煤基石墨烯/TiO2复合材料的制备及光催化性能

doi:10.16085/j.issn.1000-6613.2016-2038

化工进展 ›› 2017, Vol. 36 ›› Issue (07): 2568-2576.DOI: 10.16085/j.issn.1000-6613.2016-2038

煤基石墨烯/TiO₂复合材料的制备及光催化性能

曾会会^1,2, 仪桂云^1,2, 邢宝林^1,2, 黄光许^1,2, 谌伦建^1,2, 张传祥^1,2, 徐冰^1,2, 姚友恒¹, 张青山¹, 李颉¹

1 河南理工大学化学化工学院, 河南焦作 454000;
2 煤炭安全生产河南省协同创新中心, 河南焦作 454000

收稿日期:2016-11-08 修回日期:2017-03-24 出版日期:2017-07-05 发布日期:2017-07-05
通讯作者: 邢宝林,博士,副教授,主要从事洁净煤技术及新型炭材料方面的研究。
作者简介:曾会会(1990-),女,硕士研究生,研究方向为洁净煤技术。E-mail:huizeng1991@163.com。
基金资助:
国家自然科学基金（51404098，51174077）、河南省国际科技合作项目（152102410047）、国家级大学生创新创业训练计划（201610460040，201610460044）及河南理工大学博士基金（B2013-015）项目。

Preparation of coal-based graphene/TiO₂ composites and their photocatalytic activity

ZENG Huihui^1,2, YI Guiyun^1,2, XING Baolin^1,2, HUANG Guangxu^1,2, CHEN Lunjian^1,2, ZHANG Chuanxiang^1,2, XU Bing^1,2, YAO Youheng¹, ZHANG Qingshan¹, LI Jie¹

1 College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454000, Henan, China;
2 Collaborative Innovation Center of Coal Work Safety, Henan Province, Jiaozuo 454000, Henan, China

Received:2016-11-08 Revised:2017-03-24 Online:2017-07-05 Published:2017-07-05

摘要/Abstract

摘要： 以资源丰富的褐煤为原料，经高温石墨化处理后，采用改进的Hummers法制备氧化石墨烯（GO），再以四氯化钛（TiCl₄）为钛源，通过水热合成法制备煤基石墨烯/TiO₂（CRGO/TiO₂）复合材料。利用扫描电镜（SEM）、能谱仪（EDS）、透射电镜（TEM）、X射线衍射仪（XRD）、低温氮气物理吸附仪、傅里叶红外光谱仪（FTIR）对复合材料的微观结构进行系统表征，并重点研究不同GO添加量下所制CRGO/TiO₂复合材料对液相中罗丹明B的光催化降解性能。结果表明：以褐煤为碳质前体，TiCl₄为钛源，采用水热合成法可合成具有介孔特征的煤基石墨烯/TiO₂复合材料，其比表面积可达88.53~169.64m²/g，孔径主要分布在2~12nm，且随着GO添加量的增加，复合材料的孔径分布逐渐变窄。复合材料中的TiO₂纳米颗粒主要以锐钛矿晶型均匀分散于层状石墨烯表面。GO添加量是影响复合材料光催化降解性能的重要因素。当GO添加量为8%时，CRGO/TiO₂复合材料在可见光下对罗丹明B的降解率可达98.9%。

