ZnCl<sub>2</sub>辅助制备FeNC催化剂:增加活性位点密度以提高氧还原活性

引用本文: 毛占鑫, 王敏杰, 刘璐, 彭立山, 陈四国, 李莉, 李静, 魏子栋. ZnCl₂辅助制备FeNC催化剂:增加活性位点密度以提高氧还原活性[J]. 催化学报, 2020, 41(5): 799-806. doi: S1872-2067(19)63405-4 shu

Citation: Zhan Xin Mao, Min Jie Wang, Lu Liu, Lishan Peng, Siguo Chen, Li Li, Jing Li, Zidong Wei. ZnCl₂ salt facilitated preparation of FeNC: Enhancing the content of active species and their exposure for highly-efficient oxygen reduction reaction[J]. Chinese Journal of Catalysis, 2020, 41(5): 799-806. doi: S1872-2067(19)63405-4 shu

ZnCl₂辅助制备FeNC催化剂:增加活性位点密度以提高氧还原活性

毛占鑫 ^a, ,
王敏杰 ^a, ,
刘璐 ^b, ,
彭立山 ^a, ,
陈四国 ^a, ,
李莉 ^a, ,
李静 ^a, ,
魏子栋 ^a,

a 重庆大学化学化工学院, 重庆 400044;
b 重庆大学材料科学与工程学院, 重庆 400044
基金项目:
国家重点研发计划（2016YFB0101202）；国家自然科学基金（21878030，91534205，21436003）.

摘要: Fe、N掺杂的碳材料（FeNC）是最有希望取代贵金属用作氧还原反应的催化剂之一.然而，传统FeNC材料制备过程中所采用的高温碳化-蚀刻步骤会造成相邻Fe原子随温度升高而逐渐团聚，形成较大尺寸金属铁单质、铁氧化物或碳化物的聚集颗粒，并在后续酸刻蚀处理中被移出，铁元素损失严重，无法形成有效活性位点.同时高温下含N小分子物质也容易分解并从产物中逸出，导致N元素掺杂量较低.直接焙烧还加重了碳的团聚，造成材料内部孔道有限，比表面积低，活性位难以暴露于三相界面.因此，焙烧处理过程中如何形成Fe、N元素的高含量、均匀分散掺杂，同时构建大量内部联通孔道，是形成高活性FeNC催化剂的关键.本文采用ZnCl₂辅助焙烧方法制备出具有高活性位点密度和大材料孔隙率的FeNC催化剂；通过TEM、N₂吸附和XPS等一系列物理手段对所制备样品进行了形貌、结构及组成表征，提出了ZnCl₂辅助催化剂合成机理；结合CV和LSV等电化学测试结果详细探讨了ZnCl₂辅助方法对催化剂结构和催化性能的影响.
普通共价盐ZnCl₂在283-732℃的较宽温度范围内呈现熔融态，同卟啉铁（FePc）碳化温度区间恰好匹配，可以辅助FeNC催化剂进行元素掺杂和多级孔结构的构建.首先，在熔融状态下，过量的ZnCl₂形成分支结构，阻止相邻Fe物种直接接触和聚集，有利于形成高度分散的FeN_x活性位点.其次，熔融的ZnCl₂像盖子一样包封住催化剂前驱体，避免了挥发性含N小分子的快速逸出，使得N原子在高温下有可能重新在碳骨架中形成掺杂，有助于在材料中保留更高比例的活性N物质.在ZnCl₂的辅助下碳化FePc得到的Sphere-FeNC样品具有高达4.37%的总N含量，并且Fe-N_x含量也高达0.71%，分别是不使用ZnCl₂制备的对比催化剂FeNC-none的3.2和13倍.同时，ZnCl₂辅助合成方法将FeNC材料的比表面积增加4.5倍，总孔体积增加7倍.三电极氧还原反应性能测试表明，Sphere-FeNC在碱性和酸性介质的初始电位分别为1.080和1.015V（vs RHE），半波电位分别为0.906和0.799V（vs RHE），活性优异.以Sphere-FeNC为阴极催化剂组装的单电池功率达到0.72Wmg^-1，高于已报道的FeNC和Pt/C催化剂.因此，ZnCl₂辅助焙烧碳化的方法可以作为一种普适手段用于构建具有高密度活性元素掺杂和大量微孔介孔分布的碳基催化材料，并应用于各类催化反应.

关键词:

English

ZnCl₂ salt facilitated preparation of FeNC: Enhancing the content of active species and their exposure for highly-efficient oxygen reduction reaction

a School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China;
b School of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
Received Date: 03 October 2019
Revised Date: 13 November 2019
Fund Project:
This work was financially supported by the National Key R&

Abstract: Introducing catalytically-active Fe and N into carbon materials results in promising FeNC catalysts for oxygen reduction reaction. However, the doped Fe and N species are frequently subject to heavy loss in a traditional carbonization process owing to Fe agglomeration and evaporation of N-contained small molecules. Besides, pyrolysis may make materials sintering which embeds a large number of active sites in the bulk phase and impedes direct exposure of reactive centers to the reactants. We here report that when calcinations, the addition of ZnCl₂, an ordinary salt with very wide melting temperature range well covering the carbonization process of the precursor iron porphyrin, can significantly enhance the doping level of the active species and simultaneously create highly porous structures for FeNC catalysts. The obtained FeNC demonstrates ultrahigh catalytic activities even significantly better than Pt/C in oxygen reduction reaction.

Key words:

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ZnCl₂辅助制备FeNC催化剂:增加活性位点密度以提高氧还原活性

English

ZnCl₂ salt facilitated preparation of FeNC: Enhancing the content of active species and their exposure for highly-efficient oxygen reduction reaction

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ZnCl2辅助制备FeNC催化剂:增加活性位点密度以提高氧还原活性

English

ZnCl2 salt facilitated preparation of FeNC: Enhancing the content of active species and their exposure for highly-efficient oxygen reduction reaction

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

ZnCl₂辅助制备FeNC催化剂:增加活性位点密度以提高氧还原活性

ZnCl₂ salt facilitated preparation of FeNC: Enhancing the content of active species and their exposure for highly-efficient oxygen reduction reaction

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