Adsorption kinetics and photocatalytic activity of grapheneoxide-TiO2 composites for three dyes

doi:10.16085/j.issn.1000-6613.2018-1866

Abstract

Abstract:

The titania-loaded graphene oxide composites (GO-TiO₂) were prepared by hydrolysis of butyl titanate in graphene oxide dispersed solution. The modified samples were characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), automatic specific surface area and pore analysis (BET), and UV-vis diffuse spectroscopy (UV-vis DRS). The adsorption kinetics and photocatalytic properties of GO10-TiO₂ for methylene blue (MB), methyl orange (MO) and Rhodamine B (Rh B) dyes were studied. The results showed that the TiO₂ particles were uniformly attached to the surface of GO sheet, the adsorption process of GO10-TiO₂ for three dyes was multi-layer adsorption, and the adsorption kinetics accords with the pseudo-second-order kinetic model. At 25℃, the adsorption of MB, MO and Rh B in wastewater by GO10-TiO₂ showed selective adsorption due to the difference of conjugate structure and polarity with adsorption capacities of 9.2mg/g, 5.4mg/g and 23.0mg/g, respectively. The photocatalytic degradation of the three dye wastewaters was related to the adsorption performance. The higher the adsorption capacity, the higher the degradation efficiency. The degradation rates of MB, MO and Rh B were 89%, 75% and 98%, respectively, after photocatalytic reaction for 60min.

Key words: graphene oxide, titanium dioxide, isothermal adsorption curve, adsorption kinetics, photocatalytic reaction

摘要：

通过在氧化石墨烯分散溶液中水解钛酸丁酯成功制备氧化石墨烯-TiO₂复合材料（GO-TiO₂），采用傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、扫描电子显微镜（SEM）、X射线光电子能谱（XPS）、全自动比表面及孔径分析仪（BET）和紫外-可见漫反射光谱（UV-vis DRS）等对样品进行了表征。研究了GO10-TiO₂对亚甲基蓝（MB）、甲基橙（MO）和罗丹明B（RhB）3种染料的吸附动力学和光催化性能。结果表明：TiO₂颗粒均匀地附着在GO片层表面；GO10-TiO₂对3种染料的吸附过程为多层吸附，吸附动力学符合拟二级动力学模型；在25℃条件下GO10-TiO₂对废水中MB、MO和Rh B的吸附因共轭结构、极性等的差异而呈现选择性吸附，吸附容量分别为9.2mg/g、5.4mg/g和23.0mg/g。对3种染料废水的光催化降解效果与吸附性能相关联，吸附容量越大降解效率越高，光催化反应60min时，MB、MO和Rh B降解率分别为89%、75%和98%。

关键词: 氧化石墨烯, 二氧化钛, 等温吸附曲线, 吸附动力学, 光催化反应

CLC Number:

TQ174

Qiaoling ZHANG, Zhao QIN, Youzhi LIU, Yanting SHI, Jingwen ZHANG, Guangping ZENG. Adsorption kinetics and photocatalytic activity of grapheneoxide-TiO₂ composites for three dyes[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2870-2879.

张巧玲, 秦钊, 刘有智, 师艳婷, 张竞文, 曾广平. 氧化石墨烯-TiO₂复合材料对三种染料的吸附动力学及光催化性能[J]. 化工进展, 2019, 38(06): 2870-2879.

