新材料与新技术

氮掺杂石墨烯的制备及阻燃性能研究

展开
  • 1.兰州理工大学 石油化工学院,兰州730050;
    2.中石油川庆钻探工程有限公司 长庆钻井总公司,川庆710021
赵秋萍(1978-),女,副教授,主要从事电化学和铝电解产物的回收利用,E-mail:1134743502@qq.com。

收稿日期: 2019-12-17

  修回日期: 2021-02-28

  网络出版日期: 2021-05-07

基金资助

甘肃省科技重大专项(18ZD2GF019);甘肃省自然科学基金(20JR5RA441);兰州理工大学学生科技创新基金(KC2019ZR046)

Preparation of nitrogen-doped graphene and its flame retardantproperty

Expand
  • 1. School of Petrochemical Engineering,Lanzhou University of Technology,Lanzhou 730050;
    2. Changqing Drilling Co.,CNPC Chuanqing Drilling Engineering Co.,Ltd.,Chuanqing 710021

Received date: 2019-12-17

  Revised date: 2021-02-28

  Online published: 2021-05-07

摘要

采用简单廉价的一步热解法制备了具有良好热稳定性和阻燃性能的氮掺杂石墨烯(NG),经透射电镜表征,NG具有类石墨烯碳纳米片层结构,可观察到高度透明的纹理,以及褶皱交叉连接的薄膜片层形貌。经X射线光电子能谱(XPS)表征,NG含有碳、氮、氧元素;XPS分析结果表明,NG由大量碳和少量的氧、氮元素组成;微型量热仪分析结果表明,800℃下制备的NG的热释放速率为0W/g,总热释放量为45J/g,低于石墨烯(98J/g);热重分析表明,NG在800℃下残炭剩余量高达29%,高于卤系阻燃剂。可见,氮元素的掺杂可有效地改善石墨烯片层的热稳定性,使NG表现出良好的热稳定性和阻燃性能。

关键词: 氮掺杂; 石墨烯; 阻燃

本文引用格式

赵秋萍, 杨柳, 赵胜斌, 李春雷, 郭军红, 郭永亮 . 氮掺杂石墨烯的制备及阻燃性能研究[J]. 化工新型材料, 2021 , 49(4) : 92 -98 . DOI: 10.19817/j.cnki.issn1006-3536.2021.04.020

Abstract

Nitrogen-doped graphene (NG) with good thermal stability and flame retardancy was prepared by simple and inexpensive one-step pyrolysis method.It was characterized by transmission electron microscopy (TEM).NG had graphene-like carbon nanosheet structure,which can be observed.X-ray photoelectron spectroscopy (XPS) was used to characterize NGR containing carbon,nitrogen,phosphorus and oxygen.XPS analysis shown that NG consists of a large amount of carbon and a small amount of oxygen.The microcalorimeter analysis showed that the heat release rate of NG was 0w/g,and the total heat release was 45J/g which was lower than that of graphene(98J/g),showing excellent thermal stability.Thermogravimetric analysis showed that the residual amount of carbon residue at 800℃ was as high as 29wt%,which was higher than that of halogen-based flame retardant and had good flame retardant properties.