关键词: 褐煤, 石墨烯, 复合材料, 催化, 降解

Abstract: Graphene oxide (GO) was prepared from high temperature graphited lignite by modified Hummers method.The coal-based graphene/TiO₂ composites were synthesized subsequently via hydrothermal method using four titanium chloride (TiCl₄) as titanium source and graphene oxide as carbon source.The microstructure of the CRGO/TiO₂ composites was characterized by scanning electron microscopy (SEM),energy dispersive spectrometer (EDS),transmission electron microscope (TEM),X-ray diffraction(XRD),low temperature nitrogen adsorption and fourier transform infrared spectrometer (FTIR).The rhodamine B (RhB) photocatalytic degradation performance in liquid phase of CRGO/TiO₂ prepared at different additive amount of GO were also systematically investigated.The results show that coal-based graphene/TiO₂ composites with mesoporous characteristics can be synthesized via hydrothermal method using lignite as carbonaceous precursor and TiCl₄ as titanium source.The specific surface areas of CRGO/TiO₂ composites are as high as 88.53~169.64m²/g and the pore size is mainly in the range of 2~12nm.Moreover,the pore size distribution of CRGO/TiO₂ composites becomes more narrow with the increase of GO.The TiO₂ particles mainly in anatase phase homogeneously distribute on the surface or layers of graphene.The additive amount of GO is an important factor affecting the photocatalytic degradation performance of composites,and the removal rate of CRGO/TiO₂ for RhB can reach 98.9% under visible light irradiation when the amount of GO is 8%.

Key words: lignite, graphene, composites, catalysis, degradation

中图分类号:

O643.36

曾会会, 仪桂云, 邢宝林, 黄光许, 谌伦建, 张传祥, 徐冰, 姚友恒, 张青山, 李颉. 煤基石墨烯/TiO₂复合材料的制备及光催化性能[J]. 化工进展, 2017, 36(07): 2568-2576.

ZENG Huihui, YI Guiyun, XING Baolin, HUANG Guangxu, CHEN Lunjian, ZHANG Chuanxiang, XU Bing, YAO Youheng, ZHANG Qingshan, LI Jie. Preparation of coal-based graphene/TiO₂ composites and their photocatalytic activity[J]. Chemical Industry and Engineering Progress, 2017, 36(07): 2568-2576.

