Electrochromic(EC)smart windows utilizing a reversible metal electrodeposition device(RMED)offer a compelling alternative for dynamically regulating transmissions of optical and thermal energy.An EC device(ECD)is cons...Electrochromic(EC)smart windows utilizing a reversible metal electrodeposition device(RMED)offer a compelling alternative for dynamically regulating transmissions of optical and thermal energy.An EC device(ECD)is constructed by reversible metal electrodeposition(RME)of Bi/Cu on WO_(3)·xH_(2)O film electrodeposited onto fluorine-doped tin oxide(FTO)transparent conductive glass.The electrolyte consists of CuCl_(2),BiCl_(3),KCl and HCl aqueous solution,supplying necessary components for both electrochemical and electrodeposition processes.The ECD shows ability to rapidly transition between colorless and black states,which achieves a large optical modulation of 77.0%at 570 nm.In the black state,the ECD exhibits a near-zero transmittance in the wavelength range of 400-1100 nm while maintaining 96.6%of its initial optical modulation after coloration/bleaching cycling of 60000 s,exhibiting good cyclic stability.This RMED has relatively high stability under open-circuit voltage and also possesses excellent heat insulation performance.The results offer a solution to overcome the poor cyclic stability of RMEDs and improve the optical modulation of ECDs.展开更多
Herein,we established a Zn_(3)(OH)_(2)(V_(2)O_(7))(H_(2)O)_(2)/V-Zn(O,S)Z-scheme heterojunction labeled ZnVO/V-Zn(O,S)with a heterovalent V^(4+)/V^(5+)states and oxygen vacancies in both phases via a one-step in-situ ...Herein,we established a Zn_(3)(OH)_(2)(V_(2)O_(7))(H_(2)O)_(2)/V-Zn(O,S)Z-scheme heterojunction labeled ZnVO/V-Zn(O,S)with a heterovalent V^(4+)/V^(5+)states and oxygen vacancies in both phases via a one-step in-situ hydrolysis method.The NaBH_(4) regulated the ZnVO/V-Zn(O,S)-3 with rich Vo and suitable n(V^(4+))/n(V^(5+))ratio achieved an excellent photocatalytic nitrogen fixation activity of 301.7μmol/(g×h)and apparent quantum efficiency of 1.148%at 420 nm without any sacrificial agent,which is 11 times than that of V-Zn(O,S).The Vo acts as the active site to trap and activate N_(2) molecules and to trap and activate H_(2)O to produce the H for N_(2) molecules photocatalytic reduction.The rich Vo defects can also reduce the competitive adsorption of H_(2)O and N_(2) molecules on the surface active site of the catalyst.The heterovalent vanadium states act as the photogenerated electrons,quickly hopping between V^(4+)and V^(5+)to transfer for the photocatalytic N_(2) reduction reaction.Additionally,the Z-scheme heterojunction effectively minimizes photogenerated carrier recombination.These synergistic effects collectively boost the photocatalytic nitrogen fixation activity.This study provides a practical method for designing Z-scheme heterojunctions for efficient photocatalytic N_(2) fixation under mild conditions.展开更多
The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS...The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In_(2)O_(3)is successfully achieved using an electrostatic self-assembly method.Under visible light irradiation,all CdS-In_(2)O_(3)composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs.Notably,the photocatalytic H_(2)evolution rate of the optimal CdS-7%In_(2)O_(3)composite is determined to be 2258.59μmol g^(−1)h^(−1),approximately 12.3 times higher than that of pure CdS.The cyclic test indicates that the CdS-In_(2)O_(3)composite maintains considerable activity even after 5 cycles,indicating its excellent stability.In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In_(2)O_(3)composites adheres to a typical S-scheme heterojunction mechanism.Additionally,a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In_(2)O_(3)and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs,thus achieving enhanced photocatalytic performance.This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H_(2)production and offers novel insights into the construction of effective composite photocatalysts.展开更多
The development of high-performance cathode materials is critical to the practical application of sodiumion batteries(SIBs).O3-type NaCrO_(2)(NCO)is one of the most competitive cathodes,but it suffers from rapid capac...The development of high-performance cathode materials is critical to the practical application of sodiumion batteries(SIBs).O3-type NaCrO_(2)(NCO)is one of the most competitive cathodes,but it suffers from rapid capacity decay caused by severe irreversible structural evolution.An Mg-Ti co-doped Na_(0.99)Cr_(0.95)Mg_(0.02)Ti_(0.03)O_(2)(NCO-MT)cathode material is designed and synthesized via a facile solid-state reaction to enhance the cyclability of NCO.A capacity retention of 71.6%after 2500 cycles with the capacity fade rate of 0.011%per cycle is achieved for NCO-MT at 5 C,which is attributed to the highly reversible crystal structure during cycling.Our findings offer a novel insight into the high-performance O3-type layered cathode materials for SIBs and are beneficial to promote the development of high-rate SIBs.展开更多
