GO@MIL-101的制备及其对水中Cr（Ⅵ）的去除

doi:10.11949/j.issn.0438-1157.20161481

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

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

收稿日期:2016-10-20 修回日期:2016-12-06 出版日期:2017-05-05 发布日期:2017-05-05
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）。

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).

摘要/Abstract

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

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

中图分类号:

X522

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.

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.

参考文献 27

[1]	JOMOVA K, VALKO M. Advances in metal-induced oxidative stress and human disease [J]. Toxicology, 2011, 283 (2): 65-87.
[2]	ARITA A, COSTA M. Epigenetics in metal carcinogenesis: nickel, arsenic, chromium and cadmium [J]. Metallomics, 2009, 1 (3): 222-228.
[3]	RENGARAJ S, YEON K H, MOON S H. Removal of chromium from water and wastewater by ion exchange resins [J]. Journal of Hazardous Materials, 2001, 87 (1): 273-287.
[4]	PARGA J R, COCKE D L, VALVERDE V, et al. Characterization of electrocoagulation for removal of chromium and arsenic [J]. Chemical Engineering & Technology, 2005, 28 (5): 605-612.
[5]	GUPTA V K, GUPTA M, SHARMA S. Process development for the removal of lead and chromium from aqueous solutions using red mud-an aluminium industry waste [J]. Water Research, 2001, 35 (5): 1125-1134.
[6]	荆国华, 董梅霞, 周作明,等. 超声波对活性炭吸附/脱附Cr(Ⅵ)的影响 [J]. 化工学报, 2009, 60 (11): 2805-2812. JING G H, DONG M X, ZHOU Z M, et al. Effects of ultrasound on adsorption and desorption of chronmium(Ⅵ) on activated carbon [J]. CIESC Journal, 2009, 60 (11): 2805-2812.
[7]	谭秋荀, 张可方, 赵焱, 等. 活性氧化铝对六价铬的吸附研究 [J]. 环境科学与技术, 2012, 35 (6): 130-133. TAN Q X, ZHANG K F, ZHAO Y, et al. Adsorption of hexavalent chromium by activated alumina [J]. Environmental Science & Technology, 2012, 35 (6): 130-133.
[8]	ZHAO Y, YANG S, DING D, et al. Effective adsorption of Cr(Ⅵ) from aqueous solution using natural Akadama clay [J]. Journal of Colloid and Interface Science, 2013, 395: 198-204.
[9]	HONG D Y, HWANG Y K, SERRE C, et al. Porous chromium terephthalate MIL-101 with coordinatively unsaturated sites: surface functionalization, encapsulation, sorption and catalysis [J]. Advanced Functional Materials, 2009, 19: 1537-1552.
[10]	CHEN C, ZHANG M, GUAN Q, et al. Kinetic and thermodynamic studies on the adsorption of xylenol orange onto MIL-101(Cr) [J]. Chemical Engineering Journal, 2012, 183 (8):60-67.
[11]	BANDOSZ T J, PETIT C. MOF/graphite oxide hybrid materials: exploring the new concept of adsorbents and catalysts [J]. Adsorption-Journal of the International Adsorption Society, 2011, 17 (1):5-16.
[12]	LI L, LIU X L, GENG H Y, et al. A MOF/graphite oxide hybrid (MOF: HKUST-1) material for the adsorption of methylene blue from aqueous solution [J]. Journal of Materials Chemistry A, 2013, 1 (35): 10292-10299.
[13]	LI L, SHI Z, ZHU H, et al. Adsorption of azo dyes from aqueous solution by the hybrid MOFs/GO [J]. Water Science and Technology, 2016, 73 (7): 1728-1737.
[14]	HUMMERS J W S, OFFEMAN R E. Preparation of graphitic oxide [J]. Journal of the American Chemical Society, 1958, 80 (6): 1339-1339.
[15]	FEREY G, MELLOT-DRAZNIEKS C, SERRE C, et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area [J]. Science, 2005, 309 (5743): 2040-2042.
[16]	SHIH Y C, KE C Y, YU C J, et al. Combined Tween 20-stabilized gold nanoparticles and reduced graphite oxide-Fe3O4 nanoparticle composites for rapid and efficient removal of mercury species from a complex matrix [J]. ACS Applied Materials & Interfaces, 2014, 6 (20): 17437-17445.
[17]	SUN X, XIA Q, ZHAO Z, et al. Synthesis and adsorption performance of MIL-101(Cr)/graphite oxide composites with high capacities of n-hexane [J]. Chemical Engineering Journal, 2014, 239: 226-232.
[18]	PETIT C, BANDOSZ T J. Synthesis, characterization, and ammonia adsorption properties of mesoporous metal-organic framework MIL(Fe)-graphite oxide composites: exploring the limits of materials fabrication [J]. Advanced Functional Materials, 2011, 21 (11): 2108-2117.
[19]	GU X, LU Z H, JIANG H L, et al. Synergistic catalysis of metal-organic framework-immobilized Au-Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage [J]. Journal of the American Chemical Society, 2011, 133 (31):11822-5.
[20]	ZHAO N, WEI N, LI J, et al. Surface properties of chemically modified activated carbons for adsorption rate of Cr(Ⅵ) [J]. Chemical Engineering Journal, 2005, 115 (1): 133-138.
[21]	ZHOU X, HUANG W, SHI J, et al. A novel MOF/graphene oxide composite GrO@MIL-101 with high adsorption capacity for acetone [J]. Journal of Materials Chemistry A, 2014, 2 (13): 4722-4730.
[22]	SEREDYCH M, PETIT C, TAMASHAUSKY A V, et al. Role of graphite precursor in the performance of graphite oxides as ammonia adsorbents [J]. Carbon, 2009, 47 (2): 445-456.
[23]	POTGIETER J H, POTGIETER-VERMAAK S S, et al. Heavy metals removal from solution by palygorskite clay [J]. Minerals Engineering, 2006, 19 (5): 463-470.
[24]	SPINELLI V A, LARANJEIRA M C M, FÁVERE V T. Preparation and characterization of quaternary chitosan salt: adsorption equilibrium of chromium (Ⅵ) ion [J]. Reactive and Functional Polymers, 2004, 61 (3): 347-352.
[25]	HE Y C, YANG J, KAN W Q, et al. A new microporous anionic metal-organic framework as a platform for highly selective adsorption and separation of organic dyes [J]. Journal of Materials Chemistry A, 2015, 3 (4): 1675-1681.
[26]	NALAPARAJU A. Ion exchange in metal-organic framework for water purification: insight from molecular simulation [J]. The Journal of Physical Chemistry C, 2012, 116 (12): 6925-6931.
[27]	PISMENSKAYA N, LAKTIONOV E, NIKONENKO V, et al. Dependence of composition of anion-exchange membranes and their electrical conductivity on concentration of sodium salts of carbonic and phosphoric acids [J]. Journal of Membrane Science, 2001, 181 (2): 185-197.

