石墨烯量子点复合膜的调控制备：前体的影响

doi:10.11949/0438-1157.20231188

摘要/Abstract

摘要：

石墨烯量子点（GQDs）作为新兴的零维石墨烯衍生物，与二维材料氧化石墨烯相比，具有尺寸更小、比表面积更大、亲水性更强等优势，作为膜分离材料近年来备受关注。分别以柠檬酸、木质素磺酸钠、葡萄糖为前体，采用一步水热法成功合成出GQD并组装成GQDs复合膜，系统探究了三种前体对GQDs复合膜的微观结构和渗透汽化脱盐性能的影响。采用UV-Vis、FTIR、XRD、TEM等表征手段对膜的结构和形貌进行了分析，结果表明：不同前体会影响GQDs的粒径大小和膜层间距d-spacing值，从而影响GQDs复合膜的表面微观结构和渗透汽化脱盐性能。三种前体中以柠檬酸为前体制备的CA-GQDs复合膜的脱盐性能最佳，30℃在3.5%（质量分数）NaCl溶液中优化制备的CA-GQDs复合膜的渗透通量高达37.36 kg·m^-2·h^-1（渗透率高达1.2×10^-4 mol·m^-2·s^-1·Pa^-1），盐截留率近乎100%。此外，该复合膜在进料液pH=2～12具有较好的耐酸碱稳定性，尤其是pH=8～11时盐截留率仍保持99.95%以上。

关键词: 石墨烯量子点, 膜, 前体, 渗透汽化, 脱盐, 稳定性

Abstract:

Graphene quantum dots (GQDs), as an emerging 0D graphene derivative, have the advantages of smaller size, larger specific surface area and stronger hydrophilicity than 2D graphene oxide, which have attracted much attention as membrane separation materials in recent years. Three different serials of GQDs and assembling GQDs composite membranes were successfully prepared by one-step hydrothermal method with three different precursors: citric acid, sodium lignosulfonate and glucose. The influence of these three precursors on the microstructure and pervaporation desalination performance of GQDs composite membranes was systematically investigated. The particle sizes and d-spacing of GQDs were confirmed to be affected with these three precursors by various characterizations of UV-Vis, FTIR, XRD, and TEM, which could significantly influence surface microstructure and their desalination performance of these GQDs composite membranes. Among these three serials membranes, CA-GQDs composite membranes prepared with citric acid as the precursor exhibited the highest desalination performance. The CA-GQDs composite membrane optimized and prepared in 3.5% (mass) NaCl solution at 30℃ has a permeation flux of up to 37.36 kg·m^-2·h^-1 (permeance is as high as 1.2×10^-4 mol·m^-2·s^-1·Pa^-1), and the salt rejection rate is nearly 100%. In addition, the composite membrane has good acid and alkali resistance in the range of feed liquid pH=2 to 12, especially when the salt rejection rate remains above 99.95% at pH=8—11.

Key words: graphene quantum dots, membrane, precursors, pervaporation, desalination, stability

中图分类号:

TQ 028.8

陈佩佩, 汪秋英, 肖泽卿, 周思佳, 张小亮. 石墨烯量子点复合膜的调控制备：前体的影响[J]. 化工学报, 2023, 74(12): 5006-5015.

Peipei CHEN, Qiuying WANG, Zeqing XIAO, Sijia ZHOU, Xiaoliang ZHANG. Tailoring preparation of graphene quantum dot composite membranes: influence of precursors[J]. CIESC Journal, 2023, 74(12): 5006-5015.

图/表 12

图1 GQDs复合膜的制备流程示意图

Fig.1 Schematic diagram of preparation process of GQDs composite membranes

图2 不同前体制备GQDs溶液的UV-Vis谱及其光致发光照片[插图中分别为GQDs溶液在白炽灯（左）和365 nm紫外线（右）照射下光致发光照片]

Fig.2 UV-Vis spectra and photoluminescence photos of GQDs solutions prepared with different precursors [incandescent lamp (left) and 365 nm UV light (right) in the illustrations]

图3 不同前体制备GQDs的FTIR谱图a—CA-GQDs;b—SL-GQDs;c—GL-GQDs

Fig.3 FTIR spectra of GQDs samples prepared with different precursors

图4 不同前体制备GQDs的TEM形貌图和对应的粒径分布

Fig.4 TEM images and the corresponding particle size distribution (inset) of GQDs samples prepared with different precursors