参考文献

[1] Feng Y,He C,Wen Y,et al.Superior flame retardancy and smoke suppression of epoxy-based composites with phosphorus/nitrogen co-doped graphene[J].Hazard Mater,2018,346:140-151.
[2] Liu H,Li Q,Zhang S,et al.Electrically conductive polymer composites for smart flexible strain sensors:a critical review[J].Mater Chem,2018,6(45):12121-12141.
[3] Wang S,Gao R.Zhou K,The influence of cerium dioxide functionalized reduced graphene oxide on reducing fire hazards of thermoplastic polyurethane nanocomposites[J].Colloid Interface Sci,2019,536:127-134.
[4] Zhou K,Gui Z,Hu Y.The influence of graphene based smoke suppression agents on reduced fire hazardsof polystyrene composites[J].Composites:Part A,Applied Science and Manufacturing,2016,80:217-227.
[5] Kim F,Luo J,Cruz-Silva R,et al.Self-propagating domino-like reactions in oxidized graphite[J].Adv Funct Mater,2010,20(17):2867-2873.
[6] Erickson K,Erni R,Lee Z,et al.Determination of the local chemical structure of graphene oxide and reduced graphene oxide[J].Adv Mater,2010,22(40):4467-4472.
[7] Sandoval S,Kumar N,Sundaresan A,et al.Enhanced thermal oxidation stability of reduced graphene oxide by nitrogen doping[J].Chemistry-A European Journal,2014,20(38):11999-12003.
[8] Kim M J,Jeon I Y,Seo J M,et al.Graphene phosphonic acid as an efficient flame retardant[J].ACS Nano,2014,8(3):2820-2825.
[9] Sandoval S,Kumar N,Oro-Solé J,et al.Tuning the nature of nitrogen atoms in N-containing reduced graphene oxide[J].Carbon,2016,96:594-602.
[10] Some S,Shackery I,Kim S J,et al.Phosphorus-doped graphene oxide layer as a highly efficient flame retardant[J].Chemistry-A European Journal,2015,21(44):15480.
[11] Yuan B H,Xing W Y,Hu Y X,et al.Boron/phosphorus doping for retarding the oxidation of reduced graphene oxide[J].Carbon,2016,101:152-158.
[12] Wang H,Maiyalagan T,Wang X.Review on recent progress innitrogen-doped graphene:synthesis,characterization,and its potential applications[J].ACS Catal,2012,2:781-794.
[13] Xu H,Ma L,Jin Z.Nitrogen-doped graphene:synthesis,characterizations and energy applications[J].Energy Chem,2018,27:146-160.
[14] Zu L,Gao X,Lian H,et al.High electrochemical performance phosphorus-oxide modified graphene electrode for redox supercapacitors prepared by one-step electrochemical exfoliation[J].Nano Materials,2018,(8):417.
[15] Tian Y,Ma Y,Liu H,et al.One-step and rapid synthesis of nitrogen and sulfur co-doped graphene for hydrogen peroxide and glucose sensing[J].Electroanal Chem,2015,742:8-14.
[16] MacIntosh A R,Jiang G,Zamani P,et al.Phosphorus and nitrogen centers in doped graphene and carbon nanotubes analyzed through solid-state[J].Phys Chem,2018,122:6593-6601.
[17] Santhosh R,Raman S R S,Krishna S M,et al.Heteroatom doped graphene based hybrid electrode materials for supercapacitor applications[J].Electrochim Acta,2018,276:284-292.
[18] Feng Y Z,He C G,Wen Y F,et al.Superior flame retardancy and smoke suppression of epoxy-based composites with phosphorus/nitrogen co-doped graphene[J].Hazard Mater,2018,346:140-151.
[19] Agnoli S,Favaro M.Doping graphene with boron:a review of synthesis methods,physicochemical characterization,and emerging applications[J].Mater Chem,2016,4:5002-5025.
[20] Lv Q,Si W,Yang Z,et al.Nitrogen-doped porous graphdiyne:a highly efficient metal-free electrocatalyst for oxygen reduction reaction[J].ACS Appl Mater Interfaces,2017,9:29744.
[21] Wu Z S,Winter A,Chen L,et al.Three-dimensional nitrogen and boron co-doped graphene for high-performance all-solid-state supercapacitors[J].Adv Mater,2012,24:5130-5135.
[22] Sandoval S,Kumar N,Sundaresan A,et al.Enhanced thermal oxidation stability of reduced graphene oxide by nitrogen doping[J].Chem Eur,2014,20:11999-12003.
[23] Sandoval S,Kumar N,Oro-SoléJ,et al.Tuning the nature of nitrogen atoms in N-containing reduced graphene oxide[J].Carbon,2016,96:594-602.
[24] Shabestari M E,Kalali E N,González V J,et al.Effect of nitrogen and oxygen doped carbon nanotubes on flammability of epoxy nanocomposites[J].Carbon,2017,121:193-200.
[25] Li N,Wang Z Y,Zhao K K,et al.Large scale synthesis of N-doped multi-layered graphene sheets by simple arc-discharge method[J].Carbon,2010,48(1):255-259.
[26] Hummers W S,Offeman Jr R E.(1958) Journal of American Chemical Society,80,1339.
[27] Liu J,Zhang T,Wang Z,et al.Simple pyrolysis of urea into graphitic carbon nitride with recyclable adsorption and photocatalytic activity[J].Journal of Materials Chemistry,2011,21(38):14398-14401.
[28] Xu J,Li Y,Peng S,et al.Eosin Y-sensitized graphitic carbon nitride fabricated by heating urea for visible light photocatalytic hydrogen evolution:the effect of the pyrolysis temperature of urea[J].Physical Chemistry,2013,15(20):7657-7665.
