Co3O4/聚吡咯/石墨烯碱性溶液中电化学还原氧

doi:10.1016/S1872-2067(17)62846-8

摘要/Abstract

摘要：

燃料电池具有较高的能量密度和发电效率，以清洁能源为原料，零污染排放，是一种具有发展前景的能量储存和转化装置.阴极氧还原反应（ORR）在燃料电池中起着关键作用.ORR广泛采用贵金属铂基催化剂，但是它们价格昂贵，电子动力学转移速率慢，碱性条件下易团聚，这些亟需解决的问题阻碍了燃料电池商业化进程.近期，一些非贵金属催化剂被广泛研究，例如氮掺杂碳材料、Fe/N/C和Co/N/C材料等，它们有可能在未来替代铂基催化剂.我们的目标是合成新型高催化活性的Co/N/C及其衍生非贵金属材料，用于ORR催化反应.
由于石墨烯具有独特的形貌、较大的比表面积和良好的导电性，其表面含有功能化的官能团，所以我们选择石墨烯作为碳载体.首先，用改性休克尔方法合成了氧化石墨烯（GO），为了提高其催化活性，采用聚吡咯作为氮源对其进行了氮掺杂，制备了聚吡咯/氧化石墨烯（Ppy/GO）.通过ORR催化性能测试发现，GO对ORR具有一定的催化活性，它的起始电位和阴极电流电位分别为-0.31 V vs SCE和-0.38 V vs SCE；Ppy/GO的起始电位和阴极电流电位分别为-0.20 V vs SCE和-0.38 Vvs SCE，氮掺杂对GO的催化活性有所提高.
采用水热法沉积氧化钴合成了Co₃O₄/聚吡咯/氧化石墨烯（Co₃O₄/Ppy/GO）.其形貌为Co₃O₄分散在氮掺杂GO表面.在KOH电解质（0.1 mol/L）中测试，Co₃O₄/Ppy/GO的起始电位和阴极电流电位分别为-0.20 V和-0.38 V vs SCE.经过800℃高温煅烧处理后，Co₃O₄/Ppy/GO-800的催化活性明显提高，起始电位和阴极电流电位分别达到-0.10 V和-0.18 V vs SCE.ORR电子转移数为3.4，接近于4电子反应途径.Co₃O₄/Ppy/GO对ORR的催化活性及4电子催化选择性较高，可能是由于纳米形态的Co₃O₄和Ppy/GO之间具有较强的表面作用力，聚吡咯掺杂的氧化石墨烯具有较强的电子储存及释放能力.
综上，我们通过水热法制备了钴、氮共掺杂的GO，并研究了其对ORR的催化活性和电子转移选择性.结果表明Co₃O₄/Ppy/GO是一种高效的非贵金属电催化剂，在碱性电解质中具有很高的ORR催化活性，在燃料电池阴极催化剂方面很有前景.

关键词: 非贵金属电催化剂, 四氧化三钴, 聚吡咯, 氧化石墨烯, 氧还原反应, 质子交换膜燃料电池

Abstract:

The development of highly efficient catalysts for cathodes remains an important objective of fuel cell research. Here, we report Co₃O₄ nanoparticles assembled on a polypyrrole/graphene oxide electrocatalyst (Co₃O₄/Ppy/GO) as an efficient catalyst for the oxygen reduction reaction (ORR) in alkaline media. The catalyst was prepared via the hydrothermal reaction of Co²⁺ ions with Ppy-modified GO. The GO, Ppy/GO, and Co₃O₄/Ppy/GO were characterized using scanning electron microscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The incorporation of Ppy into GO nanosheets resulted in the formation of a nitrogen-modified GO po-rous structure, which acted as an efficient electron-transport network for the ORR. With further anchoring of Co₃O₄ on Ppy/GO, the as-prepared Co₃O₄/Ppy/GO exhibited excellent ORR activity and followed a four-electron route mechanism for the ORR in alkaline solution. An onset potential of -0.10 V vs. a saturated calomel electrode and a diffusion limiting current density of 2.30 mA/cm² were achieved for the Co₃O₄/Ppy/GO catalyst heated at 800℃; these values are comparable to those for noble-metal-based Pt/C catalysts. Our work demonstrates that Co₃O₄/Ppy/GO is highly active for the ORR. Notably, the Ppy coupling effects between Co₃O₄ and GO provide a new route for the preparation of efficient non-precious electrocatalysts with hierarchical porous structures for fuel cell applications.

Key words: Non-precious metal electrocatalyst, Co₃O₄, Polypyrrole, Graphene, Oxygen reduction reaction, Proton-exchange membrane fuel cell

任素贞, 郭亚男, 马少博, 毛庆, 吴丹丹, 杨莹, 景洪宇, 宋雪旦, 郝策. Co₃O₄/聚吡咯/石墨烯碱性溶液中电化学还原氧[J]. 催化学报, 2017, 38(7): 1281-1290.

Suzhen Ren, Yanan Guo, Shaobo Ma, Qing Mao, Dandan Wu, Ying Yang, Hongyu Jing, Xuedan Song, Ce Hao. Co₃O₄ nanoparticles assembled on polypyrrole/graphene oxide for electrochemical reduction of oxygen in alkaline media[J]. Chinese Journal of Catalysis, 2017, 38(7): 1281-1290.

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Co₃O₄/聚吡咯/石墨烯碱性溶液中电化学还原氧

Co₃O₄ nanoparticles assembled on polypyrrole/graphene oxide for electrochemical reduction of oxygen in alkaline media

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