Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily a...Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily accessible active sites for CO_(2) electroreduction remains challenging yet indispensable.In this work,a reliable poly(ethyleneimine)(PEI)-assisted strategy is developed to prepare a hollow carbon nanocomposite comprising a single-site Ni-modified carbon shell and confined Ni nanoparticles(NPs)(denoted as Ni@NHCS),where PEI not only functions as a mediator to induce the highly dispersed growth of Ni NPs within hollow carbon spheres,but also as a nitrogen precursor to construct highly active atomically-dispersed Ni-Nx sites.Benefiting from the unique structural properties of Ni@NHCS,the aggregation and exposure of Ni NPs can be effectively prevented,while the accessibility of abundant catalytically active Ni-Nx sites can be ensured.As a result,Ni@NHCS exhibits a high CO partial current density of 26.9 mA cm^(-2) and a Faradaic efficiency of 93.0% at-1.0 V vs.RHE,outperforming those of its PEI-free analog.Apart from the excellent activity and selectivity,the shell confinement effect of the hollow carbon sphere endows this catalyst with long-term stability.The findings here are anticipated to help understand the structure-activity relationship in Ni-based carbon catalyst systems for electrocatalytic CO_(2) reduction.Furthermore,the PEI-assisted synthetic concept is potentially applicable to the preparation of high-performance metal-based nanoconfined materials tailored for diverse energy conversion applications and beyond.展开更多
TiO2hollow microspheres(TiO2‐HMSs)have attracted much attention because of their high photoreactivity,low density,and good permeability.However,anatase TiO2‐HMSs have poor thermal stability.In this study,surface‐fl...TiO2hollow microspheres(TiO2‐HMSs)have attracted much attention because of their high photoreactivity,low density,and good permeability.However,anatase TiO2‐HMSs have poor thermal stability.In this study,surface‐fluorinated TiO2‐HMSs were assembled from hollow nanoparticles by the hydrothermal reaction of the mixed Ti(SO4)2–NH4HF–H2O2solution at180°C.The effect of the calcination temperature on the structure and photoreactivity of the TiO2‐HMSs was systematically investigated,which was evaluated by photocatalytic oxidation of acetone in air under ultraviolet irradiation.We found that after calcination at300°C,the photoreactivity of the TiO2‐HMSs decreases from1.39×10?3min?1(TiO2‐HMS precursor)to0.82×10?3min?1because of removal of surface‐adsorbed fluoride ions.With increasing calcination temperature from300to900°C,the building blocks of the TiO2‐HMSs evolve from truncated bipyramidal shaped hollow nanoparticles to round solid nanoparticles,and the photoreactivity of the TiO2‐HMSs steady increases from0.82×10?3to2.09×10?3min?1because of enhanced crystallization.Further increasing the calcination temperature to1000and1100°C results in a decrease of the photoreactivity,which is ascribed to a sharp decrease of the Brunauer–Emmett–Teller surface area and the beginning of the anatase–rutile phase transformation at1100°C.The effect of surface‐adsorbed fluoride ions on the thermal stability of the TiO2‐HMSs is also discussed.展开更多
The shuttle effect of lithium polysulfides(LiPSs)and their sluggish kinetic processes lead to rapid capacity fading and poor cycling stability in lithium-sulfur(Li-S)batteries,limiting their commercial viability.This ...The shuttle effect of lithium polysulfides(LiPSs)and their sluggish kinetic processes lead to rapid capacity fading and poor cycling stability in lithium-sulfur(Li-S)batteries,limiting their commercial viability.This study proposes a functionalized separator with adsorption and synergistic catalysis ability for Li-S batteries.The modified separator comprises Ti_(3)C_(2)T_(x) sheets,CoO,and MoO_(3).Experimental and theoretical calculations demonstrate that Ti_(3)C_(2)T_(x)/CoO/MoO_(3) composite not only effectively inhibits the shuttle effect of LiPSs,ensuring efficient utilization of active materials,but also enhances reversibility and reaction kinetics among LiPSs.The full exposure of active sites in the Ti_(3)C_(2)T_(x)/CoO/MoO_(3) composite and the synergistic action of different catalysts enable efficient capture and conversion of LiPSs molecules at the material surface.Besides,the lithium-sulfur batteries with Ti_(3)C_(2)T_(x)/CoO/MoO_(3)@PP separator exhibited only a 0.042%capacity decay per cycle at 0.5 C(800 cycles).Moreover,a high areal capacity of 6.85 mAh cm-2 was achieved at high sulfur loading(7.9 mg cm-2)and low electrolyte-to-sulfur ratio(10μL mg-1).展开更多
