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
The photo-Fenton reaction is a key source of the highly reactive hydroxyl radical（HOU） that is produced by the reaction of simultaneous photo-induced generation of Fe^（2＋）-dissolved organic matter（DOM） with H_2...The photo-Fenton reaction is a key source of the highly reactive hydroxyl radical（HOU） that is produced by the reaction of simultaneous photo-induced generation of Fe^（2＋）-dissolved organic matter（DOM） with H_2O_2 in sunlit surface waters as well as in the treatment of organic pollutants in the advanced oxidation processes（AOPs）.Concentrations of both H_2O_2 and Fe^（2＋）-DOM were dependent on time and total solar intensity flux,and their levels were highest in the diurnal samples collected at noon compared with the samples collected during the period before sunrise and after sunset.H_2O_2 and Fe^（2＋）-DOM concentrations during monthly readings were also found higher in comparison with the diurnal samples,shortly before sunrise or after sunset.A π-electron bonding system is formed between Fe and the functional groups in DOM（Fe-DOM）,through electron donation from the functional groups of DOM to an empty d-orbital of Fe.The π-electron is loosely bound and is highly susceptible to a rapid excitation upon light exposure that will provide better understanding of the formation of aqueous electrons,superoxide radical anions,H_2O_2 and finally,photo-Fenton reactions,too.Our results imply that simultaneous generation of H_2O_2 and Fe^（2＋）-DOM upon sunlight exposure during the daytime is most likely to be the key photo-Fenton reaction pathway,taking place in surface waters.展开更多
Two kinds of different mechanistic oscillations can be displayed in the H_2O_2-KSCN-CuSO_4-NaOH system. One discovered by this study is the pH oscillation in a continuous flow stirred tank reactor(CSTR) resulting from...Two kinds of different mechanistic oscillations can be displayed in the H_2O_2-KSCN-CuSO_4-NaOH system. One discovered by this study is the pH oscillation in a continuous flow stirred tank reactor(CSTR) resulting from the oxidation of KSCN. The other is the oscillation of H_2O_2 decomposition in both CSTR and batch reactors(reported by Orbáin in 1986). Under appropriate experimental conditions, the system exhibits a birhythmicity in a CSTR. Two different pH oscillations are reported here. The pH oscillations which accompany the decomposition of H_2O_2 exist in the batch reactor and the CSTR at a high flowrate, but the pH oscillations in a CSTR at a low flowrate originates from proton positive and negative feedback in the oxidation of KSCN. The oscillation of non-catalyzed oxidation of KSCN by hydrogen peroxide in a CSTR can be found. Also we have observed whether Cu^(2+) exists or not in the batch system, the pH increases to near neutral ultimately after pH drops twice.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the Japan Society for the Promotion of Science for the financial support through a Grant-in-Aid for Scientific Research (B) (No.18310010)partly supported by the Key Construction Program of the National "985" Project,Tianjin University,China
文摘The photo-Fenton reaction is a key source of the highly reactive hydroxyl radical（HOU） that is produced by the reaction of simultaneous photo-induced generation of Fe^（2＋）-dissolved organic matter（DOM） with H_2O_2 in sunlit surface waters as well as in the treatment of organic pollutants in the advanced oxidation processes（AOPs）.Concentrations of both H_2O_2 and Fe^（2＋）-DOM were dependent on time and total solar intensity flux,and their levels were highest in the diurnal samples collected at noon compared with the samples collected during the period before sunrise and after sunset.H_2O_2 and Fe^（2＋）-DOM concentrations during monthly readings were also found higher in comparison with the diurnal samples,shortly before sunrise or after sunset.A π-electron bonding system is formed between Fe and the functional groups in DOM（Fe-DOM）,through electron donation from the functional groups of DOM to an empty d-orbital of Fe.The π-electron is loosely bound and is highly susceptible to a rapid excitation upon light exposure that will provide better understanding of the formation of aqueous electrons,superoxide radical anions,H_2O_2 and finally,photo-Fenton reactions,too.Our results imply that simultaneous generation of H_2O_2 and Fe^（2＋）-DOM upon sunlight exposure during the daytime is most likely to be the key photo-Fenton reaction pathway,taking place in surface waters.
基金Supported by NSFC(29573109) and Research fund of CUMT.
文摘Two kinds of different mechanistic oscillations can be displayed in the H_2O_2-KSCN-CuSO_4-NaOH system. One discovered by this study is the pH oscillation in a continuous flow stirred tank reactor(CSTR) resulting from the oxidation of KSCN. The other is the oscillation of H_2O_2 decomposition in both CSTR and batch reactors(reported by Orbáin in 1986). Under appropriate experimental conditions, the system exhibits a birhythmicity in a CSTR. Two different pH oscillations are reported here. The pH oscillations which accompany the decomposition of H_2O_2 exist in the batch reactor and the CSTR at a high flowrate, but the pH oscillations in a CSTR at a low flowrate originates from proton positive and negative feedback in the oxidation of KSCN. The oscillation of non-catalyzed oxidation of KSCN by hydrogen peroxide in a CSTR can be found. Also we have observed whether Cu^(2+) exists or not in the batch system, the pH increases to near neutral ultimately after pH drops twice.
