Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer ...Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer from insufficient hole transport capability,which hinders the overall activity.The present study demonstrates that a simple photoetching strategy is able to introduce gradient distributed oxygen vacancies(GO_(V))in the thick FeOOH layer and significantly enhances the photogenerated holes transport dynamics.The incorporation of GO_(V)within FeOOH not only realizes the“relay transport”of photogenerated hole through the progressive upward shift of the valence band in the spatial distribution,but also provides abundant oxidation active sites by efficient hole trapping.These improvements effectively improve the oxygen evolution reaction(OER)activities and mitigate photocorrosion by the instantaneous hole extraction.Consequently,the FeOOH-GO_(V)layer enables the BVO/FeOOH-GO_(V)photoanode to achieve an impressive photocurrent density of 5.37 mA cm^(-2)and a robust operational stability up to 160 h at 1.23 VRHE,setting new benchmarks for current density and stability in FeOOH-based BVO photoanodes.This work provides an effective avenue to optimize OER cocatalysts for constructing highly efficient and stable photoelectrochemical water splitting devices.展开更多
Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely bee...Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition.In this study,a series of bimetallic nickel-iron phosphide(Ni_(x)Fe_(2-x)P,where 0<x<2)cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus(RP)for the photocatalytic selective oxidation of benzyl alcohol(BA)coupled with hydrogen production.The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H_(2)yield.The RP regulated by bimetallic phosphide cocatalysts(Ni_(x)Fe_(2-x)P)demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts(Ni_(2)P and Fe2P).In particular,the RP regulated by Ni_(1.25)Fe_(0.75)P exhibited the best photocatalytic performance.In addition,experimental and theoretical calculations further illustrated that Ni_(1.25)Fe_(0.75)P,with the optimized electronic structure,possessed good electrical conductivity and provided strong adsorption and abundant active sites,thereby accelerating electron migration and lowering the reaction energy barrier of RP.This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.展开更多
Photocatalysts are essential for the preparation of wanted fine chemical and biomedical intermediates via visible photocatalysis,but existing photocatalysts with low catalytic efficiency limit their wide applications....Photocatalysts are essential for the preparation of wanted fine chemical and biomedical intermediates via visible photocatalysis,but existing photocatalysts with low catalytic efficiency limit their wide applications.Herein,CdS/Ti_(3)C2T_(x)/MBI nanocomposites have been successfully fabricated through anchoring reduction cocatalyst Ti_(3)C_(2)T_(x) with electron-drawing ability and oxidation cocatalyst 2-mercaptobenzimidazole(MBI)with hole-capturing capacity on CdS nanoparticles.The Ti_(3)C_(2)T_(x) and MBI of CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites can extract electrons and holes from CdS nanoparticles to come true electron-hole separation,respectively.Moreover,the electron-drawing and hole-capturing abilities of the CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites depend on Ti_(3)C_(2)T_(x) and MBI contents,and the quantifiable electron and hole transfers finally determine photocatalytic efficiency of the CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites.The transient photocurrent density of the CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites is 6-fold higher than that of the CdS nanoparticles.The CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites with strong electron-hole separation capability exhibit outstanding visible photocatalytic organic transformation properties.The CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites produce(E)-N-benzyl-1-phenylmethylimine in~96%yield(~8000μmol·g^(-1)·h^(-1)),which is 3-fold higher than the CdS nanoparticles(~2500μmol·g^(-1)·h^(-1),30%).This work provides a new strategy for constructing efficient and stable photocatalysts that can be used for efficient visible light-driven organic transformations.展开更多
基金supported by the State Key Laboratory of Solidification Processing in NWPU(SKLSP202407)the National Natural Science Foundation of China(52402130)+2 种基金the Natural Science Basis Research Plan in Shaanxi Province of China(2024JC-YBQN-0384)the Shaanxi Science and Technology Innovation Team(2023-CX-TD-44)the National Natural Science Foundation of China(52301015).
文摘Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer from insufficient hole transport capability,which hinders the overall activity.The present study demonstrates that a simple photoetching strategy is able to introduce gradient distributed oxygen vacancies(GO_(V))in the thick FeOOH layer and significantly enhances the photogenerated holes transport dynamics.The incorporation of GO_(V)within FeOOH not only realizes the“relay transport”of photogenerated hole through the progressive upward shift of the valence band in the spatial distribution,but also provides abundant oxidation active sites by efficient hole trapping.These improvements effectively improve the oxygen evolution reaction(OER)activities and mitigate photocorrosion by the instantaneous hole extraction.Consequently,the FeOOH-GO_(V)layer enables the BVO/FeOOH-GO_(V)photoanode to achieve an impressive photocurrent density of 5.37 mA cm^(-2)and a robust operational stability up to 160 h at 1.23 VRHE,setting new benchmarks for current density and stability in FeOOH-based BVO photoanodes.This work provides an effective avenue to optimize OER cocatalysts for constructing highly efficient and stable photoelectrochemical water splitting devices.
文摘Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition.In this study,a series of bimetallic nickel-iron phosphide(Ni_(x)Fe_(2-x)P,where 0<x<2)cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus(RP)for the photocatalytic selective oxidation of benzyl alcohol(BA)coupled with hydrogen production.The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H_(2)yield.The RP regulated by bimetallic phosphide cocatalysts(Ni_(x)Fe_(2-x)P)demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts(Ni_(2)P and Fe2P).In particular,the RP regulated by Ni_(1.25)Fe_(0.75)P exhibited the best photocatalytic performance.In addition,experimental and theoretical calculations further illustrated that Ni_(1.25)Fe_(0.75)P,with the optimized electronic structure,possessed good electrical conductivity and provided strong adsorption and abundant active sites,thereby accelerating electron migration and lowering the reaction energy barrier of RP.This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.
文摘Photocatalysts are essential for the preparation of wanted fine chemical and biomedical intermediates via visible photocatalysis,but existing photocatalysts with low catalytic efficiency limit their wide applications.Herein,CdS/Ti_(3)C2T_(x)/MBI nanocomposites have been successfully fabricated through anchoring reduction cocatalyst Ti_(3)C_(2)T_(x) with electron-drawing ability and oxidation cocatalyst 2-mercaptobenzimidazole(MBI)with hole-capturing capacity on CdS nanoparticles.The Ti_(3)C_(2)T_(x) and MBI of CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites can extract electrons and holes from CdS nanoparticles to come true electron-hole separation,respectively.Moreover,the electron-drawing and hole-capturing abilities of the CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites depend on Ti_(3)C_(2)T_(x) and MBI contents,and the quantifiable electron and hole transfers finally determine photocatalytic efficiency of the CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites.The transient photocurrent density of the CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites is 6-fold higher than that of the CdS nanoparticles.The CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites with strong electron-hole separation capability exhibit outstanding visible photocatalytic organic transformation properties.The CdS/Ti_(3)C_(2)T_(x)/MBI nanocomposites produce(E)-N-benzyl-1-phenylmethylimine in~96%yield(~8000μmol·g^(-1)·h^(-1)),which is 3-fold higher than the CdS nanoparticles(~2500μmol·g^(-1)·h^(-1),30%).This work provides a new strategy for constructing efficient and stable photocatalysts that can be used for efficient visible light-driven organic transformations.
