Synthesis of a 2D copper(II)-carboxylate framework having ultrafast adsorption of organic dyes

Hamid Raza; Ibrahim Yildiz; Farhat Yasmeen; Khurram S Munawar; Muhammad Ashfaq; Muzafar Abbas; Maqsood Ahmed; Hussein A Younus; Shiguo Zhang; Nazir Ahmad

doi:10.1016/j.jcis.2021.05.169

Synthesis of a 2D copper(II)-carboxylate framework having ultrafast adsorption of organic dyes

J Colloid Interface Sci. 2021 Nov 15:602:43-54. doi: 10.1016/j.jcis.2021.05.169. Epub 2021 May 31.

Authors

Affiliations

¹ Department of Chemistry, University of Engineering and Technology, Lahore, Pakistan; Department of Chemistry, School of Science, University of Management and Technology, Johar Town, Lahore, 54770, Pakistan.
² Chemistry Department, Khalifa University, Abu Dhabi, 127788, United Arab Emirates.
³ Department of Chemistry, University of Engineering and Technology, Lahore, Pakistan.
⁴ Department of Chemistry, University of Sargodha, Sargodha, 40100, Pakistan; Department of Chemistry, University of Mianwali, Mianwali, Pakistan.
⁵ Department of Physics, University of Sargodha, Sargodha, 40100, Pakistan.
⁶ Materials Architecting Research Center, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea.
⁷ Materials Chemistry Laboratory, Institute of Chemistry, The Islamia University of Bahawalpur, 63100, Pakistan.
⁸ College of Materials Science and Engineering, Hunan University, Changsha 410082, China; Chemistry Department, Faculty of Science, Fayoum University, Fayoum 63514, Egypt. Electronic address: hay00@fayoum.edu.eg.
⁹ College of Materials Science and Engineering, Hunan University, Changsha 410082, China. Electronic address: zhangsg@hun.edu.cn.
¹⁰ Department of Chemistry, GC University Lahore, 54000, Pakistan. Electronic address: dr.nazirahmad@gcu.edu.pk.

PMID: 34118604
DOI: 10.1016/j.jcis.2021.05.169

Abstract

Two-dimensional (2D) coordination polymers are very interesting materials for their attractive applications. A novel 2D metal-organic framework (MOF) was derived from copper(II) and amino benzoic acid under both room temperature and solvothermal reaction conditions using different solvents. From both of the synthesis methods, an identical MOF was crystalized with monoclinic crystal system having P2₁/c space group. Hirshfeld surface analysis is carried out to explore the non-covalent interactions obtained from single crystal XRD investigation in terms of percentage contribution of each interatomic contact involved in packing of molecules into MOF structure. The microstructure analysis and surface morphology studies revealed the 2D layered regular pattern of rhombus disks of ~5 μm thickness throng together via clustering of these rhombic shaped flakes as flowers (ranging 50-100 μm in size) having uniform elemental composition. This 2D MOF efficiently adsorbed organic dyes (methylene blue, methyl orange, and methyl red) from their aqueous solutions. The 2D copper-carboxylate framework (1.2 g/L) exhibited high adsorption rates for organic dyes (0.15-0.19 mM), and >90% of these dyes could be captured as soon as they are exposed to MOF suspension (1 min) in each case. The dye removal efficiency is credited to synergy among structure, ionic strength, shapes and dimensions of dyes with respect to MOF structure. The microstructure of MOF along with electronic interactions like electrostatic, hydrogen bonding, π-π interactions and coordination to open metal sites, might contribute to the ultrafast dye adsorption process by MOF. The adsorption phenomenon is spontaneous and followed the pseudo-second order kinetic mechanism. DFT calculations revealed important electronic parameters of the dyes and model MOF systems, and novel insights with respect to possible dye-MOF interactions. The MOF remained quite stable during the dye adsorption and was regenerated easily for the successful subsequent use.

Keywords: 2D Materials; Copper(II)-carboxylates; DFT; MOFs; Ultrafast dye adsorption.