All-solid-state Z-scheme photocatalysts for overall water splitting to evolve H_(2) is a promising strategy for efficient conversion of solar energy.However,most of these strategies require redox mediators.Herein,a di...All-solid-state Z-scheme photocatalysts for overall water splitting to evolve H_(2) is a promising strategy for efficient conversion of solar energy.However,most of these strategies require redox mediators.Herein,a direct Z-scheme photoelectrocatalytic electrode based on a WO_(3-x)nanowire-bridged TiO_(2)nanorod array heterojunction is constructed for overall water splitting,producing H_(2).The as-prepared WO_(3-x)/TiO_(2)nanorod array heterojunction shows photoelectrochemical(PEC)overall water splitting activity evolving both H_(2) and O_(2)under UV-vis light irradiation.An optimum PEC activity was achieved over a 1.67-WO_(3-x)/TiO_(2)photoelectrode yielding maximum H_(2) and O_(2)evolution rates roughly 11 times higher than that of pure TiO_(2)nanorods without any sacrificial agent or redox mediator.The role of oxygen vacancy in WO_(3-x)in affecting the H_(2) production rate was also comprehensively studied.The superior PEC activity of the WO_(3-x)/TiO_(2)electrode for overall water splitting can be ascribed to an efficient Z-scheme charge transfer pathway between the WO_(3-x)nanowires and TiO_(2)nanorods,the presence of oxygen vacancies in WO_(3-x),and a bias potential applied on the photoelectrode,resulting in effective spatial charge separation.This study provides a novel strategy for developing highly efficient PECs for overall water splitting.展开更多
Although computational studies have demonstrated that metal ion doping can effectively narrow the bandgap of TiO_(2),the visible-light photoactivity of metal-doped TiO_(2) photoanodes is still far from satisfactory.He...Although computational studies have demonstrated that metal ion doping can effectively narrow the bandgap of TiO_(2),the visible-light photoactivity of metal-doped TiO_(2) photoanodes is still far from satisfactory.Herein,we report an effective strategy to activate the visible-light photoactivity of chromiumimplanted TiO_(2) via the incorporation of oxygen vacancies.The chromium-doped TiO_(2) activated by oxygen vacancies(Cr-TiO_(2)-vac)exhibited an incident photon-to-electron conversion efficiency(IPCE)of~6.8%at450 nm,which is one of the best values reported for metal-doped TiO_(2).Moreover,Cr-TiO_(2)-vac showed no obvious photocurrent decay after 100 h under visible-light illumination.展开更多
Owing to the environmental and inherent advantages,nitrogen reduction reaction(NRR)by electrocatalysts attracts global attention.The surface engineering is widely employed to enhance the electrocatalytic activity by a...Owing to the environmental and inherent advantages,nitrogen reduction reaction(NRR)by electrocatalysts attracts global attention.The surface engineering is widely employed to enhance the electrocatalytic activity by atomic defects and heterostructure effects.A three-dimensional(3D)free-standing integrated electrode was fabricated by numerous nearly-single-crystal TiO_(2-δ)N_δnanowire arrays.Based on the high electronic conductivity network,it exposes numerous active sites as well to facilitate the selective nitrogen adsorption and*H adsorption suppression.The synergistic effects between Ti^(3+)and oxygen vacancy(O_v)boost the intrinsic catalytic activity,in which Ti^(3+)acquired electrons via Ovcan effectively activate the N≡N bond and make it easy to bind with protons.The energy barrier of primary protonation process(*N_(2)+H^(+)+e^(-)→*NNH)can be dramatically decreased.The highest ammonia yield rate(14.33μg h^(-1)mgcat^(-1))emerges at-0.2 V,while the optimal ammonia Faradaic efficiency(9.17%)is acquired at-0.1 V.Density functional theory(DFT)calculation reveals that the Ti^(3+)can be served as the active sites for nitrogen adsorption and activation,while ammonia synthesis is accomplished by the distal pathway.The high electronic conductivity integrated network and synergistic effects can significantly facilitate nitrogen absorption and accelerate electrocatalytic reaction kinetic,which are responsible for the excellent NRR performance at room temperature.展开更多
