Tailoring preparation of graphene quantum dot composite membranes: influence of precursors

doi:10.11949/0438-1157.20231188

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 12

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

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]

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

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

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

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℃

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℃

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

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

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

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

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

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