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

doi:10.11949/j.issn.0438-1157.20180995

摘要/Abstract

摘要：

采用氧化石墨烯(GO)稳定的Pickering乳液为软模板，制备聚乙烯醇-石墨烯气凝胶。探究GO浓度、均质转速、油水比、乙二胺(EDA)和聚乙烯醇(PVA)用量等因素对乳液稳定性、粒径分布及气凝胶成型的影响，发现改变乳液配比可控制乳液粒径的大小，进而对气凝胶的密度和孔隙率进行调控。通过SEM、FT-IR、Raman、XRD对最优制备条件下制得的聚乙烯醇-石墨烯气凝胶(PGA)进行表征，可知GO经水热反应后被还原组装形成三维网络气凝胶结构(PGA)且其孔道直径与乳液粒径基本一致。对PGA进行挤压实验发现其具有轴、径双向挤压回弹性，且重复挤压200次以上PGA仍然具良好的弹性。PGA对纯有机物的吸附量最高可达280 g·g^?1，且每克PGA吸附的有机物的体积为恒定值。

关键词: 聚乙烯醇, 石墨烯, 气凝胶, 乳液, 弹性, 复合材料

Abstract:

A polyvinyl alcohol-graphene aerogel was prepared by using a graphene oxide (GO)-stabilized Pickering emulsion as a soft template. The effects of GO concentration, homogenization speed, oil/water ratio, the amount of ethylenediamine (EDA) and polyvinyl alcohol (PVA) on the stability, particle size distribution of the emulsion and the formation of aerogel were investigated. It was found that the drop size of the emulsion could be controlled by changing the emulsion composition ratio. Then, the density and porosity of the aerogel also could be controlled. The polyvinyl alcohol-graphene aerogel (PGA) prepared under optimal preparation conditions was characterized by SEM, FT-IR, Raman and XRD. It was found that GO had been reduced and assembled to form a three-dimensional network structure (PGA) after the hydrothermal reaction and the pore size of the PGA was substantially the same as the particle size of the emulsion. The extrusion test of PGA was carried out and it was observed that PGA had both longitudinal and lateral bidirectional extrusion resilience. And the PGA still had good elasticity after more than 200 times repeated extrusion. The adsorption amount of pure organics by PGA was up to 280 g·g^?1, and the volume of organics adsorbed per gram of PGA was constant value.

Key words: polyvinyl alcohol, graphene, aerogel, emulsions, elasticity, composites

中图分类号:

TQ 013.2

王振有, 刘会娥, 朱佳梦, 陈爽, 于安然. 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.

Zhenyou WANG, Hui’e LIU, Jiameng ZHU, Shuang CHEN, Anran YU. Preparation of polyvinyl alcohol-graphene aerogel by emulsion method and its adsorption on pure organics[J]. CIESC Journal, 2019, 70(3): 1152-1162.

图/表 22

表1 气凝胶制备条件

Table 1 Aerogel preparation conditions

Sample	C_GO/ (mg·ml^?1)	R/ (r·min^?1)	Oil/water ratio	V_EDA∶V_GO/%	V_PVA∶V_GO/%
1	10	16000	5∶3	2	25
2	8	16000	5∶3	2	25
3	6	16000	5∶3	2	25
4	4	16000	5∶3	2	25
5	10	12000	5∶3	2	25
6	10	10000	5∶3	2	25
7	10	16000	1∶3	2	25
8	10	16000	2∶3	2	25
9	10	16000	3∶3	2	25
10	10	16000	4∶3	2	25
11	10	16000	6∶3	2	25
12	10	16000	7∶3	2	25
13	10	16000	8∶3	2	25
14	10	16000	9∶3	2	25
15	10	16000	5∶3	1	25
16	10	16000	5∶3	3	25
17	10	16000	5∶3	4	25
18	10	16000	5∶3	2	15
19	10	16000	5∶3	2	35

图1 不同GO浓度下形成的Pickering乳液光学显微镜照片

Fig.1 Optical micrographs of Pickering emulsion with varied GO concentrations

图2 不同 GO浓度Pickering乳液粒径分布

Fig.2 Droplet size distribution of Pickering emulsions with varied GO concentrations

图3 静置24 h的不同GO浓度的Pickering乳液照片

Fig.3 Photographs of Pickering emulsion with varied GO concentrations after 24 h

图4 不同GO浓度乳液平均粒径与气凝胶密度的关系

Fig.4 Relationship between average droplet size of emulsions and aerogel density with varied GO concentrations

图5 不同GO浓度下制备的气凝胶照片

Fig.5 Photographs of aerogels prepared with varied GO concentrations

图6 不同转速乳液平均粒径与气凝胶密度的关系

Fig.6 Relationship between average droplet size of emulsions and aerogel density with varied stirring speeds