1T phase MoS_(2)(1T-MoS_(2)) is a promising substitute of platinum electrocatalyst for hydrogen evolution reaction(HER)due to its high intrinsic activity but suffering from thermodynamical instability.Although great e...1T phase MoS_(2)(1T-MoS_(2)) is a promising substitute of platinum electrocatalyst for hydrogen evolution reaction(HER)due to its high intrinsic activity but suffering from thermodynamical instability.Although great efforts have been made to synthesize 1T-MoS_(2) and enhance its stability,it remains a big challenge to realize the phase control and stabilization of 1T-MoS_(2).Herein,based on crystal field theory analysis,we propose a new solution by designing an electrocatalyst of 1T-MoS_(2) nanosheets anchoring on black TiO2-xnanotube arrays in-situ grown on Ti plate(1T-MoS_(2)/TiO_(2-x)@Ti).The black TiO_(2-x)substrate is expected to play as electron donors to increase the charge in Mo 4 d orbits of 1T-MoS_(2) and thus weaken the asymmetric occupation of electrons in the Mo 4 d orbits.Experimental results demonstrate that black TiO_(2-x)nanotubes shift electrons to MoS_(2) and induce MoS_(2) to generate more 1 T phase due to stabilizing the 1T-MoS_(2) nanosheets compared with a Ti substrate.Thus 1T-MoS_(2/)TiO_(2-x)@Ti shows much improved HER performance with a small Tafel slope of 42 m V dec^(-1) and excellent catalytic stability with negligible degradation for 24 h.Theoretical calculations confirm that the black TiO_(2-x)substrate can effectively stabilize metastable 1T-MoS_(2) due to electrons transferring from black TiO_(2-x)to Mo 4 d orbits.This work sheds light on the instability of 1T-MoS_(2) and provides an essential method to stabilize and efficiently utilize 1T-MoS_(2) for HER.展开更多
Semiconductor-molecule surface-enhanced Raman scattering(SERS),especially the stronger interfacial charge transfer process(ICTP),represents a frontier in the field of SERS with spectral reproducibility and unparallele...Semiconductor-molecule surface-enhanced Raman scattering(SERS),especially the stronger interfacial charge transfer process(ICTP),represents a frontier in the field of SERS with spectral reproducibility and unparalleled selectivity.Herein,through a laser microfabrication method in situ,the free-standing,super hydrophilic and vacancy-rich TiO_(2-x)/Ti is successfully synthesized.Using blue TiO_(x)/Ti(B-TiO_(x)/Ti)as preconcentrated substrate,a nanomolar-level limit of detection of 12 nmol/L at 1385 cm–1,is confirmed using crystal violet(CV)bacteriostat as a model under 532 nm excitation.Furthermore,the results demonstrate that the SERS enhancement mechanism is via the moderate adulteration of oxygen vacancy,which leads to a narrow value of band gap and increases the ICTP of substrate to molecules.Using a hand-held extractor assembled with B-TiO_(x)/Ti microfiber,the operando analysis of mixtures distributed information excited in different parts of Asian carp is facilely achieved.This work guides the controlled synthesis of vacancy-rich TiO_(2-x)/Ti nanostructure and its application in ultrasensitive extraction-SERS detection.It also provides the direction for the rapid and operando transmission of biological information with temporal and spatial concentration distribution in human tissues by highly sensitized materials.展开更多
Research on doping modification of ZnTiO_(3) ceramics to enhance microwave dielectric properties has been hindered by poor performance,unclear structure-function mechanisms.To expand the applicability of ZnTiO_(3) cer...Research on doping modification of ZnTiO_(3) ceramics to enhance microwave dielectric properties has been hindered by poor performance,unclear structure-function mechanisms.To expand the applicability of ZnTiO_(3) ceramics,this study explores Zn_(1-x)Li_(2x)TiO_(3)(O≤×≤1)ceramics using a phase engineering strategy.Our findings reveal that the introduction of Lit into the ZnTiO_(3) system initiates a multiple phase transition,starting at x=0.1.Initially,ilmenite ZnTiO_(3) transforms into a cubic ordered spinel phase(space group P4332).Subsequently,a transition to a disordered spinel phase(space group Fd3m)occurs at x=0.5,culminating in the formation of a monoclinic rock salt-structured LizTiO3 phase.Significantly,two sets of ceramics with near-zero temperature coefficients of resonance frequency(t:)were obtained at x=0.1 and 0.75.Moreover,the quality factor(Qxf)demonstrated a 4.4-fold increase compared to that of ZnTiO_(3) ceramics at x=0.25(105,013 GHz).Additionally,it was observed that the Ti4 polarization in Zn_(1-x)Li_(2x)TiO_(3) ceramics was underestimated by 11.3%-13.3%,causing the measured dielectric constant(e.)exceeding the theoretical dielectric constant(eth).The ionic polarizability of Ti*was adjusted to stabilize around 3.29 A.Evaluation using multiple methods,including Phillips-van Vechten-Levine(P-V-L)theory,Raman vibrational mode analysis,bond valence,bond energy theory,and octahedral distortion,confirms that the Ti-O bonds within the octahedron predominantly affect&r,the increasing lattice energy(U)contributes to the enhancement of Qxf,and the strengthened Li-O bond energy effectively regulates Tr.展开更多
