石墨烯/Ni/TiO2/CNTs复合物的制备及其光催化性能

doi:10.15541/jim20130680

摘要/Abstract

摘要：

首先通过溶剂热法, 在石墨烯表面负载掺杂镍的纳米二氧化钛膜, 制备石墨烯/Ni/TiO₂复合材料; 然后以掺杂的镍为催化剂, 采用化学气相沉积法, 原位生长碳纳米管(CNTs), 得到石墨烯/Ni/TiO₂/CNTs复合材料。通过XRD、SEM、TEM、拉曼等方法对制备样品的晶型、微观形貌等进行了表征, 考察了样品在紫外光及可见光下对甲基橙的光催化降解性能。结果表明: 石墨烯和CNTs的加入使得Ni/TiO₂、石墨烯/Ni/TiO₂、石墨烯/Ni/TiO₂/CNTs复合物的光催化活性依次提高, 并且石墨烯/Ni/TiO₂/CNTs复合物中石墨烯含量越多时, 所得复合物的光催化降解性能越好。石墨烯含量最大的石墨烯/Ni/TiO₂/CNTs样品, 在紫外光下对甲基橙的降解率达到98%, 在可见光下的光催化降解效率比掺镍TiO₂提高了3.5倍。

关键词: 石墨烯, 碳纳米管, 二氧化钛, 光催化

Abstract:

TiO₂ nanoparticals doped with nickel were coated on graphene by solvo-thermal method. Then the CNTs were grown by in-situ chemical vapor deposition using nickel as catalyst. Finally, the graphene/Ni/TiO₂/CNTs nanocomposites was obtained. The prepared graphene/Ni/TiO₂/CNTsnanocomposite photocatalyst was characterized by X-ray diffraction, field emission scanning electron microscope, transmission electron microscope and Raman spectra. The photocatalytic activities of the samples were investigated by the photocatalytic degradation of methyl orange under UV and visible light. The results indicated that the photocatalytic activities increased from Ni/TiO₂, graphene/Ni/TiO₂, to graphene/Ni/TiO₂/CNTs by the addition of graphene and CNTs. And the photocatalytic activities of graphene/Ni/TiO₂/CNTs increased with the graphene amount increase. For the sample graphene/ Ni/TiO₂/CNTs with the highest graphene content, its photocatalytic degradation of MO under UV irradiation reached 98%, and its photocatalytic degradation of MO under visible light irradiation was 3.5 fold higher than that of sample Ni/TiO₂.

Key words: graphene, CNTs, TiO2, photocatalysis

中图分类号:

TB383

吕慧, 陈爱平, 孙秀丽, 唐骏, 李春忠. 石墨烯/Ni/TiO₂/CNTs复合物的制备及其光催化性能[J]. 无机材料学报, 2014, 29(10): 1061-1066.

LV Hui, CHEN Ai-Ping, SUN Xiu-Li, TANG Jun, LI Chun-Zhong. Synthesis of Graphene/Ni/TiO₂/CNTs Composites and Photocatalytic Activities[J]. Journal of Inorganic Materials, 2014, 29(10): 1061-1066.

图/表 7

图1 氧化石墨烯、石墨烯/Ni/TiO2、石墨烯/Ni/TiO2/CNTs、Ni/TiO2 及Ni/TiO2/CNTs的XRD图谱

Fig. 1 XRD patterns of GO, graphene/Ni/TiO2, graphene/Ni/ TiO2/CNTs, Ni/TiO2 and Ni/TiO2/CNTs

图2 负载Ni/TiO2的石墨烯片层(a)和石墨烯上的TiO2颗粒(b)的SEM照片

Fig. 2 FESEM images of graphene lamella loaded with TiO2 (a) and TiO2 nanoparticles on the graphene (b)

图3 不同石墨烯/Ni/TiO2/CNTs样品的SEM照片

Fig. 3 SEM images of the different graphene/Ni/TiO2/CNTs samples (a) Ni/TiO2/CNTs; (b) 2.2GTC; (c) 11GTC; (d) 55GTC

图4 石墨烯(a)、Ni/TiO2(b)、石墨烯/Ni/TiO2(c)和石墨烯/Ni/TiO2/CNTs(d, e)的TEM照片

Fig. 4 TEM images of (a) graphene, (b) Ni/TiO2, (c) graphene/Ni/TiO2 and (d, e) graphene/Ni/TiO2/CNTs

