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膜孔聚合条件对pH响应行为、催化金属纳米颗粒合成及多氯联苯降解的作用。

Role of membrane pore polymerization conditions for pH responsive behavior, catalytic metal nanoparticle synthesis, and PCB degradation.

作者信息

Islam Md Saiful, Hernández Sebastián, Wan Hongyi, Ormsbee Lindell, Bhattacharyya Dibakar

机构信息

Department of Chemical and Materials Engineering, University of Kentucky, 177 F. Paul Anderson Tower Building, Lexington, KY 40506, USA.

Department of Civil Engineering, University of Kentucky, Lexington, KY 40506, USA.

出版信息

J Memb Sci. 2018 Jun;555:348-361. doi: 10.1016/j.memsci.2018.03.060. Epub 2018 Mar 23.

Abstract

This article describes the effects of changing monomer and cross-linker concentrations on the mass gain, water permeability, Pd-Fe nanoparticle (NP) loading, and the rate of degradation of 3,3',4,4',5-pentachlorobiphenyl (PCB 126) of pore functionalized polyvinylidene fluoride (PVDF) membranes. In this study, monomer (acrylic acid (AA)) and cross-linker (N, N'- methylene-bis (acrylamide)) concentrations were varied from 10 to 20 wt% of polymer solution and 0.5-2 mol% of monomer concentration, respectively. Results showed that responsive behavior of membrane could be tuned in terms of water permeability over a range of 270-1 L m h bar, which is a function of water pH. The NP size on the membrane surface was found in the range of 16-23 nm. With increasing cross-linker density the percentage of smaller NPs (< 10 nm) increases due to smaller mesh size formation during in-situ polymerization of membrane. NP loading was found to vary from 0.21 to 0.94 mg per cm of membrane area depending on the variation of available carboxyl groups in membrane pore domain. The NPs functionalized membranes were then tested for use as a platform for the degradation of PCB 126. The observed batch reaction rate (K) for PCB 126 degradation for per mg of catalyst loading was found 0.08-0.1 h. Degradation study in convective flow mode shows 98.6% PCB 126 is degraded at a residence time of 46.2 s. The corresponding surface area normalized reaction rate ( ) is found about two times higher than of batch degradation; suggesting elimination of the effect of diffusion resistance for degradation of PCB 126 in convective flow mode operation. These Pd-Fe-PAA-PVDF membranes and nanoparticles are characterized by TGA, contact angle measurement, surface zeta potential, XRD, SEM, XPS, FIB, TEM and other techniques reveal the details about the membrane surface, pores and nanoparticles size, shape and size-distribution. Statistical analysis based on experimental results allows us to depict responsive behavior of functionalized membrane. In our best knowledge this paper first time reports detail study on responsive behavior of pore functionalized membrane in terms of permeability, NPs size, metal loading and its effect on PCB 126 degradation in a quantified approach.

摘要

本文描述了改变单体和交联剂浓度对孔隙功能化聚偏氟乙烯(PVDF)膜的质量增加、水渗透性、钯铁纳米颗粒(NP)负载量以及3,3',4,4',5-五氯联苯(PCB 126)降解速率的影响。在本研究中,单体(丙烯酸(AA))和交联剂(N,N'-亚甲基双丙烯酰胺)的浓度分别在聚合物溶液的10至20 wt%以及单体浓度的0.5 - 2 mol%范围内变化。结果表明,膜的响应行为可根据水渗透性在270 - 1 L m h bar范围内进行调节,这是水pH值的函数。膜表面的NP尺寸在16 - 23 nm范围内。随着交联剂密度的增加,由于膜原位聚合过程中形成的网孔尺寸变小,较小NP(< 10 nm)的百分比增加。根据膜孔区域中可用羧基的变化,发现NP负载量在每平方厘米膜面积0.21至0.94 mg之间变化。然后测试了NP功能化膜作为PCB 126降解平台的用途。观察到每毫克催化剂负载量下PCB 126降解的批次反应速率(K)为0.08 - 0.1 h。对流流动模式下的降解研究表明,在46.2 s的停留时间内,98.6%的PCB 126被降解。相应的表面积归一化反应速率( )比批次降解的 高出约两倍;这表明在对流流动模式操作中消除了扩散阻力对PCB 126降解的影响。这些钯铁 - PAA - PVDF膜和纳米颗粒通过热重分析(TGA)、接触角测量、表面zeta电位、X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、聚焦离子束(FIB)、透射电子显微镜(TEM)等技术进行表征,揭示了膜表面、孔隙以及纳米颗粒的尺寸、形状和尺寸分布的详细信息。基于实验结果的统计分析使我们能够描述功能化膜的响应行为。据我们所知,本文首次以量化方法详细报道了孔隙功能化膜在渗透性、NP尺寸、金属负载及其对PCB 126降解影响方面的响应行为研究。

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