RESUMEN
The selective oxidation of methane (CH4) features attractive potentials in both mitigating global warming and producing value-added chemicals. However, due to the short-life and unpaired concentrations of reactive intermediates (such as ·OH, ·CH3, and CO), the selective formation of multicarbon products like ethanol has remained challenging. In this work, we developed a hollow multishelled CeO2@PdO@FeOx nanosphere catalyst with two asymmetric and closely connected interfaces, featuring efficient in-tandem photo-oxidation of CH4 into ethanol with O2 as the oxidant. The outer FeOx surface promotes the photoreduction of the oxazole atoms in O2. In the meantime, the two asymmetric PdO/FeOx and CeO2/PdO catalytic interfaces enable selective photoactivation of CH4 to ·CH3 and then to CO, respectively, and the hollow multishelled structure further facilitates the directional transport and coupling of the as-generated ·CH3 and CO to produce ethanol. Under 100 mW·cm-2 light intensity and ambient conditions, the hollow multishelled CeO2@PdO@FeOx nanosphere photocatalyst exhibited a peak CH4-to-ethanol yield of 728 µmol·g-1·h-1 without photosensitizers or sacrificial agents, almost three times higher than the previous best reports on photocatalytic CH4 oxidation to ethanol, suggesting the attractive potential of the asymmetric multishelled catalytic interfaces.
RESUMEN
The electrochemical CO2 reduction reaction by copper-based catalysts features a promising approach to generate value-added multicarbon (C2+) products. However, due to the unfavored formation of oxygenate intermediates on the catalyst surface, the selectivity of C2+ alcohols like ethanol remains unsatisfactory compared to that of ethylene. The bifurcation point (i.e., the CH2âCHO* intermediate adsorbed on Cu via a Cu-O-C linkage) is critical to the C2+ product selectivity, whereas the subsequent cleavage of the Cu-O or the O-C bond determines the ethanol or ethylene pathway. Inspired by the hard-soft acid-base theory, in this work, we demonstrate an electron delocalization tuning strategy of the Cu catalyst by a nitrene surface functionalization approach, which allows weakening and cleaving of the Cu-O bond of the adsorbed CH2âCHO*, as well as accelerating hydrogenation of the CâC bond along the ethanol pathway. As a result, the nitrene-functionalized Cu catalyst exhibited a much-enhanced ethanol Faradaic efficiency of 45% with a peak partial current density of 406 mA·cm-2, substantially exceeding that of unmodified Cu or amide-functionalized Cu. When assembled in a membrane electrode assembly electrolyzer, the catalyst presented a stable CO2-to-ethanol conversion for >300 h at an industrial current density of 400 mA·cm-2.