Photocatalysis has become a focal point in research as a clean and sustainable technology with the potential to solve environmental problems and energy crises.The loading of noble-metal co-catalysts can substantially ...Photocatalysis has become a focal point in research as a clean and sustainable technology with the potential to solve environmental problems and energy crises.The loading of noble-metal co-catalysts can substantially improve the photocatalytic efficiency of semiconductors.Because the high cost and scarcity of noble metals markedly limit their large-scale applications,finding a noble-metal-alternative co-catalyst is crucial.MXene,a novel 2D transition metal material,has attracted considerable attention as a promising substitute for noble metal co-catalysts owing to its cost-efficiency,unique 2D layered structure,and excellent electrical,optical,and thermodynamic properties.This review focuses on the latest advancements in research on MXenes as co-catalysts in relatively popular photocatalytic applications(hydrogen production,CO2 reduction,nitrogen fixation,and organic pollutant oxidation).The synthesis methods and photocatalytic mechanisms of MXenes as co-catalysts are also summarized according to the type of MXene-based material.Finally,the crucial opportunities and challenges in the prospective development of MXene-based photocatalysts are outlined.We emphasize that modern techniques should be used to demonstrate the effects of MXenes on photocatalysis and that the photocatalytic activity of MXene-based photocatalysts can be further improved using defective engineering and recent phenomena such as the localized surface plasmon resonance effect and single-atom catalysis.展开更多
An important challenge facing K-ion batteries lies in exploring earth-abundant and safe cathode materials that can provide high capacity with high migration rate of K ions.Here,we propose a simple and efficient method...An important challenge facing K-ion batteries lies in exploring earth-abundant and safe cathode materials that can provide high capacity with high migration rate of K ions.Here,we propose a simple and efficient method for searching potential K cathode materials with first principles calculations.Our screening is based on combinations of weight capacity,K ion occupation ratio,volume change per K,and valence limit.With this screening method we predicted a series of potential K ions cathodes with favorable electrochemical performance,such as K_(2)VPO_(4)CO_(3)-like structures with 1 D diffusion channels,3 D channel structures K_(2)CoSiO_(4),layered materials KCoO_(2),KCrO_(2),KVF_(4) and K_(5)V_(3)F_(14),and others.These potential cathodes have small volume changes,suitable voltage,and high capacity,with small diffusion barriers.They may be useful in K-ion batteries with high energy density and rate performance.展开更多
文摘Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily accessible active sites for CO_(2) electroreduction remains challenging yet indispensable.In this work,a reliable poly(ethyleneimine)(PEI)-assisted strategy is developed to prepare a hollow carbon nanocomposite comprising a single-site Ni-modified carbon shell and confined Ni nanoparticles(NPs)(denoted as Ni@NHCS),where PEI not only functions as a mediator to induce the highly dispersed growth of Ni NPs within hollow carbon spheres,but also as a nitrogen precursor to construct highly active atomically-dispersed Ni-Nx sites.Benefiting from the unique structural properties of Ni@NHCS,the aggregation and exposure of Ni NPs can be effectively prevented,while the accessibility of abundant catalytically active Ni-Nx sites can be ensured.As a result,Ni@NHCS exhibits a high CO partial current density of 26.9 mA cm^(-2) and a Faradaic efficiency of 93.0% at-1.0 V vs.RHE,outperforming those of its PEI-free analog.Apart from the excellent activity and selectivity,the shell confinement effect of the hollow carbon sphere endows this catalyst with long-term stability.The findings here are anticipated to help understand the structure-activity relationship in Ni-based carbon catalyst systems for electrocatalytic CO_(2) reduction.Furthermore,the PEI-assisted synthetic concept is potentially applicable to the preparation of high-performance metal-based nanoconfined materials tailored for diverse energy conversion applications and beyond.
