Scalable upgrading metal–organic frameworks through ambient and controllable electron-beam irradiation for CO2 capture and conversion

Abstract

Some well-established metal–organic frameworks (MOFs) have shown their commercialization for CO₂ capture and conversion. However, the development of effective and scalable modification technologies that are broadly applicable to existing MOFs still face significant challenges. Here, in contrast to sophisticated synthesis, we report a general and facile upgrading strategy for kilogram-level MOFs including IRMOF, MIL, and ZIF through ambient, controllable and cost-effective electron-beam (e-beam) irradiation. Specially, the modified HKUST-1 achieves a 16.6% improvement in CO₂ uptake with high selectivities for CO₂/N₂ mixtures, and a 2-fold production rate of CO under visible-light illumination. As demonstrated by newly-developed in-situ X-ray diffraction infrared Fourier transform (DRIFT) technology and theoretical calculations, e-beam induces the metal node reduction, ligand functionalization, and pore architecture manipulation via radiolysis of trapped water molecules, synergistically promoting the CO₂ polarization and activation. Our study reveals the advantageous of e-beam irradiation effects for MOFs, which are often considered negative in many areas.