氧还原和析氧反应的双功能电催化剂——氮磷共掺碳负载四氧化三钴

doi:10.1016/S1872-2067(16)62462-2

催化学报 ›› 2016, Vol. 37 ›› Issue (8): 1249-1256.DOI: 10.1016/S1872-2067(16)62462-2

氧还原和析氧反应的双功能电催化剂——氮磷共掺碳负载四氧化三钴

黄颖彬^a,b, 张敏^a, 柳鹏^a, 程发良^a, 王立世^b

a. 东莞理工学院广东省新型纳米材料工程技术研究中心, 广东东莞 523808;
b. 华南理工大学化学与化工学院, 广东广州 510640

收稿日期:2016-01-21 修回日期:2016-05-03 出版日期:2016-07-29 发布日期:2016-08-01
通讯作者: Faliang Cheng, Lishi Wang
基金资助:
国家自然科学基金（21375016，20475022，21505019）.

Co₃O₄ supported on N, P-doped carbon as a bifunctional electrocatalyst for oxygen reduction and evolution reactions

Yingbin Huang^a,b, Min Zhang^a, Peng Liu^a, Faliang Cheng^a, Lishi Wang^b

a. Guangdong Engineering and Technology Research Center for Advanced Nanomaterials, Dongguan University of Technology, Dongguan 523808, Guangdong, China;
b. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China

Received:2016-01-21 Revised:2016-05-03 Online:2016-07-29 Published:2016-08-01
Contact: Faliang Cheng, Lishi Wang
Supported by:
This work was supported by the National Natural Science Foundation of China (21375016, 20475022 and 21505019).

摘要/Abstract

摘要：

金属-空气电池具备诸多优势，譬如绿色环保、能量转化率高、启动快速、能量密度高、使用寿命和干态存储时间长等.与燃料电池相比，金属-空气电池结构简单，放电电压平稳，成本低，但依然存在一些制约发展的问题，如阴极催化剂.阴极催化剂在金属-空气电池中发挥催化氧还原反应（oxygen reduction reaction，ORR）和析氧反应（oxygen evolution reaction，OER）的关键作用.铂及其合金常用作ORR的单功能催化剂，而钌和铱等是目前OER催化效率最高的，但ORR活性很低，因此需要开发出一种廉价而又具备双功能催化作用的催化剂.单异原子掺杂的碳基催化剂的研究集中在ORR催化性能上，而多异原子共掺碳最近有研究表明具有双催化氧的性质，如氮磷共掺碳.在这些氮磷共掺的碳架中，氮磷共掺物起着OER催化作用，掺氮物为ORR催化的活性位点，而掺磷物起着强化作用.异原子掺杂负载的钴基催化剂（如掺氮还原氧化石墨烯载Co₃O₄）是近年来双功能催化剂研究的另一个热点.钴基催化剂有着催化ORR和OER的多价价态，然而其本身导电性能差，这一缺陷可通过杂化石墨化碳来弥补，石墨化碳有着优良的导电性能.据我们所知，目前仍没有关于氮磷共掺碳负载的Co₃O₄双催化氧的研究.我们合成了氮磷共掺碳（NPC）负载的Co₃O₄（Co₃O₄/NPC），并首次探索了其氧还原和析氧性能.Co₃O₄/NPC合成分两步进行.首先通过三聚氰胺与植酸之间的酯化或缩聚覆盖在导电炭黑颗粒表面，在保护气氛下焙烧得到NPC，然后经溶剂热反应以及空气中氧化合成Co₃O₄/NPC.催化剂的性能综合考虑了催化活性和稳定性两方面.采用线性扫描伏安法评估了OER和ORR的催化活性.对于OER，Co₃O₄/NPC的起始电势是0.54V（以饱和甘汞电极为参比电极），在0.80V时电流密度达到21.95mA/cm²，均优于Co₃O₄/C和NPC.Co₃O₄/NPC的高效OER催化可归因于氮磷共掺物与Co₃O₄之间的协同作用.对于ORR，Co₃O₄/NPC的催化效率与商用Pt/C相近，它们的扩散极限电流密度分别为-4.49和-4.76mA/cm²（E=-0.80V）.在ORR过程中，Co₃O₄起到主要的催化作用.采用计时电流（电流-时间）法评估了催化剂的稳定性.经6h测定，对于OER，Co₃O₄/NPC剩46%电流；而对于ORR，剩95%电流.整体而言，Co₃O₄/NPC在OER和ORR中都表现出高的催化效率以及良好的稳定性.