图5 不同前体制备的GQDs在干态、湿态的XRD谱图及其对应的d-spacing值

Fig.5 XRD patterns in dry and wet states and the corresponding d-spacing of GQDs samples prepared with different precursors

图6 前体及其浸涂浓度对GQDs复合膜脱盐性能的影响

Fig.6 Effect of precursors and dip-coating concentrations on the desalination performance of GQDs composite membranes towards pure water and 3.5% (mass) NaCl solution at 30℃

图7 浸涂次数和浸涂液pH对CA-GQDs复合膜脱盐性能的影响

Fig.7 Effect of dip-coating times and pH in dip-coating solution on the desalination performance of CA-GQDs composite membranes towards pure water and 3.5% (mass) NaCl solution at 30℃

图8 测试温度对CA-GQDs复合膜在不同浓度NaCl溶液中的脱盐性能影响

Fig.8 Effect of feed temperature on the desalination performance of CA-GQDs composite membranes towards pure water and NaCl solutions with different concentrations

图9 CA-GQDs复合膜的渗透通量和渗透率与温度的Arrhenius关系曲线

Fig.9 Arrhenius plots of temperature dependent permeation flux and permeance of GQDs composite membranes towards pure water and NaCl solutions with different concentrations

表1 CA-GQDs复合膜渗透汽化脱盐过程的活化能

Table 1 Activation energy of CA-GQDs composite membranes for pervaporation desalination processes

Solution	E_j/(kJ·mol^-1)	E_p/(kJ·mol^-1)	(E_j-E_p)/(kJ·mol^-1)	ΔH_v/(kJ·mol^-1)^{[15, 23-24]}
Pure water	8.57±0.38	-32.33±1.73	40.90	40.71—46.48
0.3% NaCl	10.24±0.62	-33.22±1.45	43.46	40.69—46.34
3.5% NaCl	10.73±0.95	-32.49±1.16	43.22	40.67—45.96
5.0% NaCl	10.91±0.30	-32.37±0.54	43.28	40.66—45.74

图10 CA-GQDs复合膜的耐酸碱稳定性

Fig.10 Acid-base resistance stability of CA-GQDs composite membrane

图11 渗透汽化脱盐膜的性能比较[7, 15, 24, 26-41]

Fig.11 Comparison of desalination performance of pervaporation membranes in the literatures[7, 15, 24, 26-41]

