Pt/Co-N-C电催化材料的制备及其碱性ORR性能

摘要/Abstract

摘要： 金属有机框架材料(MOFs)是一种制备过渡金属-氮-碳(M-N-C)氧还原电催化材料的有效前驱体,但在热解过程中结构坍塌等问题限制了其实际应用。本研究通过表面活性剂F-127包覆以及Zn掺杂对ZIF-67进行改性,并对改性后的Zn-ZIF-67@F-127在氩气气氛下进行热解,制得结构完整的Co-N-C载体。通过在Co-N-C载体表面进行Pt的负载,制备了Pt/Co-N-C复合氧还原反应(ORR)催化剂,并对其在碱性电解液中的ORR催化性能进行了探究。实验结果表明,F-127的加入提高了Zn-ZIF-67@F-127在热解过程中的形貌保持率,Pt/Co-N-C在O₂饱和的0.1 mol·L^-1 KOH中,催化剂的起始电位、半波电位、极限扩散电流密度分别为1.027 V、0.836 V和5.51 mA·cm^-2,与商用20% Pt/C性能相近。Pt与Co-N-C的协同作用使得催化剂不仅对ORR的四电子路径显示出高选择性,更在计时电流测试中表现出接近于商用20% Pt/C的稳定性与较商用20% Pt/C更优的抗甲醇性能。

关键词: Pt/Co-N-C电催化材料, 氧还原反应, ZIF-67, F-127, 碱性电解液, 抗甲醇性能

Abstract: Metal-organic frameworks (MOFs) are regarded as effective precursors for the preparation of M-N-C oxygen reduction electrocatalytic materials. However, the structural collapse of MOFs during the pyrolysis limits their practical application. In this study, ZIF-67 was firstly modified by coating with the surfactant of F-127 and doping with Zn. After that, the modified Zn-ZIF-67@F-127 was pyrolyzed under argon atmosphere to fabricate the Co-N-C support with complete structure. By loading Pt on the surface of Co-N-C support, the Pt/Co-N-C composite catalyst for oxygen reduction reaction (ORR) was obtained. The ORR catalytic performances in the alkaline electrolyte were systematically studied. The experimental results show that the addition of F-127 can improve the morphological retention of Zn-ZIF-67@F-127 during the pyrolysis. More importantly, the onset potential, half-wave potential, and diffusion-limited current density of Pt/Co-N-C in O₂-saturated 0.1 mol·L^-1 KOH are 1.027 V, 0.836 V, and 5.51 mA·cm^-2, respectively, which are similar to those of the commercial 20% Pt/C catalyst. The synergistic effect of Pt and Co-N-C not only exhibits a high selectivity and current density for the ORR four-electron pathway, but also shows a high stability approaching the commercial 20% Pt/C catalyst, and superior methanol resistance performance compared with the commercial 20% Pt/C in the chronoamperometry test.

Key words: Pt/Co-N-C electrocatalytic material, oxygen reduction reaction, ZIF-67, F-127, alkaline electrolyte, methanol resistance performance

中图分类号:

O643.36

任志立, 段磊, 徐守冬, 陈良, 易群, 张鼎. Pt/Co-N-C电催化材料的制备及其碱性ORR性能[J]. 人工晶体学报, 2023, 52(4): 654-662.

REN Zhili, DUAN Lei, XU Shoudong, CHEN Liang, YI Qun, ZHANG Ding. Preparation of Pt/Co-N-C Electrocatalytic Material and Its ORR Performances in Alkaline Electrolyte[J]. Journal of Synthetic Crystals, 2023, 52(4): 654-662.

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