研究报告

  • 郭琳颖,花铭.聚乙烯亚胺改性UIO-66(Zr)选择性吸附柠檬酸铬的性能及机制研究[J].环境科学学报,2023,43(2):113-124

  • 聚乙烯亚胺改性UIO-66(Zr)选择性吸附柠檬酸铬的性能及机制研究
  • The defects and pore regulation induced by PEI modulation in UIO-66 for enhanced Cr-Citrate selective capture
  • 基金项目:国家自然科学基金面上项目(No.52070096)
  • 作者
  • 单位
  • 郭琳颖
  • 南京大学环境学院,污染控制与资源化研究国家重点实验室
  • 花铭
  • 南京大学环境学院,污染控制与资源化研究国家重点实验室;南京大学,南京大学环境纳米技术研究中心
  • 摘要:以UIO-66(Zr)为基本框架,以聚乙烯亚胺(PEI)为双功能改性组分,通过绿色温和的希夫碱反应制备得到氨基改性锆系MOFs(UIO-PEI),一方面在UIO-66(Zr)上修饰了丰富的氨基官能团,另一方面在改性过程中形成新的缺陷进而扩大孔径,增加了活性位点的可及性.根据该策略,UIO-PEI在中性条件下对柠檬酸铬(Cr-Citrate)的吸附容量为58.39 mg?g-1,是未改性UIO-66(Zr)的3倍,并在高盐度(200 mmol?L-1)条件下可将初始浓度为20 mg?L-1的Cr-Citrate降低至0.3 mg?L-1以下,改善的传质条件加快了吸附动力学,在3 h之内可达吸附平衡.场发射透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FTIR)和X射线光电子能谱(XPS)等表征结果表明,Cr-Citrate是以一个整体被吸附至UIO-PEI上,UIO-PEI主要通过丰富发氨基官能团与Cr金属端和有机配体端形成一个稳定的络合结构实现捕获,是一种有前景的去除废水中重金属有机络合污染物的新型吸附剂.
  • Abstract:In this study, amino-modified zirconium-based MOFs (UIO-PEI) were prepared by green and mild Schiff-base reaction taking UIO-66(Zr) as the basic framework and polyethyleneimine (PEI) as the bifunctional modification component. The results demonstrated that abundant amino functional groups were modified on UIO-66(Zr), meanwhile, new defects were formed during the modification process to enlarge the pore size and increase the accessibility of active sites. According to this strategy, UIO-PEI obtained ultrahigh Cr-Citrate adsorption capacity of 58.39 mg?g-1 under neutral condition, which was 3 times higher than that of unmodified UIO-66(Zr). Cr-Citrate of initial concentration of 20 mg?L-1 can be reduced to below 0.3 mg?L-1 at high salinity (200 mmol?L-1). The improved mass transfer conditions accelerated the adsorption kinetics, and the adsorption equilibrium can be reached within 3 h. Combined transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) revealed that Cr-Citrate was adsorbed on UIO-PEI as an integral form, UIO-PEI mainly achieved the capture by rich amino functional groups forming a stable complex structure with Cr and organic ligand. UIO-PEI is a promising adsorbent for the removal of heavy metal organic complexes in wastewater.

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