关键词: 阴极催化剂, 氧还原反应, 析氧反应, 掺杂碳, 钴

Abstract:

Noble metals, such as platinum, ruthenium and iridium-group metals, are often used as oxygen reduction or evolution reaction (ORR/OER) electrocatalysts. To reduce the cost and provide an application of bifunctional catalysis, in this work, cobalt oxide supported on nitrogen and phosphorus co-doped carbon (Co₃O₄/NPC) was fabricated and examined as a bifunctional electrocatalyst for OER and ORR. To prepare Co₃O₄/NPC, NPC was pyrolyzed from melamine and phytic acid supported on carbon, followed by the solvothermal synthesis of Co₃O₄ on NPC. Linear sweep voltammetry was used to evaluate the activity for OER and ORR. For OER, Co₃O₄/NPC showed an onset potential of 0.54 V (versus the saturated calomel electrode) and a current density of 21.95 mA/cm² at 0.80 V, which was better than both Co₃O₄/C and NPC. The high activity of Co₃O₄/NPC was attributed to a synergistic effect of the N, P co-dopants and Co₃O₄. For ORR, Co₃O₄/NPC exhibited an activity close to commercial Pt/C in terms of the diffusion limited current density (-4.49 vs -4.76 mA/cm² at -0.80 V), and Co₃O₄ played the key role for the catalysis. Chronoamperometry (current versus time) was used to evaluate the stability, which showed that Co₃O₄/NPC maintained 46% current after the chronoamperometry test for OER and 95% current for ORR. Overall, Co₃O₄/NPC exhibited high activity and improved stability for both OER and ORR.

Key words: Cathode catalyst, Oxygen reduction reaction, Oxygen evolution reaction, Doped carbon, Cobalt

黄颖彬, 张敏, 柳鹏, 程发良, 王立世. 氧还原和析氧反应的双功能电催化剂——氮磷共掺碳负载四氧化三钴[J]. 催化学报, 2016, 37(8): 1249-1256.

Yingbin Huang, Min Zhang, Peng Liu, Faliang Cheng, Lishi Wang. Co₃O₄ supported on N, P-doped carbon as a bifunctional electrocatalyst for oxygen reduction and evolution reactions[J]. Chinese Journal of Catalysis, 2016, 37(8): 1249-1256.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(16)62462-2

