Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to en...Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to enhance H_(2)O_(2) production by oxidizing H_(2)O in a portable photoelectrocatalysis(PEC)device.The obtained solution from this system is demonstrated for effective bactericidal activity against Staphylococcus aureus and Escherichia coli,while maintaining low toxicity toward hippocampal neuronal cells.The photoanode is achieved by Mo-doped BiVO4 films,which are subsequently loaded with cobalt-porphyrin(Co-py)molecules as a co-catalyst.As a result,the optimal performance for H_(2)O_(2) production rate was achieved at 8.4μmol h^(−1) cm^(−2),which is 1.8 times that of the pristine BiVO4 photoanode.Density functional theory(DFT)simulations reveal that the improved performance results from a 1.1 eV reduction in the energy of the rate-determining step of·OH adsorption by the optimal photoanode.This study demonstrates a PEC approach for promoting H_(2)O_(2) production by converting H_(2)O for antibacterial purposes,offering potential applications in conventionally controlling microenvironments for healthcare applications.展开更多
Hydrogen peroxide(H_(2)O_(2)) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection,metal etching,textile printing and dyeing,chemical synthesi...Hydrogen peroxide(H_(2)O_(2)) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection,metal etching,textile printing and dyeing,chemical synthesis and food processing.However,over 90 % of industrial H_(2)O_(2) is currently produced through the multi-step anthraquinone oxidation process,which suffers from a process with some drawbacks such as complex,high-energy consumption,and toxic byproducts emissions.Compared to the traditional anthraquinone method,artificial photosynthesis of H_(2)O_(2) using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O_(2) as the clean reactants and sole energy as the driving force.In recent years,metal-free photocatalysts mainly including covalent organic frameworks(COFs),covalent triazine frameworks(CTFs) and carbon nitrile(g-C_(3)N_(4)) have garnered significant interest due to their superior thermal and chemical stability,diverse synthesis methods,tunable functionality,light weight nature and non-toxicity.These materials also exhibit adjustable band structure and unique photoelectric properties.Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H_(2)O_(2),however,a comprehensive summary of current research status on metalfree-based photocatalytic overall H_(2)O_(2) production remain scarce.This review outlines recent process in overall H_(2)O_(2) photosynthesis based on metal-free photocatalysts.First,we introduced the fundamental concepts of photocatalytic overall H_(2)O_(2) production.Then,we analyze representative studies on photocatalytic overall H_(2)O_(2) synthesis using metal-free materials.Finally,we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H_(2)O_(2) generation.展开更多
Photosynthesis of hydrogen peroxide(H_(2)O_(2))via oxygen reduction reaction(ORR)and water oxidation reaction(WOR)pathways requires controlled formation of radical intermediates.However,achieving precise control over ...Photosynthesis of hydrogen peroxide(H_(2)O_(2))via oxygen reduction reaction(ORR)and water oxidation reaction(WOR)pathways requires controlled formation of radical intermediates.However,achieving precise control over radical formation in metal-free catalysts remains challenging.Herein,we report a fluorinated COF(Kf-F-COF)featuring framework-bound carbonyl groups as intrinsic radical-generating sites for efficient dual-channel H_(2)O_(2)photosynthesis.This design enables the simultaneous activation of O_(2)and H_(2)O through radical-mediated hydrogen atom transfer processes.Mechanistic studies reveal that fluorination enhances the electron affinity of the carbonyl sites,facilitates diradical formation,and lowers the energy barriers of key reaction steps.As a result,Kf-F-COF achieves a high H_(2)O_(2)production rate of 6.42 mmol g^(-1)h^(-1)and long-term stability under natural sunlight and seawater conditions.This work presents a frameworkcentered radical strategy for dual-pathway H_(2)O_(2)photosynthesis and offers mechanistic insights into regulating COF-based photocatalysts.展开更多
基金support from the National Key Technologies R&D Program of China(2022YFE0114800)National Natural Science Foundation of China(22075047),and the 111 Project(D16008)。
文摘Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to enhance H_(2)O_(2) production by oxidizing H_(2)O in a portable photoelectrocatalysis(PEC)device.The obtained solution from this system is demonstrated for effective bactericidal activity against Staphylococcus aureus and Escherichia coli,while maintaining low toxicity toward hippocampal neuronal cells.The photoanode is achieved by Mo-doped BiVO4 films,which are subsequently loaded with cobalt-porphyrin(Co-py)molecules as a co-catalyst.As a result,the optimal performance for H_(2)O_(2) production rate was achieved at 8.4μmol h^(−1) cm^(−2),which is 1.8 times that of the pristine BiVO4 photoanode.Density functional theory(DFT)simulations reveal that the improved performance results from a 1.1 eV reduction in the energy of the rate-determining step of·OH adsorption by the optimal photoanode.This study demonstrates a PEC approach for promoting H_(2)O_(2) production by converting H_(2)O for antibacterial purposes,offering potential applications in conventionally controlling microenvironments for healthcare applications.
