Research of thin film nanocomposite (TFN) membranes incorporated spherical mesoporous silica nanoparticles with carboxyl group

doi:10.11949/0438-1157.20190920

Abstract

Abstract:

Thin film composite (TFC) membranes incorporated with inorganic nanoparticles to form thin film nanocomposite (TFN) membranes, which had attracted much attention recently. However, the instability of nanoparticles in the TFC membranes and the insufficient mechanical strength of the membranes became the main challenges. Mesoporous silica nanoparticles with an average particle size of ca. 110 nm were modified with carboxyl groups, noted as MSN—COOH and further immobilized on the functional layer of the TFC membranes. The carboxyl groups were successfully incorporated into the mesoporous channels of MSN by characterization techniques, MSN—COOH nanoparticles were successfully bonded to the surface functional layer of the TFC film and formed the crosslinked network. Our experimental results revealed that the TFN membrane hybridized with MSN—COOH demonstrated up to 56.2% improvement in water ?ux, higher salt rejection, and improved mechanical strength compared to the control TFC membranes. Due to the addition of hydrophilic functional groups in monodisperse mesoporous nanoparticles, the hydrophilicity of the membrane surface was increased. Because of the ordered arrangement of monodisperse mesoporous nanoparticles in the matrix, the roughness of the membrane was lowered to a great extent, which was beneficial for enhancing water molecular transfer and fouling resistance of the membranes. Compared with plain TFN membranes, it had better stability and flexibility which kept the stabilization of membranes under high pressure filtration operation.

Key words: nanoparticles, membrane, silica, TFN, modified with carboxyl groups, interfacial polymerization

摘要：

在薄层复合膜(thin-film composite membrane, TFC膜)中引入无机纳米颗粒，形成薄层纳米复合膜(thin-film nanocomposite membrane, TFN膜)，近几年作为反渗透膜开始应用于水处理研究。但是无机纳米颗粒在TFC膜中的性能的不稳定性和膜的机械强度等变成了突出问题。合成制备了粒径约为110 nm修饰羧基的介孔氧化硅球状纳米颗粒(MSN—COOH)，并将其成功地化学键合在TFC膜的表面功能层交联网络中。与TFC膜相比，键合有MSN—COOH的TFN膜，水通量提高了56.2%，保持高脱盐率；由于单分散介孔纳米颗粒表面亲水官能团的引入，使膜表面的亲水性有很大程度提高，单分散介孔纳米颗粒在基体中的有序排列，使膜表面粗糙度降低，提高了膜的抗污染能力。与普通TFN膜相比较，具有更好的稳定性和柔韧性，可以在长时间高压过滤操作下保持稳定。

关键词: 纳米粒子, 膜, 二氧化硅, TFN, 羧基修饰, 界面聚合

CLC Number:

TQ 051.893

Yan SUN, Shitao LIU, Shang DENG, Liyun YU, Dongwei LYU, Jun MA, Xianbin LIU. Research of thin film nanocomposite (TFN) membranes incorporated spherical mesoporous silica nanoparticles with carboxyl group[J]. CIESC Journal, 2020, 71(S1): 454-460.

孙艳, 刘士涛, 邓尚, 余丽芸, 吕东伟, 马军, 刘献斌. 负载羧基化球状介孔纳米颗粒TFN膜的研究[J]. 化工学报, 2020, 71(S1): 454-460.

Figures/Tables 8

Fig.1 FTIR spectra for nanoparticlesa—as-MSN；b—MSN；c—MSN—NH2；d—MSN—COOH

Table 1 Textural properties of nanoparticles

样品	孔径/nm	比表面积/(m²/g)	孔容/(cm³/g)
MSN	2.84	832	0.87
MSN—NH₂	2.52	586	0.74
MSN—COOH	2.53	493	0.75

Fig.2 XRD patterns of MSN and MSN—COOH

Fig.3 SEM and TEM (inset) images of MSN (a) and MSN—COOH (b)

Fig.4 ATR-FTIR spectra of membranesa—TFC；b—TFN-MSN-0.1；c—TFN-MSN-0.4；d—TFN-MSN—COOH-0.1；e—TFN-MSN—COOH-0.4

Fig.5 SEM images of fabricated membranes

Fig.6 Membrane water flux and salt rejection（2.0685 MPa，25°C）

Fig.7 Separation performances of TFN TFN-MSN—COOH-0.2 membrane during 100 h stability test

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