Hollow Flower-Like Cu–Co Catalysts Derived from Layered Double Hydroxides for CO ₂ Hydrogenation to Ethanol

The selective hydrogenation of CO 2 to value-added C 2+ oxygenates is a promising route toward carbon neutrality but is complicated by the parallel pathways to hydrocarbons and methanol. Herein, a precursor-topology strategy is employed to construct the hollow flower-like Cu x –Co y catalysts derived from layered double hydroxide (LDH) precursors for CO 2 hydrogenation to ethanol. The three-dimensional architectural Cu x –Co y offers a high surface area and open mesopores while promoting a homogeneous distribution of Cu–Co interfacial sites on the Al 2 O 3 matrix. Cu 1 –Co 3 achieves a CO 2 conversion of 16.9% and an ethanol selectivity of 16.5%, with the stability over 100 h when CO 2 is hydrogenated at 260 °C and 1.5 MPa under a gas hourly space velocity of 12,000 mL·g cat –1 ·h –1 and a H 2 /CO 2 volume ratio of 3:1. Multitechnique characterization by XRD, SEM/TEM, EPR, XPS, CO 2 -TPD, H 2 -TPR, H 2 -TPD, N 2 O pulse titration, and in situ DRIFTS suggests that the optimized Cu 1 –Co 3 catalyst possesses a hollow flower-like architecture, enhancing the Cu dispersion, increasing the abundant defect/basic sites, improving the CO 2 reducibility and H 2 activation ability, and accessing the Cu–Co interfacial ensembles. Cu–Co interfacial sites favor the formation and preservation of *CO and *CH x species required for C–C coupling for ethanol formation while suppressing excessive hydrogenation to CH 4 .