软模板法石墨烯气凝胶的可控制备及其吸油性能

doi:10.16085/j.issn.1000-6613.2019-1571

摘要/Abstract

摘要：

以环己烷为油相，氧化石墨烯（GO）为稳定剂，采用Pickering乳液法制备石墨烯气凝胶，利用电子显微镜对Pickering乳液进行表征，利用扫描电镜（SEM）、傅里叶红外光谱（FTIR）、拉曼光谱（Raman）、X射线衍射（XRD）对制得的石墨烯气凝胶进行表征。对比Pickering乳液的液滴大小与气凝胶的孔径大小可知，通过软模板法实现了对气凝胶的孔径控制，通过控制均质机的转速来调控气凝胶的孔径大小，当均质机转速分别为10000r/min、12000r/min和15000r/min时，所得石墨烯气凝胶的孔径分别为45μm、35μm和30μm左右，通过调节油水比实现了气凝胶的密度与孔隙率的控制，油水比越大，所得气凝胶的密度越小，孔隙率越大，通过延长还原时间可增强石墨烯气凝胶的机械性能。将所得气凝胶用于油品的吸附，可快速吸附水上浮油及水底重油，而且几乎不吸附水；对同一油品而言，气凝胶的吸附能力与其制备时的油水比呈正相关，采用挤压的方式实现石墨烯气凝胶的循环利用，经过10次循环再生后气凝胶的吸附能力仅有15%的损失。

关键词: 石墨烯气凝胶, Pickering乳液, 孔径调控, 机械性能, 吸附

Abstract:

Graphene aerogels were prepared by Pickering emulsion using cyclohexane as oil phase and graphene oxide (GO) as stabilizer. The Pickering emulsion was characterized by the electron microscope. The graphene aerogels was characterized by SEM, FTIR, Raman and XRD. By comparing the droplet size of Pickering emulsion and the pore size of aerogels, the pore size control of aerogels can be achieved by soft template method. By adjusting the agitation speed of the high-speed homogenizer, the pore size of the aerogel was adjusted. When the agitation speed of the high-speed homogenizer was 10000r/min, 12000r/min and 15000r/min, the pore size of the obtained graphene aerogels was 45μm, 35μm and 30μm, respectively. The density and porosity of aerogels were controlled by adjusting the oil/ water ratio during its preparation. It was observed that with the increase of oil/water ratio, the aerogel density reduced, while the porosity increased. The mechanical performance of graphene aerogels can be enhanced by extending the time of reduction. The obtained aerogels were used for the adsorption of oils. Graphene aerogels can adsorb floating oil and bottom heavy oil rapidly, and hardly adsorb water. For the same oil, the adsorption capacity of aerogels was positively correlated with the oil/water ratio. The recycling of graphene aerogels was achieved through extrusion method. After 10 cycles of regeneration, the adsorption capacity of aerogels decreased only by 15%.

Key words: graphene aerogel, Pickering emulsions, pore size control, mechanical properties, adsorption

中图分类号:

TQ013.2

刁帅, 刘会娥, 陈爽, 于安然, 许文龙, 张广智. 软模板法石墨烯气凝胶的可控制备及其吸油性能[J]. 化工进展, 2020, 39(7): 2742-2750.

Shuai DIAO, Huie LIU, Shuang CHEN, Anran YU, Wenlong XU, Guangzhi ZHANG. Controllable preparation of graphene aerogels with soft templates and its adsorption on oils[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2742-2750.