The increase in energy consumption and its collateral damage on the environment has encouraged the development of environment-friendly ceramic materials with good energy storage properties.In this work,(1-x)Na_(0.5)Bi...The increase in energy consumption and its collateral damage on the environment has encouraged the development of environment-friendly ceramic materials with good energy storage properties.In this work,(1-x)Na_(0.5)Bi_(0.5)TiO_(3)-xCa(Mg_(1/3)Nb_(2/3))O_(3) ceramics were synthesized by the solid-state reaction method.The 0.88Na_(0.5)Bi_(0.5)TiO_(3)-0.12Ca(Mg_(1/3)Nb_(2/3))O_(3) ceramic exhibited a high recoverable energy storage density of 8.1 J/cm3 and energy storage efficiency of 82.4% at 550 kV/cm.The introduction of Ca(Mg_(1/3)Nb_(2/3))O_(3) reduced the grain size and increased the band gap,thereby enhancing the breakdown field strength of the ceramic materials.The method also resulted in good temperature stability(20–140℃),frequency stability(1–200 Hz),and fatigue stability over 106 cycles.In addition,an ultrahigh power density of 187 MW/cm^(3) and a fast charge-discharge rate(t0.9=57.2 ns)can be obtained simultaneously.Finite element method analysis revealed that the decrease of grain size was beneficial to the increase of breakdown field strength.Therefore,the 0.88Na_(0.5)Bi_(0.5)TiO_(3)-0.12Ca(Mg_(1/3)Nb_(2/3))O_(3) ceramics resulted in high energy storage properties with good stability and were promising environment-friendly materials for advanced pulsed power systems applications.展开更多
基金supported by the National Key Research and Development Program of China(2019YFA0705400 and 2019YFD0901100)the National Natural Science Foundation of China(21991151,21925404,and 21775127)+1 种基金the“111”Project(B17027)Guangdong Basic and Applied Basic Research Foundation(2020A1515010510)。
文摘All-solid-state Z-scheme photocatalysts for overall water splitting to evolve H_(2) is a promising strategy for efficient conversion of solar energy.However,most of these strategies require redox mediators.Herein,a direct Z-scheme photoelectrocatalytic electrode based on a WO_(3-x)nanowire-bridged TiO_(2)nanorod array heterojunction is constructed for overall water splitting,producing H_(2).The as-prepared WO_(3-x)/TiO_(2)nanorod array heterojunction shows photoelectrochemical(PEC)overall water splitting activity evolving both H_(2) and O_(2)under UV-vis light irradiation.An optimum PEC activity was achieved over a 1.67-WO_(3-x)/TiO_(2)photoelectrode yielding maximum H_(2) and O_(2)evolution rates roughly 11 times higher than that of pure TiO_(2)nanorods without any sacrificial agent or redox mediator.The role of oxygen vacancy in WO_(3-x)in affecting the H_(2) production rate was also comprehensively studied.The superior PEC activity of the WO_(3-x)/TiO_(2)electrode for overall water splitting can be ascribed to an efficient Z-scheme charge transfer pathway between the WO_(3-x)nanowires and TiO_(2)nanorods,the presence of oxygen vacancies in WO_(3-x),and a bias potential applied on the photoelectrode,resulting in effective spatial charge separation.This study provides a novel strategy for developing highly efficient PECs for overall water splitting.
基金financially supported by the National Natural Science Foundation of China(U1867215,11722543,11875211,U1932134)the Suzhou Key Industrial Technology Innovation Project(SYG201828)+2 种基金the Hubei Provincial Natural Science Foundation(2019CFA036)the Fundamental Research Funds for the Central Universities(2042020kf0211)the financial support from the National Science Foundation(U.S.)under grant no.DMR-2003563。
文摘Although computational studies have demonstrated that metal ion doping can effectively narrow the bandgap of TiO_(2),the visible-light photoactivity of metal-doped TiO_(2) photoanodes is still far from satisfactory.Herein,we report an effective strategy to activate the visible-light photoactivity of chromiumimplanted TiO_(2) via the incorporation of oxygen vacancies.The chromium-doped TiO_(2) activated by oxygen vacancies(Cr-TiO_(2)-vac)exhibited an incident photon-to-electron conversion efficiency(IPCE)of~6.8%at450 nm,which is one of the best values reported for metal-doped TiO_(2).Moreover,Cr-TiO_(2)-vac showed no obvious photocurrent decay after 100 h under visible-light illumination.