The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength,ionic conductivity,and thickness.Here,we propose Al_(2)O_(3)-coated polyimide(AO/PI)porous film as ...The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength,ionic conductivity,and thickness.Here,we propose Al_(2)O_(3)-coated polyimide(AO/PI)porous film as a high-strength substrate to support fast-ion-conducting polymer-in-salt(PIS)solid-state electrolytes,aiming to suppress lithium dendrite growth and improve full-cell performance.The Al_(2)O_(3)coating layer not only refines the wettability of polyimide porous film to PIS,but also performs as a high modulus protective layer to suppress the growth of lithium dendrites.The resulting PI/AO@PIS exhibits a small thickness of only 35μm with an outstanding tensile strength of 11.3 MPa and Young's modulus of 537.6 MPa.In addition,the PI/AO@PIS delivers a high ionic conductivity of 0.1 m S/cm at 25°C.As a result,the PI/AO@PIS enables symmetric Li cells to achieve exceptional cyclability for over 1000 h at 0.1 m A/cm2without noticeable lithium dendrite formation.Moreover,the PI/AO@PIS-based LiFePO4||Li full cells demonstrate outstanding rate performance(125.7 m Ah/g at 5 C)and impressive cycling stability(96.1%capacity retention at 1 C after 200 cycles).This work highlights the efficacy of enhancing the mechanical properties of polymer matrices and extending cell performance through the incorporation of a dense inorganic interface layer.展开更多
In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC...In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC activity of TiO_(2)/Sb_(2)S_(3) composite sample was investigated by electrochemical impedance analysis,including Nyquist and Mott-Schottky(M-S)plots.It was demonstrated that vacuum annealing could crystallize Sb_(2)S_(3) component and change its color from red to black,leading to an increment of photocurrent density from 1.9 A/m^(2) to 4.25 A/m^(2) at 0 V versus saturated calomel electrode(VSCE).The enhanced PEC performance was mainly attributed to the improved visible light absorption.Moreover,annealing treatment facilitated retarding the electron-hole recombination occurred at the solid/liquid interfaces.Our work might provide a novel strategy for enhancing the PEC performance of a semiconductor electrode.展开更多
The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonizatio...The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H_(2)S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al_(2)O_(3)(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO_(2) hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H_(2)S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO_(2) hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO_(2) Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnO_(x) in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO_(2) hydrogenation to methanol,promoting the carbon emission reduction in steel industry.展开更多
Ammonia Selective Catalytic Reduction(NHs-SCR)technology has been employed to eliminate NO_(x) from diesel engine exhaust,with Cu-SSZ-13 serving as the commercial catalyst.The greenhouse gas N_(2)O is produced as a by...Ammonia Selective Catalytic Reduction(NHs-SCR)technology has been employed to eliminate NO_(x) from diesel engine exhaust,with Cu-SSZ-13 serving as the commercial catalyst.The greenhouse gas N_(2)O is produced as a byproduct when using Cu-SSZ-13 as the NH_(3)-SCR catalyst.To achieve synergistic control of pollutants and greenhouse gases in diesel engine exhaust,rational design of Cu-SSZ-13 catalysts is required.In this study,the effect of Brønsted acid sites in Cu-SSZ-13 catalysts on the formation of N_(2)O was investigated.Mild thermal treatmentwas innovatively employed to prepare Cu-SSZ-13 catalysts with different amounts of Brønsted acid sites.EPR,H_(2)-TPR,NH_(3)-TPD,NMR were utilized to determine that the Brønsted acid sites were modified while the Cu species remained unchanged.Thereby an accurate assessment of the influence of Brønsted acid sites on N_(2)O formation could be achieved.Our results showed that Cu-SSZ-13 with more Brønsted acid sites produced less N_(2)O during the NH_(3)-SCR reaction.In the low-temperature region,the presence of framework acid sites facilitates the decomposition of the NH_(4)NO_(3)assisted by NO to form N_(2)and H_(2)O,reducing the formation of N_(2)O.In the high-temperature region,the Brønsted acid sites promote the decomposition of NH_(2)NO into N_(2)and H_(2)O.Meanwhile,the N_(2)O-SCR reaction can also be promoted by Brønsted acid sites,thereby decreasing N_(2)O emissions.This study suggests that in the future design and synthesis of Cu-SSZ-13 zeolites,attention should be paid to creating more Brønsted acid sites in Cu-SSZ-13 to reduce N_(2)O emissions.展开更多
文摘Electrochromic(EC)smart windows utilizing a reversible metal electrodeposition device(RMED)offer a compelling alternative for dynamically regulating transmissions of optical and thermal energy.An EC device(ECD)is constructed by reversible metal electrodeposition(RME)of Bi/Cu on WO_(3)·xH_(2)O film electrodeposited onto fluorine-doped tin oxide(FTO)transparent conductive glass.The electrolyte consists of CuCl_(2),BiCl_(3),KCl and HCl aqueous solution,supplying necessary components for both electrochemical and electrodeposition processes.The ECD shows ability to rapidly transition between colorless and black states,which achieves a large optical modulation of 77.0%at 570 nm.In the black state,the ECD exhibits a near-zero transmittance in the wavelength range of 400-1100 nm while maintaining 96.6%of its initial optical modulation after coloration/bleaching cycling of 60000 s,exhibiting good cyclic stability.This RMED has relatively high stability under open-circuit voltage and also possesses excellent heat insulation performance.The results offer a solution to overcome the poor cyclic stability of RMEDs and improve the optical modulation of ECDs.
