New scu topological MOF based on azolyl-carboxyl bifunctional linker: Gas adsorption and luminescence properties
Graphical abstract
One new Zn-MOF with a rare (4,8)-connected scu topology was constructed by a azolyl-carboxyl bifunctional ligand, which contains polar channels decorated by uncoordinated N atoms and displays adsorption selectivity for CO2 over CH4 and luminescent properties as well.
Introduction
As a primary greenhouse gas and a major source of ocean acidification, carbon dioxide (CO2) is causing a host of intractable problems such as climate change and global warming. Global CO2 emissions have continued to grow rapidly this century due to greenhouse gas emissions from the increasing burning of fossil fuels and certain chemical reactions [1]. So many efforts have been made to capture or exclude CO2 from various gas mixtures such as natural gas, flue gas and landfill gas. In recent years, porous materials, including traditional zeolites and carbon, have been intensively studied to capture and store CO2 [[2], [3], [4], [5]]. Among them, a new type of crystalline porous material, metal-organic frameworks (MOFs) that are composed of organic bonding substrates and metal ions/clusters, have shown broad application prospects in gas separation due to their structural diversity and tunability [[6], [7], [8], [9], [10]]. Although some strategies, such as incorporating organic functional sites and producing open metal ions have been investigated to increase the adsorption amounts of MOFs, however, the deep analyses on the interactions between the framework and CO2 molecules were not well investigated [[11], [12], [13], [14]]. The development of new CO2 capture materials and uncovering the structural-effect relation are still very important.
According to the constituent units of metal nodes and organic linkers in the fabrication of MOFs, the self-assembly between them would generate versatile topologies of frameworks. Therefore, designing suitable organic ligands is very crucial for obtaining desired MOFs with targeted functions or properties. Aiming at CO2 molecules, the introduction of accessible nitrogen sites in MOFs can increase the selective attractions for CO2 due to a large quadrupole moment and high polarization rate of CO2 molecules [[15], [16], [17]]. In addition, carboxylic acids are very important and widely adopted coordinated groups in the construction of MOFs due to flexible coordinated modes and coordination with various metal ions from transition metal to lanthanide metal ions [[18], [19], [20], [21]]. However, the basic azolyl groups not only form robust coordinated bonds but also increase the interactions towards acidic CO2 molecules [[22], [23], [24]]. Therefore, adopting the organic linkers containing azolyl and carboxyl bifunctional coordinated units would deserve anticipating to build MOFs with selective CO2 capture and separation.
Considering above standards, we selected a ligand, 4,6-bis(triazol-1-yl)isophthalic acid (H2btzip) (Scheme 1), that contains azolyl and carboxyl groups to construct MOFs. H2btzip contains four separated coordinated units, including two azolyls and two carboxyls. In particular, it can serve as an almost invariant square building block to create a desired framework. H2btzip contains six N atoms, which would be very promising to increase adsorption for CO2 molecules through forming direct and indirect interactions. Herein, the self-assembly of H2btzip with Zn2+ ions has produced a new 3D MOF, [Zn(btzip)(H2O)0.5]·H2O (1). 1 is rare (4,8)-connected scu net and contains polar 1D channels decorated by uncoordinated azolyl N atoms. As a result, 1 shows high adsorption enthalpy for CO2 and significant adsorption selectivity for CO2 over CH4 as well. The interactions between the framework and CO2 were analyzed by Grand canonical Monte Carlo (GCMC) simulations. In addition, the luminescence property of 1 was also investigated.
Section snippets
Materials and instrumentation
All commercially obtained reagents were used in synthesis. An infrared (IR) spectrum was obtained through an EQUINOX-55 FT-IR spectrometer in the range of 4000 to 400 cm−1. Elemental analyses were recorded on a PerkinElmer 2400C Elemental Analyzer. Thermogravimetric analyses (TGA) were carried out in a N2 stream using a Netzsch TG209F3 instrument (5 °C min-1). Powder X-ray diffraction (PXRD) data were collected on a Bruker D8 ADVANCE diffractometer. Luminescence was measured on an Edinburgh
Description of crystal structure
Single crystal X-ray diffraction indicates that 1 with a monoclinic I2/a space group shows a 3D porous framework with a (4,8)-connected scu topology. The asymmetric unit is composed of one Zn(II) ion, one depronated btzip ligand and one coordinated H2O molecule. The Zn(II) center reveals a distorted octahedral coordinated environment formed by three carboxylate O atoms and two triazolyl N atoms from five btzip as well as one H2O molecule (Fig. 1a). One btzip connects five Zn(II) centers through
Conclusions
In summary, one porous Zn-MOF has been created through utilizing a bifunctional linker containing bitriazolyl and bicarboxyl coordinated groups. The MOF forms a rare binodal (4,8)-connected scu topological net and contains polar 1D channels with uncoordinated triazolyl N atoms. As revealed by theoretical simulations, these accessible N atoms and phenyl rings in framework are important binding sites for CO2 molecules, leading to strong interactions for CO2 and significant adsorption selectivity
CRediT authorship contribution statement
Wen-Juan Shi: Investigation, Writing - original draft. Yong-Zhi Li: Methodology, Formal analysis, Visualization. Qi-Xuan Hu: Investigation. Gang-Ding Wang: Software. Lei Hou: Writing - review & editing, Funding acquisition, Supervision. Yao-Yu Wang: Resources.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
We are grateful for financial support from the National Natural Science Foundation of China (Grants 21801205 and 21871220), and the Natural Science Foundation of Shaanxi Province (2019JM-082).
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