Exclusive Recognition of CO₂ from Hydrocarbons by Aluminum Formate with Hydrogen-Confined Pore Cavities

Exclusive capture of carbon dioxide (CO₂) from hydrocarbons via adsorptive separation is an important technology in the petrochemical industry, especially for acetylene (C₂H₂) production. However, the physicochemical similarities between CO₂ and C₂H₂ hamper the development of CO₂-preferential sorbents, and CO₂ is mainly discerned via C recognition with low efficiency. Here, we report that the ultramicroporous material Al(HCOO)₃, ALF, can exclusively capture CO₂ from hydrocarbon mixtures, including those containing C₂H₂ and CH₄. ALF shows a remarkable CO₂ capacity of 86.2 cm³ g^-1 and record-high CO₂/C₂H₂ and CO₂/CH₄ uptake ratios. The inverse CO₂/C₂H₂ separation and exclusive CO₂ capture performance from hydrocarbons are validated via adsorption isotherms and dynamic breakthrough experiments. Notably, the hydrogen-confined pore cavities with appropriate dimensional size provide an ideal pore chemistry to specifically match CO₂ via a hydrogen bonding mechanism, with all hydrocarbons rejected. This molecular recognition mechanism is unveiled by in situ Fourier-transform infrared spectroscopy, X-ray diffraction studies, and molecular simulations.