GO@MIL-101的制备及其对水中Cr（Ⅵ）的去除

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

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 27

相关文章 15

编辑推荐

Metrics

本文评价

[1]	赵亚欣, 张雪芹, 王荣柱, 孙国, 姚善泾, 林东强. 流穿模式离子交换层析去除单抗聚集体[J]. 化工学报, 2023, 74(9): 3879-3887.
[2]	高燕, 伍鹏, 尚超, 胡泽君, 陈晓东. 基于双流体喷嘴的磁性琼脂糖微球的制备及其蛋白吸附性能探究[J]. 化工学报, 2023, 74(8): 3457-3471.
[3]	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.
[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]	陈朝光, 贾玉香, 汪锰. 以低浓度废酸驱动中和渗析脱盐的模拟与验证[J]. 化工学报, 2023, 74(6): 2486-2494.
[6]	蔺彩虹, 王丽, 吴瑜, 刘鹏, 杨江峰, 李晋平. 沸石中碱金属阳离子对CO₂/N₂O吸附分离性能的影响[J]. 化工学报, 2023, 74(5): 2013-2021.
[7]	余后川, 任腾, 张宁, 姜晓滨, 代岩, 张晓鹏, 鲍军江, 贺高红. 二维氧化石墨烯膜离子选择性传递调控的研究进展[J]. 化工学报, 2023, 74(1): 303-312.
[8]	闫军营, 王皝莹, 李瑞瑞, 符蓉, 蒋晨啸, 汪耀明, 徐铜文. 选择性电渗析：机遇与挑战[J]. 化工学报, 2023, 74(1): 224-236.
[9]	杜若晗, 逄博, 王宁, 崔福军, 郭明钢, 贺高红, 吴雪梅. 连续共价有机框架筛分复合膜及全钒电池性能[J]. 化工学报, 2022, 73(9): 4163-4172.
[10]	杨宏欣, 李兴亚, 葛亮, 徐铜文. 含哌啶阳离子侧长链型一/二价阴离子选择性分离膜的制备[J]. 化工学报, 2022, 73(8): 3739-3748.
[11]	朱嫣然, 葛亮, 李兴亚, 徐铜文. 三相结构离子交换膜的构筑及应用研究[J]. 化工学报, 2022, 73(6): 2397-2414.
[12]	李智超, 郑瑜, 张润楠, 姜忠义. 高通量抗污染氧化石墨烯膜研究进展[J]. 化工学报, 2022, 73(6): 2370-2380.
[13]	杨珊珊, 姚宇洋, 董云迪, 徐志鹏, 高尚上, 阮慧敏, 沈江南. 基于二苯并-18-冠-6基体改性的K⁺选择性离子交换膜的制备及性能研究[J]. 化工学报, 2022, 73(4): 1781-1793.
[14]	张苗, 杨洪海, 尹勇, 徐悦, 沈俊杰, 卢心诚, 施伟刚, 王军. 氧化石墨烯/水脉动热管的启动及传热特性[J]. 化工学报, 2022, 73(3): 1136-1146.
[15]	徐欢, 柯律, 张生辉, 张子林, 韩广东, 崔金声, 唐道远, 黄东辉, 高杰峰, 何新建. GO表面原位生长CNTs改善聚丙烯导热复合材料分散与界面形态[J]. 化工学报, 2022, 73(11): 5150-5157.