Selective and Multicyclic CO₂ Adsorption with Visible Light-Driven Photodegradation of Organic Dyes in a Robust Metal–Organic Framework Embracing Heteroatom-Affixed Pores

Abstract

Pore environment modulation with polarizing groups is one of the essential prerequisites for selective carbon dioxide (CO2) adsorption in metal–organic frameworks (MOFs), wherein judicious installation of the photocatalytic feature can promise visible light-triggered degradation of toxic organic dye molecules. However, astute amalgamation of both these attributes over a single MOF is rather rare, yet much anticipated in view of sustainable applications. Pore engineering is effectively harnessed in a Zn­(II)-based three-dimensional (3D) MOF, CSMCRI-16 (CSMCRI = Central Salt and Marine Chemicals Research Institute), through mixed-ligand assembly of a N-rich linker (L), 4,4′-oxybis­(benzoic acid) (H2oba) ligand, and [Zn2(CO2)4N2] paddle-wheel secondary building units (SBUs). The noninterpenetrated structure contains unbound nitrogen and accessible oxygen atom-decorated porous channels and exhibits admirable stability in diverse organic solvents, open air, and at elevated temperatures. The heteroatom-decorated porous channels facilitated excellent CO2 uptake in the activated MOF (16a) with high selectivity over N2 (CO2/N2: 155.3) at 273 K. The framework further exhibits reasonable CO2 affinity and multicyclic CO2 sorption recurrence without a significant loss in the uptake capacity. Benefitting from the presence of the [Zn2(CO2)4N2] cluster in conjugation with π-conjugated organic ligands, the extended 3D network revealed an optical band gap energy of 2.55 eV, which makes the MOF an efficient photocatalyst toward the degradation of the cationic dyes crystal violet (CV) and methylene blue (MB) in the presence of a simple 40 W visible light lamp without any assistance of external oxidants. The catalyst exhibits multicyclic performance and short reaction time in addition to the fact that catalytic efficiencies (CV: 97.2%, MB: 97.8%) are comparable to those of contemporary materials.

Largely Entangled Diamondoid Framework with High-Density Urea and Divergent Metal Nodes for Selective Scavenging of CO2 and Molecular Dimension-Mediated Size-Exclusive H-Bond Donor Catalysis

“…However, the PXRD pattern (Figure S2a) showed a slight shift toward the higher 2θ upon desolvation, which is consistent with the formerly reported entangled diamondoid MOF. ,, The X-ray photoelectron spectroscopy (XPS) survey spectra (Figure a) of CSMCRI-17 reveal the presence of all the constituting elements Zn, C, N, and O in the framework. The high-resolution Zn 2p spectra (Figure b) show two peaks, corresponding to Zn 2p 1/2 (1045.34 eV) and Zn 2p 3/2 (1022.14 eV) …”

“…The high-resolution Zn 2p spectra (Figure 3b) show two peaks, corresponding to Zn 2p 1/2 (1045.34 eV) and Zn 2p 3/2 (1022.14 eV). 54 Alternatively, the deconvoluted C 1s spectrum (Figure 3c) represents three peaks at the binding energies of 287.58, 285.22, and 284.43 eV that correspond to C−O, C−N, and C�C bonds, respectively, in the ligand moiety. 55,56 Further deconvolution of O 1s provided (Figure 3d) two peaks for C�O (532.52 eV) and Zn−O (531.42 eV).…”

Two Cu(i) coordination polymers based on a new benzimidazolyl-tetrazolyl heterotopic ligand for visible-light-driven photocatalytic dye degradation

“…20,21 Recently, much attention has been given to the use of coordination polymers as visible-light-driven photocatalysts, mainly because their electronic structure can be easily regulated by metal ions and ligands. [22][23][24][25][26][27][28] Previous reports indicate that copper-based CPs usually have rich photophysical properties and exhibit photocatalytic functions towards organic and inorganic contaminants. [29][30][31][32][33] Inspired by this and our continuous studies on heterotopic triangular ligands, 15,16,[34][35][36]…”

A multifunctional [CdI4]2−·[H2Bimb]2+complex to probe high performance photocatalytic degradation of methyl violet and fluorescent detection of Cr2O72−and Hg2+ions

“…[19][20][21][22] Photocatalytic degradation is therefore thought to be a potential method for removing dangerous impurities, non-biodegradable toxins, environmental and agricultural pollutants, and pollutants from wastewater. [23][24][25] The global situation caused by heavy metal ion contamination has gotten worse in recent years. In particular, the quick detection of organic small molecules and heavy metal ions has garnered a lot of interest.…”

“…19–22 Photocatalytic degradation is therefore thought to be a potential method for removing dangerous impurities, non-biodegradable toxins, environmental and agricultural pollutants, and pollutants from wastewater. 23–25…”