Figures/Tables 17

References 31

1	WANG Z , MA W, CHEN C , et al . Light-assisted decomposition of dyes over iron-bearing soil clays in the presence of H₂O₂ [J]. Journal of Hazardous Materials, 2009,168 (2): 1246-1252.
2	张志军，胡涓，陈整生，等 . 纳米二氧化钛复合石墨烯催化剂的制备及处理染料废水[J]. 环境工程学报, 2014, 8(7): 2875-2879.
	ZHANG Zhijun ， HU Juan ， CHEN Zhengsheng ，et al . Preparation of nano-TiO₂ composite graphene catalyst and treatment of dye wastewater[J]. Journal of Environmental Engineering, 2014, 8(7): 2875-2879 .
3	JUANG R S , CHEN C H . Comparative study on photocatalytic degradation of methomyl and parathion over UV-irradiated TiO₂ particles in aqueous solutions[J]. Journal of the Taiwan Institute of Chemical Engineers, 2014, 45(3): 989-995.
4	MATTSSON A , STERLUND L . Adsorption and photoinduced decomposition of acetone and acetic acid on anatase, brookite, and rutile TiO₂ nanoparticles[J]. The Journal of Physical Chemistry C, 2010, 114(33): 14121-14132.
5	李翠霞，金海泽，杨志忠，等 . 介孔RGO/TiO₂复合光催化材料的制备及光催化性能[J]. 无机材料学报, 2017, 32(4): 357-364.
	LI Cuixia ， JIN Haize ， YANG Zhizhong ，et al . Preparation and photocatalytic activity of mesoporous RGO/TiO₂ composite photocatalytic materials[J]. Journal of Inorganic Materials, 2017, 32(4): 357-364.
6	YANGAB L , WANGA F , HAKKIB A , et al . The influence of zeolites fly ash bead/TiO₂ composite material surface morphologies on their adsorption and photocatalytic performance[J]. Applied Surface Science, 2017, 329: 687-696.
7	MUTHIRULAN P , DEVI C N , SUNDARAM M M . Synchronous role of coupled adsorption and photocatalytic degradation on CAC-TiO₂ composite generating excellent mineralization of alizarin cyanine green dye in aqueous solution[J]. Arabian Journal of Chemistry, 2017, 10(1): S1477-S1483.
8	ZHOUAB J , HAOA B , WANGA L , et al . Preparation and characterization of nano-TiO₂/chitosan/poly(N-isopropylacrylamide) composite hydrogel and its application for removal of ionic dyes[J]. Separation and Purification Technology, 2017,176: 193-199.
9	ZHANG J , LI L , LI Y , et al . Microwave-assisted synthesis of hierarchical mesoporous nano-TiO₂/cellulose composites for rapid adsorption of Pb²⁺ [J]. Chemical Engineering Journal, 2017,313: 1132-1141.
10	BAI H , ZHOU J , ZHANG H , et al . Enhanced adsorbability and photocatalytic activity of TiO₂-graphene composite for polycyclic aromatic hydrocarbons removal in aqueous phase[J]. Colloids and Surfaces B-Biointerfaces, 2017, 150: 68-77.
11	WANG D , LI X , CHEN J , et al . Enhanced photoelectrocatalytic activity of reduced graphene oxide/TiO₂ composite films for dye degradation[J]. Chemical Engineering Journal, 2012, 198/199(4): 547-554.
12	YANG Wenrong , K R RATINAC , RINGER S P , et al . Carbon nanomaterials in biosensors: should you use nanotubes or graphene[J]. Angewandte Chemie International Edition, 2010, 41(24): 2114-2138.
13	DONDONIR A . The emergence of thiolene coupling as a click process for materials and bioorganic chemistry[J]. Angewandte Chemie, 2008, 47(47): 8995-8997.
14	PUMERA M , AMBROSI A , BONANNI A , et al . Graphene for electrochemical sensing and biosensing[J]. Trends in Analytical Chemistry, 2010, 29(9): 954-965.
15	DREYER D R , PARK S , BIELAWSKI C W , et al . The chemistry of graphene oxide[J]. Chemical Society Reviews, 2010, 43(15) : 5288.
16	DIKIN D A , STANKOVICH S , ZIMNEY E J , et al . Preparation and characterization of graphene oxide paper[J]. Nature, 2007, 448(7152): 457-460.
17	DONG Z , WANG D , LIU X , et al . Bio-inspired surface-functionalization of graphene oxide for the adsorption of organic dyes and heavy metal ions with a superhigh capacity[J]. Journal of Materials Chemistry A, 2014, 2(14): 5034-5040.
18	BISSESSUR R , SCULLY S F . Intercalation of solid polymer electrolytes into graphite oxide[J]. Solid State Ionics, 2007, 178(11): 877-882.
19	ZHANG H , LV X , LI Y , et al . P25-graphene composite as a high performance photocatalyst[J]. ACS Nano, 2010, 4(1): 380-386.
20	PERERA S D , MARIANO R G , VU K, et al . Hydrothermal synthesis of graphene-TiO₂ nanotube composites with enhanced photocatalytic activity[J]. ACS Catalysis, 2012, 2(6): 949-956.
21	ZHANG L , LIU J , TANG C , et al . Palygorskite and SnO₂–TiO₂ for the photodegradation of phenol[J]. Applied Clay Science, 2011, 51(1/2): 68-73.
22	LI L , DUAN H , WANG X , et al . Adsorption property of Cr(VI) on magnetic mesoporous titanium dioxide–graphene oxide core–shell microspheres[J]. New Journal of Chemistry, 2014, 38(12): 6008-6016.
23	LEI Z , JO S B, SHU Y , et al . Rhodamine B degradation and reactive oxygen species generation by a ZnSe-graphene/TiO₂ sonocatalyst[J]. Chinese Journal of Catalysis, 2014, 35(11):1825-1832.
24	MURUGAN R , BABU V J , KHIN M M , et al . Synthesis and photocatalytic applications of flower shaped electrospun ZnO-TiO₂ mesostructures[J]. Materials Letters, 2013, 97(2): 47-51.
25	CAOA P , WANGA L , XUA Y, et al . Facile hydrothermal synthesis of mesoporous nickel oxide/reduced graphene oxide composites for high performance electrochemical supercapacitor[J]. Electrochimica Acta, 2015, 157: 359-368.
26	LIU R , ZHENG Z , SPURGEON J , et al . Enhanced photoelectrochemical water-splitting performance of semiconductors by surface passivation layers[J]. Energy and Environmental Science, 2014, 7(8): 2504-2517.
27	HANSEN C M . Hansen solubility parameters: a user’s handbook[M]. Boca Raton: CRC Press Inc. , 2007：493-505.
28	DESLANDES N , BELLENGER V , JAFFIOL F , et al . Solubility parameter of a polyester composite material[J]. Journal of Applied Polymer Science, 2015, 69(13): 2663-2671.
29	SCHRODERA J H , DOROSHENKOAD M , PIMERA D , et al . Interfacial stabilization by soft janus nanoparticles[J]. Polymer, 2016, 106: 208-217.
30	刘桂芳 . 常用吸附材料在水处理中的应用[M].北京：化学工业出版社, 2016：71-84.
	LIU Guifang . Application of common adsorbent materials in water treatment[M]. Beijing: Chemical Industry Press, 2016：71-84.
31	YUJUAN H , KAN Z , RONG D , et al . Enhanced adsorption of methyl orange onto self-assembled hydrogel with anatase titania nanotube and graphene[J]. Journal of Donghua University:English Edition, 2017, 34(2): 262-268.