图5 石墨烯/Ni/TiO2在CVD原位生长CNTs前后的Raman图谱

Fig. 5 Raman spectra of the graphene/Ni/TiO2 samples before and after in-situ growing CNTs by CVD (1) 55-GT; (2) 55-GTC; (3) 11-GTC; (4) 2.2-GTC; (5) 11-GT; (6) 2.2-GT; (7) NT; (8) GO; (9) NTC

图6 TiO2、石墨烯/Ni/TiO2、石墨烯/Ni/TiO2/CNTs、Ni/TiO2及Ni/TiO2/CNTs的紫外-可见吸收光谱图

Fig. 6 UV-Vis absorption spectra of TiO2, graphene/Ni/TiO2, graphene/Ni/TiO2/CNTs, Ni/TiO2 and Ni/TiO2/CNTs

图7 不同样品的紫外光(a)和可见光(b)光催化降解甲基橙曲线

Fig. 7 Photocatalytic degradation of different samples on MO under UV (a) and visible light (b) irradiation

参考文献 29

[1]	DONG XIANG, TAO JIE, LI YING-YING, et al. Oriented single crystalline TiO2 nano-pillar arrays directly grown on titanium substrate in tetramethylammonium hydroxide solution. Applied Surface Science, 2010, 256(8): 2532-2538.
[2]	CHEN XIAO-BO, SAMUEL S MAO. Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. Chem. Rev., 2007, 107(7): 2891-2959.
[3]	GAI YAN-QIN, LI JING-BO, LI SHU-SHEN, et al. Design of narrow-Gap TiO2: a passivated codoping approach for enhanced photoelectrochemical activity. Phys. Rev. Lett. , 2009, 102(3): 036402-1-4.
[4]	FUJISHIMA A.HONDA K .Electrochemical photolysis of water at a semiconductor electrode.Nature, 1972, 238: 37-38.
[5]	ZHANG QING-HONG, GAO LIAN, GUO JING-KUN, et al. Photocatalytic activity of nanosized TiO2. Journal of Inorganic Materials, 2000, 15(3): 556-560.
[6]	HIROYUKI FUJII, MICHITAKA OHTAKI, KOICHI EGUCHI, et al. Preparation and photocatalytic activities of a semiconductor composite of CdS embedded in a TiO2 gel as a stable oxide semiconducting matrix. J. Mol. Catal. A: Chem, 1998, 129(1): 61-68.
[7]	CAO FEI-FEI, GUO YU-GUO, ZHENG SHU-FA, et al. Symbiotic coaxial nanocables: facile synthesis and an efficient and elegant morphological solution to the lithium storage problem. Chem. Mater., 2010, 22(5): 1908-1914.
[8]	SHEN LAI-FA, ZHANG XIAO-GANG, LI HONG-SEN, et al. Design and tailoring of a three-dimensional TiO2-graphene-carbon nanotube nanocomposite for fast lithium storage. J. Phys. Chem.Lett., 2011, 2(24): 3096-3101.
[9]	MING-YU YEN, MIN-CHIEN HSIAO, SHU-HANG LIAO, et al. Preparation of graphene/multi-walled carbon nanotube hybrid and its use as photoanodes of dye-sensitized solar cells. Carbon, 2011, 49(11): 3597-3606.
[10]	LIU WEN-XIU, MA JING, QU XIAO-GUANG, et al. Hydrothermal synthesis of (Fe, N) co-doped TiO2 powders and their photocatalytic properties under visible light irradiation. Res. Chem. Intermed., 2009, 35(3): 321-328.
[11]	FRANCK TESSIER, CORDT ZOLLFRANK, NAHUM TRAVI-TZ-KY, et al. Nitrogen-substituted TiO2: investigation on the photocatalytic activity in the visible light range. J. Mater. Sci., 2009, 44(22): 6110-6116.
[12]	YU WEI-WEI, ZHANG QING-HONG, SHI GUO-YING, et al. Preparation of Pt-loaded TiO2 nanotubes/nanocrystals composite photocatalysts and their photocatalytic properties. Journal of Inorganic Materials, 2011, 26(7): 747-752.
[13]	ERIK R MORALES, MATHEWS N R, DAVID REYES-COR-ONADO, et al. Physical properties of the CNT: TiO2 thin films prepared by Sol-Gel dip coating. Solar Energy, 2012, 86(4): 1037-1044.