参考文献 41

1	Yan Y X, Manickam S, Lester E, et al. Synthesis of graphene oxide and graphene quantum dots from miscanthus via ultrasound-assisted mechano-chemical cracking method[J]. Ultrasonics Sonochemistry, 2021, 73: 105519.
2	Li X M, Rui M C, Song J Z, et al. Carbon and graphene quantum dots for optoelectronic and energy devices: a review[J]. Advanced Functional Materials, 2015, 25(31): 4929-4947.
3	刘嘉玮, 郝雨峰, 苏延磊. 石墨烯量子点纳滤膜的仿生修饰及稳定性研究[J]. 化工学报, 2021, 72(6): 3390-3398.
	Liu J W, Hao Y F, Su Y L. Biomimetic modification and stability of graphene quantum dots nanofiltration membranes[J]. CIESC Journal, 2021, 72(6): 3390-3398.
4	Li H T, Kang Z H, Liu Y, et al. Carbon nanodots: synthesis, properties and applications[J]. Journal of Materials Chemistry, 2012, 22(46): 24230-24253.
5	韩威, 詹俊, 石红, 等. 氮和硫双掺杂石墨烯量子点的合成及其性能研究[J]. 化工学报, 2021, 72(S1): 530-538.
	Han W, Zhan J, Shi H, et al. Synthesis and properties of nitrogen and sulfur codoped graphene quantum dots[J]. CIESC Journal, 2021, 72(S1): 530-538.
6	Chen W F, Lv G, Hu W M, et al. Synthesis and applications of graphene quantum dots: a review[J]. Nanotechnology Reviews, 2018, 7(2): 157-185.
7	Sun J W, Jia W, Guo J X, et al. Amino-embedded carbon quantum dots incorporated thin-film nanocomposite membrane for desalination by pervaporation[J]. Desalination, 2022, 533: 115742.
8	Zhang Y, Song J, Shi B B, et al. Graphene oxide membranes with an enlarged interlaminar nanochannel through functionalized quantum dots for pervaporative water-selective transport[J]. Separation and Purification Technology, 2022, 292: 120975.
9	Shao D D, Wang L, Yan X Y, et al. Amine-carbon quantum dots (CQDs-NH₂) tailored polymeric loose nanofiltration membrane for precise molecular separation[J]. Chemical Engineering Research and Design, 2021, 171: 237-246.
10	Sun W G, Zhang N, Li Q, et al. Bioinspired lignin-based loose nanofiltration membrane with excellent acid, fouling, and chlorine resistances toward dye/salt separation[J]. Journal of Membrane Science, 2023, 670: 121372.
11	任炼, 张鑫涛, 赵丽萍, 等. 碳源选择对荧光碳量子点光致发光性能的影响[J]. 化学与黏合, 2016, 38(5): 366-368.
	Ren L, Zhang X T, Zhao L P, et al. Effect of different carbon sources on the photoluminescence properties of fluorescent carbon quantum dots[J]. Chemistry and Adhesion, 2016, 38(5): 366-368.
12	Zhu Y, Zhang X J, Zhang L M, et al. Membranes constructed with zero-dimension carbon quantum dots for CO₂ separation[J]. Journal of Membrane Science, 2022, 664: 121086.
13	Liu W, Ning C X, Sang R R, et al. Lignin-derived graphene quantum dots from phosphous acid-assisted hydrothermal pretreatment and their application in photocatalysis[J]. Industrial Crops and Products, 2021, 171: 113963.
14	Behzadi F, Saievar-Iranizad E, Bayat A. One step synthesis of graphene quantum dots, graphene nanosheets and carbon nanospheres: investigation of photoluminescence properties[J]. Materials Research Express, 2019, 6(10): 105615.
15	张锐, 邵琦, 张华宇, 等. 硼掺杂二氧化硅杂化膜的制备及渗透汽化脱盐性能[J]. 化工学报, 2021, 72(4): 2317-2327.
	Zhang R, Shao Q, Zhang H Y, et al. Fabrication of boron-doped hybrid silica membranes for pervaporation desalination[J]. CIESC Journal, 2021, 72(4): 2317-2327.
16	Zhang H Y, Wen J L, Shao Q, et al. Fabrication of La/Y-codoped microporous organosilica membranes for high-performance pervaporation desalination[J]. Journal of Membrane Science, 2019, 584: 353-363.
17	Dong Y Q, Shao J W, Chen C Q, et al. Blue luminescent graphene quantum dots and graphene oxide prepared by tuning the carbonization degree of citric acid[J]. Carbon, 2012, 50(12): 4738-4743.
18	Shehab M, Ebrahim S, Soliman M. Graphene quantum dots prepared from glucose as optical sensor for glucose[J]. Journal of Luminescence, 2017, 184: 110-116.
19	Achadu O J, Nyokong T. Interaction of graphene quantum dots with 4-acetamido-2, 2, 6, 6-tetramethylpiperidine-oxyl free radicals: a spectroscopic and fluorimetric study[J]. Journal of Fluorescence, 2016, 26(1):283-295.
20	Gu W T, Zhang W, Li X M, et al. Graphene sheets from worm-like exfoliated graphite[J]. Journal of Materials Chemistry, 2009, 19(21): 3367-3369.
21	Li L L, Wu G H, Yang G H, et al. Focusing on luminescent graphene quantum dots: current status and future perspectives[J]. Nanoscale, 2013, 5(10): 4015-4039.
