The lithium-sulfur battery has attracted enormous attention as being one of the most significant energy storage technologies due to its high energy density and cost-effectiveness.However,the "shuttle effect"...The lithium-sulfur battery has attracted enormous attention as being one of the most significant energy storage technologies due to its high energy density and cost-effectiveness.However,the "shuttle effect" of polysulfide intermediates represents a formidable challenge towards its wide applications.Herein,we have designed and synthesized two-dimensional Cu,Zn and Sn-based multimetallic sulfide nanosheets to construct multi-active sites for the immobilization and entrapment of polysulfides with offering better performance in liquid Li2S6-based lithium-polysulfide batteries.Both experimental measurements and theoretical computations demonstrate that the interfacial multi-active sites of multimetallic sulfides not only accelerate the multi-chained redox reactions of highly diffusible polysulfides,but also strengthen affinities toward polysulfides.By adopting multimetallic sulfide nanosheets as the sulfur host,the liquid Li2 S6-based cell exhibits an impressive rate capability with 1200 mAh/g and retains 580 mAh/g at 0.5 mA/cm^(2) after 1000 cycles.With high sulfur mass loading conditions,the cell with 2.0 mg/cm^(2) sulfur loading delivers a cell capacity of 1068 mAh/g and maintains 480 mAh/g with 0.8 mA/cm^(2) and 500 cycles.This study provides new insights into the multifunctional material design with multi-active sites for elevated lithium-polysulfide batteries.展开更多
Rational construction of active components has been the biggest challenge in preparing efficient bifunctional oxygen electrocatalysts.Herein,electrospinning and chemical vapor deposition(CVD)were employed to embed act...Rational construction of active components has been the biggest challenge in preparing efficient bifunctional oxygen electrocatalysts.Herein,electrospinning and chemical vapor deposition(CVD)were employed to embed active species including FeCo nanoparticles,MNx(M=Fe,Co),and FePx in porous and graphitized carbon nanotubes(CNTs)/carbon nanofiber(CNF).The as-prepared FeCo@CoNx@FePx/C exhibited a half-wave potential as high as 0.86 V in oxygen reduction reaction(ORR)and low oxygen evolution reaction(OER)overpotential of 368 mV at 10 mA·cm^(−2),which are superior to Pt/C(0.83 V)and IrO_(2)(375 mV)respectively.The assembled Zn-air battery(ZAB)showed a high energy efficiency(Edischarge/Echarge)of 65%at 20 mA·cm^(−2)and stabilized for 700 charge-discharge cycles.The spectroscopic and microscopic characterizations evidenced that the outstanding bifunctionality of the electrocatalyst can be ascribed to three main reasons:First,FeCo nanoparticles are rich in MOH/MOOH active sites for OER,and FePx/CNTs constructed with CVD also modulate electronic structure to improve electron transfer;second,both MNx in carbon matrix and FePx/CNTs are highly active towards ORR;third,the CNTs/CNF are highly porous and graphitized,which promotes mass transport and improves electrical conductivity and stability of the electrocatalysts.This work gives important implications on the design of bifunctional electrocatalysts.展开更多
The electrochemical nitrate reduction reaction(NO_(3)^(-)RR)represents a promising and environmentally friendly approach for both the removal of nitrate(NO_(3)^(-))pollutants and the production of high-value ammonia(N...The electrochemical nitrate reduction reaction(NO_(3)^(-)RR)represents a promising and environmentally friendly approach for both the removal of nitrate(NO_(3)^(-))pollutants and the production of high-value ammonia(NH_(3)).However,this process faces significant challenges in achieving industrial application due to mismatched reaction kinetics involved in the conversion of NO_(3)^(-)to NO_(2)^(-),the formation of active hydrogen(H^(*))via water dissociation,and the stepwise hydrogenation processes.In this study,we developed a trimetallic CuCoRu catalyst with multiple active sites to enhance the selective NH_(3)synthesis at industrial-scale current density,where Cu primarily catalyzes the reduction of NO_(3)^(-)to NO_(2)^(-),Co facilitates the deep hydrogenation of NO_(2)^(-)to NH_(3),and Ru promotes water dissociation to generate H^(*),effectively bridging the aforementioned processes.The optimized CuCoRu catalyst achieves near-100%NH_(3)Faradaic efficiency with an NH_(3)yield rate of 14.6 mmol h^(-1)cm^(-2)at a current density of 2.5 A cm^(-2).The practical application in simulated wastewater with different NO_(3)^(-)concentrations and in the membrane electrode assembly demonstrates great potential for industrial application.展开更多
The development of smart coatings with potential for active anticorrosion and self-healing protection of metals is essential for long-term performance of metallic structures in aggressive chemical environments.Present...The development of smart coatings with potential for active anticorrosion and self-healing protection of metals is essential for long-term performance of metallic structures in aggressive chemical environments.Presently,emphasis has been placed on the development of advanced smart coatings for corrosion protection in different applications.Innovative multifunctional coatings with fascinating stimuliresponsive functionalities are considered“smart”.The stimuli-responsive functionalities of these smart coatings when properly harnessed result in a class of coatings with inherent autonomous control of corrosion.Fundamentally,when metals are exposed to aggressive environments,occurrences at the metalsolution interface cause environmental changes.These changes can be controlled when triggers from external environment set off active components of smart coating,thereby enhancing coating’s life and functionality.Common triggers include the availability of moisture,concentration of chloride ion,p H gradient,mechanical damage,impact,fatigue,light,redox activity and temperature.In this review,recent technological trends in active anticorrosion and self-healing coatings as functional routes for metal protection are summarized,stimuli responsiveness and mechanisms of inhibition are discussed,and recent multi-action protective systems are particularly focused on.展开更多
