As a noble metal substitute,two-dimensional(2D)hierarchical nano-frame structures have attracted great interest as candidate catalysts due to their remarkable advantages-high intrinsic activity,high electron mobility,...As a noble metal substitute,two-dimensional(2D)hierarchical nano-frame structures have attracted great interest as candidate catalysts due to their remarkable advantages-high intrinsic activity,high electron mobility,and straightforward surface functionalization.Therefore,they may replace Pt-based catalysts in oxygen reduction reaction(ORR)applications.Herein,a simple method is developed to design hierarchical nano-frame structures assembled via 2D NiO and N-doped graphene(NG)nanosheets.This procedure can yield nanostructures that satisfy the criteria correlated with improved electrocatalytic performance,such as large surface area,numerous undercoordinated atoms,and high defect densities.Further,porous NG nanosheet architectures,featuring NiO nanosheets densely coordinated with accessible holey Fe_(2)O_(3) moieties,can enhance mesoporosity and balance hydrophilicity.Such improvements can facilitate charge transport and expose formerly inaccessible reaction sites,maximizing active site density utilization.Density functional theory(DFT)calculations reveal favored O_(2) adsorption and dissociation on Fe_(2)O_(3) hybrid structures when supported by 2D NiO and NG nanomaterials,given 2D materials donated charge to Fe_(2)O_(3) active sites.Our systematic studies reveal that synergistic contributions are responsible for enriching the catalytic activity of Fe_(2)O_(3)@NiO/NG in alkaline media-encompassing internal voids and pores,unique hierarchical support structures,and concentrated N-dopant and bimetallic atomic interactions.Ultimately,this work expands the toolbox for designing and synthesizing highly efficient 2D/2D shelled functional nanomaterials with transition metals,endeavoring to benefit energy conversion and related ORR applications.展开更多
Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely li...Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely limits the overall electrocatalytic performance due to their insufficient cooperative effects.Herein,we report a controllable and robust heterointerface engineering strategy for the bottom-up fabrication of rhombic Rh nanosheets in situ confined on Ti_3C_(2)T_x MXene nanolamellas(Rh NS/MXene)via a convenient stereoassembly process.This unique design concept gives the resulting 2D/2D Rh NS/MXene heterostructure intriguing textural features,including large accessible surface areas,strong"face-toface"interfacial interactions,homogeneous Rh nanosheet distribution,ameliorative electronic structure,and high electronic conductivity.As a consequence,the as-prepared Rh NS/MXene nanoarchitectures exhibit exceptional electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area of 126.2 m~2 g_(Rh)~(-1),a high mass activity of 1056.9 mA mg_(Rh)-~1,and a long service life,which significantly outperform those of conventional particle-shaped Rh catalysts supported by carbon black,carbon nanotubes,reduced graphene oxide,and MXene matrixes as well as the commercial Pt nanoparticle/carbon black and Pd nanoparticle/carbon black catalysts with the same noble metal loading amount.Density functional theory calculations further demonstrate that the direct electronic interaction at the well-contacted 2D/2D heterointerfaces effectively enhances the adsorption energy of Rh nanosheets and induces a left shift of the d-band center,thereby making the Rh NS/MXene configuration suffer less from CO poisoning.This work highlights the importance of rational heterointerface design in the construction of advanced noble metal/MXene electrocatalysts,which may provide new avenues for developing the next-generation DMFC devices.展开更多
