The facile designs and fabrication of noble metal-free electrocatalysts are highly required to achieve multifunctional catalytic activity with excellent stability in Zn-air batteries,fuel cells and water splitting sys...The facile designs and fabrication of noble metal-free electrocatalysts are highly required to achieve multifunctional catalytic activity with excellent stability in Zn-air batteries,fuel cells and water splitting systems.Herein,a heterostructure engineering is applied to construct the high performance Co,Ncontaining carbon-based multifunctional electrocatalysts with the feature of isotype(i.e.n-n type Co_(2)N_(0.67)-BHPC)and anisotype(i.e.p-n type Co_(2)O_(3)-BHPC)heterojunctions for ORR,OER and HER.The nn type Co_(2)N_(0.67)-BHPC,in which biomass(e.g.mushroom)-derived hierarchical porous carbon(BHPC)incorporated with nonstoichiometric active species Co_(2)N_(0.67),is fabricated by using an in situ protective strategy of macrocyclic central Co-N_(4) from CoTPP(5,10,15,20-tetrakis(phenyl)porphyrinato cobalt)precursor through the intermolecularπ-πinteractions between CoTPP and its metal-free analogue H_(2) TPP.Meanwhile,an unprotected strategy of macrocyclic central Co-N_(4) from CoTPP can afford the anisotype Co_(2)O_(3)-BHPC p-n heterojunction.The as-prepared n-n type Co_(2)N_(0.67)-BHPC heterojunction exhibited a higher density of Co-based active sites with outstanding stability and more efficient charge transfer at the isotype heterojunction interface in comparison with p-n type Co_(2)O_(3)-BHPC heterojunction.Consequently,for ORR,Co_(2)N_(0.67)-BHPC exhibits the more positive onset and half-wave potentials of 0.93 and 0.86 V vs.RHE,respectively,superior to those of the commercial 20 wt%Pt/C and most of Cobased catalysts reported so far.To drive a current density of 10 mA cm^(-2),Co_(2)N_(0.67)-BHPC also shows the lower overpotentials of 0.34 and 0.21 V vs.RHE for OER and HER,respectively.Furthermore,the Zn-air battery equipped with Co_(2)N_(0.67)-BHPC displays higher maximum power density(109 mW cm^(-2))and charge-discharge cycle stability.Interestingly,the anisotype heterojunction Co_(2)O_(3)-BHPC as trifunctional electrocatalyst reveals evidently photoelectrochemical enhancement compared with the photostable Co_(2)N_(0.67)-BHPC.That is to say,isotype heterojunction material(n-n type Co^(2)N_(0.67)-BHPC)is equipped with better electrocatalytic performance than anisotype one(p-n type Co_(2)O_(3)-BHPC),but the opposite is true in photoelectrochemical catalysis.Meanwhile,the possible mechanism is proposed based on the energy band structures of the Co_(2)N_(0.67)-BHPC and Co_(2)O_(3)-BHPC and the cocatalyst effects.The present work provides much more possibilities to tune the electrocatalytic and photoelectrochemical properties of catalysts through a facile combination of heterostructure engineering protocol and macrocyclic central metal protective strategy.展开更多
Transforming carbon dioxide(CO_(2))into products using renewable electricity is a crucial and captivating quest for a green and circular economy.Compared with commonly used alkali electrolytes,acidic media for electro...Transforming carbon dioxide(CO_(2))into products using renewable electricity is a crucial and captivating quest for a green and circular economy.Compared with commonly used alkali electrolytes,acidic media for electrocatalytic CO_(2) reduction(CO_(2)RR)boasts several advantages,such as high carbon utilization efficiency,high overall energy utilization rate,and low carbonate formation,making it a compelling choice for industrial applications.However,the acidic CO_(2)RR also struggles with formidable hurdles,encompassing the fierce competition with the hydrogen evolution reaction,the low CO_(2) solubility and availability,and the suboptimal performance of catalysts.This review provides a comprehensive overview of the CO_(2)RR in acidic media.By elucidating the underlying regulatory mechanism,we gain valuable insights into the fundamental principles governing the acidic CO_(2)RR.Furthermore,we examine cutting-edge strategies aimed at optimizing its performance and the roles of reactor engineering,especially membrane electrode assembly reactors,in facilitating scalable and carbon efficient conversion.Moreover,we present a forward-looking perspective,highlighting the promising prospects of acidic CO_(2)RR research in ushering us towards a carbon-neutral society.展开更多
Recently, hydrogen-bonding has attracted extensive attention in the design of chromophores. Here, a new class of hydrogen-bond locked purine chromophores(HOPs) were reported by introducing a hydroxyphenyl group into t...Recently, hydrogen-bonding has attracted extensive attention in the design of chromophores. Here, a new class of hydrogen-bond locked purine chromophores(HOPs) were reported by introducing a hydroxyphenyl group into the C(6) position of purine. The intramolecular hydrogen bond plays a dominant role to light up these probes. As a bonus, HOPs show high photostability. Moreover, HOPs exhibit remarkable capability for the specific lipid droplets imaging in living cells with excellent biocompatibility and are also potential for diagnosing fatty liver diseases. These results bring important new insights into the photophysics of the purine-based chromophores and provide a new scaffold with high photostability for bioimaging.展开更多
