One‐Pot CO ₂ Hydrogenation Coupled With In Situ Esterification for Polyester Monomers Production Over Single‐Atom Cu ^δ+ ‐Doped 1.8 Nm T‐ZrO

ABSTRACT

Here, we report a one‐pot tandem catalytic system that integrates CO ₂ hydrogenation to CH ₃ O* 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 ZrO ₂ nanoparticles (Cu _SA ‐ZrO ₂ ‐C), which achieves an efficient CO ₂ 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 CO ₂ 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‐ZrO ₂ 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 CO ₂ hydrogenation and intermediate valorization, establishing an integrated and carbon‐efficient route from CO ₂ to polymer feedstocks.