The development of robust and efficient trifunctional catalysts showing excellent oxygen evolution reaction(OER), oxygen reduction reaction(ORR) and hydrogen evolution reaction(HER) kinetics has been challenging.Herei...The development of robust and efficient trifunctional catalysts showing excellent oxygen evolution reaction(OER), oxygen reduction reaction(ORR) and hydrogen evolution reaction(HER) kinetics has been challenging.Herein, we prepared a hybrid iron and cobalt-based metal alloy phosphide on a phosphorus and nitrogen co-doped carbon substrate(Fe Co-P/PNC) as a catalyst using a one-step Pregulation method. The catalyst exhibited a positive half-wave potential of 0.86 V versus the reversible hydrogen electrode(RHE) for ORR, and low overpotentials of 350 and 158 m V for OER and HER, respectively, to achieve a current density of10 m A cm^(-2). Density functional theory calculations demonstrated the dominant role of P in both Fe Co phosphide and carbon matrix, which led to the good ORR, OER and HER kinetics. The assembled aqueous and flexible Zn-air batteries with Fe Co-P/PNC as the air cathode displayed excellent peak power densities of 195.1 and 90.8 m W cm^(-2), respectively, as well as outstanding charging-discharging performance, long lifetime, and high flexibility. Moreover, the self-powered overall water-splitting cell exhibited a low working voltage of1.71 V to achieve a current density of 10 m A cm^(-2), confirming its excellent multifunctional OER/ORR/HER activity.展开更多
Currently,single-atom combo catalysts(SACCs)for carbon dioxide reduction reaction(CO_(2)RR)to the formation of HCOOH are still very limited,especially the lanthanide-based SACCs.In this work,the novel SACCs with atomi...Currently,single-atom combo catalysts(SACCs)for carbon dioxide reduction reaction(CO_(2)RR)to the formation of HCOOH are still very limited,especially the lanthanide-based SACCs.In this work,the novel SACCs with atomically dispersed In and Ce active sites were successfully prepared on the nitrogen-doped carbon matrix(InCe/CN).Both aberration-corrected high-angle annular dark-field scanning transmission electron microscopy(AC-HAADF-STEM)images and the extended X-ray absorption fine structure(EXAFS)spectra proved the well-isolated In and Ce atoms.The as-prepared InCe/CN shows a high Faradaic efficiency(FE)(77%)and current density of HCOOH formation(j_(HCOOH))at-1.35 V vs.reversible hydrogen electrode(RHE),much higher than the single atom catalysts.Theoretical calculations have indicated that the introduced Ce single atom sites not only significantly promote electron transfer but also optimize the In-5p orbitals towards higher selectivity towards the HCOOH formation.This work innovatively extends the design of SACCs towards the main group and Ln metals for more applications.展开更多
基金supported by the Start-up Foundation of Nanjing Tech Universitythe National Natural Science Foundation of China (61904080, 61801210, 91833302)+3 种基金the Natural Science Foundation of Jiangsu Province (BK20190670, BK20180686)the Natural Science Foundation of Colleges and Universities in Jiangsu Province (19KJB530008)the Innovation Scientists and Technicians Team Construction Projects of Henan Province (CXTD2017002)the funding for “Distinguished professors” and “High-level talents in six industries” of Jiangsu Province and Technology Innovation Project for Overseas Scholar in Nanjing。
文摘The lithium-sulfur battery has attracted enormous attention as being one of the most significant energy storage technologies due to its high energy density and cost-effectiveness.However,the "shuttle effect" of polysulfide intermediates represents a formidable challenge towards its wide applications.Herein,we have designed and synthesized two-dimensional Cu,Zn and Sn-based multimetallic sulfide nanosheets to construct multi-active sites for the immobilization and entrapment of polysulfides with offering better performance in liquid Li2S6-based lithium-polysulfide batteries.Both experimental measurements and theoretical computations demonstrate that the interfacial multi-active sites of multimetallic sulfides not only accelerate the multi-chained redox reactions of highly diffusible polysulfides,but also strengthen affinities toward polysulfides.By adopting multimetallic sulfide nanosheets as the sulfur host,the liquid Li2 S6-based cell exhibits an impressive rate capability with 1200 mAh/g and retains 580 mAh/g at 0.5 mA/cm^(2) after 1000 cycles.With high sulfur mass loading conditions,the cell with 2.0 mg/cm^(2) sulfur loading delivers a cell capacity of 1068 mAh/g and maintains 480 mAh/g with 0.8 mA/cm^(2) and 500 cycles.This study provides new insights into the multifunctional material design with multi-active sites for elevated lithium-polysulfide batteries.