参考文献

[1] 中华人民共和国环境保护部全国环境统计公报(2014年)[EB/OL]. http://zls.mep.gov.cn/hjtj/qghjtjgb/201510/t20151029_315798.htm. Ministry of Environmental Protection of the People's Republic of China (2014)[EB/OL]. http://zls.mep.gov.cn/hjtj/qghjtjgb/201510/t20151029_315798.htm.
[2] AZIZULLAH A,KHATTAK M N K,RICHTER P,et al. Water pollution in Pakistan and its impact on public health-a review[J]. Environment International,2011,37(2):479-497.
[3] GEIM A K,NOVOSELOV K S. The rise of graphene[J]. Nature Materials,2007,6(3):183-191.
[4] WU J,PISULA W,MÜLLEN K. Graphenes as potential material for electronics[J]. Chemical Reviews,2007,107(3):718-747.
[5] BALANDIN A A,GHOSH S,BAO W,et al. Superior thermal conductivity of single-layer graphene[J]. Nano Letters,2008,8(3):902-907.
[6] LEE C,WEI X,KYSAR J W,et al. Measurement of the elastic properties and intrinsic strength of monolayer graphene[J]. Science,2008,321(5887):385-388.
[7] NAIR R R,BLAKE P,GRIGORENKO A N,et al. Fine structure constant defines visual transparency of graphene[J]. Science,2008,320(5881):1308.
[8] STANKOVICH S,DIKIN D A,DOMMETT G H,et al. Graphene-based composite materials[J]. Nature,2006,442(7100):282-286.
[9] STOLLER M D,PARK S,ZHU Y,et al. Graphene-based ultracapacitors[J]. Nano Letters,2008,8(10):3498-3502.
[10] KYZAS G Z,DELIYANNI E A,MATIS K A. Graphene oxide and its application as an adsorbent for wastewater treatment[J]. Journal of Chemical Technology and Biotechnology,2014,89(2):196-205.
[11] 滕洪辉,彭雪,高彬. 石墨烯基复合材料去除水中重金属研究进展[J]. 化工进展,2017,36(2):602-610. TENG H T,PENG X,GAO B. Removal of heavy metals from water by graphene composites[J]. Chemical Industry and Engineering Progress,2017,36(2):602-610.
[12] 杨丽坤,蒲明峰. 太西无烟煤基石墨制备石墨烯的研究[J]. 煤炭加工与综合利用,2013(5):58-61. YANG L K,PU M F. Preparation of the graphene from taxi anthracite[J]. Coal Processing and Comprehensive Utilization,2013(5):58-61.
[13] 张亚婷,周安宁,张晓欠,等. 以太西无烟煤为前驱体制备煤基石墨烯的研究[J]. 煤炭转化,2013(4):57-61. ZHANG Y T,ZHOU A N,ZHANG X Q,et al. Preparation of the graphene from Taixi anthracite[J]. Coal Conversion,2013(4):57-61.
[14] YAN F C,WANG X. Treatment of dye wastewater using hydrothermally prepared nano-TiO₂ under natural light[J]. Journal of Inorganic and Organometallic Polymers and Materials,2016,26(1):142-146.
[15] JIANG P,REN D,HE D,et al. An easily sedimentable and effective TiO₂ photocatalyst for removal of dyes in water[J]. Separation and Purification Technology,2014,122:128-132.
[16] 吴跃辉,邓岩松,吴建辉. 纳米TiO₂光催化剂在工业有机废水处理中的研究[J]. 江西化工,2004(1):18-20. WU Y H,DENG Y S,WU J H. Study on nano-meter TiO₂ photocatalyst in the industrial organic wastewater treatment[J]. Jiang Xi Hua Gong,2004(1):18-20.
[17] 党丽萍,赵彬侠,孙圆媛. 二氧化钛复合光催化剂降解染料废水的性能[J]. 化工进展,2011,30(s1):359-361. DANG L P,ZHAO B X,SUN Y Y. Degradation of dye wastewater by titanium dioxide composite photocatalyst[J]. Chemical Industry and Engineering Progress,2011,30(s1):359-361.
[18] 刘文芳,周汝利,王燕子. 光催化剂TiO₂改性的研究进展[J]. 化工进展,2016,35(8):2446-2454. LIU W F,ZHOU R L,WANG Y Z. Research progress on modification of TiO₂ photocatalyst[J]. Chemical Industry and Engineering Progress,2016,35(8):2446-2454.
[19] LEE J S,YOU K H,PARK C B. Highly photoactive,low bandgap TiO₂ nanoparticles wrapped by graphene[J]. Advanced Materials,2012,24(8):1084-1088.
[20] 张晓艳,李浩鹏,崔晓莉. TiO₂/石墨烯复合材料的合成及光催化分解水产氢活性[J]. 无机化学学报,2009,25(11):1903-1907. ZHANG X Y,LI H P,CUI X L. Preparation and photocatalytic activity for hydrogen evolution of TiO₂/Graphene sheets composite[J]. Chinese Journal of Inorganic Chemistry,2009,25(11):1903-1907.
