Polymers are usually restricted on the high exciton binding energies and sluggish electron transfer because of the low dielectric constants.Regulating spin-polarized electrons is regarded as an attractive strategy,but...Polymers are usually restricted on the high exciton binding energies and sluggish electron transfer because of the low dielectric constants.Regulating spin-polarized electrons is regarded as an attractive strategy,but often confined to the d-orbital elements.Here,the nonmetal P and N elements co-mediated the spin polarization of carbon nitrides(PCN)have been elaborately designed.The optimized PCN-3 shows an outstanding hydrogen production(22.2 mmol·g^(-1)·h^(-1))coupled with selective benzylamine oxidation without using any solvent and cocatalysts,which is 200 times of original C_(3)N_(4)and superior to the photocatalysts has been reported to date.Experimental and theoretical results verified that the spin-orbital coupling of N 2p and P 2p remarkably increased the parallel spin states of charge and reduced the formation of singlet excitons to accelerate exciton dissociation in carbon nitride.In addition,charge separation and surface catalysis can be significantly enhanced by the electron spin polarization of carbon nitride with the parallel arrangement,huge built-in electric field and disturbed electronic structure.Our finding deepens the insight into the charge separation and exciton dissociation in spin polarization,and offers new tactics to develop high-efficiency catalysts.展开更多
基金financially supported by Guizhou Provincial Science and Technology Foundation(No.ZK2021069)Young Science and Technology Talents Development Project of Education Department in Guizhou Province(No.KY2022144)National Natural Science Foundation of China(No.22268015).
文摘Polymers are usually restricted on the high exciton binding energies and sluggish electron transfer because of the low dielectric constants.Regulating spin-polarized electrons is regarded as an attractive strategy,but often confined to the d-orbital elements.Here,the nonmetal P and N elements co-mediated the spin polarization of carbon nitrides(PCN)have been elaborately designed.The optimized PCN-3 shows an outstanding hydrogen production(22.2 mmol·g^(-1)·h^(-1))coupled with selective benzylamine oxidation without using any solvent and cocatalysts,which is 200 times of original C_(3)N_(4)and superior to the photocatalysts has been reported to date.Experimental and theoretical results verified that the spin-orbital coupling of N 2p and P 2p remarkably increased the parallel spin states of charge and reduced the formation of singlet excitons to accelerate exciton dissociation in carbon nitride.In addition,charge separation and surface catalysis can be significantly enhanced by the electron spin polarization of carbon nitride with the parallel arrangement,huge built-in electric field and disturbed electronic structure.Our finding deepens the insight into the charge separation and exciton dissociation in spin polarization,and offers new tactics to develop high-efficiency catalysts.