Wet chemistry methods,including hot-injection and precipitation methods,have emerged as major synthetic routes for high-quality perovskite nanocrystals in backlit display and scintillation applications.However,low che...Wet chemistry methods,including hot-injection and precipitation methods,have emerged as major synthetic routes for high-quality perovskite nanocrystals in backlit display and scintillation applications.However,low chemical yield hinders their upscale production for practical use.Meanwhile,the labile nature of halide-based perovskite poses a major challenge for long-term storage of perovskite nanocrystals.Herein,we report a green synthesis at room temperature for gram-scale production of CsPbBr3 nanosheets with minimum use of solvent,saving over 95% of the solvent for the unity mass nanocrystal production.The perovskite colloid exhibits record stability upon long-term storage for up to 8 months,preserving a photoluminescence quantum yield of 63% in solid state.Importantly,the colloidal nanosheets show self-assembly behavior upon slow solidification,generating a crack-free thin film in a large area.The uniform film was then demonstrated as an efficient scintillation screen for X-ray imaging.Our findings bring a scalable tool for synthesis of high-quality perovskite nanocrystals,which may inspire the industrial optoelectronic application of large-area perovskite film.展开更多
A possible mechanism for boosting the visible-light photoactivities of graphitic carbon nitride(g-C3N4)nanosheets for CO2 reduction via coupling with the electron donor Co-metal-organic framework(MOF)is proposed in th...A possible mechanism for boosting the visible-light photoactivities of graphitic carbon nitride(g-C3N4)nanosheets for CO2 reduction via coupling with the electron donor Co-metal-organic framework(MOF)is proposed in this study.Specifically,Co-MOF as an electron donor is capable of transferring the photogenerated electrons in the lowest unoccupied molecular orbital(LUMO)to the conduction band of g-C3N4 to facilitate charge separation.As expected,the prepared Co-MOF/g-C3N4 nanocomposites display excellent visible-light-driven photocatalytic CO2 reduction activities.The CO production rate of 6.75μmol g–1 h–1 and CH4 evolution rate of 5.47μmol g–1 h–1 are obtained,which are approximately 2 times those obtained with the original g-C3N4 under the same conditions.Based on a series of analyses,it is shown that the introduction of Co-MOF not only broadens the range of visible-light absorption but also enhances the charge separation,which improves the photocatalytic activity of g-C3N4 to a higher level.In particular,the hydroxyl radical(·OH)experiment was operated under 590 nm(single-wavelength)irradiation,which further proved that the photogenerated electrons in the LUMO of Co-MOF can successfully migrate to g-C3N4.This work may provide an important strategy for the design of highly efficient g-C3N4-based photocatalysts for CO2 reduction.展开更多
In this study, the effect of reduced graphene oxide(rGO) on interconnected Co_3O_4 nanosheets and the improved supercapacitive behaviors is reported. By optimizing the experimental parameters, we achieved a specific c...In this study, the effect of reduced graphene oxide(rGO) on interconnected Co_3O_4 nanosheets and the improved supercapacitive behaviors is reported. By optimizing the experimental parameters, we achieved a specific capacitance of ~1016.4 F g^(-1) for the Co_3O_4/rGO/NF(nickel foam) system at a current density of 1 A g^(-1). However, the Co_3O_4/NF structure without rGO only delivers a specific capacitance of ~520.0 F g^(-1)at the same current density. The stability test demonstrates that Co_3O_4/rGO/NF retains ~95.5% of the initial capacitance value even after 3000 charge–discharge cycles at a high current density of 7 A g^(-1). Further investigation reveals that capacitance improvement for the Co_3O_4/rGO/NF structure is mainly because of a higher specific surface area(~87.8 m^2g^(-1))and a more optimal mesoporous size(4–15 nm) compared to the corresponding values of 67.1 m^2g^(-1) and 6–25 nm,respectively, for the Co_3O_4/NF structure. rGO and the thinner Co_3O_4 nanosheets benefit from the strain relaxation during the charge and discharge processes, improving the cycling stability of Co_3O_4/rGO/NF.展开更多
