不同粒径UiO-66混掺改性TFN-FO膜的构建及性能评价

doi:10.11949/0438-1157.20240081

摘要/Abstract

摘要：

本文以锆基金属-有机骨架材料（MOFs）UiO-66作为研究对象，制备了三种不同粒径的UiO-66纳米颗粒，并将其混掺到薄层复合膜（TFC）的聚酰胺（PA）层内，研究了UiO-66纳米颗粒的粒径对薄层复合纳米正渗透（TFN-FO）膜性能的影响。通过扫描电子显微镜（SEM）、原子力显微镜（AFM）、水接触角（WCA）测量仪、X射线光电子能谱仪（XPS）等表征手段，探究了TFN-FO膜的性质变化，结果表明，减小UiO-66的粒径不会影响TFN-FO膜的高亲水性，并且随着UiO-66粒径的减小，TFN-FO膜的粗糙度降低、交联度升高。通过以去离子水和2 mol/L氯化钠溶液作为进料液和汲取液的实验室自制的正渗透系统对膜性能进行评价，发现混掺小粒径（50 nm）UiO-66的TFN-FO膜可以在保持较低反向盐通量的同时实现35 %的水通量提升，而且，有机污染实验表明TFN-FO膜具有良好的抗污染性能。

关键词: 膜, 过滤, 纳米粒子, 正渗透, MOFs, 粒径, 混掺改性

Abstract:

With Zirconiumv(IV)-carboxylate metal–organic framework (MOF) UiO-66 nanoparticles as representative, UiO-66 nanoparticles with different particle sizes were prepared and incorporated in polyamide (PA) layer of thin-film composite (TFC) membranes to investigate the impact of UiO-66 nanoparticle size on the performance of thin film composite nano-forward osmosis (TFN-FO) membranes. The effects of incorporated UiO-66 nanoparticle on the property of TFN-FO membranes were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), water contact angle (WCA) instrument and X-ray photoelectron spectroscopy (XPS). Results showed that reducing the particle size of UiO-66 would not affect the high hydrophilicity of TFN-FO membrane. Meanwhile, as the particle size of UiO-66 decreased, the roughness of TFN-FO membrane decreased and the crosslinking degree increased. Moreover, the performance of TFN-FO membrane was evaluated by a homemade forward osmosis system with deionized water and 2 mol/L sodium chloride solution as feed and draw solution. TFN-FO membrane incorporated with small particle size (50 nm) UiO-66 achieved 35% water flux improvement while maintaining a low reverse salt flux. Furthermore, the organic fouling experiment demonstrated that TFN-FO membrane possessed a good anti-fouling performance.

Key words: membrane, filtration, nanoparticles, forward osmosis, MOFs, particle size, incorporate

中图分类号:

TQ028.8

张文焱, 刘浩, 宋伟龙, 赵频, 王新华. 不同粒径UiO-66混掺改性TFN-FO膜的构建及性能评价[J]. 化工学报, DOI: 10.11949/0438-1157.20240081.

Wenyan ZHANG, Hao LIU, Weilong SONG, Pin ZHAO, Xinhua WANG. Construction and performance evaluation of TFN-FO membranes incorporated with UiO-66 nanoparticles of different sizes[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240081.

图/表 10

图1 混掺有UiO-66纳米颗粒的TFN膜的制备

Fig. 1 Schematic diagram of the fabrication of TFN membrane incorporated with UiO-66 nanoparticles

图2 膜性能评价装置

Fig. 2 Schematic diagram of membranes evaluation system

图3 不同粒径UiO-66的SEM图像

Fig. 3 SEM of UiO-66 with different sizes

图4 不同粒径UiO-66的XRD图谱注:a-50 nm UiO-66; b-100 nm UiO-66; c-150 nm UiO-66

Fig. 4 XRD of UiO-66 with different sizes

图5 TFC膜和TFN膜的SEM及AFM图像

Fig. 5 SEM and AFM images of TFC and TFN

表1 TFC和TFN膜的XPS

Table 1 XPS of TFC and TFN membranes

	C	N	O	Zr	O/N	O/N^①	交联度
TFC	74.45	10.80	14.71	0	1.36	1.36	54%
TFN-50	73.19	10.08	16.28	0.42	1.60	1.39	51%
TFN-100	72.72	10.15	16.68	0.40	1.64	1.43	47%
TFN-150	73.23	9.80	16.35	0.35	1.70	1.47	43%

图6 TFC膜和TFN膜的红外光谱图注:a-TFN-150; b-TFN-100; c-TFN-50; d-TFC

Fig. 6 ATR-FIIR of TFC and TFN membranes

图7 TFC膜和TFN膜的水接触角

Fig. 7 Water contact angle of TFC and TFN membranes

图8 TFC和TFN膜在不同混掺浓度下的渗透性能注:a-TFN-50; b-TFN-100; c-TFN-150

Fig. 8 Permeability of TFC and TFN membranes

图9 TFC和TFN膜的污染实验水通量和归一化通量

Fig. 9 Flux and normalized flux curve of TFC and TFN membranes

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