图7 不同转速下制备的气凝胶照片

Fig.7 Photographs of aerogels prepared with varied stirring speeds

图8 不同油水比乳液平均粒径与气凝胶密度的关系

Fig.8 Relationship between average droplet size of emulsions and aerogel density with varied oil/water ratio

表2 不同油水比的乳液平均粒径、气凝胶密度、孔隙率

Table 2 Average droplet size of emulsions, density and porosity of aerogel with different oil/water ratios

Oil/water ratio	d/μm	ρ/(mg·cm^?3)	η/%
1∶3	20.81	9.609	99.56
2∶3	24.66	7.279	99.67
3∶3	26.81	5.94	99.73
4∶3	27.45	5.243	99.76
5∶3	28.64	4.565	99.79
6∶3	30.72	4.195	99.81
7∶3	37.21	5.421	99.75
8∶3	38.94	5.313	99.76
9∶3	41.83	5.358	99.76

图9 不同EDA用量乳液平均粒径与气凝胶密度的关系

Fig.9 Relationship between average droplet size of emulsions and aerogel density with varied EDA dosage

图10 不同EDA用量下的气凝胶照片

Fig.10 Photographs of aerogels prepared with varied EDA dosages

图11 不同PVA用量乳液平均粒径与气凝胶密度的关系

Fig.11 Relationship between average droplet size of emulsions and aerogel density with varied PVA dosages

图12 不同PVA用量下的气凝胶照片

Fig.12 Photographs of aerogels prepared with varied PVA dosages

图13 GO和PGA的拉曼谱图(a)和红外谱图(b)

Fig.13 Raman (a) and FT-IR spectra (b) of GO and PGA

图14 PGA的SEM图

Fig.14 SEM images of PGA

图15 GO和PGA的XRD谱图

Fig.15 XRD patterns of GO and PGA

图16 PGA挤压-回弹性能测试

Fig.16 Extrusion-resilience test of PGA

图17 PGA的应力应变曲线

Fig.17 Strain-stress curves of PGA

表3 PGA对不同有机物的吸附数据

Table 3 Adsorption data of PGA on different organic solvents

Organic solvent	ρ_o^①/(g·ml^?1)	q/(g·g^?1)
n-heptane	0.683	126.778
diesel	0.838	137.018.
DMF	0.945	148.259
methyl benzoate	1.09	150.096
dichloromethane	1.33	230.062
carbon tetrachloride	1.592	268.667