https://www.cjcatal.com/CN/Y2016/V37/I8/1249

参考文献

[1] F. Y. Cheng, J. Chen, Chem. Soc. Rev., 2012, 41, 2172-2192.
[2] A. K. Shukla, R. K. Raman, N. A. Choudhury, K. R. Priolkar, P. R. Sarode, S. Emura, R. Kumashiro, J. Electroanal. Chem., 2004, 563, 181-190.
[3] L. Xiong, A. Manthiram, Electrochim. Acta, 2004, 49, 4163-4170.
[4] B. Lim, M. J. Jiang, P. H. C. Camargo, E. C. Cho, J. Tao, X. M. Lu, Y. M. Zhu, Y. N. Xia, Science, 2009, 324, 1302-1305.
[5] J. R. C. Salgado, E. Antolini, E. R. Gonzalez, Appl. Catal. B, 2005, 57, 283-290.
[6] E. A. Franceschini, M. M. Bruno, F. A. Viva, F. J. Williams, M. Jobbágy, H. R. Corti, Electrochim. Acta, 2012, 71, 173-180.
[7] T. Reier, M. Oezaslan, P. Strasser, ACS Catal., 2012, 2, 1765-1772.
[8] E. Antolini, ACS Catal., 2014, 4, 1426-1440.
[9] D. S. Yang, D. Bhattacharjya, S. Inamdar, J. Park, J. S. Yu, J. Am. Chem. Soc., 2012, 134, 16127-16130.
[10] R. Silva, D. Voiry, M. Chhowalla, T. Asefa, J. Am. Chem. Soc., 2013, 135, 7823-7826.
[11] C. H. Choi, S. H. Park, S. I. Woo, ACS Nano, 2012, 6, 7084-7091.
[12] F. P. Pan, J. T. Jin, X. G. Fu, Q. Liu, J. Y. Zhang, ACS Appl. Mater. Interfaces, 2013, 5, 11108-11114.
[13] H. L. Jiang, Y. H. Zhu, Q. Feng, Y. H. Su, X. L. Yang, C. Z. Li, Chem. Eur. J., 2014, 20, 3106-3112.
[14] J. L. Zhu, S. P. Jiang, R. H. Wang, K. Y. Shi, P. K. Shen. J. Mater. Chem. A, 2014, 2, 15448-15453.
[15] R. Wu, S. G. Chen, Y. L. Zhang, Y. Wang, W. Ding, L. Li, X. Q. Qi, X. Shen, Z. D. Wei, J. Power. Sources, 2015, 274, 645-650.
[16] J. Wu, C. Jin, Z. R. Yang, J. H. Tian, R. Z. Yang, Carbon, 2015, 82, 562-571.
[17] Y. J. Gong, H. L. Fei, X. L. Zou, W. Zhou, S. B. Yang, G. L. Ye, Z. Liu, Z. W. Peng, J. Lou, R. Vajtai, B. I. Yakobson, J. M. Tour, P. M. Ajayan, Chem. Mater., 2015, 27, 1181-1186.
[18] H. Zhang, Y. Zhou, C. G. Li, S. L. Chen, L. Liu, S. W. Liu, H. M. Yao, H. Q. Hou, Carbon, 2015, 95, 388-395.
[19] X. Gong, S. S. Liu, C. Y. Ouyang, P. Strasser, R. Z. Yang, ACS Catal., 2015, 5, 920-927.
[20] G. F. Long, K. Wan, M. Y. Liu, X. H. Li, Z. X. Liang, J. H. Piao, Chin. J. Catal., 2015, 36, 1197-1204.
[21] J. T. Zhang, Z. H. Zhao, Z. H. Xia, L. M. Dai, Nat. Nanotechnol., 2015, 10, 444-452.
[22] R. Li, Z. D. Wei, X. L. Gou, ACS Catal., 2015, 5, 4133-4142.
[23] T. Y. Ma, J. R. Ran, S. Dai, M. Jaroniec, S. Z. Qiao, Angew. Chem. Int. Ed., 2015, 54, 4646-4650.
[24] Y. Y. Liang, Y. G. Li, H. L. Wang, J. G. Zhou, J. Wang, T. Regier, H. J. Dai, Nat. Mater., 2011, 10, 780-786.
[25] Z. L. Wang, S. Xiao, Z. L. Zhu, X. Long, X. L. Zheng, X. H. Lu, S. H. Yang. ACS Appl. Mater. Interfaces, 2015, 7, 4048-4055.
[26] S. Y. Liu, L. J. Li, H. S. Ahn, A. Manthiram, J. Mater. Chem. A, 2015, 3, 11615-11623.
[27] Y. Y. Liang, H. L. Wang, J. G. Zhou, Y. G. Li, J. Wang, T. Regier, H. J. Dai, J. Am. Chem. Soc., 2012, 134, 3517-3523.
[28] X. M. Ge, Y. Y. Liu, F. W. T. Goh, T. S. A. Hor, Y. Zong, P. Xiao, Z. Zhang, S. H. Lim, B. Li, X. Wang, Z. L. Liu, ACS Appl. Mater. Interfaces, 2014, 6, 12684-12691.
[29] J. W. Xiao, Q. Kuang, S. H. Yang, F. Xiao, S. Wang, L. Guo, Sci. Rep., 2013, 3, 2300.
[30] Q. Liu, J. T. Jin, J. Y. Zhang, ACS Appl. Mater. Interfaces, 2013, 5, 5002-5008.
[31] W. N. Yan, X. C. Cao, J. H. Tian, C. Jin, K. Ke, R. Z. Yang, Carbon, 2016, 99, 195-202.
[32] H. Y. Jin, J. Wang, D. F. Su, Z. Z. Wei, Z. F. Pang, Y. Wang, J. Am. Chem. Soc., 2015, 137, 2688-2694.
[33] L. J. Li, S. Y. Liu, A. Manthiram, Nano Energy, 2015, 12, 852-860.
[34] A. J. Bard, L. R. Faulkner, Electrochemical Method, Fundamentals and Applications, 2nd ed, Wiley, New York, 2001.
[35] J. Masa, W. Xia, I. Sinev, A. Q. Zhao, Z. Y. Sun, S. Grützke, P. Weide, M. Muhler, W. Schuhmann, Angew. Chem. Int. Ed, 2014, 53, 8508-8512.
[36] C. C. L. McCrory, S. Jung, J. C. Peters, T. F. Jaramillo, J. Am. Chem. Soc., 2013, 135, 16977-16987.

