Two-electron oxygen reduction reaction(2e^(-)ORR)to produce hydrogen peroxide(H_(2)O_(2))presents an efficient,secure,and sustainable method.However,the competing four-electron pathway produces H2O,yielding low H2O2 s...Two-electron oxygen reduction reaction(2e^(-)ORR)to produce hydrogen peroxide(H_(2)O_(2))presents an efficient,secure,and sustainable method.However,the competing four-electron pathway produces H2O,yielding low H2O2 selectivity(~70%).In this work,a high-dimensional rod-like structure of niobium oxide(Nb_(2)O_(5)-HD)containing NbO6 octahedra was synthesized using a hydrothermal method combined with a calcination strategy.Under 50 mA·cm^(-2),the Faradaic efficiency(FE)of H2O2 reached 94%,with the H_(2)O_(2) yield reaching as high as 874 mmol·gcat^(-1)·h^(-1).After 34 h of operation,FE was still 76%,and the stability is great.In situ Raman spectroscopy analysis and experiments revealed that the NbO6 octahedra on Nb_(2)O_(5)-HD were the key factor for its excellent ORR activity and H_(2)O_(2) FE.This inspires the development of high-performance ORR transition metal electrocatalysts.展开更多
The photoexcitation of heterostructures consisting of metallic nanoclusters and a semiconductor has been extensively investigated in relation to interests in photocatalysis and optical devices.The optoelectronic funct...The photoexcitation of heterostructures consisting of metallic nanoclusters and a semiconductor has been extensively investigated in relation to interests in photocatalysis and optical devices.The optoelectronic functions of the heterostructures originate from localized surface plasmon resonance,which can induce electron and resonance energy transfers.While it is well known that photoinduced electronic interaction between a metallic nanocluster and a semiconductor is responsible for the resonance energy transfer,the electron transfer associated with the photoinduced electronic interaction has not been discussed.In this paper,we elucidate the photoexcitation dynamics of a silver nanocluster/TiO_(2) heterostructure using an original first-principles computational approach that explicitly deals with light–matter interactions.It is shown that the photoinduced silver–TiO_(2) electronic interaction causes excited electrons to be directly transferred from the silver nanocluster to the TiO2 layer without passing through the conduction band of the silver nanocluster.展开更多
基金support received from the National Key Research and Development Program of China(No.2022YFC3703503)the Science and Technology Commission of Shanghai Municipality(No.24ZR1416000)Shanghai Municipal Bureau of Ecology and Environment(No.2025,HUHUANKE No.35).
文摘Two-electron oxygen reduction reaction(2e^(-)ORR)to produce hydrogen peroxide(H_(2)O_(2))presents an efficient,secure,and sustainable method.However,the competing four-electron pathway produces H2O,yielding low H2O2 selectivity(~70%).In this work,a high-dimensional rod-like structure of niobium oxide(Nb_(2)O_(5)-HD)containing NbO6 octahedra was synthesized using a hydrothermal method combined with a calcination strategy.Under 50 mA·cm^(-2),the Faradaic efficiency(FE)of H2O2 reached 94%,with the H_(2)O_(2) yield reaching as high as 874 mmol·gcat^(-1)·h^(-1).After 34 h of operation,FE was still 76%,and the stability is great.In situ Raman spectroscopy analysis and experiments revealed that the NbO6 octahedra on Nb_(2)O_(5)-HD were the key factor for its excellent ORR activity and H_(2)O_(2) FE.This inspires the development of high-performance ORR transition metal electrocatalysts.
基金This research was supported by JSPS KAKENHI(Grant no.19K15513)MEXT as a social and scientific priority issue(Creation of new functional devices and high-performance materials to support next-generation industries)to be tackled using the post-K computer(ID:hp180196,hp190193)This work mainly used computational resources of the K computer provided by the RIKEN Advanced Institute for Computational Science through the HPCI System Research project(ID:hp180196,hp190193).
文摘The photoexcitation of heterostructures consisting of metallic nanoclusters and a semiconductor has been extensively investigated in relation to interests in photocatalysis and optical devices.The optoelectronic functions of the heterostructures originate from localized surface plasmon resonance,which can induce electron and resonance energy transfers.While it is well known that photoinduced electronic interaction between a metallic nanocluster and a semiconductor is responsible for the resonance energy transfer,the electron transfer associated with the photoinduced electronic interaction has not been discussed.In this paper,we elucidate the photoexcitation dynamics of a silver nanocluster/TiO_(2) heterostructure using an original first-principles computational approach that explicitly deals with light–matter interactions.It is shown that the photoinduced silver–TiO_(2) electronic interaction causes excited electrons to be directly transferred from the silver nanocluster to the TiO2 layer without passing through the conduction band of the silver nanocluster.
