Zn(II)-Embedded Nanoporous Covalent Organic Frameworks for Catalytic Conversion of CO₂ under Solvent-Free Conditions

Abstract

Covalent organic frameworks (COFs) have been gaining substantial attention over the past decade due to their developing crystalline porous polymeric nature linked by strong covalent bonds and widespread applications in various fields. Currently, three-dimensional COFs (3D COFs) are engaging the spotlight due to their distinctive porous features, greater surface area, and exceptional performances in comparison with formerly published two-dimensional (2D) frameworks with the AA-stacking layered mode. In this paper, we present, for the first time, a nanoporous 3D-COF-based zinc­(II) catalyst (Zn@RIO-1), which shows an efficient pathway for the chemical conversion of carbon dioxide to produce α-alkylidene cyclic carbonates and oxazolidinones from propargylic alcohols. The microporous material with a high surface area (312.61 m2/g) facilitates both types of catalytic reactions under atmospheric CO2 pressure. More importantly, easily recyclable and reusable catalysts produced moderate to high yields of desired carbonates as well as oxazolidinone products under solvent-free conditions. This study emphasizes the capability of nanoporous 3D-COF-based material in the catalysis field, more specifically in the field of CO2 capture and chemical fixation to fine chemicals. These results pave a spectacular pathway for the chemical fixation of CO2 into α-alkylidene cyclic carbonates and oxazolidinones from propargylic alcohols using 3D-COF as a potential heterogeneous ligand under sustainable conditions (i.e., solvent-free).

Porphyrin-Based Nanoporous Organic Polymers for Adsorption of Carbon Dioxide, Ethane, and Methane

“…This has led to the development of new types of nanoporous organic polymers with high nanoporosity, excellent physicochemical stability, and low energy adsorption for the adsorption and separation of CO 2 , as well as for other applications, such as the adsorption and separation of other simple molecular gases (e.g., C 2 H 6 , CH 4 , N 2 , etc. ), , catalysis, − drug delivery, , sensors for toxic pesticide detection, , and water treatment. , Owing to extensive application as well as excellent physicochemical properties, the design and construction of nanoporous organic polymers for simple molecular CO 2 adsorption/separation has become a hot research area in science and industry.…”

Visible-light-driven sustainable conversion of carbon dioxide to methanol using a metal-free covalent organic framework as a recyclable photocatalyst

“…These two significant concerns have encouraged scientists to discover the optional sources of green, sustainable and clean energy sources (for instance, solar energy) and the application of extreme potential, modern, and renewable energy storage materials to achieve the desired level of the photocatalytic application whenever needed. 1 Covalent organic frameworks (COFs) are an important type of layered material that possess superior crystallinity and adjustable pore size and have been demonstrated worldwide for uses in the storage of energy, 2–5 adsorption of gas and catalysis, 6–10 isolation of metal ions and recovery, 11–13 chemical sensing, 14–16 and photocatalytic application, 17–19 etc. comparing a few 2D agents featuring an inorganic character or graphene and 2D COFs, the layered COFs have considerable advantages, such as numerous additional monomeric units, FBBs (flexible building blocks thereby leading to adjustable features of the stacked agents.…”

Porous organic polymer (POP) nanosheets: an efficient photo-catalyst for visible-light assisted CO2 reduction

“…However, CO 2 is a non-toxic, renewable, inexpensive and abundant raw C1 feedstock and it is a C1 building block for the synthesis of various valuable chemicals with added economic value such as carbonate, carbamate, urea, etc. 3–8 Furthermore, through CO 2 reduction some C1 chemicals such as HCHO, HCOOH, CH 4 , CO, and CH 3 OH can easily be formed through thermo-catalysis, electrocatalysis and photocatalysis methods. 9 Recently, to maintain the ecological balance of the earth, photocatalytic reduction 10 of CO 2 has become a more efficient and greener approach to convert atmospheric CO 2 into eco-friendly fuels and organic materials in a sustainable and cost-effective manner which provides a way to obtain carbon resources.…”