Preparation of graphene oxide@MIL-101 composite and its performance in Cr(Ⅵ) removal from aqueous solution

doi:10.11949/j.issn.0438-1157.20161481

CIESC Journal ›› 2017, Vol. 68 ›› Issue (5): 2105-2111.DOI: 10.11949/j.issn.0438-1157.20161481

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Preparation of graphene oxide@MIL-101 composite and its performance in Cr(Ⅵ) removal from aqueous solution

WANG Liang^1,2, TIAN Dan^1,2, LIU Anqi^1,2, ZHAO Bin^1,2, MA Shushuang², LI Junjing^1,2, ZHANG Zhaohui^1,2, HUI Xu²

1 State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin 300387, China;
2 School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China

Received:2016-10-20 Revised:2016-12-06 Online:2017-05-05 Published:2017-05-05
Supported by:
supported by the National Natural Science Foundation of China (51638011, 51478314, 51138008), the National Basic Research Program of China (2016YFC0400503), Tianjin Natural Science Foundation (14JCQNJC09000, 14ZCDGSF00128).

GO@MIL-101的制备及其对水中Cr（Ⅵ）的去除

王亮^1,2, 田聃^1,2, 刘安琪^1,2, 赵斌^1,2, 马树双², 李君敬^1,2, 张朝晖^1,2, 惠旭²

1 省部共建分离膜与膜过程国家重点实验室, 天津 300387;
2 天津工业大学环境与化学工程学院, 天津 300387

通讯作者: 王亮
基金资助:
国家自然科学基金项目（51638011，51478314，51138008）；国家重点基础研究发展计划项目（2016YFC0400503）；天津市自然科学基金项目（14JCQNJC09000）；天津市科技计划项目（14ZCDGSF00128）。

Abstract

Abstract:

A novel composite (GO@MIL-101) containing metal organic framework (MIL-101) and graphene oxide (GO) was prepared by hydrothermal method. The effects of GO concentration on the composite morphology and structure were investigated. The doping of GO affected the crystallization of MIL-101 and its integrity reduced with the increase in GO concentration. The crystal size decreased and the agglomeration phenomenon became significant. GO@MIL-101 can be used to remove Cr(Ⅵ) from aqueous solution, and the removal kinetics can be fitted by the pseudo-second-order kinetic model. The maximum Cr(Ⅵ) uptake capacity obtained by Langmuir adsorption isotherm depended on the GO concentration. When the GO concentration of 2% [based on the mass of Cr(NO₃)₃·9H₂O] was applied, GO@MIL-101 exhibited higher Cr(Ⅵ) uptake capacity compared to MIL-101 due to its larger specific surface area and pore volume. The removal of Cr(Ⅵ) was accompanied by the release of NO₃^- and the decrease of pH. The charge balance analysis indicated that the removal mechanism involved in the Cr(Ⅵ) removal by MIL-101 and GO@MIL-101 was mainly ion exchange. The removed Cr(Ⅵ) existed in the form of CrO₄^2- in the adsorbent.

Key words: MIL-101, GO, Cr(Ⅵ), ion exchange

摘要：

通过水热法制备了掺杂氧化石墨烯（GO）的金属有机框架GO@MIL-101，并考察了GO掺杂量对GO@MIL-101形貌和性质的影响规律。GO的掺杂影响了MIL-101晶体的形成过程。随着GO掺杂量的增加，GO@MIL-101晶体的完整性降低、粒径减小，团聚现象越发显著。GO@MIL-101能够有效去除溶液中的Cr（Ⅵ），该过程符合拟二级动力学方程。由Langmuir吸附等温线拟合得到的最大吸附量与GO掺杂量有关，在2%[相对于Cr（NO₃）₃·9H₂O质量]时达到最大，这与此时GO@MIL-101同时具有较大的比表面积和较大的孔体积有关。Cr（Ⅵ）的去除过程伴随着溶液中NO₃^-浓度的升高以及pH的下降，电荷平衡计量分析表明MIL-101和GO@MIL-101对Cr（Ⅵ）的去除机制相同，主要依靠MIL-101的离子交换作用，并且所去除的Cr（Ⅵ）以CrO₄^2-形式存在于固相中。

关键词: MIL-101, 氧化石墨烯, Cr（Ⅵ）, 离子交换

CLC Number:

X522

WANG Liang, TIAN Dan, LIU Anqi, ZHAO Bin, MA Shushuang, LI Junjing, ZHANG Zhaohui, HUI Xu. Preparation of graphene oxide@MIL-101 composite and its performance in Cr(Ⅵ) removal from aqueous solution[J]. CIESC Journal, 2017, 68(5): 2105-2111.

王亮, 田聃, 刘安琪, 赵斌, 马树双, 李君敬, 张朝晖, 惠旭. GO@MIL-101的制备及其对水中Cr（Ⅵ）的去除[J]. 化工学报, 2017, 68(5): 2105-2111.

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Preparation of graphene oxide@MIL-101 composite and its performance in Cr(Ⅵ) removal from aqueous solution

GO@MIL-101的制备及其对水中Cr（Ⅵ）的去除

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