参考文献

1	马园园, 寇伟, 丁国生, 等. 石墨烯负载纳米银的制备及其对H₂O₂的电化学检测[J]. 化工进展, 2019, 38(9): 4191-4196.
1	MA Y Y, KOU W, DING G S, et al. Preparation of graphene-supported nano-silver and its electrochemical detection of H₂O₂[J]. Chemical Industry and Engineering Progress, 2019, 38(9): 4191-4196.
2	GEIM A K, NOVOSELOV K S. The rise of graphene[J]. Nature Materials, 2007, 6(3): 183-191.
3	杨绍斌, 籍遥函, 沈丁. 氧化石墨烯液晶相结构的调控及应用进展[J]. 化工进展, 2019, 38(3): 1443-1451.
3	YANG S B, JI Y H, SHEN D. Phase structure control and applications of graphene oxide liquid crystals[J]. Chemical Industry and Engineering Progress, 2019, 38(3): 1443-1451.
4	LI J H, LI W X, HUANG W P, et al. Fabrication of highly reinforced and compressible graphene/carbon nanotube hybrid foams via a facile self-assembly process for application as strain sensors and beyond[J]. Journal of Materials Chemistry C, 2017, 5: 2723-2730.
5	QIAN Y, ISMAIL I M, STEIN A. Ultralight, high-surface-area, multifunctional graphene-based aerogels from self-assembly of graphene oxide and resol[J]. Carbon, 2014, 68: 221-231.
6	ZHAO D, YU L, LIU D X. Ultralight graphene/carbon nanotubes aerogels with compressibility and oil absorption properties[J]. Materials, 2018, 11(4): 641.
7	ZHOU S, ZHOU X, HAO G Z, et al. Property control of graphene aerogels by in situ growth of silicone polymer[J]. Applied Surface Science, 2018, 439: 946-953.
8	CAO J J, WANG Z Y, YANG X H, et al. Green synthesis of amphipathic graphene aerogel constructed by using the framework of polymer-surfactant complex for water remediation[J]. Applied Surface Science, 2018, 444: 399-406.
9	DONG S Y, CUI L F, LIU C Y, et al. Fabrication of 3D ultra-light graphene aerogel/Bi₂WO₆ composite with excellent photocatalytic performance: a promising photocatalysts for water purification[J]. Journal of the Taiwan Institute of Chemical Engineers, 2019, 97: 288-296.
10	黄扬帆, 刘会娥, 马雁冰, 等. 乳液法制备石墨烯气凝胶及其吸附水中亚甲基蓝[J]. 化工进展, 2019, 37(8): 3092-3099.
10	HUANG Y F, LIU H E, MA Y B, et al. Fabrication of graphene aerogels by emulsion method and their adsorption of methylene blue[J]. Chemical Industry and Engineering Progress, 2019, 37(8): 3092-3099.
11	JUNG S M, MAFRA D L, LIN C T, et al. Controlled porous structures of graphene aerogels and their effect on supercapacitor performance[J]. Nanoscale, 2015, 7(10): 4386-4393.
12	GARCíA-BORDEJé E, VíCTOR-ROMáN S, SANAHUJA-PAREJO O, et al. Control of the microstructure and surface chemistry of graphene aerogels via pH and time manipulation by a hydrothermal method[J]. Nanoscale, 2018, 10(7): 3526-3539.
13	QIAN K, LIU F, YANG J, et al. Pore size-optimized periodic mesoporous organosilicas for the enrichment of peptides and polymers[J]. RSC Advances, 2013, 3(34): 14466-14472.
14	ITO Y, TANABE Y, QIU H J, et al. High-quality three-dimensional nano-porous graphene[J]. Angewandte Communications International Edition, 2014, 53: 4822-4826.
15	YI W, WU H, WANG H, et al. Interconnectivity of macroporous hydrogels prepared via graphene oxide-stabilized pickering high internal phase emulsions[J]. Langmuir, 2016, 32(4): 982.
16	WAN W, ZHAO Z, HUGHES T C, et al. Graphene oxide liquid crystal Pickering emulsions and their assemblies[J]. Carbon, 2015, 85: 16-23.
17	ALDOSARI M A, OTHMAN A A, ALSHARAEH E H. Synthesis and characterization of the in-situ bulk polymerization of PMMA containing graphene sheets using microwave irradiation[J]. Molecules, 2013, 18(3): 3152-3167.
18	BINKS B P. Particles as surfactants-similarities and differences[J]. Current Opinion in Colloid & Interface Science, 2002, 7(1): 21-41.
19	ZHENG Z, ZHENG X H, WANG H T, et al. Macroporous grapheme oxide-polymer composite prepared through Pickering high internal phase emulsions[J]. Applied Materials & Interfaces, 2013, 5(16): 7974-7982.
20	王振有, 刘会娥, 朱佳梦, 等. 乳液法制备聚乙烯醇-石墨烯气凝胶及其对纯有机物的吸附[J]. 化工学报, 2019, 70(3): 1152-1162.
20	WANG Z Y, LIU H E, ZHU J M, et al. Preparation of polyvinyl alcohol-graphene aerogel by emulsion method and its adsorption on pure organics[J]. CIESC Journal, 2019, 70(3): 1152-1162.
21	COTE L J, KIM F, HUANG J, et al. Langmuir-Blodgett assembly of graphite oxide single layers[J]. Journal of the American Chemical Society, 2009, 131(3): 1043-1049.
22	CHEN J, CHI F Y, HUANG L, et al. Synthesis of graphene oxide sheets with controlled sizes from sieved graphite flakes[J]. Carbon, 2016, 110: 34-40.
23	SHIN H J, KIM K K, BENAYAD A, et al. Efficient reduction of graphite oxide by sodium borohydride and its effect on electrical conductance[J]. Advanced Functional Materials, 2009, 19(12): 1987-1992.
24	ZHANG Y, TAO B, XING W, et al. Sandwich-like nitrogen-doped porous carbon/graphene nanoflakes with high-rate capacitive performance[J]. Nanoscale, 2016, 8(15): 7889-7898.
25	CHEN L, DU R, ZHANG J, et al. Density controlled oil uptake and beyond: from carbon nanotubes to graphene nanoribbon aerogels[J]. Journal of Materials Chemistry A, 2015, 3(41): 20547-20553.