[14]	MA LEI, CHEN AI-PING, LU JIN-DONG, et al. Synthesis and photocatalytic properties of CNT/Fe-Ni/TiO2 by fluidized bed-chemical vapor deposition method. Journal of Inorganic Materials, 2012, 27(1): 33-37.
[15]	YONG-YE LIANG, HAI-LIANG WANG, HERNAN SANCHEZ CASALONGUE, et al. TiO2 nanocrystals grown on graphene as advanced photocatalytic hybrid materials. Nano Res., 2010, 3(10): 701-705.
[16]	WANG CHANG-HUA, SHAO CHANG-LU, ZHANG XIN-TO-NG, et al. SnO2 nanostructures-TiO2 nanofibers heterostr-uctures: controlled fabrication and high photocatalytic properties. Inorg. Chem., 2009, 48(15): 7261-7268.
[17]	QIU YONG-LIANG, CHEN HONG-LING, XU NAN-PING. Preparation of CdS/TiO2 by hydrothermal method and its photocatalytic activity. CIESC Journal, 2005, 56(7): 1338-1342.
[18]	NOVOSELOV K S, GEIM A K, MOROZOV S V, et al. Electric field effect in atomically thin carbon films. Science, 2004, 306(5696): 666-669.
[19]	YANG KAI, ZHANG SHUAI, ZHANG GUO-XIN, et al. Graphene in mice: ultrahigh in vivo tumor uptake and efficient photothermal therapy. Nano Lett, 2010, 10(9): 3318-3323.
[20]	CLAIRE BERGER, SONG ZHI-MIN, WU XIAO-SONG, et al. Electronic confinement and coherence in patterned epitaxial graphene. Science, 2006, 312(5777): 1191-1196.
[21]	LUO QIU-PING, YU XIAO-YUN, LEI BING-XIN, et al. Reduced graphene oxide-hierarchical ZnO hollow sphere composites with enhanced photocurrent and photocatalytic activity. J. Phys. Chem. C, 2012, 116(14): 8111-8117.
[22]	SANJAYA D PERERA, RUPERTO G MARIANO, KHIEM VU, et al. Hydrothermal synthesis of graphene-TiO2 nanotube composites with enhanced photocatalytic activity. ACS Catal., 2012, 2(6): 949-956.
[23]	YU ZHEN-JUN, WANG YAN-LI, DENG HONG-GUI, et al. Synthesis and electrochemical performance of SnO2/graphene anode material for lithium ion batteries. Journal of Inorganic Materials, 2013, 28(5): 515-520.
[24]	ZHOU GUANG-MIN, WANG DA-WEI, YIN LI-CHANG, et al. Oxygen bridges between NiO nanosheets and graphene for improvement of lithium storage. ACS Nano, 2012, 6(4): 3214-3223.
[25]	SU QI, LIANG YAN-YU, FENG XIN-LIANG, et al. Towards free-standing graphene/carbon nanotube composite films via acet-ylene-assisted thermolysis of organocobalt functionalized graphene sheets. Chem. Commu., 2010, 46: 8279-8281.
[26]	DONG GANG, ZHU QI-ZHONG, LIU QING-JU. Preparation and photocatalytic property of Ni-doped TiO2 photocatalyst. Journal of Functional Materials, 2012, 43(3): 294-298.
[27]	ZHANG LI-LI, XIONG ZHI-GANG, ZHAO X S. Pillaring chemically exfoliated graphene oxide with carbon nanotubes for photocatalytic degradation of dyes under visible light irradiation. ACS Nano, 2010, 4(11): 7030-7036.
[28]	SANJAYA D PERERA, RUPERTO G MARIANO, KHIEM VU, et al. Hydrothermal synthesis of Graphene-TiO2 nanotube composites with enhanced photocatalytic activity. ACS Catalysis, 2012, 2(6): 949-956.
[29]	PEI SONG-FENG, CHENG HUI-MING. The reduction of graphene oxide. Carbon, 2012, 50(9): 3210-3228.

石墨烯/Ni/TiO₂/CNTs复合物的制备及其光催化性能

Synthesis of Graphene/Ni/TiO₂/CNTs Composites and Photocatalytic Activities

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