[29] Li X L,Wang H L,Robinson J T,et al.Simultaneous Nitrogen Doping and Reduction of Graphene Oxide[J].Journal of the American Chemical Society,2009,131(43):15939-15944.
[30] Ruiz-Hitzky E,Darder M,Fernandes F M,et al.Supported graphene from natural resources:easy preparation and applications[J].Advanced Materials,2011,23(44):5250-5255.
[31] Westenfelder B,Meyer J C,Biskupek J,et al.Transformations of carbon adsorbates on graphene substrates under extreme heat[J].Nano Letters,2011,11(12):5123-5127.
[32] Holst J R,Gillan E G.From triazines to heptazines:deciphering the local structure of amorphous nitrogen-rich carbon nitride materials[J].Journal of the American Chemical Society,2008,130(23):7373-7379.
[33] Jun Y S,Hong W H,Antonietti M,et al.Mesoporous,2D hexagonal carbon nitride and titanium nitride/carbon composites[J].Advanced Materials,2009,21(42):4270-4274.
[34] Barreiro A,Boerrnert F,Avdoshenko S M,et al.Understanding the catalyst-free transformation of amorphous carbon into graphene by current-induced annealing[J].Scientific Reports,2013,3:1115.
[35] Paredez P,Maia da Costa M E H,Zagonel L F,et al.Growth of nitrogenated fullerene-like carbon on Ni islands by ion beam sputtering[J].Carbon,2007,45(13):2678-2684.
[36] Dimovski S,Nikitin A,Ye H,et al.Synthesis of graphite by chlorination of iron carbide at moderate temperatures[J].Mater Chem,2004,14:238-243.
[37] Ran S,Guo Z,Han L,et al.Effect of friedel-crafts reaction on the thermal stability and flammability of high-density polyethylene /brominated polystyrene /graphene nanoplatelet composites[J].Polym Int,2014,63(10):1835-1841.
[38] Ran S,Chen C,Guo Z.Char barrier effect of graphene nanoplatelets on the flame retardancy and thermal stability of high-density polyethylene flame-retarded by brominated polystyrene[J].Appl Polym Sci,2014,131(15):4401-4404.
[39] Qi W,Shapter J G,Wu Q,et al.Nano structured anode materials for lithium-ion batteries:principle,recent progress and future perspectives[J].Mater Chem,2017,(5):19521-19540.
[40] Xu B,Shi L,Guo X W,et al.Nano-CaCO3 templated mesoporous carbon as anode material for Li-ion batteries[J].Electrochim Acta,2011,56:6464-6468.
[41] Li T T,Yang G W,Wang J,et al.Excellent electrochemical performance of nitrogen-enriched hierarchical porous carbon electrodes prepared using nano-CaCO3 as template[J].Solid State Electrochem,2013,2013,17:2651-2660.
[42] 洪宁宁.石墨烯的功能化改性及其典型聚合物复合材料的热解与阻燃性能研究[D].合肥:中国科学技术大学,2014.
[43] Byon H R,Suntivich J,Shao-Horn Y,et al.Graphene-based non-noble-metal catalysts for oxygen reduction reaction in acid[J].Chemistry of Materials,2011,23(15):3421-3428.
[44] Pels J R,Kapteijn F,Moulijn J A,et al.Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis[J].Carbon,1995,33(11):1641-1653.
[45] Choi J Y,Higgins D,Chen Z W,et al.Highly durable graphene nanosheet supported iron catalyst for oxygen reduction reaction in PEM fuel cells[J].Journal of the Electrochemical Society,2012,159(1):B87-B90.
[46] Das A,Pisana S,Chakraborty B,et al.Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor[J].Nature Nanotechnology,2008,3(4):210.
[47] Zhu Y,Murali S,Stoller M D,et al.Microwave assisted exfoliation and reduction of graphite oxide for ultracapacitors[J].Carbon,2010,48(7):2118-2122.
[48] Chen W F,Yan L F,Bangal P R.Preparation of graphene by the rapid and mild thermal reduction of graphene oxide induced by microwaves[J].Carbon,2010,48(4):1146-1152.
[49] Liu H,Li Q,Zhang S,et al.Electrically conductive polymer composites for smart flexible strain sensors:a critical review[J].Mater Chem,2018,6(45):12121-12141.
[50] Huang G B,Gao J R,Wang X,et al.How can graphene reduce the flam mability of polymer nanocom posites[J].Mater Lett,2012,66:187-189.
[51] Ma H L,Zhang H B,Hu Q H,et al.Functionalization and reduction of graphene oxide with p-phenylene diamine for electrically conductive and thermally stable polystyrene composites[J].ACS Appl Mater Interf,2012,4:1948-1953.
[52] Xu L,Xiao L,Jia P,et al.Lightweight and ultrastrong polymer foams with unusually superior flame retardancy[J].ACS Appl Mater,Interfaces,2017,9(31):26392-26399.
[53] Pethsangave D A,Khose R V,Wadekar P H,et al.Deep eutectic solvent functionalized graphene composite as an extremely high potency flame retardant[J].ACS Appl Mater Interfaces,2017,9(40):35319-35324.
[54] Jeon I Y,Shin S H,Choi H J,et al.Heavily aluminated graphene nanoplatelets as an efficient flame-retardant[J].Carbon,2017,116:77-83.
[55] In-Yup Jeon,Seo-Yoon Bae,Jeong-Min Seo.Scalable production of edge-functionalized graphene nanoplatelets via mechanochemical ball-milling[J].Adv Funct Mater,2015,25(45):6961-6975.
[56] Li N,Wang Z Y,Zhao K K,et al.Large scale synthesis of N-doped multi-layered graphene sheets by simple arc-discharge method[J].Carbon,2010,48(1):255-259.
Options
文章导航

/