水热法制备还原氧化石墨烯及其导电性调控

doi:10.11949/j.issn.0438-1157.20171582

化工学报 ›› 2018, Vol. 69 ›› Issue (7): 3263-3269.DOI: 10.11949/j.issn.0438-1157.20171582

• 材料化学工程与纳米技术 • 上一篇下一篇

水热法制备还原氧化石墨烯及其导电性调控

翁程杰¹, 史叶勋¹, 何大方^1,2,3, 沈丽明¹, 暴宁钟^1,2,3

1 南京工业大学化工学院, 材料化学工程国家重点实验室, 江苏南京 210009;
2 江苏省产业技术研究院石墨烯材料研究所, 江苏常州 213100;
3 江南石墨烯研究院, 江苏常州 213149

收稿日期:2017-11-30 修回日期:2018-02-01 出版日期:2018-07-05 发布日期:2018-07-05
通讯作者: 沈丽明, 暴宁钟
基金资助:
国家自然科学基金项目（51425202，51772150）；江苏省自然科学基金项目（BK20160093，BK20171012）；常州市科技支撑计划项目（CE20150054）；江苏高校优势学科建设工程资助项目。

Hydrothermal synthesis of reduced graphene oxide with tunable conductivity

WENG Chengjie¹, SHI Yexun¹, HE Dafang^1,2,3, SHEN Liming¹, BAO Ningzhong^1,2,3

1 College of Chemical Engineering, State Key Laboratory of Material-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, China;
2 Jiangsu Industrial Technology Research Institute, Graphene Material Research Institute, Changzhou 213100, Jiangsu, China;
3 Jiangnan Graphene Research Institute, Changzhou 213149, Jiangsu, China

Received:2017-11-30 Revised:2018-02-01 Online:2018-07-05 Published:2018-07-05
Supported by:
supported by the National Natural Science Foundation of China (51425202, 51772150), the Natural Science Foundation of Jiangsu Province (BK20160093, BK20171012), the Industrial Support Program of Changzhou (CE20150054) and the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).

摘要/Abstract

摘要：

导电性可调控的还原氧化石墨烯（rGO）在结构功能材料和化工新材料等领域具有重要的应用前景。本文利用水热还原法实现了rGO的绿色制备，并通过调控反应温度和时间，获得了电导率可控的rGO产品，其电导率范围为10^-4～1 S·cm^-1。采用UV-vis、FT-IR、XPS、SEM、XRD和Raman等表征方法系统研究了rGO还原过程中结构与组成的变化。发现GO还原过程中，其含氧官能团于120℃时开始明显分解，高于140℃后含量显著降低，GO片层sp2区域逐渐恢复，电导率逐渐增大到1 S·cm^-1，同时层间距从8.2 Å减少到3.6 Å（1 Å=0.1 nm）。对比热还原法，水热法有效避免了rGO片层的堆叠，产物分散性较好，有望规模化制备导电性可控的rGO产品。本研究成果对rGO生产和应用具有重要意义。

关键词: 还原氧化石墨烯, 分散液, 制备, 纳米材料, 显微结构, 电导率

Abstract:

Reduced graphene oxide (rGO) with tunable conductivity has great promise for potential applications in the fields of advanced structural-functional composites, new chemical materials and so on. In this research, environment-friendly hydrothermal method was applied to prepare rGO. The conductivity of the synthesized rGO can be controlled from 10^-4 to 1 S·cm^-1 by changing the hydrothermal reaction temperature and time. Various characterization techniques such as UV-vis, FT-IR, XPS, SEM, XRD, and Raman spectroscopy were used to analyze the composition and structure change of the rGO. The results showed that the oxygen contained functional groups on the rGO surface decomposed rapidly at ≥ 120℃, and the content of oxygen contained functional groups decreased drastically at ≥ 140℃. Meanwhile, the carbon sp2 region of the rGO was recovered gradually, which caused the conductivity increased to 1 S·cm^-1 and the interlayer spacing decreased from 8.2 Å to 3.6 Å. Compared with thermal reduction method, hydrothermal method avoids the aggregation and stacking of the rGO, which has great significance in large-scale production of the rGO with tunable conductivity.

Key words: reduced graphene oxide, dispersion, preparation, nanomaterials, microstructure, conductivity

中图分类号:

TB303

翁程杰, 史叶勋, 何大方, 沈丽明, 暴宁钟. 水热法制备还原氧化石墨烯及其导电性调控[J]. 化工学报, 2018, 69(7): 3263-3269.

WENG Chengjie, SHI Yexun, HE Dafang, SHEN Liming, BAO Ningzhong. Hydrothermal synthesis of reduced graphene oxide with tunable conductivity[J]. CIESC Journal, 2018, 69(7): 3263-3269.

