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Adsorption Behaviors of Organic Micropollutants on Zirconium Metal-Organic Framework UiO-66: Analysis of Surface Interactions.

  • Chen, Caiqin1
  • Chen, Dezhi1
  • Xie, Shasha1
  • Quan, Hongying2
  • Luo, Xubiao1
  • Guo, Lin1, 3
  • 1 Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, School of Environmental and Chemical Engineering, Nanchang Hangkong University , Nanchang 330063, China. , (China)
  • 2 School of Materials Science and Engineering, Nanchang Hangkong University , Nanchang 330063, China. , (China)
  • 3 Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry and Environment, Beihang University , Beijing 100191, China. , (China)
Published Article
ACS Applied Materials & Interfaces
American Chemical Society
Publication Date
Nov 22, 2017
DOI: 10.1021/acsami.7b13443
PMID: 29077388


Herein, we studied the adsorption behaviors of organic micropollutants, such as anticonvulsant carbamazepine (CBZ) and antibiotic tetracycline hydrochloride (TC), on zirconium metal-organic framework UiO-66 in water. The maximum adsorption capacities of CBZ and TC on the UiO-66 were 37.2 and 23.1 mg·g-1 at 25 °C, respectively. The adsorption isotherms and kinetics of CBZ and TC were well described by using the Langmuir model and pseudo-second-order model, respectively, and the adsorptions on UiO-66 are endothermic reactions. The adsorption capacities of CBZ and TC on UiO-66 were decreased with the increase of solution pH. The presence of humic acid could improve the adsorption of CBZ and TC on UiO-66, but K+ ion inhibited their adsorption obviously. In addition, Ca2+ and Al3+ ions also suppressed the adsorption of TC on UiO-66. The competitive adsorption suggested that the adsorption sites for CBZ on UiO-66 were different from those for TC. The surface interactions between UiO-66 and the two micropollutants were demonstrated by powder X-ray diffraction, Fourier transform infrared (FT-IR) spectra, scanning electron microscopy, nitrogen adsorption/desorption isotherms, and X-ray photoelectron (XPS) spectra. The characterizations showed that the adsorption of CBZ on UiO-66 is mainly a physisorption, and the hydrophobic effect played a crucial role during the adsorption of CBZ; meanwhile weak π-π electron donor-acceptor interaction and electrostatic attraction also existed. However, the adsorption of TC on UiO-66 is mainly a chemisorption; in addition to the strong electrostatic attraction and π-π electron donor-acceptor interaction forces, the nitrogenous groups of TC played an important role, which can replace the carboxylic groups coordinated with Zr-O clusters. The obtained results will aid us to comprehend the surface interaction between organic micropollutants and UiO-66 and expand the application of UiO-66 as sorbent for removal of pollutants from water.

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