2θ/（°）	晶面	2θ/（°）	晶面
25	（101）	62	（204）
38	（004）	69	（116）
48	（200）	70	（220）
53	（105）	75	（215）

2θ/（°）	晶面	2θ/（°）	晶面
25	（101）	62	（204）
38	（004）	69	（116）
48	（200）	70	（220）
53	（105）	75	（215）

2θ/（°）	晶面
27	（110）
55	（211）

2θ/（°）	晶面
27	（110）
55	（211）

材料	比表面积/m²·g^-1
GO	339.0
TiO₂	53.9
GO1-TiO₂	63.8
GO5-TiO₂	89.7
GO10-TiO₂	109.7
GO15-TiO₂	121.1
GO20-TiO₂	134.6

Adsorption kinetics and photocatalytic activity of grapheneoxide-TiO₂ composites for three dyes

氧化石墨烯-TiO₂复合材料对三种染料的吸附动力学及光催化性能

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 17

References 31

Related Articles 15

Recommended Articles

Metrics

Comments

复合材料	吸附率/%	60min总降解率/%
TiO₂	0	52.4
GO1-TiO₂	6.3	85.3
GO5-TiO₂	8.0	87.3
GO10-TiO₂	15.3	94.0
GO15-TiO₂	16.7	65.0
GO20-TiO₂	17.0	52.7

染料	q _m,exp /mg·g^-1	Langmuir 模型			Freundlich 模型
染料	q _m,exp /mg·g^-1	q _m,cal/mg·g^-1	K _L/L·mg^-1	R ²	K _F	n	R ²
MB	9.2	10.10	0.020	0.734	0.114	0.726	0.982
MO	5.4	2.53	0.027	0.701	0.023	0.603	0.994
Rh B	23.0	26,31	0.038	0.763	0.902	0.859	0.993