基金the grants from the National Natural Science Foundation of China(No.22004085)Regional Joint Fund of Guangdong Province(No.2019A1515111054).
文摘Rational construction of active components has been the biggest challenge in preparing efficient bifunctional oxygen electrocatalysts.Herein,electrospinning and chemical vapor deposition(CVD)were employed to embed active species including FeCo nanoparticles,MNx(M=Fe,Co),and FePx in porous and graphitized carbon nanotubes(CNTs)/carbon nanofiber(CNF).The as-prepared FeCo@CoNx@FePx/C exhibited a half-wave potential as high as 0.86 V in oxygen reduction reaction(ORR)and low oxygen evolution reaction(OER)overpotential of 368 mV at 10 mA·cm^(−2),which are superior to Pt/C(0.83 V)and IrO_(2)(375 mV)respectively.The assembled Zn-air battery(ZAB)showed a high energy efficiency(Edischarge/Echarge)of 65%at 20 mA·cm^(−2)and stabilized for 700 charge-discharge cycles.The spectroscopic and microscopic characterizations evidenced that the outstanding bifunctionality of the electrocatalyst can be ascribed to three main reasons:First,FeCo nanoparticles are rich in MOH/MOOH active sites for OER,and FePx/CNTs constructed with CVD also modulate electronic structure to improve electron transfer;second,both MNx in carbon matrix and FePx/CNTs are highly active towards ORR;third,the CNTs/CNF are highly porous and graphitized,which promotes mass transport and improves electrical conductivity and stability of the electrocatalysts.This work gives important implications on the design of bifunctional electrocatalysts.
基金support from the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(22278307,22008170,22222808,21978200)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘The electrochemical nitrate reduction reaction(NO_(3)^(-)RR)represents a promising and environmentally friendly approach for both the removal of nitrate(NO_(3)^(-))pollutants and the production of high-value ammonia(NH_(3)).However,this process faces significant challenges in achieving industrial application due to mismatched reaction kinetics involved in the conversion of NO_(3)^(-)to NO_(2)^(-),the formation of active hydrogen(H^(*))via water dissociation,and the stepwise hydrogenation processes.In this study,we developed a trimetallic CuCoRu catalyst with multiple active sites to enhance the selective NH_(3)synthesis at industrial-scale current density,where Cu primarily catalyzes the reduction of NO_(3)^(-)to NO_(2)^(-),Co facilitates the deep hydrogenation of NO_(2)^(-)to NH_(3),and Ru promotes water dissociation to generate H^(*),effectively bridging the aforementioned processes.The optimized CuCoRu catalyst achieves near-100%NH_(3)Faradaic efficiency with an NH_(3)yield rate of 14.6 mmol h^(-1)cm^(-2)at a current density of 2.5 A cm^(-2).The practical application in simulated wastewater with different NO_(3)^(-)concentrations and in the membrane electrode assembly demonstrates great potential for industrial application.
