氧化程度对氧化石墨烯吸附亚甲基蓝性能的影响

doi:10.11949/j.issn.0438-1157.20161497

化工学报 ›› 2017, Vol. 68 ›› Issue (4): 1712-1720.DOI: 10.11949/j.issn.0438-1157.20161497

• 材料化学工程与纳米技术 • 上一篇下一篇

氧化程度对氧化石墨烯吸附亚甲基蓝性能的影响

王泉珺¹, 孙红娟², 彭同江^2,3, 岳焕娟²

1 西南科技大学理学院, 四川绵阳 621010;
2 西南科技大学矿物材料及应用研究所, 四川绵阳 621010;
3 西南科技大学分析测试中心, 四川绵阳 621010

收稿日期:2016-10-26 修回日期:2016-12-11 出版日期:2017-04-05 发布日期:2017-04-05
通讯作者: 孙红娟
基金资助:
国家自然科学基金项目（41272051，U1630132）；西南科技大学博士基金项目(11ZX7135)。

Influence of oxidation degree of graphene oxide on adsorption performance for methylene blue

WANG Quanjun¹, SUN Hongjuan², PENG Tongjiang^2,3, YUE Huanjuan²

1 School of Science, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China;
2 Institute of Mineral Materials & Application, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China;
3 Analytical and Testing Center, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China

Received:2016-10-26 Revised:2016-12-11 Online:2017-04-05 Published:2017-04-05
Supported by:
supported by the National Natural Science Foundation of China (41272051, U1630132) and the Doctor Foundation of Southwest University of Science and Technology (11ZX7135).

摘要/Abstract

摘要：

基于改进Hummers法，调控氧化剂KMnO₄用量制备了不同含氧官能团含量的氧化石墨烯（GOs）。采用XRD、XPS、AFM和FTIR分析了KMnO₄用量对GOs的结构特征、含氧官能团类型及含量的影响，研究了氧化程度对GOs吸附亚甲基蓝（MB）性能的影响。结果表明：KMnO₄用量对GOs-n（n=2，3，4（的含氧官能团类型和含量有显著影响；MB最大饱和吸附量依次为728.44、965.63和807.29 mg·g^-1，与Langmuir模型单分子层饱和吸附量的标准差为3.6%、3.7%和4.2%，吸附动力学过程符合准二级动力学模型，R²> 0.99。以GOs结构层上去质子化的羟基（-C-O^-）和羧基（-COO^-）为主要活性位点与MB发生化学控速的单分子层放热吸附，吸附热在20~27 kJ·mol^-1之间；低氧化程度的GOs以离子交换吸附为主导，吸附性能与GOs结构中-C-O（H（和-COO（H（的总量呈正相关。随氧化程度加深，GOs结构中环氧基（C-O-C）和羰基（C═O）以氢键作用吸附MB对吸附量的影响凸显。

关键词: 氧化石墨烯, 含氧官能团, 动力学, 热力学, MB吸附

Abstract:

Graphene oxide (GOs) with different oxygen-containing functional groups was prepared by adjusting the amount of oxidant KMnO₄. The effects of KMnO₄ dosage on the structural characteristics, the type and content of the functional groups of GOs were analyzed by XRD, XPS, AFM and FTIR, and the performance of GOs on methylene blue (MB) were studied. The results indicated that KMnO₄ dosage has a significant effect on the oxidation degree of GOs-n (n=2, 3, 4), the maximum saturated adsorption capacity of MB⁺ was 728.44、965.63 and 807.29 mg·g^-1, compared with Langmuir model fitted values of single molecular layer saturated adsorption capacity of standard deviation was 3.6%, 3.7% and 4.2%, respectively. Pseudo-second-order kinetic model could better describe the dynamic process of adsorption, and R² > 0.99, which based on GOs structure on the most abundant hydroxyl (-C-O^-) and carboxyl (-COO^-) as the main active sites with MB⁺ occur single molecular layer, exothermic and chemical speed control process. Adsorption heat was between 20-27 kJ·mol^-1, and adsorption mechanism was dominated by ion exchange adsorption. Adsorption performance was positively correlated with the total amount of -C-O^- and -COO^- in GOs structure. Effects of epoxy groups and carbonyl groups on the adsorption capacity of MB by hydrogen bonding become prominent with increasing the extent of oxidation.

Key words: graphene oxide, oxygen-containing functional groups, kinetics, thermodynamics, methylene blue adsorption

中图分类号:

王泉珺, 孙红娟, 彭同江, 岳焕娟. 氧化程度对氧化石墨烯吸附亚甲基蓝性能的影响[J]. 化工学报, 2017, 68(4): 1712-1720.