[1]	崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.
[2]	陈崇明, 陈秋, 宫云茜, 车凯, 郁金星, 孙楠楠. 分子筛基CO₂吸附剂研究进展[J]. 化工进展, 2023, 42(S1): 411-419.
[3]	许春树, 姚庆达, 梁永贤, 周华龙. 共价有机框架材料功能化策略及其对Hg(Ⅱ)和Cr(Ⅵ)的吸附性能研究进展[J]. 化工进展, 2023, 42(S1): 461-478.
[4]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[5]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[6]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[7]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[8]	杨莹, 侯豪杰, 黄瑞, 崔煜, 王兵, 刘健, 鲍卫仁, 常丽萍, 王建成, 韩丽娜. 利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附[J]. 化工进展, 2023, 42(9): 5011-5018.
[9]	姜晶, 陈霄宇, 张瑞妍, 盛光遥. 载锰生物炭制备及其在环境修复中应用研究进展[J]. 化工进展, 2023, 42(8): 4385-4397.
[10]	张振, 李丹, 陈辰, 吴菁岚, 应汉杰, 乔浩. 吸附树脂对唾液酸的分离纯化[J]. 化工进展, 2023, 42(8): 4153-4158.
[11]	王知彩, 刘伟伟, 周璁, 潘春秀, 闫洪雷, 李占库, 颜井冲, 任世彪, 雷智平, 水恒福. 基于煤基腐殖酸的高效减水剂合成与性能表征[J]. 化工进展, 2023, 42(7): 3634-3642.
[12]	于静文, 宋璐娜, 刘砚超, 吕瑞东, 武蒙蒙, 冯宇, 李忠, 米杰. 一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用[J]. 化工进展, 2023, 42(7): 3674-3683.
[13]	李艳玲, 卓振, 池亮, 陈曦, 孙堂磊, 刘鹏, 雷廷宙. 氮掺杂生物炭的制备与应用研究进展[J]. 化工进展, 2023, 42(7): 3720-3735.
[14]	白亚迪, 邓帅, 赵睿恺, 赵力, 杨英霞. 变温吸附碳捕集机组标准化测试方案探讨及性能实验[J]. 化工进展, 2023, 42(7): 3834-3846.
[15]	张雪伟, 黄亚继, 许月阳, 程好强, 朱志成, 李金壘, 丁雪宇, 王圣, 张荣初. 碱性吸附剂对燃煤烟气中SO₃的吸附特性[J]. 化工进展, 2023, 42(7): 3855-3864.