Synergistically enhancing the selective adsorption of cationic dyes through copper impregnation and amino functionality into iron-based metal-organic frameworks

Qiangshun Wu; Muhammad Saboor Siddique; Mi Wu; Huijuan Wang; Yonghao Zhang; Ruili Yang; Liqiang Cui; Weixing Ma; Jinlong Yan; Yadong Yang

doi:10.1016/j.scitotenv.2024.171280

Synergistically enhancing the selective adsorption of cationic dyes through copper impregnation and amino functionality into iron-based metal-organic frameworks

Sci Total Environ. 2024 May 1:923:171280. doi: 10.1016/j.scitotenv.2024.171280. Epub 2024 Feb 27.

Authors

Qiangshun Wu¹, Muhammad Saboor Siddique², Mi Wu³, Huijuan Wang⁴, Yonghao Zhang⁵, Ruili Yang⁵, Liqiang Cui⁵, Weixing Ma⁵, Jinlong Yan⁵, Yadong Yang⁶

Affiliations

¹ School of Environmental Science and Engineering, Yancheng Institute of Technology, Yancheng 224051, China. Electronic address: qswu@ycit.edu.cn.
² Institute of Environment and Ecology, Tsinghua-Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, China.
³ Key Laboratory of Integrated Regulation and Resource Development on Shallow Lakes, Ministry of Education, College of Environment, Hohai University, Nanjing 210098, China.
⁴ School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013, China.
⁵ School of Environmental Science and Engineering, Yancheng Institute of Technology, Yancheng 224051, China.
⁶ School of Environmental Science and Engineering, Yancheng Institute of Technology, Yancheng 224051, China. Electronic address: yangyd19@mails.jlu.edu.cn.

PMID: 38423330
DOI: 10.1016/j.scitotenv.2024.171280

Abstract

Dyes contaminating the sewages have seriously threatened the living beings and their separation from wastewater in terms of potential resource recovery is of high value. Herein, both of metal node doping and ligand group grafting were taken into account to enhance the adsorption selectivity of Fe-MOFs towards cationic dyes. The positive correlation between copper doping amount and selective coefficient (∂_MO^MB) for methylene blue (MB) over methyl orange (MO) within a certain range was mainly attributed to the increased surface negative charges via partial replacement of Fe(III) with Cu(II). Moreover, the amount of surface negative charges was further increased after amino functionalization and there was a synergism between Cu(II) and -NH₂ in selectivity enhancement. As a result, Fe_0.6Cu_0.4-BDC-NH₂ exhibited a 22.5-times increase in ∂_MO^MB and other cationic dyes including malachite green (MG) and rhodamine B (Rh. B) could also be selectively separated from binary and quaternary mixed dye systems. Moreover, Fe_0.6Cu_0.4-BDC-NH₂ showed many superiorities like a wide pH range of 4.0-8.0, strong anti-interference ability over various inorganic ions, good recyclability, and stability. The adsorption kinetics and isotherm suggested that the MB adsorption process was a homogeneous single-layer chemisorption. Additionally, the thermodynamics manifested that the overall process was exothermic and spontaneous. According to the FT-IR and XPS spectra analysis, the electrostatic interaction and hydrogen bonding were determined as the main driving forces, and π-π interaction also contributed to the adsorption process.

Keywords: Adsorption mechanism; Amino functionality; Cationic dyes; Copper impregnation; Selectivity enhancement; Synergism.