Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenati...Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenation and C–C coupling limit the C_(2)H_(4)generation.Herein,CuxP/g-C_(3)N_(4) heterojunction prepared by an in-situ phosphating technique,achieved collaborative photocatalytic CO_(2) and H2O,producing CO and C_(2)H_(4)as the main products.Notably,the selectivity of C_(2)H_(4)produced by CuxP/g-C_(3)N_(4) attained to 64.25%,which was 9.85 times that of CuxP(6.52%).Detailed time-resolution photoluminescence spectra,femtosecond transient absorption spectroscopy tests and density functional theory(DFT)calculation validate the ultra-fast interfacial electron transfer mechanism in CuxP/g-C_(3)N_(4) heterojunction.Successive*H on P sites caused by adsorbed H2O splitting with moderate hydrogenation ability enables the multi-step hydrogenation during CO_(2)RR process over CuxP/g-C_(3)N_(4).With the aid of mediated asymmetric Cu and P dual sites by g-C_(3)N_(4) nanosheet,the produced*CHO shows an energetically favorable for C–C coupling.The coupling formed*CHOCHO further accepts photoexcited efficient e–and*H to deeply produce C_(2)H_(4)according to the C^(2+)intermediates,which has been detected by in-situ diffuse reflectance infrared Fourier transform spectroscopy and interpreted by DFT calculation.The novel insight mechanism offers an essential understanding for the development of CuxP-based heterojunctions for photocatalytic CO_(2) to C^(2+)value-added fuels.展开更多
文摘Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenation and C–C coupling limit the C_(2)H_(4)generation.Herein,CuxP/g-C_(3)N_(4) heterojunction prepared by an in-situ phosphating technique,achieved collaborative photocatalytic CO_(2) and H2O,producing CO and C_(2)H_(4)as the main products.Notably,the selectivity of C_(2)H_(4)produced by CuxP/g-C_(3)N_(4) attained to 64.25%,which was 9.85 times that of CuxP(6.52%).Detailed time-resolution photoluminescence spectra,femtosecond transient absorption spectroscopy tests and density functional theory(DFT)calculation validate the ultra-fast interfacial electron transfer mechanism in CuxP/g-C_(3)N_(4) heterojunction.Successive*H on P sites caused by adsorbed H2O splitting with moderate hydrogenation ability enables the multi-step hydrogenation during CO_(2)RR process over CuxP/g-C_(3)N_(4).With the aid of mediated asymmetric Cu and P dual sites by g-C_(3)N_(4) nanosheet,the produced*CHO shows an energetically favorable for C–C coupling.The coupling formed*CHOCHO further accepts photoexcited efficient e–and*H to deeply produce C_(2)H_(4)according to the C^(2+)intermediates,which has been detected by in-situ diffuse reflectance infrared Fourier transform spectroscopy and interpreted by DFT calculation.The novel insight mechanism offers an essential understanding for the development of CuxP-based heterojunctions for photocatalytic CO_(2) to C^(2+)value-added fuels.
