Green, General and Low‐cost Synthesis of Porous Organic Polymers in Sub‐kilogram Scale for Catalysis and CO₂ Capture

Abstract

Porous organic polymers (POPs) with high porosity and tunable functionalities have been widely studied for use in gas separation, catalysis, energy conversion and energy storage. However, the high cost of organic monomers, and the use of toxic solvents and high temperatures during synthesis pose obstacles for large-scale production. Herein, we report the synthesis of imine and aminal-linked POPs using inexpensive diamine and dialdehyde monomers in green solvents. Theoretical calculations and control experiments show that using meta-diamines is crucial for forming aminal linkages and branching porous networks from [2+2] polycondensation reactions. The method demonstrates good generality in that 6 POPs were successfully synthesized from different monomers. Additionally, we scaled up the synthesis in ethanol at room temperature, resulting in the production of POPs in sub-kilogram quantities at a relatively low cost. Proof-of-concept studies demonstrate that the POPs can be used as highperformance sorbents for CO 2 separation and as porous substrates for efficient heterogeneous catalysis. This method provides an environmentally friendly and costeffective approach for large-scale synthesis of various POPs.

A metal–organic cage with light-switchable motifs for controllable CO2 adsorption

“…4 The key to adsorption separation is the development and application of highly efficient adsorbents. 5 Porous material-based absorbents including metal–organic frameworks (MOFs), 6–8 covalent organic frameworks (COFs), 9–11 and porous organic polymers (POPs), 12–14 have been extensively researched due to their excellent capacity and selectivity for CO 2 capture. However, the regeneration and reuse of these adsorbents often require high energy consumption.…”

Superlative Porous Organic Polymers for Photochemical and Electrochemical CO2 Reduction Applications: From Synthesis to Functionality

“…POPs have been envisaged as a strong contender for CO 2 RR applicability on account of its excellent structural and compositional tailoring, higher stability, versatile polymerization, and perennial porosity, which are the primary parameters that govern the catalytic application of any material. − In order to augment the CO 2 RR activity of POP-based materials, heteroatom-abundant microporous frameworks and surface functionalization have been utilized. However, recently, researcher interest has been inclined toward pore tailoring, which has given rise to state-of-the-art POP materials rich in surface-active sites responsible for catalysis .…”

Dual Brønsted acidic-basic function immobilized on the 3D mesoporous polycalix [4]resorcinarene: As a highly recyclable catalyst for the synthesis of spiro acenaphthylene/indene heterocycles

“…They are made by linking organic monomers together through covalent bonds [ 1 , 2 ]. Their utilization in various fields such as heterogeneous catalysis [ 3 , 4 ], photocatalysis [ 5 , 6 ], separation [ 7 , 8 ], sensing, energy-related applications [ 9 ], and adsorption [ 10 ] is due to their unique features, including low density, high surface area (>6000 m 2 /g), good designability, high thermal stability, tunable porosity, stable physical and chemical properties, and abundance of active sites [ [11] , [12] , [13] , [14] , [15] , [16] , [17] , [18] , [19] , [20] , [21] , [22] ]. The POPs divide into two categories: amorphous and crystalline [ 6 , 16 , 17 , 19 , 23 , 24 ].…”

“…These categories themselves consist of two groups with mesoporous and microporous structures [ 25 ]. Unlike amorphous pops with flexible and uncomplicated scaffolds that usually require easy synthetic conditions and simple production methods, crystalline covalent organic frameworks (COFs) require specific organic reactions to form their regular porous structures [ 12 , 26 ].…”