A thermally-induced multi-component reaction of CF_(3)-substituted imidoyl sulfoxonium ylides(TFISYs),amines and(triphenylphosphonio)difluoroacetate(PDFA)has been developed,allowing a facile access to 2-trifluoromethy...A thermally-induced multi-component reaction of CF_(3)-substituted imidoyl sulfoxonium ylides(TFISYs),amines and(triphenylphosphonio)difluoroacetate(PDFA)has been developed,allowing a facile access to 2-trifluoromethyl-4-aminoquinolines in high yields.The reaction proceeds smoothly with or without the addition of sulfur and utilizes difluorocarbene as a C1 synthon under simply heating conditions.Mechanistic study reveals that in-situ generated thiocarbonyl fluoride,isothiocyanate or gem-difluoroalkene might act as the key reaction intermediates.展开更多
With recent advances in power electronic packaging technologies,liquid-cooled ceramic heat sinks have been considered as a promising solution for further improving the performance of power electronic devices.In this s...With recent advances in power electronic packaging technologies,liquid-cooled ceramic heat sinks have been considered as a promising solution for further improving the performance of power electronic devices.In this study,several aluminum oxide heat sinks were fabricated and tested using the digital light processing-based ad-ditive manufacturing method,to verify their practical performance.The results showed that the complex cooling structures inside the heat sinks can be completely formed and exhibited high surface quality.The experimental thermal and hydraulic performances of the heat sinks were consistent with the numerically modeled predictions.Furthermore,by exploiting the advantages of additive manufacturing,a direct manifold microchannel(MMC)configuration was designed to reduce the vertical flow of the traditional MMC configuration and achieve an im-proved cooling efficiency.At a constant volumetric flow rate of 1 L/min,the direct MMC configuration achieved a 19.8%reduction in pressure drop and an 11.8%reduction in thermal resistance,as well as a more uniform temperature distribution.展开更多
基金financially supported by the National Natural Science Foundation of China(21771192)Major Program of Shandong Province Natural Science Foundation(ZR2017ZB0315)+3 种基金Program for Taishan Scholar of Shandong Province(ts201712019)the Fundamental Research Funds for the Central Universities(19CX05001A,18CX02053A)Qingdao Applied Basic Research Project(19-6-2-20-cg)Yankuang Group 2019 Science and Technology Program。
文摘The facile designs and fabrication of noble metal-free electrocatalysts are highly required to achieve multifunctional catalytic activity with excellent stability in Zn-air batteries,fuel cells and water splitting systems.Herein,a heterostructure engineering is applied to construct the high performance Co,Ncontaining carbon-based multifunctional electrocatalysts with the feature of isotype(i.e.n-n type Co_(2)N_(0.67)-BHPC)and anisotype(i.e.p-n type Co_(2)O_(3)-BHPC)heterojunctions for ORR,OER and HER.The nn type Co_(2)N_(0.67)-BHPC,in which biomass(e.g.mushroom)-derived hierarchical porous carbon(BHPC)incorporated with nonstoichiometric active species Co_(2)N_(0.67),is fabricated by using an in situ protective strategy of macrocyclic central Co-N_(4) from CoTPP(5,10,15,20-tetrakis(phenyl)porphyrinato cobalt)precursor through the intermolecularπ-πinteractions between CoTPP and its metal-free analogue H_(2) TPP.Meanwhile,an unprotected strategy of macrocyclic central Co-N_(4) from CoTPP can afford the anisotype Co_(2)O_(3)-BHPC p-n heterojunction.The as-prepared n-n type Co_(2)N_(0.67)-BHPC heterojunction exhibited a higher density of Co-based active sites with outstanding stability and more efficient charge transfer at the isotype heterojunction interface in comparison with p-n type Co_(2)O_(3)-BHPC heterojunction.Consequently,for ORR,Co_(2)N_(0.67)-BHPC exhibits the more positive onset and half-wave potentials of 0.93 and 0.86 V vs.RHE,respectively,superior to those of the commercial 20 wt%Pt/C and most of Cobased catalysts reported so far.To drive a current density of 10 mA cm^(-2),Co_(2)N_(0.67)-BHPC also shows the lower overpotentials of 0.34 and 0.21 V vs.RHE for OER and HER,respectively.Furthermore,the Zn-air battery equipped with Co_(2)N_(0.67)-BHPC displays higher maximum power density(109 mW cm^(-2))and charge-discharge cycle stability.Interestingly,the anisotype heterojunction Co_(2)O_(3)-BHPC as trifunctional electrocatalyst reveals evidently photoelectrochemical enhancement compared with the photostable Co_(2)N_(0.67)-BHPC.That is to say,isotype heterojunction material(n-n type Co^(2)N_(0.67)-BHPC)is equipped with better electrocatalytic performance than anisotype one(p-n type Co_(2)O_(3)-BHPC),but the opposite is true in photoelectrochemical catalysis.Meanwhile,the possible mechanism is proposed based on the energy band structures of the Co_(2)N_(0.67)-BHPC and Co_(2)O_(3)-BHPC and the cocatalyst effects.The present work provides much more possibilities to tune the electrocatalytic and photoelectrochemical properties of catalysts through a facile combination of heterostructure engineering protocol and macrocyclic central metal protective strategy.
