Metal Oxide-Promoted Calcium Cuprate Catalysts for Diol Oxidative Dehydrocyclization to Lactones: Article No. 101777

This work investigates structure-function relationships in electronically tunable, redox-active, basic Cu-Ca mixed metal oxide catalysts for oxidative dehydrocyclization of liquid diols to lactones. Compositional screening identified Ni2+ and Zn2+ as effective promoters that increase the surface Cu2+ population by ~1.7x and Cu-normalized activity for liquid 1,4-butanediol conversion to ..gamma..-butyrolactone by ~3-4x. In situ Raman spectroscopy, in situ X-ray absorption spectroscopy (XAS), in situ diffuse-reflectance Fourier transform infrared spectroscopy (DRIFTS), ex situ X-ray diffraction (XRD), and H2-temperature-programmed reduction (H2-TPR) show that Ni2+ or Zn2+ incorporation promotes the formation of Ca0.82Cu1.00O2 nanoparticles under mild calcination conditions. This cuprate phase features stronger and shorter Cu-O bonds (1.90 A) than inactive bulk CuO (1.95 A) and square-planar Cu2+O4 sites with enhanced dz2 electrophilicity, strengthening alkoxy adsorption. Pyridine-DRIFTS confirms the purely basic nature of the catalyst surface, while methanol-DRIFTS indicates Cu2+ surface enrichment with Ni or Zn promotion, where Cu-O(Ca)-Cu sites can exist as amorphous domains or a truncation layer on crystalline nanoparticles.