WANG Quanjun, SUN Hongjuan, PENG Tongjiang, YUE Huanjuan. Influence of oxidation degree of graphene oxide on adsorption performance for methylene blue[J]. CIESC Journal, 2017, 68(4): 1712-1720.

参考文献 30

[1]	DIKIN D A, STANKOVICH S, ZIMNEY E J, et al. Preparation and characterization of graphene oxide paper[J]. Nature, 2007, 448(7152):457-460.
[2]	LOH K P, BAO Q, EDA G, et al. Graphene oxide as a chemically tunable platform for optical applications[J]. Nature Chemistry, 2010, 2(12):1015-1024.
[3]	KRISHNAMOORTHY K, VEERAPANDIAN M, YUN K, et al. The chemical and structural analysis of graphene oxide with different degrees of oxidation[J]. Carbon, 2013, 53:38-49.
[4]	ZHU Y W, MURALI S, CAI W W, et al. Graphene and graphene oxide:synthesis, properties, and applications[J]. Advanced Materials, 2010, 22(35):3906-3924.
[5]	RODR G A, GARC A J, OVEJERO G, et al. Adsorption of anionic and cationic dyes on activated carbon from aqueous solutions:equilibrium and kinetics[J]. J. Hazard. Mater., 2009, 172(172):1311-1320.
[6]	YAO Y, XU F, CHEN M, et al. Adsorption behavior of methylene blue on carbon nanotubes[J]. Bioresource Technol., 2010, 101(9):3040-3046.
[7]	MILLAR G J, MILLER G L, COUPERTHWAITE S J, et al. Factors influencing kinetic and equilibrium behaviour of sodium ion exchange with strong acid cation resin[J]. Separation & Purification Technology, 2016, 163:79-91.
[8]	SZABÓ T, BERKESI O, FORGÓ P, et al. Evolution of surface functional groups in a series of progressively oxidized graphite oxides[J]. Chem. Mater., 2006, 18(11):2740-2749.
[9]	EIGLER S, HIRSCH A. Chemistry with graphene and graphene oxide & mdash;challenges for synthetic chemists[J]. Angewandte Chemie, 2014, 53(30):7720-7738.
[10]	ZAGHBANI N, HAFIANE A, DHAHBI M. Separation of methylene blue from aqueous solution by micellar enhanced ultrafiltration[J]. Sep. Purif. Technol., 2007, 55(1):117-124.
[11]	LIU F, CHUNG S, OH G, et al. Three-dimensional graphene oxide nanostructure for fast and efficient water-soluble dye removal[J]. ACS Appl. Mater. Inter., 2012, 4(2):922-927.
[12]	ZHANG W, ZHOU C, ZHOU W, et al. Fast and considerable adsorption of methylene blue dye onto graphene oxide[J]. B. Environ. Contam. Tox., 2011, 87(1):86-90.
[13]	YANG S T, CHEN S, CHANG Y, et al. Removal of methylene blue from aqueous solution by graphene oxide[J]. J. Colloid Interf. Sci., 2011, 359(1):24-29.
[14]	WANG J, CHEN B. Adsorption and coadsorption of organic pollutants and a heavy metal by graphene oxide and reduced graphene materials[J]. Chem. Eng. J., 2015, 281:379-388.
[15]	KANG J H, KIM T, CHOI J, et al. Hidden second oxidation step of hummers method[J]. Chem. Mater., 2016, 28(3):756-764.
[16]	孙红娟, 彭同江. 石墨氧化-还原法制备石墨烯材料[M]. 北京:科学出版社, 2015:52-79.SUN H J, PENG T J. Graphene Materials Prepared by Oxidation-Reduction Method from Graphite[M]. Beijing:Science Press, 2015:52-79.
[17]	DIMIEV A M, ALEMANY L B, TOUR J M. Graphene oxide. Origin of acidity, its instability in water, and a new dynamic structural model[J]. ACS Nano, 2013, 7(1):576-588.
[18]	ROZADA R, PAREDES J I, L PEZ M J, et al. From graphene oxide to pristine graphene:revealing the inner workings of the full structural restoration[J]. Nanoscale, 2015, 7(6):2374-2390.
[19]	黄桥, 孙红娟, 杨勇辉. 氧化石墨的谱学表征及分析[J]. 无机化学学报, 2011, 27(9):1721-1726.HUANG Q, SUN H J, YANG Y H. Spectroscopy characterization and analysis of graphite oxide[J]. Chin. J. Inorg. Chem., 2011, 27(9):1721-1726.
[20]	MI X, HUANG G, XIE W, et al. Preparation of graphene oxide aerogel and its adsorption for Cu2+ ions[J]. Carbon, 2012, 50(13):4856-4864.
[21]	HO Y S, MCKAY G. Sorption of dge from aqueous solution by peat[J]. Chem. Eng. J., 1998, 70(2):115-124.
[22]	YIN Z, XIONG J, CHEN M, et al. Recovery of uranium (Ⅵ) from aqueous solution by amidoxime functionalized wool fibers[J]. J. Radioanal. Nucl. Chem., 2016, 307(2):1471-1479.
[23]	HO Y S. Review of second-order models for adsorption systems[J]. J. Hazard. Mater., 2006, 136(3):681-689.
[24]	LANGMUIR I. The adsorption of gases on plane surfaces of glass, mica and platinum[J]. J. Am. Chem. Soc., 1918, 40(9):1361-1403.
[25]	FREUNDLICH H. Over the adsorption in solution[J]. J. Phys. Chem., 1906, 57(385471):1100-1107.
[26]	CHEN M, CHEN Y, DIAO G. Adsorption kinetics and thermodynamics of methylene blue onto p-tert-butyl-calix[4, 6, 8] arene-bonded silica gel[J]. Journal of Chemical & Engineering Data, 2010, 55(11):5109-5116.
[27]	WANG D, LIU L, JIANG X, et al. Adsorbent for p-phenylenediamine adsorption and removal based on graphene oxide functionalized with magnetic cyclodextrin[J]. Appl. Surf. Sci., 2015, 329:197-205.
[28]	FERNANDES A N, ALMEIDA C A P, DEBACHER N A, et al. Isotherm and thermodynamic data of adsorption of methylene blue from aqueous solution onto peat[J]. J. Mol. Struct., 2010, 982(1):62-65.
[29]	冯明珠, 彭同江, 孙红娟, 等. 氧化程度对氧化石墨结构与阳离子交换容量的影响[J]. 无机化学学报, 2016, 32(3):427-433.FENG M Z, PENG T J, SUN H J, et al. Effect of oxidation degree on structure and cation exchange capacity of graphite oxide[J]. Chin. J. Inorg. Chem., 2016, 32(3):427-433.
[30]	LIU F, CHUNG S, OH G, et al. Three-dimensional graphene oxide nanostructure for fast and efficient water-soluble dye removal[J]. ACS Appl. Mater. Interfaces, 2012, 4(2):922-927.