文摘Herein,we established a Zn_(3)(OH)_(2)(V_(2)O_(7))(H_(2)O)_(2)/V-Zn(O,S)Z-scheme heterojunction labeled ZnVO/V-Zn(O,S)with a heterovalent V^(4+)/V^(5+)states and oxygen vacancies in both phases via a one-step in-situ hydrolysis method.The NaBH_(4) regulated the ZnVO/V-Zn(O,S)-3 with rich Vo and suitable n(V^(4+))/n(V^(5+))ratio achieved an excellent photocatalytic nitrogen fixation activity of 301.7μmol/(g×h)and apparent quantum efficiency of 1.148%at 420 nm without any sacrificial agent,which is 11 times than that of V-Zn(O,S).The Vo acts as the active site to trap and activate N_(2) molecules and to trap and activate H_(2)O to produce the H for N_(2) molecules photocatalytic reduction.The rich Vo defects can also reduce the competitive adsorption of H_(2)O and N_(2) molecules on the surface active site of the catalyst.The heterovalent vanadium states act as the photogenerated electrons,quickly hopping between V^(4+)and V^(5+)to transfer for the photocatalytic N_(2) reduction reaction.Additionally,the Z-scheme heterojunction effectively minimizes photogenerated carrier recombination.These synergistic effects collectively boost the photocatalytic nitrogen fixation activity.This study provides a practical method for designing Z-scheme heterojunctions for efficient photocatalytic N_(2) fixation under mild conditions.
文摘The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In_(2)O_(3)is successfully achieved using an electrostatic self-assembly method.Under visible light irradiation,all CdS-In_(2)O_(3)composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs.Notably,the photocatalytic H_(2)evolution rate of the optimal CdS-7%In_(2)O_(3)composite is determined to be 2258.59μmol g^(−1)h^(−1),approximately 12.3 times higher than that of pure CdS.The cyclic test indicates that the CdS-In_(2)O_(3)composite maintains considerable activity even after 5 cycles,indicating its excellent stability.In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In_(2)O_(3)composites adheres to a typical S-scheme heterojunction mechanism.Additionally,a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In_(2)O_(3)and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs,thus achieving enhanced photocatalytic performance.This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H_(2)production and offers novel insights into the construction of effective composite photocatalysts.
基金financially supported by National Key Research and Development Program of China(No.2022YFE0202400)the National Natural Science Foundation of China(No.22379103)+2 种基金Natural Science Foundation of Guangdong Province of China(No.2021A1515010388)the Science and Technology Projects of Suzhou City(No.SYC2022043)the Qing Lan Project of Jiangsu Province(2022)。
文摘The development of high-performance cathode materials is critical to the practical application of sodiumion batteries(SIBs).O3-type NaCrO_(2)(NCO)is one of the most competitive cathodes,but it suffers from rapid capacity decay caused by severe irreversible structural evolution.An Mg-Ti co-doped Na_(0.99)Cr_(0.95)Mg_(0.02)Ti_(0.03)O_(2)(NCO-MT)cathode material is designed and synthesized via a facile solid-state reaction to enhance the cyclability of NCO.A capacity retention of 71.6%after 2500 cycles with the capacity fade rate of 0.011%per cycle is achieved for NCO-MT at 5 C,which is attributed to the highly reversible crystal structure during cycling.Our findings offer a novel insight into the high-performance O3-type layered cathode materials for SIBs and are beneficial to promote the development of high-rate SIBs.
