Copper Nanoparticles Supported on ZIF-8: Comparison of Cu(II) Reduction Processes and Application as Benzyl Alcohol Oxidation Catalysts.

We report the synthesis of a stable heterogeneous catalyst based on copper metal nanoparticles with oxidized surface supported on ZIF-8 for the oxidation of benzyl alcohol under mild temperature and using air as a sustainable oxygen source as well as for the implementation of the tandem "one-pot" catalytic system allowing the sustainable synthesis of benzylidene malononitrile. The influence of the reduction process applied to form the nanoparticle upon the catalyst texture and its performances was extensively examined. After ZIF-8 impregnation with a copper chloride precursor, the reduction of cupric ions into Cu nanoparticles was carried out according to two procedures: (i) by soaking the solid into a solution of NaBH and (ii) by submitting it to a flow of gaseous H at 340 °C. The in-depth physicochemical characterization and comparison of the resulting two types of Cu/ZIF-8 materials reveal significant differences: the reduction with NaBH led to the formation of 16 nm sized Cu nanoparticles (NP) mainly localized on the external surface of the ZIF-8 crystals together with ZnO nanocrystallites, while the reduction under H flow resulted in Cu nanoparticles with a mean size of 22 nm embedded within the bulk of ZIF-8 crystals. More, when NaBH was used to reduce cupric ions, ZnO particles were highlighted by high-resolution microcospy imaging. Formation of ZnO impurities was confirmed by the photoluminescence analysis of ZIF-8 after NaBH treatment. In contrast, ZnO was not detected on ZIF-8 treated with H. Both types of Cu NPs supported on ZIF-8 were found to be active as catalysts toward the aerobic oxidation of benzyl alcohol under moderate temperature ( < 80 °C) and using air as a sustainable O source. Benzaldehyde yield of 66% and selectivity superior to 90% were obtained with the Cu/ZIF-8 catalyst prepared under H flow after 24 h under these conditions. The same material could be recycled 5 times without loss of activity, unlike the catalysts synthesized with NaBH, as a result of the leaching of the surface copper NPs over the consecutive catalytic cycles. Finally, the most stable catalyst was successfully implemented in a tandem "one-pot" catalytic system associating benzyl alcohol oxidation and Knoevenagel condensation to synthesize benzylidene malononitrile.