基金financial support from the National Natural Science Foundation of China(Nos.52171089 and 51571202)Ling Chuang Research Project of China National Nuclear Corporation。
文摘The development of smart coatings with potential for active anticorrosion and self-healing protection of metals is essential for long-term performance of metallic structures in aggressive chemical environments.Presently,emphasis has been placed on the development of advanced smart coatings for corrosion protection in different applications.Innovative multifunctional coatings with fascinating stimuliresponsive functionalities are considered“smart”.The stimuli-responsive functionalities of these smart coatings when properly harnessed result in a class of coatings with inherent autonomous control of corrosion.Fundamentally,when metals are exposed to aggressive environments,occurrences at the metalsolution interface cause environmental changes.These changes can be controlled when triggers from external environment set off active components of smart coating,thereby enhancing coating’s life and functionality.Common triggers include the availability of moisture,concentration of chloride ion,p H gradient,mechanical damage,impact,fatigue,light,redox activity and temperature.In this review,recent technological trends in active anticorrosion and self-healing coatings as functional routes for metal protection are summarized,stimuli responsiveness and mechanisms of inhibition are discussed,and recent multi-action protective systems are particularly focused on.
基金financially supported by the National Natural Science Foundation of China (22075211, 62005173 and 21601136)Tianjin Science Fund for Distinguished Young Scholars (19JCJQJC61800)+1 种基金the Research Fund of State Key Laboratory for Marine Corrosion and Protection of Luoyang Ship Material Research Institute (LSMRI) under the contract No. KF190411the Science and Technology Development Fund of Tianjin Education Commission for Higher Education (2018KJ126)。
文摘The development of robust and efficient trifunctional catalysts showing excellent oxygen evolution reaction(OER), oxygen reduction reaction(ORR) and hydrogen evolution reaction(HER) kinetics has been challenging.Herein, we prepared a hybrid iron and cobalt-based metal alloy phosphide on a phosphorus and nitrogen co-doped carbon substrate(Fe Co-P/PNC) as a catalyst using a one-step Pregulation method. The catalyst exhibited a positive half-wave potential of 0.86 V versus the reversible hydrogen electrode(RHE) for ORR, and low overpotentials of 350 and 158 m V for OER and HER, respectively, to achieve a current density of10 m A cm^(-2). Density functional theory calculations demonstrated the dominant role of P in both Fe Co phosphide and carbon matrix, which led to the good ORR, OER and HER kinetics. The assembled aqueous and flexible Zn-air batteries with Fe Co-P/PNC as the air cathode displayed excellent peak power densities of 195.1 and 90.8 m W cm^(-2), respectively, as well as outstanding charging-discharging performance, long lifetime, and high flexibility. Moreover, the self-powered overall water-splitting cell exhibited a low working voltage of1.71 V to achieve a current density of 10 m A cm^(-2), confirming its excellent multifunctional OER/ORR/HER activity.
基金We gratefully acknowledge the support from the National Key R&D Program of China(No.2021YFA1501101)the National Natural Science Foundation of China(No.21971117)+11 种基金the National Natural Science Foundation of China/Research Grant Council of Hong Kong Joint Research Scheme(No.N_PolyU502/21)Functional Research Funds for the Central Universities,Nankai University(No.63186005)Tianjin Key Lab for Rare Earth Materials and Applications(No.ZB19500202)111 Project(No.B18030)from Chinathe Outstanding Youth Project of Tianjin Natural Science Foundation(No.20JCJQJC00130)the funding for Projects of Strategic Importance of The Hong Kong Polytechnic University(Project Code:1-ZE2V)Shenzhen Fundamental Research Scheme-General Program(No.JCYJ20220531090807017)the Key Project of Tianjin Natural Science Foundation(No.20JCZDJC00650)the National Postdoctoral Program for Innovative Talents(No.BX20220157)Open Foundation of State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures(No.2022GXYSOF07)Departmental General Research Fund(Project Code:ZVUL)from Department of Applied Biology and Chemical Technology of Hong Kong Polytechnic UniversityHaihe Laboratory of Sustainable Chemical Transformations.
文摘Currently,single-atom combo catalysts(SACCs)for carbon dioxide reduction reaction(CO_(2)RR)to the formation of HCOOH are still very limited,especially the lanthanide-based SACCs.In this work,the novel SACCs with atomically dispersed In and Ce active sites were successfully prepared on the nitrogen-doped carbon matrix(InCe/CN).Both aberration-corrected high-angle annular dark-field scanning transmission electron microscopy(AC-HAADF-STEM)images and the extended X-ray absorption fine structure(EXAFS)spectra proved the well-isolated In and Ce atoms.The as-prepared InCe/CN shows a high Faradaic efficiency(FE)(77%)and current density of HCOOH formation(j_(HCOOH))at-1.35 V vs.reversible hydrogen electrode(RHE),much higher than the single atom catalysts.Theoretical calculations have indicated that the introduced Ce single atom sites not only significantly promote electron transfer but also optimize the In-5p orbitals towards higher selectivity towards the HCOOH formation.This work innovatively extends the design of SACCs towards the main group and Ln metals for more applications.