染料	q _e,exp /mg·g^-1	拟一级动力学			拟二级动力学			颗粒内扩散模型
染料	q _e,exp /mg·g^-1	q _e,cal /mg·g^-1	k ₁ /min^-1	R ²	q _e,cal /mg·g^-1	k ₂ /mg·g^-1·min^-1	R ²	k_i, ₁ /mg·g^-1·min^-1/2	k_i, ₂ /mg·g^-1·min^-1/2
MB	9.203	9.936	0.053	0.937	9.379	11.43×10^-3	0.991	1.331	0.083
MO	5.421	5.708	0.049	0.988	5.408	34.19×10^-3	0.990	0.701	0.056
Rh B	23.123	26.316	0.088	0.986	24.456	1.672×10^-3	0.997	2.042	0.102

[1]	XU Chunshu, YAO Qingda, LIANG Yongxian, ZHOU Hualong. Effects of graphene oxide/carbon nanotubes on the properties of several typical polymer materials [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3012-3028.
[2]	HE Yang, LI Siying, LI Chuanqiang, YUAN Xiaoya, ZHENG Xuxu. Anticorrosion performance of thermal reduction graphene oxide /epoxy resin composite coating [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1983-1994.
[3]	KONG Qian, SUN Jinchao, GE Jiaqi, ZHANG Peng, MA Yanlong, LIU Baijun. Effect of precipitant on the hydrocracking performance of NiW/TiO₂-ASA catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(1): 265-271.
[4]	YUAN Quan, LI Haihong, LIU Haojie. Electric adsorption laws of HNO₃-modified activated carbon for different valence ions [J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4986-4994.
[5]	XIONG Jian, XIA Liufen, YU Lei, FEI Anjie, XU Chu, CHEN Shengya, JIANG Guodong. Preparation and electrochromic properties of graphene oxide and TiO₂-B composite films [J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3794-3800.
[6]	CHEN Yong, CHENG Ning, YANG Yubing, LU Kailing, LUO Ying, YI Hui. Highly efficient adsorption of Basic Violet 3 dye by composite material derived from graphene oxide intercalated bentonite [J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3324-3332.
[7]	MAO Menglei, SUN Danyang, MENG Zihui, LIU Wenfang. Enzyme immobilization on graphene oxide and transition metal carbon/nitrogen compounds [J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1941-1955.
[8]	YANG Honghai, ZHANG Miao, LIU Liwei, ZHOU Yi, SHEN Junjie, SHI Weigang, YIN Yong. Heat transfer performance enhancement and prediction in GO/water pulsating heat pipe [J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1725-1734.
[9]	CUI Weiyi, DING Guomin, TAN Naidi. Research progress on titanium dioxide based catalysts for catalytic oxidation of formaldehyde [J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6310-6318.
[10]	ZHENG Anda, YANG Chenggong, WANG Dong’e, TIAN Zhijian. Highly active MoS₂/reduced graphene oxide catalyst for anthracene hydrogenation [J]. Chemical Industry and Engineering Progress, 2022, 41(1): 244-252.
[11]	SUN Tong, XU Dongdong, SONG Minhang, JIN Xing, HUANG Yun. Research progress of the burners in synthesis of TiO₂ by combustion method [J]. Chemical Industry and Engineering Progress, 2022, 41(1): 17-29.
[12]	HU Nan, CHEN Lin, LI Huizhen, ZHANG Siyao, ZHANG Zhijun. Enrichment and recovery of engineered nanoparticle using flotation with intensified foam drainage [J]. Chemical Industry and Engineering Progress, 2022, 41(1): 485-492.
[13]	YANG Xiaofang, WEI Ming, SUN Li. Preparation and research of PAM/CQDs/GO composite hydrogel [J]. Chemical Industry and Engineering Progress, 2021, 40(S2): 301-308.
[14]	ZHANG Xuan, ZHENG Lijun. Process of single phase photocatalysts for hydrogen production [J]. Chemical Industry and Engineering Progress, 2021, 40(S1): 215-222.
[15]	HU Huimin, FANG Xiaofeng, LOU Mengmeng, LIU Shuai, XU Chenye, LI Fang. Research process on performance regulation and mass transfer mechanism of graphene oxide separation membrane [J]. Chemical Industry and Engineering Progress, 2021, 40(S1): 291-300.

染料	相对分子质量	极性汉森参数δ _p
MB	319	2.904
MO	327	3.113
Rh B	479	4.298

染料	相对分子质量	极性汉森参数δ _p
MB	319	2.904
MO	327	3.113
Rh B	479	4.298