基金the National Key Research and Development Program of China (2022YFB4102000)NSFC (22102018 and 52171201),the NSFC (22278067 and 22322201)+6 种基金the Natural Science Foundation of Sichuan Province (2022NSFSC0194)the“Pioneer”and“Leading Goose”R&D Program of Zhejiang (2023C03017)the Huzhou Science and Technology Bureau (2022GZ45)the Hefei National Research Center for Physical Sciences at the Microscale (KF2021005)the University of Electronic Science and Technology of China for startup funding (A1098531023601264)the Natural Science Foundation of Sichuan Province (2023NSFSC0094)the University of Electronic Science and Technology of China for startup funding (A1098531023601356)。
文摘Transforming carbon dioxide(CO_(2))into products using renewable electricity is a crucial and captivating quest for a green and circular economy.Compared with commonly used alkali electrolytes,acidic media for electrocatalytic CO_(2) reduction(CO_(2)RR)boasts several advantages,such as high carbon utilization efficiency,high overall energy utilization rate,and low carbonate formation,making it a compelling choice for industrial applications.However,the acidic CO_(2)RR also struggles with formidable hurdles,encompassing the fierce competition with the hydrogen evolution reaction,the low CO_(2) solubility and availability,and the suboptimal performance of catalysts.This review provides a comprehensive overview of the CO_(2)RR in acidic media.By elucidating the underlying regulatory mechanism,we gain valuable insights into the fundamental principles governing the acidic CO_(2)RR.Furthermore,we examine cutting-edge strategies aimed at optimizing its performance and the roles of reactor engineering,especially membrane electrode assembly reactors,in facilitating scalable and carbon efficient conversion.Moreover,we present a forward-looking perspective,highlighting the promising prospects of acidic CO_(2)RR research in ushering us towards a carbon-neutral society.
基金financially supported by the National Natural Science Foundation of China (Nos. 22077088, 21877082,U21A20308)the Foundation from the Science and Technology Department of Sichuan Province (Nos. 2020JDJQ0017,2021YFH0132, 2020ZHCG0097)。
文摘Recently, hydrogen-bonding has attracted extensive attention in the design of chromophores. Here, a new class of hydrogen-bond locked purine chromophores(HOPs) were reported by introducing a hydroxyphenyl group into the C(6) position of purine. The intramolecular hydrogen bond plays a dominant role to light up these probes. As a bonus, HOPs show high photostability. Moreover, HOPs exhibit remarkable capability for the specific lipid droplets imaging in living cells with excellent biocompatibility and are also potential for diagnosing fatty liver diseases. These results bring important new insights into the photophysics of the purine-based chromophores and provide a new scaffold with high photostability for bioimaging.
基金financial support from K.C.Wong Education Foundation(GJTD-2020-08).
文摘A thermally-induced multi-component reaction of CF_(3)-substituted imidoyl sulfoxonium ylides(TFISYs),amines and(triphenylphosphonio)difluoroacetate(PDFA)has been developed,allowing a facile access to 2-trifluoromethyl-4-aminoquinolines in high yields.The reaction proceeds smoothly with or without the addition of sulfur and utilizes difluorocarbene as a C1 synthon under simply heating conditions.Mechanistic study reveals that in-situ generated thiocarbonyl fluoride,isothiocyanate or gem-difluoroalkene might act as the key reaction intermediates.
基金This study was supported by the National Natural Science Founda-tion of China(Grant.No.52175333)Basic Research Program of China(Grant.No.JCKY∗∗∗∗∗∗∗C102)+1 种基金Tribology Science Fund of the China State Key Laboratory of Tribology,Tsinghua University(Grant.No.SKLT2021B05)This study was also supported by the Ten Dimensions(Guangdong,China)Technology Co.,Ltd.,in the course of the lead-ing project“Additive Manufacturing of Ceramic Heat Sinks”(Grant.No.20232000308).
文摘With recent advances in power electronic packaging technologies,liquid-cooled ceramic heat sinks have been considered as a promising solution for further improving the performance of power electronic devices.In this study,several aluminum oxide heat sinks were fabricated and tested using the digital light processing-based ad-ditive manufacturing method,to verify their practical performance.The results showed that the complex cooling structures inside the heat sinks can be completely formed and exhibited high surface quality.The experimental thermal and hydraulic performances of the heat sinks were consistent with the numerically modeled predictions.Furthermore,by exploiting the advantages of additive manufacturing,a direct manifold microchannel(MMC)configuration was designed to reduce the vertical flow of the traditional MMC configuration and achieve an im-proved cooling efficiency.At a constant volumetric flow rate of 1 L/min,the direct MMC configuration achieved a 19.8%reduction in pressure drop and an 11.8%reduction in thermal resistance,as well as a more uniform temperature distribution.