参考文献 31

[1]	EDA G, CHHOWALLA M. Chemically derived graphene oxide:towards large-area thin-film electronics and optoelectronics[J]. Advanced Materials, 2010, 22(22):2392-415.
[2]	LAVEK R K, NANDI A K. A review on synthesis and properties of polymer functionalized graphene[J]. Polymer, 2013, 54(19):5087-5103.
[3]	MOHAN V B, BROWN R, JAYARAMAN K, et al. Characterisation of reduced graphene oxide:effects of reduction variables on electrical conductivity[J]. Materials Science & Engineering B, 2015, 193(2):49-60.
[4]	GEORGAKILAS V, OTYEPKA M, BOURLINOS A B, et al. Functionalization of graphene:covalent and non-covalent approaches, derivatives and applications[J]. Chemical Reviews, 2012, 112(11):6156-6214.
[5]	RAY S C. Chapter 2. Application and uses of graphene oxide and reduced graphene oxide[M]//Applications of Graphene and GrapheneOxide Based Nanomaterials. Elsevier Inc., 2015:39-55.
[6]	SHIM G, KIM M G, PARK J Y, et al. Graphene-based nanosheets for delivery of chemotherapeutics and biological drugs[J]. Advanced Drug Delivery Reviews, 2016, 105(Part B):205-227.
[7]	STANKOVICH S, DIKIN D A, PINER R D, et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide[J]. Carbon, 2007, 45(7):1558-1565.
[8]	LI C, SHI G. Functional gels based on chemically modified graphenes[J]. Advanced Materials, 2014, 26(24):3992-4012.
[9]	AUNKOR M T, MAHBUBUL I M, SAIDUR R, et al. The green reduction of graphene oxide[J]. RSC Advances, 2016, 6(33):27807-27828.
[10]	何大方, 吴健, 刘战剑, 等. 面向应用的石墨烯制备研究进展[J]. 化工学报, 2015, 66(8):2888-2894. HE D F, WU J, LIU Z J, et al. Recent advances in preparation of graphene for applications[J]. CIESC Journal, 2015, 66(8):2888-2894.
[11]	PARK S, AN J, POTTS J R, et al. Hydrazine-reduction of graphite-and graphene oxide[J]. Carbon, 2011, 49(9):3019-3023.
[12]	HAFIZ S M, RITIKOS R, WHITCHER T J, et al. A practical carbon dioxide gas sensor using room-temperature hydrogen plasma reduced graphene oxide[J]. Sensors & Actuators B Chemical, 2014, 193(3):692-700.
[13]	BAI Y F, ZHANG Y F, ZHOU A W, et al. Self-assembly of a thin highly reduced graphene oxide film and its high electrocatalytic activity[J]. Nanotechnology, 2014, 25(40):405601.
[14]	CHEN C, ZHANG Q, YANG M, et al. Structural evolution during annealing of thermally reduced graphene nanosheets for application in supercapacitors[J]. Carbon, 2012, 50(10):3572-3584.
[15]	CAO J, WANG Y, XIAO P, et al. Hollow graphene spheres selfassembled from graphene oxide sheets by a one-step hydrothermal process[J]. Carbon, 2013, 56(5):389-391.
[16]	SILVA K K H D, HUANG H H, JOSHI R K, et al. Chemical reduction of graphene oxide using green reductants[J]. Carbon, 2017, 119:190-199.
[17]	PEI S, CHENG H. The reduction of graphene oxide[J]. Carbon, 2012, 50(9):3210-3228.
[18]	ZHOU Y, BAO Q L, TANG L A L, et al. Hydrothermal dehydration for the "green" reduction of exfoliated graphene oxide to graphene and demonstration of tunable optical limiting properties[J]. Chemistry of Materials, 2009, 21(13):2950-2956.
[19]	WAN W C, ZHANG F, YU S, et al. Hydrothermal formation of graphene aerogel for oil sorption:the role of reducing agent, reaction time and temperature[J]. New Journal of Chemistry, 2016, 40(4):3040-3046.
[20]	SHEN J F, YAN B, SHI M, et al. One step hydrothermal synthesis of TiO2-reduced graphene oxide sheets[J]. Journal of Materials Chemistry, 2011, 21(10):3415-3421.
[21]	李吉, 魏彤, 闫俊, 等. 石墨烯纳米片/CoS2复合材料的制备及其在超级电容器中的应用[J]. 化工学报, 2014, 65(7):2849-2854. LI J, WEI T, YAN J, et al. Preparation of graphene nanosheet/CoS2 composite and its application in supercapacitors[J]. CIESC Journal, 2014, 65(7):2849-2854.
[22]	贾海鹏, 苏勋家, 侯根良, 等. 石墨烯/聚合物纳米复合材料制备与微波吸收性能研究进展[J]. 化工学报, 2012, 63(6):1663-1668. JIA H P, SU X J, HOU G L, et al. Progress of fabrication and microwave absorption capacity of graphene/polymer nanocomposites[J]. CIESC Journal, 2012, 63(6):1663-1668.
[23]	刘芳, 樊丰涛, 吕玉翠, 等. 石墨烯/TiO2复合材料光催化降解有机污染物的研究进展[J]. 化工学报, 2016, 67(5):1635-1643. LIU F, FAN F T, LÜ Y C, et al. Research progress on photocatalytic degradation of organic pollutants by graphene/TiO2 composite materials[J]. CIESC Journal, 2016, 67(5):1635-1643.
[24]	LI C, SHI Y X, CHEN X, et al. Controlled synthesis of graphite oxide:formation process, oxidation kinetic sand optimized conditions[J]. Chemical Engineering Science, 2018, 176:319-328.
[25]	HE D F, SHEN L M, ZHANG X Y, et al. An efficient and eco-friendly solution-chemical route for preparation of ultrastable reduced graphene oxide suspensions[J]. AIChE Journal, 2014, 60(8):2757-2764.
[26]	KRISHNAMOORTHY K, VEERAPANDⅡAN M, YUN K, et al. The chemical and structural analysis of graphene oxide with different degrees of oxidation[J]. Carbon, 2013, 53(1):38-49.
[27]	KUMAR P V, BARDHAN N M, TONGAY S, et al. Scalable enhancement of graphene oxide properties by thermally driven phase transformation[J]. Nature Chemistry, 2014, 6(2):151-158.
[28]	ABRAHAM J, VASU K S, WILLIAMS C D, et al. Tunable sieving of ions using graphene oxide membranes[J]. Nature Nanotechnology, 2017, 12(6):546-550.
[29]	FERRARI A C, BASKO D M. Raman spectroscopy as a versatile tool for studying the properties of graphene[J]. Nature Nanotechnology, 2013, 8(4):235-246.
[30]	HU K, XIE X, SZKOPEK T, et al. Understanding hydrothermally reduced graphene oxide hydrogels:from reaction products to hydrogel properties[J]. Chemistry of Materials, 2016, 28(6):1756-1768.
[31]	MALARD L M, PIMENTA M A, DRESSELHAUS G, et al. Raman spectroscopy in graphene[J]. Physics Reports, 2009, 473(5):51-87.