基金financially supported by the Liao Ning Revitalization Talents Program(XLYC2007155)the Fundamental Research Funds for the Central Universities(N2025018,N2025009)。
文摘Owing to the environmental and inherent advantages,nitrogen reduction reaction(NRR)by electrocatalysts attracts global attention.The surface engineering is widely employed to enhance the electrocatalytic activity by atomic defects and heterostructure effects.A three-dimensional(3D)free-standing integrated electrode was fabricated by numerous nearly-single-crystal TiO_(2-δ)N_δnanowire arrays.Based on the high electronic conductivity network,it exposes numerous active sites as well to facilitate the selective nitrogen adsorption and*H adsorption suppression.The synergistic effects between Ti^(3+)and oxygen vacancy(O_v)boost the intrinsic catalytic activity,in which Ti^(3+)acquired electrons via Ovcan effectively activate the N≡N bond and make it easy to bind with protons.The energy barrier of primary protonation process(*N_(2)+H^(+)+e^(-)→*NNH)can be dramatically decreased.The highest ammonia yield rate(14.33μg h^(-1)mgcat^(-1))emerges at-0.2 V,while the optimal ammonia Faradaic efficiency(9.17%)is acquired at-0.1 V.Density functional theory(DFT)calculation reveals that the Ti^(3+)can be served as the active sites for nitrogen adsorption and activation,while ammonia synthesis is accomplished by the distal pathway.The high electronic conductivity integrated network and synergistic effects can significantly facilitate nitrogen absorption and accelerate electrocatalytic reaction kinetic,which are responsible for the excellent NRR performance at room temperature.
基金supported by the New Zealand China Doctoral Research Scholarship (Grant no. 201706080124)support from the China Scholarships Council (CSC) for his study at the University of Auckland
文摘1T phase MoS_(2)(1T-MoS_(2)) is a promising substitute of platinum electrocatalyst for hydrogen evolution reaction(HER)due to its high intrinsic activity but suffering from thermodynamical instability.Although great efforts have been made to synthesize 1T-MoS_(2) and enhance its stability,it remains a big challenge to realize the phase control and stabilization of 1T-MoS_(2).Herein,based on crystal field theory analysis,we propose a new solution by designing an electrocatalyst of 1T-MoS_(2) nanosheets anchoring on black TiO2-xnanotube arrays in-situ grown on Ti plate(1T-MoS_(2)/TiO_(2-x)@Ti).The black TiO_(2-x)substrate is expected to play as electron donors to increase the charge in Mo 4 d orbits of 1T-MoS_(2) and thus weaken the asymmetric occupation of electrons in the Mo 4 d orbits.Experimental results demonstrate that black TiO_(2-x)nanotubes shift electrons to MoS_(2) and induce MoS_(2) to generate more 1 T phase due to stabilizing the 1T-MoS_(2) nanosheets compared with a Ti substrate.Thus 1T-MoS_(2/)TiO_(2-x)@Ti shows much improved HER performance with a small Tafel slope of 42 m V dec^(-1) and excellent catalytic stability with negligible degradation for 24 h.Theoretical calculations confirm that the black TiO_(2-x)substrate can effectively stabilize metastable 1T-MoS_(2) due to electrons transferring from black TiO_(2-x)to Mo 4 d orbits.This work sheds light on the instability of 1T-MoS_(2) and provides an essential method to stabilize and efficiently utilize 1T-MoS_(2) for HER.
基金supported by National Key Research and Development Program of China(No.2023YFB3210400)Major Scientific and Technological Innovation Project of Shandong Province(No.2021CXGC010603)+1 种基金Natural Science Foundation of Shandong Province(Nos.ZR2020QE057,ZR2020QE071,ZR2020LLZ006)Innovative Team Project of Jinan(No.2021GXRC019)。
文摘Semiconductor-molecule surface-enhanced Raman scattering(SERS),especially the stronger interfacial charge transfer process(ICTP),represents a frontier in the field of SERS with spectral reproducibility and unparalleled selectivity.Herein,through a laser microfabrication method in situ,the free-standing,super hydrophilic and vacancy-rich TiO_(2-x)/Ti is successfully synthesized.Using blue TiO_(x)/Ti(B-TiO_(x)/Ti)as preconcentrated substrate,a nanomolar-level limit of detection of 12 nmol/L at 1385 cm–1,is confirmed using crystal violet(CV)bacteriostat as a model under 532 nm excitation.Furthermore,the results demonstrate that the SERS enhancement mechanism is via the moderate adulteration of oxygen vacancy,which leads to a narrow value of band gap and increases the ICTP of substrate to molecules.Using a hand-held extractor assembled with B-TiO_(x)/Ti microfiber,the operando analysis of mixtures distributed information excited in different parts of Asian carp is facilely achieved.This work guides the controlled synthesis of vacancy-rich TiO_(2-x)/Ti nanostructure and its application in ultrasensitive extraction-SERS detection.It also provides the direction for the rapid and operando transmission of biological information with temporal and spatial concentration distribution in human tissues by highly sensitized materials.
