Both MnOx and g‐C3N4 have been proved to be active in the catalytic oxidation of NO,and their individual mechanisms for catalytic NO conversion have also been investigated.However,the mechanism of photo‐thermal cata...Both MnOx and g‐C3N4 have been proved to be active in the catalytic oxidation of NO,and their individual mechanisms for catalytic NO conversion have also been investigated.However,the mechanism of photo‐thermal catalysis of the MnOx/g‐C3N4 composite remains unresolved.In this paper,MnOx/g‐C3N4 catalysts with different molar ratios were synthesized by the precipitation approach at room temperature.The as‐prepared catalysts exhibit excellent synergistic photo‐thermal catalytic performance towards the purification of NO in air.The MnOx/g‐C3N4 catalysts contain MnOx with different valence states on the surface of g‐C3N4.The thermal catalytic reaction for NO oxidation on MnOx and the photo‐thermal catalytic reaction on 1:5 MnOx/g‐C3N4 were investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS).The results show that light exerted a weak effect on NO oxidation over MnOx,and it exerted a positive synergistic effect on NO conversion over 1:5 MnOx/g‐C3N4.A synergistic photo‐thermal catalytic cycle of NO oxidation on MnOx/g‐C3N4 is proposed.Specifically,photo‐generated electrons(e?)are transferred to MnOx and participate in the synergistic photo‐thermal reduction cycle(Mn4+→Mn3+→Mn2+).The reverse cycle(Mn2+→Mn3+→Mn4+)can regenerate the active oxygen vacancy sites and inject electrons into the g‐C3N4 hole(h+).The active oxygen(O?)was generated in the redox cycles among manganese species(Mn4+/Mn3+/Mn2+)and could oxidize the intermediates(NOH and N2O2?)to final products(NO2?and NO3?).This paper can provide insightful guidance for the development of better catalysts for NOx purification.展开更多
ln-situ transmission electron microscopy in combination with a heating stage has been employed to real-time monitor varia- tions of δ-phase MnO2 nanoflowers in terms of their morphology and crystalline structures upo...ln-situ transmission electron microscopy in combination with a heating stage has been employed to real-time monitor varia- tions of δ-phase MnO2 nanoflowers in terms of their morphology and crystalline structures upon thermal annealing at elevated temperatures up to -665 ℃. High-temperature annealing drives the diffusion of the small δ-MnO2 nanocrystallites within short distances less than 15 nm and the fusion of the adjacent δ-MnO： nanocrystallites, leading to the formation of larger crystalline domains including highly crystalline nanorods. The annealed nanoflowers remain their overall flower-like morphology while they are converted to α-MnO2. The preferred transformation of the δ-MnO2 to the α-MnO2 can be ascribed to the close lattice spacing of most crystalline lattices between δ-MnO2 and α-MnO2, that might lead to a possible epitaxial growth of ct-MnO2 lattices on the 8-MnO2 lattices during the thermal annealing process.展开更多
文摘Both MnOx and g‐C3N4 have been proved to be active in the catalytic oxidation of NO,and their individual mechanisms for catalytic NO conversion have also been investigated.However,the mechanism of photo‐thermal catalysis of the MnOx/g‐C3N4 composite remains unresolved.In this paper,MnOx/g‐C3N4 catalysts with different molar ratios were synthesized by the precipitation approach at room temperature.The as‐prepared catalysts exhibit excellent synergistic photo‐thermal catalytic performance towards the purification of NO in air.The MnOx/g‐C3N4 catalysts contain MnOx with different valence states on the surface of g‐C3N4.The thermal catalytic reaction for NO oxidation on MnOx and the photo‐thermal catalytic reaction on 1:5 MnOx/g‐C3N4 were investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS).The results show that light exerted a weak effect on NO oxidation over MnOx,and it exerted a positive synergistic effect on NO conversion over 1:5 MnOx/g‐C3N4.A synergistic photo‐thermal catalytic cycle of NO oxidation on MnOx/g‐C3N4 is proposed.Specifically,photo‐generated electrons(e?)are transferred to MnOx and participate in the synergistic photo‐thermal reduction cycle(Mn4+→Mn3+→Mn2+).The reverse cycle(Mn2+→Mn3+→Mn4+)can regenerate the active oxygen vacancy sites and inject electrons into the g‐C3N4 hole(h+).The active oxygen(O?)was generated in the redox cycles among manganese species(Mn4+/Mn3+/Mn2+)and could oxidize the intermediates(NOH and N2O2?)to final products(NO2?and NO3?).This paper can provide insightful guidance for the development of better catalysts for NOx purification.
基金the Center for Nanoscale Materials, a U.S.Department of Energy, Office of Science, Office of Basic Energy Sciences User Facility under contract No. DE-AC02-06CH11357Use of the Electron Microscopy Center for Materials Research and Advanced Photon Source (Beam line 11-ID-C) at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of BasicEnergy Sciences, under contract No. DE-AC02-06CH11357
文摘ln-situ transmission electron microscopy in combination with a heating stage has been employed to real-time monitor varia- tions of δ-phase MnO2 nanoflowers in terms of their morphology and crystalline structures upon thermal annealing at elevated temperatures up to -665 ℃. High-temperature annealing drives the diffusion of the small δ-MnO2 nanocrystallites within short distances less than 15 nm and the fusion of the adjacent δ-MnO： nanocrystallites, leading to the formation of larger crystalline domains including highly crystalline nanorods. The annealed nanoflowers remain their overall flower-like morphology while they are converted to α-MnO2. The preferred transformation of the δ-MnO2 to the α-MnO2 can be ascribed to the close lattice spacing of most crystalline lattices between δ-MnO2 and α-MnO2, that might lead to a possible epitaxial growth of ct-MnO2 lattices on the 8-MnO2 lattices during the thermal annealing process.