Searching for advanced anode materials with excellent electrochemical properties in sodium-ion battery is essential and imperative for next-generation energy storage system to solve the energy shortage problem.In this...Searching for advanced anode materials with excellent electrochemical properties in sodium-ion battery is essential and imperative for next-generation energy storage system to solve the energy shortage problem.In this work,two-dimensional(2D)ultrathin FePS3 nanosheets,a typical ternary metal phosphosulfide,are first prepared by ultrasonic exfoliation.The novel 2D/2D heterojunction of FePS3 nanosheets@MXene composite is then successfully synthesized by in situ mixing ultrathin MXene nanosheets with FePS3 nanosheets.The resultant FePS3 nanosheets@MXene hybrids can increase the electronic conductivity and specific surface area,assuring excellent surface and interfacial charge transfer abilities.Furthermore,the unique heterojunction endows FePS3 nanosheets@MXene composite to promote the diffusion of Na^+ and alleviate the drastic change in volume in the cyclic process,enhancing the sodium storage capability.Consequently,the few-layered FePS3 nanosheets uniformly coated by ultrathin MXene provide an exceptional reversible capacity of 676.1 mAh g^−1 at the current of 100 mA g^−1 after 90 cycles,which is equivalent to around 90.6% of the second-cycle capacity(746.4 mAh g^−1).This work provides an original protocol for constructing 2D/2D material and demonstrates the FePS3@MXene composite as a potential anode material with excellent property for sodium-ion batteries.展开更多
PtPd bimetallic alloy nanoparticle (NP)-modified graphitic carbon nitride (g-C3N4) nanosheet photocatalysts were synthesized via chemical deposition precipitation. Characterization of the photocatalytic H2 evolution o...PtPd bimetallic alloy nanoparticle (NP)-modified graphitic carbon nitride (g-C3N4) nanosheet photocatalysts were synthesized via chemical deposition precipitation. Characterization of the photocatalytic H2 evolution of the g-C3N4 nanosheets shows that it was significantly enhanced when PtPd alloy NPs were introduced as a co-catalyst. The 0.2 wt% PtPd/g-C3N4 composite photocatalyst gave a maximum H2 production rate of 1600.8 μmol g^–1 h^–1. Furthermore, when K2HPO4 was added to the reaction system, the H2 production rate increased to 2885.0 μmol g^–1 h^–1. The PtPd/g-C3N4 photocatalyst showed satisfactory photocatalytic stability and was able to maintain most of its photocatalytic activity after four experimental photocatalytic cycles. In addition, a possible mechanism for the enhanced photocatalytic activity was proposed and verified by various photoelectric techniques. These results demonstrate that the synergistic effect between PtPd and g-C3N4 helps to greatly improve the photocatalytic activity of the composite photocatalyst.展开更多
基金supported by the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(MSIT)(RS2023-00235596)and ERC Center(2022R1A5A1033719)。
文摘As a noble metal substitute,two-dimensional(2D)hierarchical nano-frame structures have attracted great interest as candidate catalysts due to their remarkable advantages-high intrinsic activity,high electron mobility,and straightforward surface functionalization.Therefore,they may replace Pt-based catalysts in oxygen reduction reaction(ORR)applications.Herein,a simple method is developed to design hierarchical nano-frame structures assembled via 2D NiO and N-doped graphene(NG)nanosheets.This procedure can yield nanostructures that satisfy the criteria correlated with improved electrocatalytic performance,such as large surface area,numerous undercoordinated atoms,and high defect densities.Further,porous NG nanosheet architectures,featuring NiO nanosheets densely coordinated with accessible holey Fe_(2)O_(3) moieties,can enhance mesoporosity and balance hydrophilicity.Such improvements can facilitate charge transport and expose formerly inaccessible reaction sites,maximizing active site density utilization.Density functional theory(DFT)calculations reveal favored O_(2) adsorption and dissociation on Fe_(2)O_(3) hybrid structures when supported by 2D NiO and NG nanomaterials,given 2D materials donated charge to Fe_(2)O_(3) active sites.Our systematic studies reveal that synergistic contributions are responsible for enriching the catalytic activity of Fe_(2)O_(3)@NiO/NG in alkaline media-encompassing internal voids and pores,unique hierarchical support structures,and concentrated N-dopant and bimetallic atomic interactions.Ultimately,this work expands the toolbox for designing and synthesizing highly efficient 2D/2D shelled functional nanomaterials with transition metals,endeavoring to benefit energy conversion and related ORR applications.
