The g-C_(3)N_(4)/BiOI/CdS double Z-scheme heterojunction photocatalyst with I_(3)^(-)/I^(-) redox pairs is prepared using simple calcination,solvothermal,and solution chemical deposition methods.The photocatalyst comp...The g-C_(3)N_(4)/BiOI/CdS double Z-scheme heterojunction photocatalyst with I_(3)^(-)/I^(-) redox pairs is prepared using simple calcination,solvothermal,and solution chemical deposition methods.The photocatalyst comprised mesoporous,thin g-C_(3)N_(4) nanosheets loaded on flower-like microspheres of BiOI with CdS quantum dots.The g-C_(3)N_(4)/BiOI/CdS double Z-scheme heterojunction has abundant active sites and in situ redox I_(3)^(-)/I^(-) mediators and shows quantum size effects,which are all conducive to enhancing the separation of photoinduced charges and increasing the photocatalytic degradation efficiency for bisphenol A,a model pollutant.Specifically,the heterojunction photocatalyst achieves a photocatalytic degradation efficiency for bisphenol A of 98.62%in 120 min and photocatalytic hydrogen production of 863.44 mmol h^(-1) g^(-1) on exposure to visible light.The excellent visible-light photocatalytic performance is as a result of the Z-scheme heterojunction,which extends absorption to the visible light region,as well as the I_(3)^(-)/I^(-) pairs,which accelerate photoinduced charge carrier transfer and separation,thus dramatically boosting the photocatalytic performance.In addition,the key role of the charge transfer across the indirect Z-scheme heterojunction has been elucidated and the transfer mechanism is confirmed based on the detection of intermediate I_(3)^(-)ions.Thus,this study provides guidelines for the design of indirect Z-scheme heterojunction photocatalysts.展开更多
A single-Rh-site catalyst(Rh-TPISP)that was ionically-embedded on a P(V)quaternary phosphonium porous polymer was evaluated for heterogeneous ethanol carbonylation.The[Rh(CO)I_(3)]^(2-)unit was proposed to be the acti...A single-Rh-site catalyst(Rh-TPISP)that was ionically-embedded on a P(V)quaternary phosphonium porous polymer was evaluated for heterogeneous ethanol carbonylation.The[Rh(CO)I_(3)]^(2-)unit was proposed to be the active center of Rh-TPISP for the carbonylation reaction based on detailed Rh L3-edge X-ray absorption near edge structure(XANES),X-ray photoelectron spectroscopy(XPS),and Rh extended X-ray absorption fine structure(EXAFS)analyses.As the highlight of this study,Rh-TPISP displayed distinctly higher activity for heterogeneous ethanol carbonylation than the reported catalytic systems in which[Rh(CO)_(2)I_(2)]^(-)is the traditional active center.A TOF of 350 h^(-1)was obtained for the reaction over[Rh(CO)I_(3)]^(2-),with>95%propionyl selectivity at 3.5 MPa and 468 K.No deactivation was detected during a near 1000 h running test.The more electron-rich Rh center was thought to be crucial for explaining the superior activity and selectivity of Rh-TPISP,and the formation of two ionic bonds between[Rh(CO)I_(3)]^(2-)and the cationic P(V)framework([P]^(+))of the polymer was suggested to play a key role in firmly immobilizing the active species to prevent Rh leaching.展开更多
基金support of this work by the National Natural Science Foundation of China(51869006)Jiangxi Natural Science Foundation of China(20171BAB216050)Water Science and Technology Fund of Jiangxi Province in China(KT201702).
文摘The g-C_(3)N_(4)/BiOI/CdS double Z-scheme heterojunction photocatalyst with I_(3)^(-)/I^(-) redox pairs is prepared using simple calcination,solvothermal,and solution chemical deposition methods.The photocatalyst comprised mesoporous,thin g-C_(3)N_(4) nanosheets loaded on flower-like microspheres of BiOI with CdS quantum dots.The g-C_(3)N_(4)/BiOI/CdS double Z-scheme heterojunction has abundant active sites and in situ redox I_(3)^(-)/I^(-) mediators and shows quantum size effects,which are all conducive to enhancing the separation of photoinduced charges and increasing the photocatalytic degradation efficiency for bisphenol A,a model pollutant.Specifically,the heterojunction photocatalyst achieves a photocatalytic degradation efficiency for bisphenol A of 98.62%in 120 min and photocatalytic hydrogen production of 863.44 mmol h^(-1) g^(-1) on exposure to visible light.The excellent visible-light photocatalytic performance is as a result of the Z-scheme heterojunction,which extends absorption to the visible light region,as well as the I_(3)^(-)/I^(-) pairs,which accelerate photoinduced charge carrier transfer and separation,thus dramatically boosting the photocatalytic performance.In addition,the key role of the charge transfer across the indirect Z-scheme heterojunction has been elucidated and the transfer mechanism is confirmed based on the detection of intermediate I_(3)^(-)ions.Thus,this study provides guidelines for the design of indirect Z-scheme heterojunction photocatalysts.
文摘A single-Rh-site catalyst(Rh-TPISP)that was ionically-embedded on a P(V)quaternary phosphonium porous polymer was evaluated for heterogeneous ethanol carbonylation.The[Rh(CO)I_(3)]^(2-)unit was proposed to be the active center of Rh-TPISP for the carbonylation reaction based on detailed Rh L3-edge X-ray absorption near edge structure(XANES),X-ray photoelectron spectroscopy(XPS),and Rh extended X-ray absorption fine structure(EXAFS)analyses.As the highlight of this study,Rh-TPISP displayed distinctly higher activity for heterogeneous ethanol carbonylation than the reported catalytic systems in which[Rh(CO)_(2)I_(2)]^(-)is the traditional active center.A TOF of 350 h^(-1)was obtained for the reaction over[Rh(CO)I_(3)]^(2-),with>95%propionyl selectivity at 3.5 MPa and 468 K.No deactivation was detected during a near 1000 h running test.The more electron-rich Rh center was thought to be crucial for explaining the superior activity and selectivity of Rh-TPISP,and the formation of two ionic bonds between[Rh(CO)I_(3)]^(2-)and the cationic P(V)framework([P]^(+))of the polymer was suggested to play a key role in firmly immobilizing the active species to prevent Rh leaching.