图18 有机溶剂密度与吸附量的关系

Fig.18 Relationship between organic matter density and adsorption amount

表4 q-ρo线性拟合结果

Table 4 Results of q-ρo linear fitting

Slope	Intercept	R²/%
167.96	0	99.81

参考文献 33

1	ZhuQ, ChuY, WangZ, et al. Robust superhydrophobic polyurethane sponge as a highly reusable oil-absorption material[J]. Journal of Materials Chemistry A, 2013, 1(17): 5386-5393.
2	XiaoN, ZhouY, LingZ, et al. Synthesis of a carbon nanofiber/carbon foam composite from coal liquefaction residue for the separation of oil and water[J]. Carbon, 2013, 59(4): 530-536.
3	WangH J, ZhouA L, PengF, et al. Adsorption characteristic of acidified carbon nanotubes for heavy metal Pb(II) in aqueous solution[J]. Materials Science & Engineering A, 2007, 466(1): 201-206.
4	LiY H, WangS, WeiJ, et al. Lead adsorption on carbon nanotubes[J]. Chemical Physics Letters, 2002, 357(3): 263-266.
5	FanZ, YanJ, NingG, et al. Oil sorption and recovery by using vertically aligned carbon nanotubes[J]. Carbon, 2010, 48(14): 4197-4200.
6	WangH, LinK Y, JingB, et al. Removal of oil droplets from contaminated water using magnetic carbon nanotubes[J]. Water Research, 2013, 47(12): 4198-4205.
7	LiuT T, TianS S. Management with leaking oil on the sea and its future development trend[J].China Water Transport, 2006, 4(11): 27-29.
8	HuH, ZhaoZ, WanW, et al. Ultralight and highly compressible graphene aerogels[J]. Advanced Materials, 2013, 25(15): 2219-2223.
9	WorsleyM A, PauzauskieP J, OlsonT Y, et al. Synthesis of graphene aerogel with high electrical conductivity[J]. Journal of the American Chemical Society, 2010, 132(40): 14067-14069.
10	MaoS, LuG, ChenJ. Three-dimensional graphene-based composites for energy applications[J]. Nanoscale, 2015, 7(16): 6924.
11	ZhouS, JiangW, WangT H, et al. Highly hydrophobic, compressible, and magnetic polystyrene/Fe₃O₄/graphene aerogel composite for oil-water separation[J]. Industrial & Engineering Chemistry Research, 2015, 54(20): 5460-5467.
12	CongH P, RenX C, WangP, et al. Macroscopic multifunctional graphene-based hydrogels and aerogels by a metal ion induced self-assembly process[J]. ACS Nano, 2012, 6(3): 2693-2703.
13	SunH, XuZ, GaoC. Multifunctional, ultra-flyweight, synergistically assembled carbon aerogels[J]. Advanced Materials, 2013, 25(18): 2554-2560.
14	XuL, XiaoG, ChenC, et al. Superhydrophobic and superoleophilic graphene aerogel prepared by facile chemical reduction[J]. Journal of Materials Chemistry A, 2015, 3(14): 7498-7504.
15	HongJ Y, SohnE H, ParkS, et al. Highly-efficient and recyclable oil absorbing performance of functionalized graphene aerogel[J]. Chemical Engineering Journal, 2015, 269: 229-235.
16	DengW, FangQ, ZhouX, et al. Hydrothermal self-assembly of graphene foams with controllable pore size[J]. RSC Advances, 2016, 6(25): 20843-20849.
17	QiuL, LiuJ Z, ChangS L, et al. Biomimetic superelastic graphene-based cellular monoliths[J]. Nature Communications, 2011, 3(4): 1241.
18	QianK, LiuF, YangJ, et al. Pore size-optimized periodic mesoporous organosilicas for the enrichment of peptides and polymers[J]. RSC Advances, 2013, 3(34): 14466-14472.
19	SilversteinM S. Emulsion-templated polymers: contemporary contemplations[J]. Polymer, 2017, 126: 261-282.
20	BinksB P. Particles as surfactants-similarities and differences[J]. Current Opinion in Colloid & Interface Science, 2002, 7(1): 21-41.
21	张琪. 基于二维纳米片的Pickering乳液模板法制备无机/有机复合材料[D]. 广州: 华南理工大学, 2015.
	ZhangQ. Fabrication of inorganic/organic composite materials templated from two-dimensional nanosheets-stabilized Pickering emulsions[D]. Guangzhou: South China University of Technology,2015.
22	YiW, WuH, WangH, et al. Interconnectivity of macroporous hydrogels prepared via graphene oxide-stabilized Pickering high internal phase emulsions[J]. Langmuir, 2016, 32(4): 982-990.
23	ZhengZ, ZhengX, WangH, et al. Macroporous grapheme oxide-polymer composite prepared through Pickering high internal phase emulsions[J]. Applied Materials & Interfaces, 2013, 5(16): 7974-7982.
24	WanW, ZhaoZ, HughesT C, et al. Graphene oxide liquid crystal Pickering emulsions and their assemblies[J]. Carbon, 2015, 85: 16-23.
25	CoteL J, KimF, HuangJ. Langmuir-Blodgett assembly of graphite oxide single layers[J]. Journal of the American Chemical Society, 2009, 131(3): 1043-1049.
26	ChenY, WangY, ShiX, et al. Hierarchical and reversible assembly of graphene oxide/polyvinyl alcohol hybrid stabilized Pickering emulsions and their templating for macroporous composite hydrogels[J]. Carbon, 2017, 111: 38-47.
27	马雁冰, 刘会娥, 陈爽, 等. 碳纳米管-石墨烯气凝胶制备及其对水中乳化油的吸附特性[J]. 化工学报, 2018, 69(4): 1508-1517.
	MaY B, LiuH E, ChenS, et al. Facile synthesis of carbon nanotubes-graphene aerogels and its adsorption property for emulsified oil in water[J]. CIESC Journal, 2018, 69(4): 1508-1517.
28	ZhangY, TaoB, XingW, et al. Sandwich-like nitrogen-doped porous carbon/graphene nanoflakes with high-rate capacitive performance[J]. Nanoscale, 2016, 8(15): 78897898.
29	ChenJ, ChiF, HuangL, et al. Synthesis of graphene oxide sheets with controlled sizes from sieved graphite flakes[J]. Carbon, 2016, 110: 34-40.
30	YangW, GaoH, ZhaoY, et al. Facile preparation of nitrogen-doped graphene sponge as a highly efficient oil absorption material[J]. Materials Letters, 2016, 178: 95-99.
31	ShinH J, KimK K, BenayadA, 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.
32	HuH, ZhaoZ, WanW, et al. Ultralight and highly compressible graphene aerogels[J]. Advanced Materials, 2013, 25(15): 2219-2223.
33	XuL M, XiaoG Y, ChenC B, et al. Superhydrophobic and superoleophilic graphene aerogel prepared by facile chemical reduction[J]. Journal of Materials Chemistry A, 2015, 3: 7498-7504.

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