Josephson junction plays a key role not only in studying the basic physics of unconventional iron-based superconductors but also in realizing practical application of thin-film based devices,therefore the preparation ...Josephson junction plays a key role not only in studying the basic physics of unconventional iron-based superconductors but also in realizing practical application of thin-film based devices,therefore the preparation of high-quality iron pnictide Josephson junctions is of great importance.In this work,we have successfully fabricated Josephson junctions from Co-doped BaFe_(2)As_(2)thin films using a direct junction fabrication technique which utilizes high energy focused helium ion beam(FHIB).The electrical transport properties were investigated for junctions fabricated with various He^(+)irradiation doses.The junctions show sharp superconducting transition around 24 K with a narrow transition width of 2.5 K,and a dose correlated foot-structure resistance which corresponds to the effective tuning of junction properties by He^(+)irradiation.Significant J_c suppression by more than two orders of magnitude can be achieved by increasing the He^(+)irradiation dose,which is advantageous for the realization of low noise ion pnictide thin film devices.Clear Shapiro steps are observed under 10 GHz microwave irradiation.The above results demonstrate the successful fabrication of high quality and controllable Co-doped BaFe_(2)As_(2)Josephson junction with high reproducibility using the FHIB technique,laying the foundation for future investigating the mechanism of iron-based superconductors,and also the further implementation in various superconducting electronic devices.展开更多
The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface def...The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures.Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9-x(SDC)containing a fixed valence dopant Sm3+are very different from those published for Pr0.1Ce0.9O_(2)-x(PCO) with the variable valence dopant Pr4+/Pr3+being reduced under milder conditions.The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO.It leads to the following predictions:the highly reduced surface of SDC is metallic and neutral,the metallic surface electron density of state is gs=0.9×10^(38)J-1·m^(-2)(1.4×1015eV^(-1)·cm^(-2)),the electron effective mass is meff,s=3.3me,and the phase diagram of the reduced surface has theα(fcc)structure as in the bulk.In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting.The surface of PCO maintains high Pr^(3+) defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk.The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO_(2) are reviewed,as well as the key theoretical considerations applied in coping with this problem.For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.展开更多
Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)na...Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)nanoflakes for hydrogen evolution reaction(HER).The doping of MoS_(2)with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics,which significantly enhances its electrical conductivity and structural stability,which are verified by various characterization tools,including X‐ray photoelectron spectroscopy,high‐resolution transmission electron microscopy,X‐ray absorption near‐edge spectroscopy,and extended X‐ray absorption fine structure.Moreover,the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites,which remarkably enhance its HER activity.The optimized P‐BMS electrocatalysts exhibit low overpotentials(60 and 72 mV at 10 mA cm^(−2))in H_(2)SO_(4)(0.5 M)and KOH(1.0 M),respectively.The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques.This study has shown that phase engineering is a promising strategy for enhancing the H*adsorption of metal sulfides.展开更多
Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) un...Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_(1)2_(1)2_(1).Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.展开更多
SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish ...SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish reaction kinetics,low electronic conductivity,and large volume changes during charge and discharge hinder the practical applications of SnO_(2)-based electrodes for SIBs and PIBs.Engineering rational structures with fast charge/ion transfer and robust stability is important to overcoming these challenges.Herein,S-doped SnO_(2)(S-SnO_(2))quantum dots(QDs)(≈3 nm)encapsulated in an N,S codoped carbon fiber networks(S-SnO_(2)-CFN)are rationally fabricated using a sequential freeze-drying,calcination,and S-doping strategy.Experimental analysis and density functional theory calculations reveal that the integration of S-SnO_(2) QDs with N,S codoped carbon fiber network remarkably decreases the adsorption energies of Na/K atoms in the interlayer of SnO_(2)-CFN,and the S doping can increase the conductivity of SnO_(2),thereby enhancing the ion transfer kinetics.The synergistic interaction between S-SnO_(2) QDs and N,S codoped carbon fiber network results in a composite with fast Na+/K+storage and extraordinary long-term cyclability.Specifically,the S-SnO_(2)-CFN delivers high rate capacities of 141.0 mAh g^(−1) at 20 A g^(−1) in SIBs and 102.8 mAh g^(−1) at 10 A g^(−1) in PIBs.Impressively,it delivers ultra-stable sodium storage up to 10,000 cycles at 5 A g^(−1) and potassium storage up to 5000 cycles at 2 A g^(−1).This study provides insights into constructing metal oxide-based carbon fiber network structures for high-performance electrochemical energy storage and conversion devices.展开更多
Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation o...Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation of charges,resulting in poor photocatalytic activity.In the present study,we successfully synthesize SrTaO_(2)N photocatalyst with low density of defect states,uniform morphology and particle size by flux-assisted one-pot nitridation combined with Mg doping.Some important parameters,such as the size of unit cell,the content of nitrogen,and microstructure,prove the successful doping of Mg.The defect-related carrier recombination has been significantly reduced by Mg doping,which effectively promotes the charge separation.Moreover,Mg doping induces a change of the band edge,which makes proton reduction have a stronger driving force.After modifying with the core/shell-structured Pt/Cr_(2)O_(3)cocatalyst,the H_(2)evolution activity of the optimized SrTaO_(2)N:Mg is 10 times that of the undoped SrTaO_(2)N,with an impressive apparent quantum yield of 1.51%at 420 nm.By coupling with Au-FeCoO_(x)modified BiVO_(4)as an O_(2)-evolution photocatalyst and[Fe(CN)_(6)]_(3)−/[Fe(CN)_(6)]_(4)−as the redox couple,a redox-based Z-scheme overall water splitting system is successfully constructed with an apparent quantum yield of 1.36%at 420 nm.This work provides an alternative way to prepare oxynitride semiconductors with reduced defects to promote the conversion of solar energy.展开更多
Nano-spherical Co^(2+)-doped FeS_2 was synthesized through a simple solvothermal method. The products were investigated using XRD, FE-SEM, BET, ICP, EDS, TEM, HRTEM, XPS, and UV-vis spectroscopy. The results indica...Nano-spherical Co^(2+)-doped FeS_2 was synthesized through a simple solvothermal method. The products were investigated using XRD, FE-SEM, BET, ICP, EDS, TEM, HRTEM, XPS, and UV-vis spectroscopy. The results indicated that Co^(2+) ion could change the particle nucleation process and inhibited the particle growth of FeS_2. In addition, when the content of doped Co^(2+) was 15%, the degradation efficiency of methylene blue(MB) achieved 60.72% after 210 min irradiation, which increased by 52.01% than that of the undoped FeS_2. Moreover, comparison experiments also demonstrated that the M(M=Co^2+,Co^2+/Ni^2+)-doped FeS_2 photocatalytic activity efficiency sequence was Co^(2+) 〉 Ni^(2+)〉Co^(2+)/Ni^(2+). This is ascribed to the fact that the Co^(2+) doping could induce the absorption edge shifting into the visible-light region and increased the surface area of the samples. The effect mechanisms of M-doping on the band gap and the photocatalytic activity of FeS_2 were also discussed.展开更多
The preparation and characteristics of a new transparent glass ceramic were described. Crystal phase particles with nanometer size were successfully precipitated in glass matrix, which was confirmed to be one of indiu...The preparation and characteristics of a new transparent glass ceramic were described. