氮掺杂石墨烯@碳纳米纤维的原位制备及其电催化氧还原性能

doi:10.15541/jim20150400

无机材料学报 ›› 2016, Vol. 31 ›› Issue (4): 351-357.DOI: 10.15541/jim20150400 CSTR: 32189.14.10.15541/jim20150400

氮掺杂石墨烯@碳纳米纤维的原位制备及其电催化氧还原性能

施旗¹, 雷永鹏^{2, 3}, 王应德¹, 王仲民⁴

(1. 国防科技大学新型陶瓷纤维及其复合材料重点实验室, 长沙 410073; 2. 清华大学低维量子物理国家重点实验室, 北京 100084; 3. 国防科技大学基础教育学院, 长沙 410073; 4. 桂林电子科技大学广西信息材料重点实验室, 桂林 541004)

收稿日期:2015-08-25 修回日期:2015-10-14 出版日期:2016-04-20 网络出版日期:2016-03-25
作者简介:施旗(1989–), 女, 硕士研究生. E-mail: shiqi0806@163.com
基金资助:
国家自然科学基金(51203182, 51173202);湖南省优秀博士学位论文获得者科研项目(YB2014B004);低维量子物理国家重点实验室(清华大学)开放基金(KF201312);广西信息材料重点实验室(桂林电子科技大学)开放基金(桂能科1210908-01-K)

In-situ Preparation and Electrocatalytic Oxygen Reduction Performance of N-doped Graphene@CNF

SHI Qi¹, LEI Yong-Peng^{2, 3}, WANG Ying-De¹, WANG Zhong-Min⁴

(1. Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, National University of Defense Technology, Changsha 410073, China; 2. State Key Laboratory of Low-Dimensional Quantum Physics, Tsinghua University, Beijing, 100084, China; 3. College of Basic Education, National University of Defense Technology, Changsha 410073, China; 4. Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004, China)

Received:2015-08-25 Revised:2015-10-14 Published:2016-04-20 Online:2016-03-25
About author:SHI Qi. E-mail: shiqi0806@163.com
Supported by:
National Natural Science Foundation of China (51203182, 51173202);Foundation for the Author of Excellent Doctoral Dissertation of Hunan Province (YB2014B004);Open Research Fund Program of the State Key Laboratory of Low-Dimensional Quantum Physics (KF201312);Open Fund of Guangxi Key Laboratory of Information Materials (Guilin University of Electronic Technology) (1210908-01-K)

摘要/Abstract

摘要：

结合静电纺丝和热处理技术, 在含钴碳纳米纤维上原位生长了氮掺杂石墨烯, 制备了三维互通纤维网结构。研究了钴含量对产物氧还原活性的影响。结果表明: 氮掺杂石墨烯的生成和钴的引入均显著提高了电催化活性。纺丝液中六水合硝酸钴与聚丙烯腈的质量比为1: 10时, 获得的催化剂活性最优, 起始电势为0.84 V(vs RHE), 反应为近四电子路径, 具有比铂碳更好的稳定性和耐甲醇毒化能力。三维互通结构促进了电子和质子传输, 并能提供更多的活性位点, 提高电催化活性。这种方法也可用于设计其它三维互通的纤维复合物, 在能源与环境领域具有更广泛的应用前景。

关键词: 氧还原反应, 氮掺杂石墨烯, 原位制备, 三维互通纤维网

Abstract:

By combining the techniques of electrospinning and heat-treatment, N-doped graphene (NG) were in situ grown on cobalt-containing electronspun carbon nanofibers (CNF) to form three-dimensional (3D) interconnected fiber network structure. The effect of cobalt (Co) content on the oxygen reduction reaction (ORR) activity of the as-prepared samples was studied. It is demonstrated that both the formation of NG and introduction of Co significantly increase the electrocatalytic activity. The hybrid shows optimized ORR performance when the weight ratio of Co(NO₃)₂·6H₂O to PAN in electronspun solution is 1: 10. The as-obtained catalyst exhibits superior ORR catalytic performance with onset potential of 0.84 V (vs RHE), near four electron transfer pathway. In addition, the sample presents better stability and methanol tolerance than Pt/C in alkaline media. As-obtained interconnected fiber networks facilitate electron and mass transfer to provide more active sites, favorable to the enhancement of electrocatalytic activity. This strategy is also available to prepare other 3D interconnected fiber composites for using in energy and environmental fields.

Key words: oxygen reduction reaction, N-doped graphene, in situ-preparation, 3D interconnected fiber network

中图分类号:

TQ174

施旗, 雷永鹏, 王应德, 王仲民. 氮掺杂石墨烯@碳纳米纤维的原位制备及其电催化氧还原性能[J]. 无机材料学报, 2016, 31(4): 351-357.

SHI Qi, LEI Yong-Peng, WANG Ying-De, WANG Zhong-Min. In-situ Preparation and Electrocatalytic Oxygen Reduction Performance of N-doped Graphene@CNF[J]. Journal of Inorganic Materials, 2016, 31(4): 351-357.

图/表 7

图1 NG@CNF-Cox的制备流程图

Fig. 1 Schematic illustration for the preparation of NG@CNF-Cox

图2 (a)不同样品在1600 r/min下的极化曲线, NG@CNF-Co10(b)在不同转速下的极化曲线和(c)相应的在0.29 到0.49 V下的K-L图, (d)不同样品在0.29~0.49 V下的电子转移数

Fig. 2 (a) Polarization curves at 1600 r/min of different samples, (b) polarization curves at different rotating speeds and (c) the corresponding K-L plots of NG@CNF-Co10, (d) electron transfer number of different samples from 0.29 V to 0.49 V

图3 (a)NG@CNF-Co10和(b)Pt/C的稳定性及耐甲醇毒化能力

Fig. 3 Durability and methanol tolerance of (a) NG@CNF-Co10 and (b) Pt/C

图4 CNF和NG@CNF-Co10(插图)的SEM照片

Fig. 4 SEM images of CNF and NG@CNF-Co10 (inset)

图5 NG@CNF-Co10在77 K下的氮气吸附-解吸附曲线图(插入图)及孔径分布图

Fig. 5 Nitrogen adsorption-desorption isotherm at 77 K (inset) and pore size distribution of NG@CNF-Co10

图6 NG@CNF-Co10的(a)XRD、(b)Raman谱图和(c)TGA 曲线

Fig. 6 (a) XRD pattern, (b) Raman spectrum and (c) TGA curve of NG@CNF-Co10

图7 NG@CNF-Co10的(a)XPS全谱图, 相应的高分辨(b)N1s, (c)Co2p和(d)C1s谱图

Fig. 7 (a) XPS survey and corresponding high-resolution (b) N1s (c) Co2p and (d) C1s spectra of NG@CNF-Co10

参考文献 30

[1]	GONG K P, DU F, XIA Z H, et al.Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction.Science, 2009, 323(5915): 760-764.
[2]	LIN Z, WALLER G H, LIU Y, et al.Simple preparation of nanoporous few-layer nitrogen-doped graphene for use as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions.Carbon, 2013, 53(3): 130-136.
[3]	SHI Q, LEI Y P, WANG Y D, et al.B, N-codoped 3D micro-/ mesoporous carbon nanofibers web as efficient metal-free catalysts for oxygen reduction.Curr. Appl. Phys., 2015, 15(12): 1606-1614.
[4]	WU G, MORE K L, JOHNSTON C M, et al.High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt.Science, 2011, 332(6028): 443-447.
[5]	HAN C, WANG Y D, LEI Y P, et al.In situ synthesis of graphitic-C3N4 nanosheet hybridized N-doped TiO2 nanofibers for efficient photocatalytic H2 production and degradation.Nano Res., 2015, 8(4): 1199-1209.
[6]	WU N, WANG Y D, LEI Y P, et al.Preparation and photocatalytic activity of N-Ag co-doped TiO2/C porous ultrafine fibers mat.Ceram. Int., 2014, 40(1): 2017-2022.
[7]	XIE S, WANG Y D, LEI Y P, et al.Simply prepared flexible SiBOC ultrafine fiber mat with enhanced high-temperature stability and chemical resistance.RSC Adv., 2015, 5(80): 64911-64917.
[8]	WANG Y D, WANG B, LEI Y P, et al.Scalable in situ growth of SnO2 nanoparticle chains on SiC ultrathin fibers via a facile Sol-Gel-flame method.Appl. Surf. Sci., 2015, 335: 208-212.
[9]	GUO L P, BAI J, LIANG H O, et al.Preparation and application of carbon nanofibers-supported palladium nanoparticles catalysts based on electrospinning.J. Inorg. Mater., 2014, 29(8): 814-820.
[10]	WANG B, WANG Y D, LEI Y P, et al. Tailoring of porous structure in macro-meso-microporous SiC ultrathin fibers via electrospinning combined with polymer-derived ceramics route. Mater. Manuf. Process., .
[11]	WANG B, WANG Y D, LEI Y P, et al.Hierarchically porous SiC ultrathin fibers mat with enhanced mass transport, amphipathic property and high-temperature erosion resistance.J. Mater. Chem. A, 2014, 2(48): 20873-20881.
[12]	WANG Y D, HAN C, ZHENG D C, et al.Large-scale, flexible and high-temperature resistant ZrO2/SiC ultrafine fibers with a radial gradient composition.J. Mater. Chem. A, 2014, 2(25): 9607-9612.
[13]	WANG H G, YUAN S, MA D L, et al.Electrospun materials for lithium and sodium rechargeable batteries: from structure evolution to electrochemical performance.Energy Environ. Sci., 2015, 6(8): 1660-1681.
[14]	DALLMEYER I, LIN L T, LI Y J, et al.Preparation and characterization of interconnected, kraft lignin-based carbon fibrous materials by electrospinning.Macromol. Mater. Eng., 2014, 299(5): 540-551.
[15]	CHENG Y L, HUANG L, XIAO X, et al.Flexible and cross-linked N-doped carbon nanofiber network for high performance free standing supercapacitor electrode.Nano Energy, 2015, 15: 66-74.
[16]	YE T N, LV L B, LI X H, et al.Strongly veined carbon nanoleaves as highly efficient metal-free electrocatalyst.Angew. Chem. Int. Ed., 2014, 53(27): 6905-6909.
[17]	SHI Q, WANG Y D, WANG Z M, et al.3D interconnected networks constructed by in situ growth of N-doped graphene/carbon nanotubes on cobalt-containing carbon nanofibers for enhanced oxygen reduction.Nano Res., 2015, doi: 10.1007/s12274-015-0911-y.
[18]	HUANG D, LUO Y, LI S, et al.Active catalysts based on cobalt oxide@cobalt/N-C nanocomposites for oxygen reduction reaction in alkaline solutions.Nano Res., 2014, 7(7): 1054-1064.
[19]	LIANG J, ZHOU R F, CHEN X M, et al.Fe-N decorated hybrids of CNTs grown on hierarchically porous carbon for high-performance oxygen reduction.Adv. Mater., 2014, 26(35): 6074-6079.
[20]	LIANG J, DU X, GIBSON C, et al.N-doped graphene natively grown on hierarchical ordered porous carbon for enhanced oxygen reduction.Adv. Mater., 2013, 25(43): 6226-6231.
[21]	KANG Y, CHU Z Y, ZHANG D J, et al.Incorporate boron and nitrogen into graphene to make BCN hybrid nanosheets with enhanced microwave absorbing properties.Carbon, 2013, 61(11): 200-208.
[22]	ZHANG Y H, YI Q F, LIU X P, et al.Carbonizing products of the Fe/Co doped polypyrrole as efficient electrocatalysts for exygen reduction reaction.J. Inorg. Mater., 2014, 29(3): 269-274.
[23]	WU N, WANG Y D, LEI Y P, et al.Flexible N-doped TiO2/C ultrafine fiber mat and its photocatalytic activity under simulated sunlight.Appl. Surf. Sci., 2014, 319: 136-142.
[24]	MA Y, WANG S, CHEN Z H.In situ growth of a carbon interphase between carbon fibres and a polycarbosilane-derived silicon carbide matrix.Carbon, 2011, 49(8): 2869-2872.
[25]	ZHENG Y, JIAO Y, GE L, et al.Two-step boron and nitrogen doping in graphene for enhanced synergistic catalysis.Angew. Chem. Int. Ed., 2013, 125(11): 3192-3198.
[26]	REN G Y, LI Y N, GUO Z Y, et al.Bio-inspired Co3O4- polypyrrole-graphene complex as efficient oxygen reduction catalyst by one-step ball-milling.Nano Res., 2015, 8(11): 3461-3471.
[27]	JAGADEESH R, JUNGE H, POHL M, et al.Selective oxidation of alcohols to esters using heterogeneous Co3O4-N@C catalysts under mild conditions.J. Am. Chem. Soc., 2013, 135(29): 10776-10782.
[28]	LIANG Y, LI Y, WANG H, et al.Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction.Nat. Mater., 2011, 10(10): 780-786.
[29]	LEE J S, PARK G S, KIM S T, et al.A highly efficient electrocatalyst for the oxygen reduction reaction: N-doped ketjenblack incorporated into Fe/Fe3C-functionalized melamine foam.Angew. Chem. Int. Ed., 2013, 52(3): 1026-1030.
[30]	ZHANG G X, XU Y Q, WANG L, et al.Rational design of graphene oxide and its hollow CoO composite for superior oxygen reduction reaction.Sci. China Mater., 2015, 58(7): 534-542.

氮掺杂石墨烯@碳纳米纤维的原位制备及其电催化氧还原性能

In-situ Preparation and Electrocatalytic Oxygen Reduction Performance of N-doped Graphene@CNF

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 30

相关文章 11

编辑推荐

Metrics

本文评价

[1]	杨代辉, 孙甜, 田合鑫, 史晓斐, 马东伟. 铁氮共掺杂介孔碳材料的简易制备及其氧还原反应催化性能[J]. 无机材料学报, 2023, 38(11): 1309-1315.
[2]	孙炼, 顾全超, 杨雅萍, 王洪磊, 余金山, 周新贵. 二维过渡金属硫属化合物氧还原反应催化剂的研究进展[J]. 无机材料学报, 2022, 37(7): 697-709.
[3]	安琳, 吴淏, 韩鑫, 李耀刚, 王宏志, 张青红. 非贵金属Co_5.47N/N-rGO助催化剂增强TiO₂光催化制氢性能[J]. 无机材料学报, 2022, 37(5): 534-540.
[4]	蒋丽丽, 徐帅帅, 夏宝凯, 陈胜, 朱俊武. 缺陷调控石墨烯复合催化剂在氧还原反应中的作用[J]. 无机材料学报, 2022, 37(2): 215-222.
[5]	刘自若, 刘炜, 郝策, 胡金文, 史彦涛. 蜂窝状碳负载铁基单原子催化剂的制备及ORR催化性能研究[J]. 无机材料学报, 2021, 36(9): 943-949.
[6]	郝策, 刘自若, 刘炜, 史彦涛. 用于氧还原反应的碳基负载金属单原子催化剂研究进展[J]. 无机材料学报, 2021, 36(8): 820-834.
[7]	朱勇, 顾军, 于涛, 何海佟, 姚睿. 铂钴合金纳米电催化剂的制备及性能研究[J]. 无机材料学报, 2021, 36(3): 299-305.
[8]	丁昇, 宁锴, 袁斌霞, 潘卫国, 尹诗斌, 刘建峰. 碱性溶液中不同微观结构的Fe-N/C催化剂氧还原性能的稳定性对比研究[J]. 无机材料学报, 2020, 35(8): 953-958.
[9]	何王涛, 马汝广, 朱钰方, 杨明杰, 王家成. 氢氧化钾活化制备可再生多孔碳及其电催化氧还原性能研究[J]. 无机材料学报, 2019, 34(10): 1115-1122.
[10]	崔香枝, 张琳琳, 曾黎明, 张晓华, 陈航榕, 施剑林. 石墨化介孔碳包裹WC纳米粒子的构建及其氧还原性能研究[J]. 无机材料学报, 2018, 33(2): 213-220.
[11]	于建华, 许丽丽, 张武寿, 朱倩倩, 王晓霞, 董立峰. 氮掺杂和SnO₂纳米粒子负载对全固态对称型石墨烯超级电容器性能的影响[J]. 无机材料学报, 2015, 30(6): 662-666.