摘要
Pt基催化剂是氧还原反应的优良催化剂,改善其活性和稳定性是燃料电池商业化的关键。本文利用金属有机框架衍生的氮掺杂碳材料为载体,通过浸渍、冻干和简单热处理的方法合成了Pt/NC、Pt3Zn/NC-L和Pt3Zn/NC-H催化剂,平均粒径均在2 nm左右。在Pt中引入Zn元素引起其晶格收缩,使Pt-Pt键变短,优化了Pt与含氧中间体的结合,增强氧还原反应的活性。在高合金化程度的Pt3Zn/NC-H催化剂上,氧还原反应的半波电位为0.903 V,较商业Pt/C正移57 mV。0.9 V下的质量活性和面积比活性分别是商业Pt/C的4.50倍和3.33倍。在O2饱和的0.1 mol·L^(-1) HClO4溶液,0.6~1.0 V(vs.RHE)进行10000周稳定性测试,商业Pt/C的质量活性和面积比活性分别衰减25.00%和23.80%,而在Pt3Zn/NC-H催化剂上未观察到衰减。
Proton exchange membrane fuel cell(PEMFC)is a new type of energy device,a relatively excellent way to achieve carbon neutrality.However,due to the relatively slow reaction rate of oxygen reduction reaction(ORR)at the cathode,platinum(Pt)is the key material of the cathode catalyst.However,Pt is a kind of noble metal,and its high cost restricts the PEMFC commercialization process.At present,the main approach is to combine transition metals with Pt to prepare Pt-based alloys and to reduce the use of Pt.Pt-based alloys are excellent catalysts for ORR,improving both the activity and stability,and increasing the Pt utilization rate and the number of active sites of the catalyst.In this paper,by employing nitrogen-doped carbon material derived from a metal organic framework as a support,Pt/NC,Pt3Zn/NC-L and Pt3Zn/NC-H catalysts were successfully synthesized by impregnation,freeze-drying and simple heat treatment.The particle sizes were around 2 nm and uniformly supported on the carbon.Raman data shows that the defect degree was slightly reduced after loading metal,mainly because the nanoparticles would be anchored in the defect position,and the metal would help the graphitization of carbon at high temperature.The introduction of Zn into Pt caused the Pt lattice to be shrunk,which shortens the Pt-Pt bond length,and optimizes the combination of Pt and oxygen-containing intermediates,ultimately enhances the ORR activity.On the highly alloyed Pt_(3)Zn/NC-H catalyst,the half-wave potential was 0.903 V,which is a positive shift of 57 mV compared with commercial Pt/C,moreover,the mass activity and area specific activity at 0.9 V were 4.50 times and 3.33 times to those of commercial Pt/C,respectively.The 10000-cycle stability test was carried out in an O_(2)-saturated 0.1 mol·L^(-1) HClO_(4) solution at 0.6~1.0 V(vs.RHE).The mass activity and area specific activity of commercial Pt/C decreased by 25.00%and 23.80%,respectively,while Pt_(3)Zn/NC-H catalyst revealed excellent stability.Transmission electron microscopic(TEM)observation shows that after the stability test,the nanoparticles were well dispersed on the nitrogen-doped carbon support,however,the commercial Pt/C became a slight agglomeration.Small particle sized Pt-based catalysts,constructed with a metal-organic framework-derived nitrogen-doped carbon material as a carrier,can improve the electrocatalytic activity and stability toward ORR,providing new ideas for the design and construction of Pt-based oxygen reduction catalysts.
作者
张天恩
颜雅妮
张俊明
瞿希铭
黎燕荣
姜艳霞
Tian-En Zhang;Ya-Ni Yan;Jun-Ming Zhang;Xi-Ming Qu;Yan-Rong Li;Yan-Xia Jiang(State Key Laboratory of Physical Chemistry of Solid Surfaces,Department of Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,Fujian,China)
出处
《电化学》
CAS
CSCD
北大核心
2022年第4期19-29,共11页
Journal of Electrochemistry
基金
科技部重点研发计划(No.2017YFA0206500)
国家自然科学基金项目(No.21773198,No.U1705253)资助
作者简介
通讯作者:姜艳霞,Tel:(86-592)2181081,E-mail:yxjiang@xmu.edu.cn。