22	Zheng H, Mou Z H, Lim Y J, et al. Incorporating ionic carbon dots in polyamide nanofiltration membranes for high perm-selectivity and antifouling performance[J]. Journal of Membrane Science, 2023, 672: 121401.
23	Wu D H, Gao A R, Zhao H T, et al. Pervaporative desalination of high-salinity water[J]. Chemical Engineering Research and Design, 2018, 136: 154-164.
24	Halakoo E, Feng X S. Layer-by-layer assembly of polyethyleneimine/graphene oxide membranes for desalination of high-salinity water via pervaporation[J]. Separation and Purification Technology, 2020, 234: 116077.
25	Baker R W, Wijmans J G, Huang Y. Permeability, permeance and selectivity: a preferred way of reporting pervaporation performance data[J]. Journal of Membrane Science, 2010, 348(1/2): 346-352.
26	Yang G, Xie Z L, Cran M, et al. Enhanced desalination performance of poly(vinyl alcohol)/carbon nanotube composite pervaporation membranes via interfacial engineering[J]. Journal of Membrane Science, 2019, 579: 40-51.
27	Feng B, Xu K, Huang A S. Covalent synthesis of three-dimensional graphene oxide framework (GOF) membrane for seawater desalination[J]. Desalination, 2016, 394: 123-130.
28	Zhao X Y, Tong Z Q, Liu X F, et al. Facile preparation of polyamide-graphene oxide composite membranes for upgrading pervaporation desalination performances of hypersaline solutions[J]. Industrial & Engineering Chemistry Research, 2020, 59(26): 12232-12238.
29	Liang B, Zhan W, Qi G G, et al. High performance graphene oxide/polyacrylonitrile composite pervaporation membranes for desalination applications[J]. Journal of Materials Chemistry A, 2015, 3(9): 5140-5147.
30	Song Y M, Li R, Pan F S, et al. Ultrapermeable graphene oxide membranes with tunable interlayer distances via vein-like supramolecular dendrimers[J]. Journal of Materials Chemistry A, 2019, 7(31): 18642-18652.
31	Sun J W, Qian X W, Wang Z H, et al. Tailoring the microstructure of poly(vinyl alcohol)-intercalated graphene oxide membranes for enhanced desalination performance of high-salinity water by pervaporation[J]. Journal of Membrane Science, 2020, 599: 117838.
32	Cao Z S, Zeng S X, Xu Z, et al. Ultrathin ZSM-5 zeolite nanosheet laminated membrane for high-flux desalination of concentrated brines[J]. Science Advances, 2018, 4(11): eaau8634.
33	Liang B, Pan K, Li L, et al. High performance hydrophilic pervaporation composite membranes for water desalination[J]. Desalination, 2014, 347: 199-206.
34	Li L, Hou J W, Ye Y, et al. Composite PVA/PVDF pervaporation membrane for concentrated brine desalination: salt rejection, membrane fouling and defect control[J]. Desalination, 2017, 422: 49-58.
35	Prihatiningtyas I, Gebreslase G A, van der Bruggen B. Incorporation of Al₂O₃ into cellulose triacetate membranes to enhance the performance of pervaporation for desalination of hypersaline solutions[J]. Desalination, 2020, 474: 114198.
36	Wang Q Z, Lu Y Y, Li N. Preparation, characterization and performance of sulfonated poly(styrene-ethylene/butylene-styrene) block copolymer membranes for water desalination by pervaporation[J]. Desalination, 2016, 390: 33-46.
37	Prihatiningtyas I, Li Y, Hartanto Y, et al. Effect of solvent on the morphology and performance of cellulose triacetate membrane/cellulose nanocrystal nanocomposite pervaporation desalination membranes[J]. Chemical Engineering Journal, 2020, 388: 124216.
38	Drobek M, Yacou C, Motuzas J, et al. Long term pervaporation desalination of tubular MFI zeolite membranes[J]. Journal of Membrane Science, 2012, 415/416: 816-823.
39	He Y, Cui X M, Liu X D, et al. Preparation of self-supporting NaA zeolite membranes using geopolymers[J]. Journal of Membrane Science, 2013, 447: 66-72.
40	Reino Olegário da Silva D A, Bosmuler Zuge L C, de Paula Scheer A. Preparation and characterization of a novel green silica/PVA membrane for water desalination by pervaporation[J]. Separation and Purification Technology, 2020, 247: 116852.
41	Xie Z L, Hoang M, Duong T, et al. Sol-gel derived poly(vinyl alcohol)/maleic acid/silica hybrid membrane for desalination by pervaporation[J]. Journal of Membrane Science, 2011, 383(1/2): 96-103.

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