Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging,with the activation of molecular oxygen(O2)as a crucial capability of the catalysts.Herein,we demonstrate that an Al...Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging,with the activation of molecular oxygen(O2)as a crucial capability of the catalysts.Herein,we demonstrate that an Al2O3-supported Pd single-atom catalyst leads to higher activity and selectivity compared to Pd nanoparticles for the oxidation of cinnamyl alcohol.The Al2O3 support used in this study is rich in coordinately unsaturated Al3+sites,which are apt for binding to Pd atoms through oxygen bridges and present a distinct metal-support interaction(MSI).The suitable MSI then leads to a unique electronic characteristic of the Pd single atoms,which can be confirmed via X-ray photoelectron spectroscopy,normalized X-ray absorption near-edge structure,and diffuse reflectance Fourier transform infrared spectroscopy.Moreover,this unique electronic state is proposed to be responsible for its high catalytic activity.With the help of in-situ UV-vis spectra and electron spin resonance spectra,a specific alcohol oxidation route with O2 activation mechanism is then identified.Active oxygen species behaving chemically like singlet-O2 are generated from the interaction of O2 with Pd1/Al2O3,and then oxidize the partially dehydrogenated intermediates produced by the adsorbed allylic alcohols and Pd atoms to the desired alkenyl aldehyde.This work provides a promising path for the design and development of high-activity catalysts for aerobic oxidation reactions.展开更多
TiO2 and TiO2-SiO2 photocatalysts were prepared by sol-gel and supercritical CO2 fluid drying method and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), etc. Their catalytic propertie...TiO2 and TiO2-SiO2 photocatalysts were prepared by sol-gel and supercritical CO2 fluid drying method and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), etc. Their catalytic properties were tested through the photocatalytic degradation of phenol and aniline in wastewater. The results show that the developed fluidized photocatalytic reactor (FPR) and TiO2 catalyst had better performance in degrading pollutants as compared with slurry photocatalytic reactor (SPR) and commercial TiO2 catalyst. The composition and crystal form of TiO2-SiO2 composite oxide had obvious influence on catalytic effect and TiO2-SiO2 photocatalysts showed better catalytic activity and stability.展开更多
基金中国博士后科学基金(2021M693125)大连市高层次人才创新支持计划(2019RT09)+1 种基金中国科学院洁净能源创新研究院合作基金(DNL202016,DNL202019)中国科学院洁净能源创新研究院-榆林学院联合基金(YLU-DNL Fund 2021002,YLU-DNL Fund 2021009).
文摘Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging,with the activation of molecular oxygen(O2)as a crucial capability of the catalysts.Herein,we demonstrate that an Al2O3-supported Pd single-atom catalyst leads to higher activity and selectivity compared to Pd nanoparticles for the oxidation of cinnamyl alcohol.The Al2O3 support used in this study is rich in coordinately unsaturated Al3+sites,which are apt for binding to Pd atoms through oxygen bridges and present a distinct metal-support interaction(MSI).The suitable MSI then leads to a unique electronic characteristic of the Pd single atoms,which can be confirmed via X-ray photoelectron spectroscopy,normalized X-ray absorption near-edge structure,and diffuse reflectance Fourier transform infrared spectroscopy.Moreover,this unique electronic state is proposed to be responsible for its high catalytic activity.With the help of in-situ UV-vis spectra and electron spin resonance spectra,a specific alcohol oxidation route with O2 activation mechanism is then identified.Active oxygen species behaving chemically like singlet-O2 are generated from the interaction of O2 with Pd1/Al2O3,and then oxidize the partially dehydrogenated intermediates produced by the adsorbed allylic alcohols and Pd atoms to the desired alkenyl aldehyde.This work provides a promising path for the design and development of high-activity catalysts for aerobic oxidation reactions.
文摘TiO2 and TiO2-SiO2 photocatalysts were prepared by sol-gel and supercritical CO2 fluid drying method and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), etc. Their catalytic properties were tested through the photocatalytic degradation of phenol and aniline in wastewater. The results show that the developed fluidized photocatalytic reactor (FPR) and TiO2 catalyst had better performance in degrading pollutants as compared with slurry photocatalytic reactor (SPR) and commercial TiO2 catalyst. The composition and crystal form of TiO2-SiO2 composite oxide had obvious influence on catalytic effect and TiO2-SiO2 photocatalysts showed better catalytic activity and stability.
