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

Abstract

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 γ‐Al2O3‐supported Cu‐ZnO nanocomposites (Cu‐ZnO/γ‐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.

Selective Gas‐Phase Hydrogenation of CO2 to Methanol Catalysed by Metal‐Organic Frameworks

“…The performance of Cu/amUiO-66 for CO 2 hydrogenation to CH 3 OH was 3-fold higher compared to Cu/ crystalline UiO-66. [84] Furthermore, CuÀ ZnO/amUiO-66 reached STY for MeOH production of 710.5 μmol g Cu À 1 h À 1 , surpassing by a factor of 1.5-fold to the performance of Cu/ amUiO-66 and 2.5-fold to the productivity value for CuÀ ZnO/γ-Al 2 O 3 (Figure 10). In situ FT-IR spectroscopy and XPS measurements were performed to characterize the nature of support and understand its high activity.…”

Thermocatalytic Conversion of CO2 to Valuable Products Activated by Noble‐Metal‐Free Metal‐Organic Frameworks

“…Chemie Minireviews ure 14b) utilized amorphous MOFs to protect Cu nanoparticles and Cu-ZnO nanocomposites, [193] and both of the synthesized catalysts Cu/amUiO-66 and Cu-ZnO/amUiO-66 exhibit a higher activity than that of Cu/crystalline UiO-66 and Cu-ZnO/γ-Al 2 O 3 for CO 2 hydrogenation to methanol. Lercher and co-workers (Figure 14c) anchored Cu ions on the Zr nodes of UiO-66 by ion-exchange method.…”

Thermocatalytic Conversion of CO2 to Valuable Products Activated by Noble‐Metal‐Free Metal‐Organic Frameworks

“…Mechanism studies revealed that the introduced Zn 2 + sites are responsible for H 2 activation, and Zn 2 + À OÀ Zr 4 + moieties are critical for CO 2 adsorption and conversion. Mitsuka and co-workers (Fig- ure 14b) utilized amorphous MOFs to protect Cu nanoparticles and Cu-ZnO nanocomposites, [193] and both of the synthesized catalysts Cu/amUiO-66 and Cu-ZnO/amUiO-66 exhibit a higher activity than that of Cu/crystalline UiO-66 and Cu-ZnO/γ-Al 2 O 3 for CO 2 hydrogenation to methanol. Lercher and co-workers (Figure 14c) anchored Cu ions on the Zr nodes of UiO-66 by ion-exchange method.…”