One-Pot CO₂ Hydrogenation Coupled With In Situ Esterification for Polyester Monomers Production Over Single-Atom...

Here, we report a one-pot tandem catalytic system that integrates CO₂ hydrogenation to CH₃O* intermediates with their in situ esterification using dicarboxylic acids, directly yielding dimethyl esters (e.g., polyester monomers for polyethylene terephthalate (PET) manufacturing) as final products with >99% selectivity. This system is enabled by a metal-organic framework (MOF)-derived catalyst featuring carbon-nanoconfined atomic Cu^δ+ sites anchored on ca. 1.8 nm tetragonal ZrO₂ nanoparticles (Cu_SA-ZrO₂-C), which achieves an efficient CO₂ conversion of 28% at a reduced temperature of 150°C in a batch reactor. The process delivers a high space-time yield of esters, corresponding to a CO₂ conversion efficiency of 158.6 g_CO2 g_cat ^-1 h^-1. Mechanistic studies gained from control experiments, in situ time-resolved diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) calculations reveal that a tripartite synergy among atomic Cu^δ+ sites, oxygen vacancies, and surface hydroxyls on t-ZrO₂ nanoparticles stabilizes key intermediates (*CO, *COOH, *HCOO^-, *CHO) and opens a hydroxyl mediated pathway. This pathway redirects the typically poisoning *CO species toward *CHO, thereby circumventing the persistent *CO poisoning challenge. This work presents an atomic-level design strategy that simultaneously advances low-temperature CO₂ hydrogenation and intermediate valorization, establishing an integrated and carbon-efficient route from CO₂ to polymer feedstocks.