Ligand Functionalization in Zirconium‐Based Metal‐Organic Frameworks for Enhanced Carbon Dioxide Fixation

Abstract

Ligand functionalization has always been considered as an effective method for regulating the catalytic activity of the metal‐organic frameworks (MOFs) materials. Herein, three stable zirconium‐based MOFs (Zr‐MOFs), constructed by the 10‐connected Zr6 cluster and different groups‐decorated V‐shaped ligands (H2L), are successfully synthesized through a facile ligand functionalization method. Subsequently, three isostructural Zr‐MOFs, including the parent structure Zr(H2L), amino‐decorated Zr(H2L) (NH2‐Zr(H2L)), and fluorine and amino bi‐decorated Zr(H2L) (F‐NH2‐Zr(H2L)), are employed as the platform for systematically investigating the effect of Lewis basic groups on the CO2 adsorption and separation behavior, more importantly the CO2 chemical fixation. Benefitting from the decorated Lewis basic groups, not only the CO2 adsorption enthalpy and selectivity over CH4 of NH2‐Zr(H2L) and F‐NH2‐Zr(H2L) are improved, but also their catalytic activities for cycloaddition of CO2 to form cyclic carbonates are significantly enhanced. Among them, F‐NH2‐Zr(H2L) exhibits the most effective performance for cycloaddition of CO2 and styrene epoxide, which can be attributed to the strong polarization between the CO2 molecule and the framework of F‐NH2‐Zr(H2L). Under a mild condition, the yield of F‐NH2‐Zr(H2L) for cycloaddition of CO2 with styrene epoxide can reach up to 97%, which surpasses most of the reported MOFs‐based catalysts.

Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO2 to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study

“…Although both metal-based and organocatalytic systems can be applied for the catalytic coupling of CO 2 and epoxides, − there is still a significant performance gap between these families of catalysts, with the former being generally more efficient. Therefore, several metal-based homogeneous catalysts have been prepared for the cycloaddition of CO 2 to epoxides where Lewis acidic metal or metalloid centers are harnessed by salen-type, − porphyrin, − triphenolate − ligands, and other scaffolds. − The limitation of such compounds is that their preparation may require several synthetic steps, often by using expensive building blocks/reagents, and generally leads to high-molecular weight metal–organic species that would require highly efficient heterogenization and recyclability in order to be cost-competitive.…”

Mechanistic Insight into Charge and Energy Transfers of Luminescent Metal–Organic Frameworks Based Sensors for Toxic Chemicals

“…The RET and spectral overlap involved the transport of resonance energy from the MOF to RhB. The nitenpyram emission spectra were close to the MOF spectra, [4]arene-based Cd(II)-MOF to the sensing of pesticide molecules. Reproduced with permission.…”

“…Metal-organic frameworks (MOFs) are highly effective coordinated materials with tunable properties, such as porous sites, high thermal and kinetic stabilities, metal centers, and different dimensional structures. These properties explored their applications in recognition of guest analytes, [1] water treatment, [2] gas adsorption and separation, [3,4] bioactive and imaging devices, [5][6][7] printing materials, [8] catalysis, and drug delivery. [9][10][11][12] MOFs were first reported from the preparation of coordination polymers in 1964, with early investigations systematically studying received limited attention.…”

“…Figure 5. a) Application of 5-nitro-1,3-benzenedicarboxylic acid andcalix[4]arene-based Cd(II)-MOF to the sensing of pesticide molecules. Reproduced with permission [127].…”

Chemically Bonded Plasmonic Triazole‐Functionalized Au/Zeolitic Imidazole Framework (ZIF‐67) for Enhanced CO2 Photoreduction

“…However, the efficient hot electron transfer between plasmonic Au NPs and ZIF-67 requires strong electronic coupling between the two components, which in turn requires the effective contact between Au PNPs and ZIF through covalent bonding or electrostatic interaction. [42,43] Thus, the functionalization of MOFs through the incorporation of chemical groups into their structure has emerged as one of the latest and most effective techniques to design selective materials. [28,44,45] The use of amino groups, like triazole, has been a promising alternative to overcome interfacial issues when coupling metal nanoparticles like Zn, Cu, or Ag on a semiconductor.…”