基金This work was supported by the National Natural Science Foundation of China(No.52102129)the Hunan Provincial Natural Science Foundation of China(No.2023JJ30138)the science and technology innovation Program of Hunan Province(No.2023RC3094).
文摘Research on doping modification of ZnTiO_(3) ceramics to enhance microwave dielectric properties has been hindered by poor performance,unclear structure-function mechanisms.To expand the applicability of ZnTiO_(3) ceramics,this study explores Zn_(1-x)Li_(2x)TiO_(3)(O≤×≤1)ceramics using a phase engineering strategy.Our findings reveal that the introduction of Lit into the ZnTiO_(3) system initiates a multiple phase transition,starting at x=0.1.Initially,ilmenite ZnTiO_(3) transforms into a cubic ordered spinel phase(space group P4332).Subsequently,a transition to a disordered spinel phase(space group Fd3m)occurs at x=0.5,culminating in the formation of a monoclinic rock salt-structured LizTiO3 phase.Significantly,two sets of ceramics with near-zero temperature coefficients of resonance frequency(t:)were obtained at x=0.1 and 0.75.Moreover,the quality factor(Qxf)demonstrated a 4.4-fold increase compared to that of ZnTiO_(3) ceramics at x=0.25(105,013 GHz).Additionally,it was observed that the Ti4 polarization in Zn_(1-x)Li_(2x)TiO_(3) ceramics was underestimated by 11.3%-13.3%,causing the measured dielectric constant(e.)exceeding the theoretical dielectric constant(eth).The ionic polarizability of Ti*was adjusted to stabilize around 3.29 A.Evaluation using multiple methods,including Phillips-van Vechten-Levine(P-V-L)theory,Raman vibrational mode analysis,bond valence,bond energy theory,and octahedral distortion,confirms that the Ti-O bonds within the octahedron predominantly affect&r,the increasing lattice energy(U)contributes to the enhancement of Qxf,and the strengthened Li-O bond energy effectively regulates Tr.
基金This work is supported by the Natural Science Foundation of Shandong Province of China(Nos.ZR2020ME035,ZR2020QE043 and ZR2020QE044)National Natural Science Foundation of China(Nos.51872166 and 52102132)+1 种基金Postdoctoral Research Foundation of China(2017M622196)Opening Project of Key Laboratory of Inorganic Functional Materials and Devices,Chinese Academy of Sciences(KLIFMD201705).
文摘The increase in energy consumption and its collateral damage on the environment has encouraged the development of environment-friendly ceramic materials with good energy storage properties.In this work,(1-x)Na_(0.5)Bi_(0.5)TiO_(3)-xCa(Mg_(1/3)Nb_(2/3))O_(3) ceramics were synthesized by the solid-state reaction method.The 0.88Na_(0.5)Bi_(0.5)TiO_(3)-0.12Ca(Mg_(1/3)Nb_(2/3))O_(3) ceramic exhibited a high recoverable energy storage density of 8.1 J/cm3 and energy storage efficiency of 82.4% at 550 kV/cm.The introduction of Ca(Mg_(1/3)Nb_(2/3))O_(3) reduced the grain size and increased the band gap,thereby enhancing the breakdown field strength of the ceramic materials.The method also resulted in good temperature stability(20–140℃),frequency stability(1–200 Hz),and fatigue stability over 106 cycles.In addition,an ultrahigh power density of 187 MW/cm^(3) and a fast charge-discharge rate(t0.9=57.2 ns)can be obtained simultaneously.Finite element method analysis revealed that the decrease of grain size was beneficial to the increase of breakdown field strength.Therefore,the 0.88Na_(0.5)Bi_(0.5)TiO_(3)-0.12Ca(Mg_(1/3)Nb_(2/3))O_(3) ceramics resulted in high energy storage properties with good stability and were promising environment-friendly materials for advanced pulsed power systems applications.
基金Program for Innovation Talents in University of Liaoning Province (LR2019044)Natural Science Foundation of Liaoning Province of China (2019-ZD-0540)+1 种基金Program for Young and Middle-aged Innovation Talents in Science and Technologies of Shenyang (RC190359)Project of Guangxi Key Laboratory of Information Materials (Guilin University of Electronic Technology),China (191007-K)。