基金supported by the National Natural Science Foundation of China (No.22409038,52473221)Zhejiang Province Postdoctoral Science Foundation (No.ZJ2024021)+2 种基金Hubei Provincial Natural Science Foundation of China (Nos.2024DJC032,2025AFB889)Key Project of Science and Technology Research of Hubei Provincial Department of Education (Nos.D20232701,D20232702)the research grant funded by the Research,Development,and Innovation Authority (RDIA)-Kingdom of Saudi Arabia (No.12615-iu-2023-IU-R-2-1-EI-)。
文摘Hydrogen peroxide(H_(2)O_(2)) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection,metal etching,textile printing and dyeing,chemical synthesis and food processing.However,over 90 % of industrial H_(2)O_(2) is currently produced through the multi-step anthraquinone oxidation process,which suffers from a process with some drawbacks such as complex,high-energy consumption,and toxic byproducts emissions.Compared to the traditional anthraquinone method,artificial photosynthesis of H_(2)O_(2) using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O_(2) as the clean reactants and sole energy as the driving force.In recent years,metal-free photocatalysts mainly including covalent organic frameworks(COFs),covalent triazine frameworks(CTFs) and carbon nitrile(g-C_(3)N_(4)) have garnered significant interest due to their superior thermal and chemical stability,diverse synthesis methods,tunable functionality,light weight nature and non-toxicity.These materials also exhibit adjustable band structure and unique photoelectric properties.Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H_(2)O_(2),however,a comprehensive summary of current research status on metalfree-based photocatalytic overall H_(2)O_(2) production remain scarce.This review outlines recent process in overall H_(2)O_(2) photosynthesis based on metal-free photocatalysts.First,we introduced the fundamental concepts of photocatalytic overall H_(2)O_(2) production.Then,we analyze representative studies on photocatalytic overall H_(2)O_(2) synthesis using metal-free materials.Finally,we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H_(2)O_(2) generation.
基金supported by the National Key R&D Program of China(2022YFA1502902)the National Natural Science Foundation of China(22201209,22271218,22071182,21931007,22301235)+1 种基金the Shaanxi Province Young Talent Support Plan(2023SYJ28)the Start-Up Funding of Tianjin University and Xi’an Jiaotong University。
文摘Photosynthesis of hydrogen peroxide(H_(2)O_(2))via oxygen reduction reaction(ORR)and water oxidation reaction(WOR)pathways requires controlled formation of radical intermediates.However,achieving precise control over radical formation in metal-free catalysts remains challenging.Herein,we report a fluorinated COF(Kf-F-COF)featuring framework-bound carbonyl groups as intrinsic radical-generating sites for efficient dual-channel H_(2)O_(2)photosynthesis.This design enables the simultaneous activation of O_(2)and H_(2)O through radical-mediated hydrogen atom transfer processes.Mechanistic studies reveal that fluorination enhances the electron affinity of the carbonyl sites,facilitates diradical formation,and lowers the energy barriers of key reaction steps.As a result,Kf-F-COF achieves a high H_(2)O_(2)production rate of 6.42 mmol g^(-1)h^(-1)and long-term stability under natural sunlight and seawater conditions.This work presents a frameworkcentered radical strategy for dual-pathway H_(2)O_(2)photosynthesis and offers mechanistic insights into regulating COF-based photocatalysts.