基金supported by the National Natural Science Foundation of China(11872171 and 22209037)the Project on Excellent Post-graduate Dissertation of Hohai University。
文摘Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely limits the overall electrocatalytic performance due to their insufficient cooperative effects.Herein,we report a controllable and robust heterointerface engineering strategy for the bottom-up fabrication of rhombic Rh nanosheets in situ confined on Ti_3C_(2)T_x MXene nanolamellas(Rh NS/MXene)via a convenient stereoassembly process.This unique design concept gives the resulting 2D/2D Rh NS/MXene heterostructure intriguing textural features,including large accessible surface areas,strong"face-toface"interfacial interactions,homogeneous Rh nanosheet distribution,ameliorative electronic structure,and high electronic conductivity.As a consequence,the as-prepared Rh NS/MXene nanoarchitectures exhibit exceptional electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area of 126.2 m~2 g_(Rh)~(-1),a high mass activity of 1056.9 mA mg_(Rh)-~1,and a long service life,which significantly outperform those of conventional particle-shaped Rh catalysts supported by carbon black,carbon nanotubes,reduced graphene oxide,and MXene matrixes as well as the commercial Pt nanoparticle/carbon black and Pd nanoparticle/carbon black catalysts with the same noble metal loading amount.Density functional theory calculations further demonstrate that the direct electronic interaction at the well-contacted 2D/2D heterointerfaces effectively enhances the adsorption energy of Rh nanosheets and induces a left shift of the d-band center,thereby making the Rh NS/MXene configuration suffer less from CO poisoning.This work highlights the importance of rational heterointerface design in the construction of advanced noble metal/MXene electrocatalysts,which may provide new avenues for developing the next-generation DMFC devices.
基金supported by National Natural Science Foundation of China (Nos. 21805111 and 11405073)Taishan Scholar Fund
文摘Wet chemistry methods,including hot-injection and precipitation methods,have emerged as major synthetic routes for high-quality perovskite nanocrystals in backlit display and scintillation applications.However,low chemical yield hinders their upscale production for practical use.Meanwhile,the labile nature of halide-based perovskite poses a major challenge for long-term storage of perovskite nanocrystals.Herein,we report a green synthesis at room temperature for gram-scale production of CsPbBr3 nanosheets with minimum use of solvent,saving over 95% of the solvent for the unity mass nanocrystal production.The perovskite colloid exhibits record stability upon long-term storage for up to 8 months,preserving a photoluminescence quantum yield of 63% in solid state.Importantly,the colloidal nanosheets show self-assembly behavior upon slow solidification,generating a crack-free thin film in a large area.The uniform film was then demonstrated as an efficient scintillation screen for X-ray imaging.Our findings bring a scalable tool for synthesis of high-quality perovskite nanocrystals,which may inspire the industrial optoelectronic application of large-area perovskite film.
基金supported by the National Natural Science Foundation of China(21871079,21501052)the Outstanding Youth Project of Natural Science Foundation of Heilongjiang Province(YQ2019B006)~~
文摘A possible mechanism for boosting the visible-light photoactivities of graphitic carbon nitride(g-C3N4)nanosheets for CO2 reduction via coupling with the electron donor Co-metal-organic framework(MOF)is proposed in this study.Specifically,Co-MOF as an electron donor is capable of transferring the photogenerated electrons in the lowest unoccupied molecular orbital(LUMO)to the conduction band of g-C3N4 to facilitate charge separation.As expected,the prepared Co-MOF/g-C3N4 nanocomposites display excellent visible-light-driven photocatalytic CO2 reduction activities.The CO production rate of 6.75μmol g–1 h–1 and CH4 evolution rate of 5.47μmol g–1 h–1 are obtained,which are approximately 2 times those obtained with the original g-C3N4 under the same conditions.Based on a series of analyses,it is shown that the introduction of Co-MOF not only broadens the range of visible-light absorption but also enhances the charge separation,which improves the photocatalytic activity of g-C3N4 to a higher level.In particular,the hydroxyl radical(·OH)experiment was operated under 590 nm(single-wavelength)irradiation,which further proved that the photogenerated electrons in the LUMO of Co-MOF can successfully migrate to g-C3N4.This work may provide an important strategy for the design of highly efficient g-C3N4-based photocatalysts for CO2 reduction.