氧化程度对氧化石墨烯吸附亚甲基蓝性能的影响

Influence of oxidation degree of graphene oxide on adsorption performance for methylene blue

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

[1]	杨欣, 王文, 徐凯, 马凡华. 高压氢气加注过程中温度特征仿真分析[J]. 化工学报, 2023, 74(S1): 280-286.
[2]	常明慧, 王林, 苑佳佳, 曹艺飞. 盐溶液蓄能型热泵循环特性研究[J]. 化工学报, 2023, 74(S1): 329-337.
[3]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[4]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[5]	张化福, 童莉葛, 张振涛, 杨俊玲, 王立, 张俊浩. 机械蒸汽压缩蒸发技术研究现状与发展趋势[J]. 化工学报, 2023, 74(S1): 8-24.
[6]	肖明堃, 杨光, 黄永华, 吴静怡. 浸没孔液氧气泡动力学数值研究[J]. 化工学报, 2023, 74(S1): 87-95.
[7]	毕丽森, 刘斌, 胡恒祥, 曾涛, 李卓睿, 宋健飞, 吴翰铭. 粗糙界面上纳米液滴蒸发模式的分子动力学研究[J]. 化工学报, 2023, 74(S1): 172-178.
[8]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[9]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[10]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[11]	胡建波, 刘洪超, 胡齐, 黄美英, 宋先雨, 赵双良. 有机笼跨细胞膜易位行为的分子动力学模拟研究[J]. 化工学报, 2023, 74(9): 3756-3765.
[12]	杨越, 张丹, 郑巨淦, 涂茂萍, 杨庆忠. NaCl水溶液喷射闪蒸-掺混蒸发的实验研究[J]. 化工学报, 2023, 74(8): 3279-3291.
[13]	张曼铮, 肖猛, 闫沛伟, 苗政, 徐进良, 纪献兵. 危废焚烧处理耦合有机朗肯循环系统工质筛选与热力学优化[J]. 化工学报, 2023, 74(8): 3502-3512.
[14]	汪林正, 陆俞冰, 张睿智, 罗永浩. 基于分子动力学模拟的VOCs热氧化特性分析[J]. 化工学报, 2023, 74(8): 3242-3255.
[15]	曾如宾, 沈中杰, 梁钦锋, 许建良, 代正华, 刘海峰. 基于分子动力学模拟的Fe₂O₃纳米颗粒烧结机制研究[J]. 化工学报, 2023, 74(8): 3353-3365.