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 [Zr 6 O 4 (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 CO 2 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‐Al 2 O 3 ‐supported Cu‐ZnO nanocomposites ( Cu‐ZnO/γ‐Al 2 O 3 ) 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.