基金supported by the National Natural Science Foundation of China(51672312,21373275)the Science and Technology Program of Wuhan,China(2016010101010018,2015070504020220)the Dean’s Research Fund–04257 from the Education University of Hong Kong~~
文摘TiO2hollow microspheres(TiO2‐HMSs)have attracted much attention because of their high photoreactivity,low density,and good permeability.However,anatase TiO2‐HMSs have poor thermal stability.In this study,surface‐fluorinated TiO2‐HMSs were assembled from hollow nanoparticles by the hydrothermal reaction of the mixed Ti(SO4)2–NH4HF–H2O2solution at180°C.The effect of the calcination temperature on the structure and photoreactivity of the TiO2‐HMSs was systematically investigated,which was evaluated by photocatalytic oxidation of acetone in air under ultraviolet irradiation.We found that after calcination at300°C,the photoreactivity of the TiO2‐HMSs decreases from1.39×10?3min?1(TiO2‐HMS precursor)to0.82×10?3min?1because of removal of surface‐adsorbed fluoride ions.With increasing calcination temperature from300to900°C,the building blocks of the TiO2‐HMSs evolve from truncated bipyramidal shaped hollow nanoparticles to round solid nanoparticles,and the photoreactivity of the TiO2‐HMSs steady increases from0.82×10?3to2.09×10?3min?1because of enhanced crystallization.Further increasing the calcination temperature to1000and1100°C results in a decrease of the photoreactivity,which is ascribed to a sharp decrease of the Brunauer–Emmett–Teller surface area and the beginning of the anatase–rutile phase transformation at1100°C.The effect of surface‐adsorbed fluoride ions on the thermal stability of the TiO2‐HMSs is also discussed.
基金Institute of Advanced Study of Central South UniversityHigh Performance Computing Center of Central South University。
文摘The shuttle effect of lithium polysulfides(LiPSs)and their sluggish kinetic processes lead to rapid capacity fading and poor cycling stability in lithium-sulfur(Li-S)batteries,limiting their commercial viability.This study proposes a functionalized separator with adsorption and synergistic catalysis ability for Li-S batteries.The modified separator comprises Ti_(3)C_(2)T_(x) sheets,CoO,and MoO_(3).Experimental and theoretical calculations demonstrate that Ti_(3)C_(2)T_(x)/CoO/MoO_(3) composite not only effectively inhibits the shuttle effect of LiPSs,ensuring efficient utilization of active materials,but also enhances reversibility and reaction kinetics among LiPSs.The full exposure of active sites in the Ti_(3)C_(2)T_(x)/CoO/MoO_(3) composite and the synergistic action of different catalysts enable efficient capture and conversion of LiPSs molecules at the material surface.Besides,the lithium-sulfur batteries with Ti_(3)C_(2)T_(x)/CoO/MoO_(3)@PP separator exhibited only a 0.042%capacity decay per cycle at 0.5 C(800 cycles).Moreover,a high areal capacity of 6.85 mAh cm-2 was achieved at high sulfur loading(7.9 mg cm-2)and low electrolyte-to-sulfur ratio(10μL mg-1).
文摘Photocatalysis has become a focal point in research as a clean and sustainable technology with the potential to solve environmental problems and energy crises.The loading of noble-metal co-catalysts can substantially improve the photocatalytic efficiency of semiconductors.Because the high cost and scarcity of noble metals markedly limit their large-scale applications,finding a noble-metal-alternative co-catalyst is crucial.MXene,a novel 2D transition metal material,has attracted considerable attention as a promising substitute for noble metal co-catalysts owing to its cost-efficiency,unique 2D layered structure,and excellent electrical,optical,and thermodynamic properties.This review focuses on the latest advancements in research on MXenes as co-catalysts in relatively popular photocatalytic applications(hydrogen production,CO2 reduction,nitrogen fixation,and organic pollutant oxidation).The synthesis methods and photocatalytic mechanisms of MXenes as co-catalysts are also summarized according to the type of MXene-based material.Finally,the crucial opportunities and challenges in the prospective development of MXene-based photocatalysts are outlined.We emphasize that modern techniques should be used to demonstrate the effects of MXenes on photocatalysis and that the photocatalytic activity of MXene-based photocatalysts can be further improved using defective engineering and recent phenomena such as the localized surface plasmon resonance effect and single-atom catalysis.
基金supported by the National Key R&D Program of China(Grant No.2016YFA0200400)the National Natural Science Foundation of China(Grant No.11504123 and No.51627805)。
文摘An important challenge facing K-ion batteries lies in exploring earth-abundant and safe cathode materials that can provide high capacity with high migration rate of K ions.Here,we propose a simple and efficient method for searching potential K cathode materials with first principles calculations.Our screening is based on combinations of weight capacity,K ion occupation ratio,volume change per K,and valence limit.With this screening method we predicted a series of potential K ions cathodes with favorable electrochemical performance,such as K_(2)VPO_(4)CO_(3)-like structures with 1 D diffusion channels,3 D channel structures K_(2)CoSiO_(4),layered materials KCoO_(2),KCrO_(2),KVF_(4) and K_(5)V_(3)F_(14),and others.These potential cathodes have small volume changes,suitable voltage,and high capacity,with small diffusion barriers.They may be useful in K-ion batteries with high energy density and rate performance.