氧还原和析氧反应的双功能电催化剂——氮磷共掺碳负载四氧化三钴

Co₃O₄ supported on N, P-doped carbon as a bifunctional electrocatalyst for oxygen reduction and evolution reactions

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	赵磊, 张震, 朱昭昭, 李平波, 蒋金霞, 杨婷婷, 熊佩, 安旭光, 牛晓滨, 齐学强, 陈俊松, 吴睿. 缺陷氮掺杂碳耦合Co-N₅单原子位点用于高效锌-空气电池[J]. 催化学报, 2023, 51(8): 216-224.
[2]	王潇涵, 田汉, 余旭, 陈立松, 崔香枝, 施剑林. 非晶相电催化剂在电解水领域的研究进展[J]. 催化学报, 2023, 51(8): 5-48.
[3]	韩璟怡, 管景奇. 通过表面镧改性和体相锰掺杂协助钴尖晶石酸性下析氧[J]. 催化学报, 2023, 51(8): 1-4.
[4]	贡立圆, 王颖, 刘杰, 王显, 李阳, 侯帅, 武志坚, 金钊, 刘长鹏, 邢巍, 葛君杰. 重塑位于火山曲线右支的弱吸附金属单原子位点的配位环境及电子结构[J]. 催化学报, 2023, 50(7): 352-360.
[5]	李孜孜, 王嘉蔚, 黄衍钧, 欧阳钢锋. 钴(II)酞菁全氟化策略用于提升非贵金属体系中光催化还原CO₂性能[J]. 催化学报, 2023, 49(6): 160-167.
[6]	张光颖, 刘旭, 张欣欣, 梁志坚, 邢耕宇, 蔡斌, 沈迪, 王蕾, 付宏刚. P修饰提高Fe-N-C的氧反应活性用于高稳定的锌-空气电池[J]. 催化学报, 2023, 49(6): 141-151.
[7]	刘培功, 林铁军, 郭磊, 刘晓哲, 龚坤, 尧泰真, 安芸蕾, 钟良枢. 调控Co₂C局域浸润环境实现高碳效合成气直接制烯烃[J]. 催化学报, 2023, 48(5): 150-163.
[8]	姜润, 乔泽龙, 许昊翔, 曹达鹏. 用于氧还原反应的Fe-N-C单原子催化剂的缺陷工程[J]. 催化学报, 2023, 48(5): 224-234.
[9]	张文静, 李静, 魏子栋. 碳基氧还原电催化剂: 机理研究和多孔结构[J]. 催化学报, 2023, 48(5): 15-31.
[10]	詹麒尼, 帅婷玉, 徐慧民, 黄陈金, 张志杰, 李高仁. 单原子催化剂的合成及其在电化学能量转换中的应用[J]. 催化学报, 2023, 47(4): 32-66.
[11]	张志普, 卢珊珊, 张兵, 史艳梅. 揭示硫掺杂的碳材料在水电氧化过程中活性苯醌基团及惰性硫残留物的形成[J]. 催化学报, 2023, 47(4): 129-137.
[12]	唐甜蜜, 王寅, 韩憬怡, 张巧巧, 白雪, 牛效迪, 王振旅, 管景奇. 用于氧还原反应的双原子钴-铁催化剂[J]. 催化学报, 2023, 46(3): 48-55.
[13]	吴则星, 高玉肖, 王子璇, 肖卫平, 王新萍, 李彬, 李镇江, 刘晓斌, 马天翼, 王磊. 表面富集的超小铂纳米颗粒耦合缺陷磷化钴用于高效的电催化水分解和柔性锌空气电池[J]. 催化学报, 2023, 46(3): 36-47.
[14]	刘轩, 梁嘉顺, 李箐. 燃料电池金属间Pt-M合金氧还原催化剂的设计原理及合成方法[J]. 催化学报, 2023, 45(2): 17-26.
[15]	吴尧, 杨杰夫, 郑媚, 胡点轶, Teddy Salim, 汤碧珺, 刘政, 李述周. 直接化学气相沉积法制备二维钴铁氧体用于高效析氧反应[J]. 催化学报, 2023, 55(12): 265-277.

氧还原和析氧反应的双功能电催化剂——氮磷共掺碳负载四氧化三钴

Co3O4 supported on N, P-doped carbon as a bifunctional electrocatalyst for oxygen reduction and evolution reactions

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

Co₃O₄ supported on N, P-doped carbon as a bifunctional electrocatalyst for oxygen reduction and evolution reactions