDS oxygen reduction reaction; cathode material; nitrogen doping; carbon material