Ag‐Nanocatalysts Based on Porous Organic Polymers in Chemical Fixation of CO₂ for the N‐Methylation and N‐Formylation of Amines

Abstract

Chemical fixation of CO2 for the synthesis of valuable chemicals is very demanding in the context of green and sustainable chemistry. Herein, we report highly efficient silver‐loaded porous organic polymer catalysts for the exclusive N‐formylation and N‐methylation of amines under ambient reaction conditions using CO2 as a green C1 source. By adjusting the solvent and temperature of the reaction, the successful production of formamides and methylamines could be accomplished with high levels of selectivity and efficiency. POP‐based materials Ag@TTP‐1 and Ag@PAN‐T are utilized as low‐cost catalysts for both the N‐methylation and N‐formylation of primary and secondary amines and the product yields up to 98 % could be achieved. Ag@TTP‐1 demonstrated superior catalytic efficiency compared to Ag@PAN‐T in the N‐methylation and N‐formylation reactions. This result suggests that the grafting of Ag nanoparticles onto POP surface with a high surface area plays a crucial role in these CO2 fixation reactions. The above‐mentioned catalysts (Ag@TTP‐1 and Ag@PAN‐T) are characterized through powder XRD, FT IR spectroscopy, FE‐SEM, TEM, thermogravimetric techniques, N2 sorption and XPS analysis. Ag‐nanocatalysts demonstrated heterogeneous nature and high recycling efficiency for several cycles in this CO2 fixation reaction.