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 ₂

Abstract

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.