Size-Controlled Growth of Silver Nanoparticles onto Functionalized Ordered Mesoporous Polymers for Efficient CO₂ Upgrading

Highly dispersed metallic silver nanoparticles (AgNPs) are promising heterogeneous catalysts for carboxylative coupling of terminal alkynes with CO₂ under mild conditions. Yet, their size-controlled synthesis is very challenging because of the high surface energy. Here, we prepared a series of amino-functionalized ordered mesoporous polymers as hosts for anchoring AgNPs. Control experiments and computations showed that electron-rich amines were confined in mesochannels with varying electron density and steric hindrance, creating "localized active zones (LAZ)" to control the growth of AgNPs. The particle size of AgNPs grows along with the increased volume of LAZ around nitrogen species. We also revealed that the catalytic activity of Ag-based catalysts is size-dependent and increases with decreasing particle size. Building on these findings, we report a facile one-pot synthesis strategy for preparing an amine-incorporated ordered mesoporous polymer (NOMP) with a high specific surface area, small LAZ volume, and uniform amine sites with controllable loading. These features result in the formation of ultrasmall and monodispersed Ag nanoparticles. Remarkably, Ag@NOMP gave a quantitative target yield under the conditions of 1 atm CO₂ pressure and 50 °C, showing superior catalytic activity in CO₂ carboxylation compared to other mesoporous analogues.