[21] XING B L,SHI C L,ZHANG C X,et al. Preparation of TiO₂/activated carbon composites for photocatalytic degradation of RhB under UV light irradiation[J]. Journal of Nanomaterials,2016,2016:1-10.
[22] ZHANG H,LV X,LI Y,et al. P25-graphene composite as a high performance photocatalyst[J]. ACS Nano,2009,4(1):380-386.
[23] 龙梅,丛野,李轩科,等. 部分还原氧化石墨烯/二氧化钛复合材料的水热合成及其光催化活性[J]. 物理化学学报,2013,29(6):1344-1350. LONG M,CONG Y,LI X K,et al. Hydrothermal synthesis and photocatalytic activity of partially reduced graphene oxide/TiO₂ composite[J]. Acta phys.-Chim. Sin.,2013,29(6):1344-1350.
[24] MARCANO D C,KOSYNKIN D V,BERLIN J M,et al. Improved synthesis of graphene oxide[J]. ACS Nano,2010,4(8):4806-4814.
[25] 董如林,莫剑臣,张汉平,等. 二氧化钛/氧化石墨烯复合光催化剂的合成[J]. 化工进展,2014,33(3):679-684. DONG R L,MO J C,ZHANG H P,et al. Synthesis of the titania/graphene oxide composite photocatalyst[J]. Chemical Industry and Engineering Progress,2014,33(3):679-684.
[26] 陈军刚,彭同江,孙红娟,等. TiO₂/氧化石墨烯纳米复合物的制备及结构变化[J]. 人工晶体学报,2014(1):180-187. CHEN J G,PENG T J,SUN H J,et al. Preparation and structure variation of TiO₂/graphene oxide nano-composites[J]. Journal of Synthetic Crystals,2014,43(1):180-187.
[27] 高伟,吴凤清,罗臻,等. TiO₂晶型与光催化活性关系的研究[J]. 高等学校化学学报,2001,22(4):660-662. GAO W,WU F Q,LUO Z,et al. Studies on relationship between the crystal form of TiO₂ and its photocatalyzing degradation efficiency[J]. Chemical Journal of Chinese Universities,2001,22(4):660-662.
[28] ZHANG Y,TANG Z,FU X,et al. TiO₂-graphene nanocomposites for gas-phase photocatalytic degradation of volatile aromatic pollutant:is TiO₂-graphene truly different from other TiO₂-carbon composite materials?[J]. ACS Nano,2010,4(12):7303-7314.
[29] 廖雪峰,陈菓,刘钱钱,等. 二氧化钛相变研究现状[J]. 无机盐工业,2016,48(8):6-10. LIAO X F,CHEN G,LIU Q Q,et al. Recent advances in phase transition of TiO₂[J]. Inorganic Chemicals Industry,2016,48(8):6-10.
[30] PAN X,ZHAO Y,LIU S,et al. Comparing graphene-TiO₂ nanowire and graphene-TiO₂ nanoparticle composite photocatalysts[J]. ACS Applied Materials & Interfaces,2012,4(8):3944-3950.
[31] FAN W,LAI Q,ZHANG Q,et al. Nanocomposites of TiO₂ and reduced graphene oxide as efficient photocatalysts for hydrogen evolution[J]. The Journal of Physical Chemistry C,2011,115(21):10694-10701.
[32] YI G Y,XING B L,JIA J B,et al. Fabrication and characteristics of macroporous photocatalyst[J]. International Journal of Photoenergy,2014(5):1-7.
[33] SHER SHAH M S A,PARK A R,ZHANG K,et al. Green synthesis of biphasic TiO₂-reduced graphene oxide nanocomposites with highly enhanced photocatalytic activity[J]. ACS Applied Materials & Interfaces,2012,4(8):3893-3901.
[34] SUN J,ZHANG H,GUO L,et al. Two-dimensional interface engineering of a titania-graphene nanosheet composite for improved photocatalytic activity[J]. ACS Applied Materials & Interfaces,2013,5(24):13035-13041.

煤基石墨烯/TiO₂复合材料的制备及光催化性能

Preparation of coal-based graphene/TiO₂ composites and their photocatalytic activity

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	胡喜, 王明珊, 李恩智, 黄思鸣, 陈俊臣, 郭秉淑, 于博, 马志远, 李星. 二硫化钨复合材料制备与储钠性能研究进展[J]. 化工进展, 2023, 42(S1): 344-355.
[7]	王正坤, 黎四芳. 双子表面活性剂癸炔二醇的绿色合成[J]. 化工进展, 2023, 42(S1): 400-410.
[8]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[9]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[10]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[11]	许友好, 王维, 鲁波娜, 徐惠, 何鸣元. 中国炼油创新技术MIP的开发策略及启示[J]. 化工进展, 2023, 42(9): 4465-4470.
[12]	耿源泽, 周俊虎, 张天佑, 朱晓宇, 杨卫娟. 部分填充床燃烧器中庚烷均相/异相耦合燃烧[J]. 化工进展, 2023, 42(9): 4514-4521.
[13]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[14]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[15]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.