Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a st...Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a star visible‐light photocatalyst in this field due to its various advantages.However,pristine g‐C3N4usually exhibits limited activity.Herein,to enhance the performance of g‐C3N4,alkali metal ion(Li+,Na+,or K+)‐doped g‐C3N4are prepared via facile high‐temperature treatment.The prepared samples are characterized and analyzed using the technique of XRD,ICP‐AES,SEM,UV‐vis DRS,BET,XPS,PL,TRPL,photoelectrochemical measurements,photocatalytic tests,etc.The resultant doped photocatalysts show enhanced visible‐light photocatalytic activities for hydrogen production,benefiting from the increased specific surface areas(which provide more active sites),decreased band gaps for extended visible‐light absorption,and improved electronic structures for efficient charge transfer.In particular,because of the optimal tuning of both microstructure and electronic structure,the Na‐doped g‐C3N4shows the most effective utilization of photogenerated electrons during the water reduction process.As a result,the highest photocatalytic performance is achieved over the Na‐doped g‐C3N4photocatalyst(18.7?mol/h),3.7times that of pristine g‐C3N4(5.0?mol/h).This work gives a systematic study for the understanding of doping effect of alkali metals in semiconductor photocatalysis.展开更多
It is still a great challenge to effectively optimize the electronic structure of photocatalysts for the sustainable and efficient conversion of solar energy to H2 energy.To resolve this issue,we report on the optimiz...It is still a great challenge to effectively optimize the electronic structure of photocatalysts for the sustainable and efficient conversion of solar energy to H2 energy.To resolve this issue,we report on the optimization of the electronic structure of hollow-concave carbon nitride(C3N4)by deviating the sp2-hybridized structure of its tri-s-triazine component from the two-dimensional plane.The embedded CuInS2 into C3N4(CuInS2@C3N4)demonstrates an increased light-capturing capability and the promoted directional transfer of the charge carrier.Research results reveal that the hollow structure with an apparent potential difference between the concave and convex C3N4 drives the directional transfer of the photoinduced electrons from the Cu 2p orbital of CuInS2 to the N 1s orbital of C3N4 with the S-scheme principle.The H2 evolution efficiency over CuInS2@C3N4 is up to 373μmol?h^-1 g^-1 under visible irradiation,which is 1.57 and 1.35 times higher than those over the bulk g-C3N4 with 1 wt%Pt(238μmol?h^-1 g^-1)and g-C3N4 with 3 wt%Pd(276μmol?h^-1 g^-1),respectively.This suggests that the apparent potential difference of the hollow C3N4 results in an efficient reaction between the photogenerated electrons and H2O.This work supplies a new strategy for enhancing the sustainable solar conversion performance of carbon nitride,which can also be suitable for other semiconductors.展开更多
基金supported by the National Natural Science Foundation of of China(51472191,21407115,21773179)the Natural Science Foundation of Hubei Province of China(2017CFA031)the Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education(JDGD-201509)~~
文摘Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a star visible‐light photocatalyst in this field due to its various advantages.However,pristine g‐C3N4usually exhibits limited activity.Herein,to enhance the performance of g‐C3N4,alkali metal ion(Li+,Na+,or K+)‐doped g‐C3N4are prepared via facile high‐temperature treatment.The prepared samples are characterized and analyzed using the technique of XRD,ICP‐AES,SEM,UV‐vis DRS,BET,XPS,PL,TRPL,photoelectrochemical measurements,photocatalytic tests,etc.The resultant doped photocatalysts show enhanced visible‐light photocatalytic activities for hydrogen production,benefiting from the increased specific surface areas(which provide more active sites),decreased band gaps for extended visible‐light absorption,and improved electronic structures for efficient charge transfer.In particular,because of the optimal tuning of both microstructure and electronic structure,the Na‐doped g‐C3N4shows the most effective utilization of photogenerated electrons during the water reduction process.As a result,the highest photocatalytic performance is achieved over the Na‐doped g‐C3N4photocatalyst(18.7?mol/h),3.7times that of pristine g‐C3N4(5.0?mol/h).This work gives a systematic study for the understanding of doping effect of alkali metals in semiconductor photocatalysis.
基金Study was supported by the National Natural Science Foundation of China(21871155)the K.C.Wong Magna Fund in Ningbo University,Fan 3315 PlanYongjiang Scholar Plan~~
文摘It is still a great challenge to effectively optimize the electronic structure of photocatalysts for the sustainable and efficient conversion of solar energy to H2 energy.To resolve this issue,we report on the optimization of the electronic structure of hollow-concave carbon nitride(C3N4)by deviating the sp2-hybridized structure of its tri-s-triazine component from the two-dimensional plane.The embedded CuInS2 into C3N4(CuInS2@C3N4)demonstrates an increased light-capturing capability and the promoted directional transfer of the charge carrier.Research results reveal that the hollow structure with an apparent potential difference between the concave and convex C3N4 drives the directional transfer of the photoinduced electrons from the Cu 2p orbital of CuInS2 to the N 1s orbital of C3N4 with the S-scheme principle.The H2 evolution efficiency over CuInS2@C3N4 is up to 373μmol?h^-1 g^-1 under visible irradiation,which is 1.57 and 1.35 times higher than those over the bulk g-C3N4 with 1 wt%Pt(238μmol?h^-1 g^-1)and g-C3N4 with 3 wt%Pd(276μmol?h^-1 g^-1),respectively.This suggests that the apparent potential difference of the hollow C3N4 results in an efficient reaction between the photogenerated electrons and H2O.This work supplies a new strategy for enhancing the sustainable solar conversion performance of carbon nitride,which can also be suitable for other semiconductors.