基金the financial support from the 261Project of MIIT and Natural Science Foundation of Jiangsu Province(No.BK20240179)。
文摘The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength,ionic conductivity,and thickness.Here,we propose Al_(2)O_(3)-coated polyimide(AO/PI)porous film as a high-strength substrate to support fast-ion-conducting polymer-in-salt(PIS)solid-state electrolytes,aiming to suppress lithium dendrite growth and improve full-cell performance.The Al_(2)O_(3)coating layer not only refines the wettability of polyimide porous film to PIS,but also performs as a high modulus protective layer to suppress the growth of lithium dendrites.The resulting PI/AO@PIS exhibits a small thickness of only 35μm with an outstanding tensile strength of 11.3 MPa and Young's modulus of 537.6 MPa.In addition,the PI/AO@PIS delivers a high ionic conductivity of 0.1 m S/cm at 25°C.As a result,the PI/AO@PIS enables symmetric Li cells to achieve exceptional cyclability for over 1000 h at 0.1 m A/cm2without noticeable lithium dendrite formation.Moreover,the PI/AO@PIS-based LiFePO4||Li full cells demonstrate outstanding rate performance(125.7 m Ah/g at 5 C)and impressive cycling stability(96.1%capacity retention at 1 C after 200 cycles).This work highlights the efficacy of enhancing the mechanical properties of polymer matrices and extending cell performance through the incorporation of a dense inorganic interface layer.
基金supported by the Fundamental Research Funds for the Central Universities(No.2019ZDPY04).
文摘In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC activity of TiO_(2)/Sb_(2)S_(3) composite sample was investigated by electrochemical impedance analysis,including Nyquist and Mott-Schottky(M-S)plots.It was demonstrated that vacuum annealing could crystallize Sb_(2)S_(3) component and change its color from red to black,leading to an increment of photocurrent density from 1.9 A/m^(2) to 4.25 A/m^(2) at 0 V versus saturated calomel electrode(VSCE).The enhanced PEC performance was mainly attributed to the improved visible light absorption.Moreover,annealing treatment facilitated retarding the electron-hole recombination occurred at the solid/liquid interfaces.Our work might provide a novel strategy for enhancing the PEC performance of a semiconductor electrode.
基金supported by the National Natural Science Foundation of China(Nos.22276060 and 21976059)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515012636)China Scholarship Council Scholarship(No.201906155006)。
文摘The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H_(2)S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al_(2)O_(3)(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO_(2) hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H_(2)S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO_(2) hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO_(2) Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnO_(x) in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO_(2) hydrogenation to methanol,promoting the carbon emission reduction in steel industry.
基金supported by the National Key R&D Program of China(Nos.2023YFC3707200 and 2022YFC3704400)the National Natural Science Foundation of China(Nos.52200136,22402220,and 52225004)Hangzhou Qianjiang Distinguished Experts Project.
文摘Ammonia Selective Catalytic Reduction(NHs-SCR)technology has been employed to eliminate NO_(x) from diesel engine exhaust,with Cu-SSZ-13 serving as the commercial catalyst.The greenhouse gas N_(2)O is produced as a byproduct when using Cu-SSZ-13 as the NH_(3)-SCR catalyst.To achieve synergistic control of pollutants and greenhouse gases in diesel engine exhaust,rational design of Cu-SSZ-13 catalysts is required.In this study,the effect of Brønsted acid sites in Cu-SSZ-13 catalysts on the formation of N_(2)O was investigated.Mild thermal treatmentwas innovatively employed to prepare Cu-SSZ-13 catalysts with different amounts of Brønsted acid sites.EPR,H_(2)-TPR,NH_(3)-TPD,NMR were utilized to determine that the Brønsted acid sites were modified while the Cu species remained unchanged.Thereby an accurate assessment of the influence of Brønsted acid sites on N_(2)O formation could be achieved.Our results showed that Cu-SSZ-13 with more Brønsted acid sites produced less N_(2)O during the NH_(3)-SCR reaction.In the low-temperature region,the presence of framework acid sites facilitates the decomposition of the NH_(4)NO_(3)assisted by NO to form N_(2)and H_(2)O,reducing the formation of N_(2)O.In the high-temperature region,the Brønsted acid sites promote the decomposition of NH_(2)NO into N_(2)and H_(2)O.Meanwhile,the N_(2)O-SCR reaction can also be promoted by Brønsted acid sites,thereby decreasing N_(2)O emissions.This study suggests that in the future design and synthesis of Cu-SSZ-13 zeolites,attention should be paid to creating more Brønsted acid sites in Cu-SSZ-13 to reduce N_(2)O emissions.
