One-pot synthesis of oxygen-vacancy-rich Cu-doped UiO-66 for collaborative adsorption and photocatalytic degradation of ciprofloxacin

Linmiao Yin; Dongbo Wang; Xiaopei Li; Yanying He; Xiaoqing Liu; Yiyi Xu; Hong Chen

doi:10.1016/j.scitotenv.2021.151962

One-pot synthesis of oxygen-vacancy-rich Cu-doped UiO-66 for collaborative adsorption and photocatalytic degradation of ciprofloxacin

Sci Total Environ. 2022 Apr 1:815:151962. doi: 10.1016/j.scitotenv.2021.151962. Epub 2021 Nov 27.

Authors

Linmiao Yin¹, Dongbo Wang², Xiaopei Li³, Yanying He³, Xiaoqing Liu⁴, Yiyi Xu³, Hong Chen⁵

Affiliations

¹ College of Environmental Science and Engineering, Hunan University, Changsha 410082, PR China; Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082, PR China. Electronic address: myylm@hnu.edu.cn.
² College of Environmental Science and Engineering, Hunan University, Changsha 410082, PR China; Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082, PR China. Electronic address: dongbowang@hnu.edu.cn.
³ College of Environmental Science and Engineering, Hunan University, Changsha 410082, PR China; Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082, PR China.
⁴ Centre for Technology in Water and Wastewater, School of Civil and Environmental Engineering, University of Technology Sydney, Sydney, NSW 2007, Australia.
⁵ Key Laboratory of Water-Sediment Sciences and Water Disaster Prevention of Hunan Province, School of Hydraulic Engineering, Changsha University of Science & Technology, Changsha 410004, PR China.

PMID: 34843770
DOI: 10.1016/j.scitotenv.2021.151962

Abstract

UiO-66, as one of the most stable metal-organic frameworks (MOFs), has attracted a lot of attention in the field of adsorption and photocatalysis. However, this application of UiO-66 is still limited due to either the low accessibility of micropores or the poor electron-hole charge separation capability. This study aims to promote UiO-66 accessibility of micropores and charge separation through the construction of oxygen vacancies (OVs) and mesopore defects as well as copper incorporation. Herein, mesopore Cu doped UiO-66 with rich OVs was synthesized by a one-pot method and demonstrated high efficiency for the removal of ciprofloxacin (CIP) from the aquatic system. First of all, denatured mesopore defects were produced in Cu doped UiO-66 which possessed a 58% increase in specific surface area compared to UiO-66, facilitating the adsorption of molecular oxygen. Secondly, e^- was preferentially trapped by OVs under light irradiation. Electron (e^-) reacted rapidly with the surface adsorbed oxygen to generate superoxide radical (O₂^-). Meanwhile, copper incorporation increased the photocurrent and reduced the interfacial charge transfer resistance, thereby improving the charge separation efficiency. As a result, the adsorption efficiency and photocatalytic performance of mesopore Cu doped UiO-66 with OVs were 8.1 and 3.7 times higher than those of UiO-66, respectively. This study paved a way for the one-step synthesis of MOFs containing OVs and broadened the possibilities of practical applications for photo-induced removal of antibiotics from effluent.

Keywords: CIP; Cu incorporation; Metal-organic frameworks; OVs; One-step method.

MeSH terms

Adsorption
Catalysis
Ciprofloxacin*
Metal-Organic Frameworks
Oxygen*
Phthalic Acids

Substances

Metal-Organic Frameworks
Phthalic Acids
UiO-66
Ciprofloxacin
Oxygen