基金financially supported from the National Natural Science Foundation of China (Grant Nos.: 61376068, 11304132, 11304133, and 11405144)the Specialized Research Fund of the Doctoral Program of Higher Education (Grant Nos.: 20120211120003 and 20130211120009)the Fundamental Research Funds for the Central Universities (Grant Nos.: lzujbky2013-36 and lzujbky-2014-30)
文摘In this study, the effect of reduced graphene oxide(rGO) on interconnected Co_3O_4 nanosheets and the improved supercapacitive behaviors is reported. By optimizing the experimental parameters, we achieved a specific capacitance of ~1016.4 F g^(-1) for the Co_3O_4/rGO/NF(nickel foam) system at a current density of 1 A g^(-1). However, the Co_3O_4/NF structure without rGO only delivers a specific capacitance of ~520.0 F g^(-1)at the same current density. The stability test demonstrates that Co_3O_4/rGO/NF retains ~95.5% of the initial capacitance value even after 3000 charge–discharge cycles at a high current density of 7 A g^(-1). Further investigation reveals that capacitance improvement for the Co_3O_4/rGO/NF structure is mainly because of a higher specific surface area(~87.8 m^2g^(-1))and a more optimal mesoporous size(4–15 nm) compared to the corresponding values of 67.1 m^2g^(-1) and 6–25 nm,respectively, for the Co_3O_4/NF structure. rGO and the thinner Co_3O_4 nanosheets benefit from the strain relaxation during the charge and discharge processes, improving the cycling stability of Co_3O_4/rGO/NF.
基金support funding is from the National Natural Science Foundation of China(51871119 and 51901100)China Jiangsu Specially Appointed Professor,Jiangsu Provincial Founds for Natural Science Foundation(BK20170793 and BK20180015)+2 种基金China Postdoctoral Science Foundation(2018M640481 and 2019T120426)Jiangsu Postdoctoral Research Fund(2019K003 and 2019K201)Jiangsu-Innovate UK Business Competition(BZ2017061)
文摘Searching for advanced anode materials with excellent electrochemical properties in sodium-ion battery is essential and imperative for next-generation energy storage system to solve the energy shortage problem.In this work,two-dimensional(2D)ultrathin FePS3 nanosheets,a typical ternary metal phosphosulfide,are first prepared by ultrasonic exfoliation.The novel 2D/2D heterojunction of FePS3 nanosheets@MXene composite is then successfully synthesized by in situ mixing ultrathin MXene nanosheets with FePS3 nanosheets.The resultant FePS3 nanosheets@MXene hybrids can increase the electronic conductivity and specific surface area,assuring excellent surface and interfacial charge transfer abilities.Furthermore,the unique heterojunction endows FePS3 nanosheets@MXene composite to promote the diffusion of Na^+ and alleviate the drastic change in volume in the cyclic process,enhancing the sodium storage capability.Consequently,the few-layered FePS3 nanosheets uniformly coated by ultrathin MXene provide an exceptional reversible capacity of 676.1 mAh g^−1 at the current of 100 mA g^−1 after 90 cycles,which is equivalent to around 90.6% of the second-cycle capacity(746.4 mAh g^−1).This work provides an original protocol for constructing 2D/2D material and demonstrates the FePS3@MXene composite as a potential anode material with excellent property for sodium-ion batteries.
基金supported by the National Natural Science Foundation of China(51572295,21273285,21003157)the Beijing Nova Program(2008B76)the Science Foundation of China University of Petroleum Beijing(KYJJ2012-06-20 and 2462016YXBS05)~~
文摘PtPd bimetallic alloy nanoparticle (NP)-modified graphitic carbon nitride (g-C3N4) nanosheet photocatalysts were synthesized via chemical deposition precipitation. Characterization of the photocatalytic H2 evolution of the g-C3N4 nanosheets shows that it was significantly enhanced when PtPd alloy NPs were introduced as a co-catalyst. The 0.2 wt% PtPd/g-C3N4 composite photocatalyst gave a maximum H2 production rate of 1600.8 μmol g^–1 h^–1. Furthermore, when K2HPO4 was added to the reaction system, the H2 production rate increased to 2885.0 μmol g^–1 h^–1. The PtPd/g-C3N4 photocatalyst showed satisfactory photocatalytic stability and was able to maintain most of its photocatalytic activity after four experimental photocatalytic cycles. In addition, a possible mechanism for the enhanced photocatalytic activity was proposed and verified by various photoelectric techniques. These results demonstrate that the synergistic effect between PtPd and g-C3N4 helps to greatly improve the photocatalytic activity of the composite photocatalyst.
