The electrocatalytic selective oxidation of alcohol for direct heterocyclic ring compound production under ambient conditions is highly desirable but greatly challenging,due to the fast oxidation kinetics of aldehyde ...The electrocatalytic selective oxidation of alcohol for direct heterocyclic ring compound production under ambient conditions is highly desirable but greatly challenging,due to the fast oxidation kinetics of aldehyde intermediate species during electrocatalysis.Here,for the first time,an electro-acidic catalytic cascade reaction strategy has been developed for the efficient and selective conversion from ethylene glycol to 1,4-Dioxane-2,5-diol under ambient conditions on synthesized CeO_(2)-e-Pd/CP electrocatalyst,which features a significantly high faraday efficiency of 83.6%.The CeO_(2)in the electrocatalyst induces the downshift of the d-band center of Pd,which favors the fast desorption of glycolaldehyde from the electrocatalyst with ease into the acidic electrolyte,facilitating its subsequent condensation into 1,4-Dioxane-2,5-diol through C-O coupling while preventing the overoxidation of the glycolaldehyde intermediate into carboxylic acids.This work provides a novel strategy and insight into the reaction design for the synthesis of heterocyclic ring productions from simple molecules.展开更多
The energy barrier for the rate-determining step(RDS)is exceptionally critical for the catalytic oxygen evolution reaction(OER)efficiency of an electrocatalyst;however,facilely decreasing the energy barrier of RDS and...The energy barrier for the rate-determining step(RDS)is exceptionally critical for the catalytic oxygen evolution reaction(OER)efficiency of an electrocatalyst;however,facilely decreasing the energy barrier of RDS and realizing the precise manipulation of the reaction process remains challenging.Herein,through constructing a nanosheet assembled sunflower-like Co(OH)_(2) with Ir,Fe codoping,the electronic structure and binding strengths with oxygen-involved intermediates of Co active sites are considerably moderated.First-principles calculations and comprehensive characterizations suggest that Fe and Ir codoping significantly lowers the electrochemical reaction barrier and promotes the OER reaction kinetics by precisely accelerating the formation process of*O.Moreover,the nanosheet-assembled open architectures enable the catalyst with plentiful catalytically active sites and facilitate mass transport and electron transfer.As a result,the optimal electrocatalyst can exhibit outstanding oxygen-evolving activity with an ultralow overpotential of 254 mV at 10 mA cm^(-2).This study realizes the precise manipulation of the reaction energy barrier of OER via Ir,Fe dual doping,which will be a generic paradigm for designing advanced yet cost-effective electrocatalysts.展开更多
Thiospinels,members of the spinel family,have been demonstrated to be promising for boosting the electrocatalytic oxygen evolution reaction(OER),but their practical application is severely impeded by limited catalytic...Thiospinels,members of the spinel family,have been demonstrated to be promising for boosting the electrocatalytic oxygen evolution reaction(OER),but their practical application is severely impeded by limited catalytically active sites and low intrinsic activity.Geometric configuration and electronic structure engineering have been demonstrated to play a paramount role in improving the electrocatalytic OER.展开更多
基金supported by the National Key R&D Program of China(grant no.2022YFB4002700)the Shanghai Science and Technology Committee Rising-Star Program(grant no.22QA1403400)the Natural Science Foundation of Shanghai(grant no.21ZR1418700).
文摘The electrocatalytic selective oxidation of alcohol for direct heterocyclic ring compound production under ambient conditions is highly desirable but greatly challenging,due to the fast oxidation kinetics of aldehyde intermediate species during electrocatalysis.Here,for the first time,an electro-acidic catalytic cascade reaction strategy has been developed for the efficient and selective conversion from ethylene glycol to 1,4-Dioxane-2,5-diol under ambient conditions on synthesized CeO_(2)-e-Pd/CP electrocatalyst,which features a significantly high faraday efficiency of 83.6%.The CeO_(2)in the electrocatalyst induces the downshift of the d-band center of Pd,which favors the fast desorption of glycolaldehyde from the electrocatalyst with ease into the acidic electrolyte,facilitating its subsequent condensation into 1,4-Dioxane-2,5-diol through C-O coupling while preventing the overoxidation of the glycolaldehyde intermediate into carboxylic acids.This work provides a novel strategy and insight into the reaction design for the synthesis of heterocyclic ring productions from simple molecules.
基金supported by the start-up funding to H.Xu from Changzhou University(ZMF22020055)grants from Advanced Catalysis and Green Manufacturing Collaborative Innovation Center(ACGM2022-10-01),Changzhou University.
文摘The energy barrier for the rate-determining step(RDS)is exceptionally critical for the catalytic oxygen evolution reaction(OER)efficiency of an electrocatalyst;however,facilely decreasing the energy barrier of RDS and realizing the precise manipulation of the reaction process remains challenging.Herein,through constructing a nanosheet assembled sunflower-like Co(OH)_(2) with Ir,Fe codoping,the electronic structure and binding strengths with oxygen-involved intermediates of Co active sites are considerably moderated.First-principles calculations and comprehensive characterizations suggest that Fe and Ir codoping significantly lowers the electrochemical reaction barrier and promotes the OER reaction kinetics by precisely accelerating the formation process of*O.Moreover,the nanosheet-assembled open architectures enable the catalyst with plentiful catalytically active sites and facilitate mass transport and electron transfer.As a result,the optimal electrocatalyst can exhibit outstanding oxygen-evolving activity with an ultralow overpotential of 254 mV at 10 mA cm^(-2).This study realizes the precise manipulation of the reaction energy barrier of OER via Ir,Fe dual doping,which will be a generic paradigm for designing advanced yet cost-effective electrocatalysts.
基金financially supported by the National Natural Science Foundation of China(No.22078028,21978026)Changzhou Key Laboratory of Graphene-Based Materials for Environment and Safety(CM20153006,CE20185043)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX21_2854)and PAPD of Jiangsu Higher Education Institution.
文摘Thiospinels,members of the spinel family,have been demonstrated to be promising for boosting the electrocatalytic oxygen evolution reaction(OER),but their practical application is severely impeded by limited catalytically active sites and low intrinsic activity.Geometric configuration and electronic structure engineering have been demonstrated to play a paramount role in improving the electrocatalytic OER.