水热法制备还原氧化石墨烯及其导电性调控

Hydrothermal synthesis of reduced graphene oxide with tunable conductivity

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价

[1]	刘远超, 关斌, 钟建斌, 徐一帆, 蒋旭浩, 李耑. 单层XSe₂（X=Zr/Hf）的热电输运特性研究[J]. 化工学报, 2023, 74(9): 3968-3978.
[2]	胡亚丽, 胡军勇, 马素霞, 孙禹坤, 谭学诣, 黄佳欣, 杨奉源. 逆电渗析热机新型工质开发及电化学特性研究[J]. 化工学报, 2023, 74(8): 3513-3521.
[3]	陈佳起, 赵万玉, 姚睿充, 侯道林, 董社英. 开心果壳基碳点的合成及其对Q235碳钢的缓蚀行为研究[J]. 化工学报, 2023, 74(8): 3446-3456.
[4]	葛加丽, 管图祥, 邱新民, 吴健, 沈丽明, 暴宁钟. 垂直多孔碳包覆的FeF₃正极的构筑及储锂性能研究[J]. 化工学报, 2023, 74(7): 3058-3067.
[5]	刘春雨, 周桓宇, 马跃, 岳长涛. CaO调质含油污泥干燥特性及数学模型[J]. 化工学报, 2023, 74(7): 3018-3027.
[6]	吴文涛, 褚良永, 张玲洁, 谭伟民, 沈丽明, 暴宁钟. 腰果酚生物基自愈合微胶囊的高效制备工艺研究[J]. 化工学报, 2023, 74(7): 3103-3115.
[7]	邢美波, 张中天, 景栋梁, 张洪发. 磁调控水基碳纳米管协同多孔材料强化相变储/释能特性[J]. 化工学报, 2023, 74(7): 3093-3102.
[8]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.
[9]	王志龙, 杨烨, 赵真真, 田涛, 赵桐, 崔亚辉. 搅拌时间和混合顺序对锂离子电池正极浆料分散特性的影响[J]. 化工学报, 2023, 74(7): 3127-3138.
[10]	董茂林, 陈李栋, 黄六莲, 吴伟兵, 戴红旗, 卞辉洋. 酸性助水溶剂制备木质纳米纤维素及功能应用研究进展[J]. 化工学报, 2023, 74(6): 2281-2295.
[11]	杨琴, 秦传鉴, 李明梓, 杨文晶, 赵卫杰, 刘虎. 用于柔性传感的双形状记忆MXene基水凝胶的制备及性能研究[J]. 化工学报, 2023, 74(6): 2699-2707.
[12]	刘远超, 蒋旭浩, 邵钶, 徐一帆, 钟建斌, 李耑. 几何尺寸及缺陷对石墨炔纳米带热输运特性的影响[J]. 化工学报, 2023, 74(6): 2708-2716.
[13]	朱风, 陈凯琳, 黄小凤, 鲍银珠, 李文斌, 刘嘉鑫, 吴玮强, 高王伟. KOH改性电石渣脱除羰基硫的性能研究[J]. 化工学报, 2023, 74(6): 2668-2679.
[14]	张雪婷, 胡激江, 赵晶, 李伯耿. 高分子量聚丙二醇在微通道反应器中的制备[J]. 化工学报, 2023, 74(3): 1343-1351.
[15]	靳志远, 单国荣, 潘鹏举. AM/AMPS/SSS三元共聚物的制备及耐温耐盐性能[J]. 化工学报, 2023, 74(2): 916-923.