碳模板诱导生长Fe-N<sub><i>x</i></sub>活性位点

引用本文: 张世明, 张鹤友, 张维民, 原鲜霞, 陈胜利, 马紫峰. 碳模板诱导生长Fe-N_x活性位点[J]. 催化学报, 2018, 39(8): 1427-1435. doi: 10.1016/S1872-2067(18)63107-9 shu

Citation: Shiming Zhang, Heyou Zhang, Weimin Zhang, Xianxia Yuan, Shengli Chen, Zi-Feng Ma. Induced growth of Fe-N_x active sites using carbon templates[J]. Chinese Journal of Catalysis, 2018, 39(8): 1427-1435. doi: 10.1016/S1872-2067(18)63107-9 shu

碳模板诱导生长Fe-N_x活性位点

a 上海交通大学化学工程系, 上海电化学能源器件工程技术研究中心, 上海 200240;
b 武汉大学化学与分子科学学院, 湖北省化学电源材料与技术重点实验室, 教育部生物医学分析化学重点实验室, 湖北武汉 430072;
c 上海中聚佳华电池科技有限公司, 中聚电池研究院, 上海 200241
基金项目:
国家自然科学基金（21606149，2163308）；中国博士后基金（2016M591678）；上海市青年科技启明星计划资助（18QB1404400）；上海市科研计划项目（18511110803）.

摘要: 能源危机和环境恶化是当今社会面临的巨大挑战.燃料电池作为一种高效、清洁的发电装置，受到了社会各界特别是新能源行业的高度关注.尤其是，日本丰田推出Mirai燃料电池汽车量产上市计划，把燃料电池及其关键技术发展推向了一个新的发展纪元.然而，制约燃料电池走向大规模商业化的核心问题依然是其综合性能不具竞争力.其中，氧电极的缓慢动力学以及贵金属Pt的有限资源、高昂成本等是关键所在，因此，亟待实现高性能非贵金属催化剂的突破.
近年来，大量研究表明，Fe-N_x掺杂的碳催化剂具有极大的代Pt潜力，研究者们尝试各种手段进行开发，如：调控Fe化合物及N前驱体的类型与添加量，改变温度、压力等合成条件，采用轴向配位体连接、共价接枝、球磨等非热解路线，构建核壳、有序介孔碳、阵列、类石墨烯薄片、多孔碳等碳纳米结构，制备石墨烯/碳纳米管、石墨烯/碳黑、碳纳米带/碳纳米管、碳纳米颗粒/碳纤维、碳球/碳纳米管/石墨烯等复合材料，进行酸洗、造孔、二次加热等后处理，调控不同类型Fe物种相生成等.此外，EXAFS及Mössbauer等谱学技术已经证实Fe-N_x特别是Fe-N₄为强活性位点.因此，有待提出合理策略以促进非贵金属碳催化剂中Fe-N_x强活性位点的高密度掺杂.
本文提出了一种碳模板诱导Fe-N_x活性位点生长的方法即通过高温热解含有Fe盐的三聚氰胺前驱体混合物，成功制备了Fe-N_x掺杂的碳催化剂，并结合多种表征技术证实了碳模板对制备碳催化剂结构组成及电化学性能的影响.形貌结果说明，碳模板的引入有利于Fe、N化合物的均匀吸附以至于Fe基纳米颗粒的均一成核，促使竹状碳纳米管在碳模板表面以及中间均一生长；氮气吸脱附及孔径分布曲线显示，引入碳模板形成的复合材料较单一的碳纳米管和碳黑材料具有提高的比表面积和总孔体积，说明复合材料中存在两种单体的有效协同； Mössbauer、XPS及XRD测试数据证实，碳模板可以调控Fe、N两种元素的耦合方式，能够抑制金属Fe和Fe碳化物等非活性Fe物种的生成、诱导Fe-N₄和其它Fe氮化物等强活性Fe-N_x物种的生长.电化学测试数据表明，复合材料具有提升的面积活性和质量活性，且TOF值明显提高，说明碳模板的引入增强了Fe-N_x位点的本征活性；此外，复合材料的氧还原过程为高效的4e^-途径，且较商业Pt/C催化剂表现出了优异的循环稳定性和甲醇耐受性.

关键词:

English

Induced growth of Fe-N_x active sites using carbon templates

a Department of Chemical Engineering, Shanghai Electrochemical Energy Devices Research Center, Shanghai Jiao Tong University, Shanghai 200240, China;
b College of Chemistry and Molecular Sciences, Hubei Key Laboratory of Electrochemical Power Sources, Key Laboratory of Analytical Chemistry for Biology and Medicine(Ministry of Education), Wuhan University, Wuhan 430072, Hubei, China;
c Sinopoly Battery Research Center, Shanghai Sinopoly Jiahua Battery Technology Co., Ltd., Shanghai 200241, China
Received Date: 04 January 2018
Revised Date: 27 May 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (21606149, 2163308), the China Postdoctoral Science Foundation (2016M591678), the Shanghai Rising-Star Program (18QB1404400), and the Shanghai Scientific Research Project (18511110803).

Abstract: Highly active Fe-N_x sites that effectively improve the performance of non-precious metal electrocatalysts for oxygen reduction reactions (ORRs) are desirable. Herein, we propose a strategy for introducing a carbon template into a melamine/Fe-salt mixture to inductively generate highly active Fe-N_x sites for ORR. Using ⁵⁷Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction, we studied the structural composition of the Fe and N co-doped carbon catalysts. Interestingly, the results showed that this system not only converted inactive Fe and Fe-carbides into active Fe-N₄ and other Fe-nitrides, but also improved their intrinsic activities.

Key words:

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碳模板诱导生长Fe-N_x活性位点

English

Induced growth of Fe-N_x active sites using carbon templates

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

碳模板诱导生长Fe-Nx活性位点

English

Induced growth of Fe-Nx active sites using carbon templates

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

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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