Fabrication of Integrated Copper-Based Nanoparticles/Amorphous Metal-Organic Framework by a Facile Spray-Drying Method: Highly Enhanced CO2 Hydrogenation Activity for Methanol Synthesis

We report on Cu/amUiO-66, a composite made of Cu nanoparticles (NPs) and amorphous [Zr6O4(OH)(4)(BDC)(6)] (amUiO-66, BDC=1,4-benzenedicarboxylate), and Cu-ZnO/amUiO-66 made of Cu-ZnO nanocomposites and amUiO-66. Both structures were obtained via a spray-drying method and characterized using high-resolution transmission electron microscopy, energy dispersive spectra, powder X-ray diffraction and extended X-ray absorption fine structure. The catalytic activity of Cu/amUiO-66 for CO2 hydrogenation to methanol was 3-fold that of Cu/crystalline UiO-66. Moreover, Cu-ZnO/amUiO-66 enhanced the methanol production rate by 1.5-fold compared with Cu/amUiO-66 and 2.5-fold compared with gamma-Al2O3-supported Cu-ZnO nanocomposites (Cu-ZnO/gamma-Al2O3) as the representative hydrogenation catalyst. The high catalytic performance was investigated using in situ Fourier transform IR spectra. This is a first report of a catalyst comprising metal NPs and an amorphous metal-organic framework in a gas-phase reaction.

Automated summary

The Cu/amUiO-66 and Cu-ZnO/amUiO-66 catalysts, prepared via spray-drying method, demonstrated high catalytic activity in CO2 hydrogenation to methanol, showing significant improvement compared to other catalysts.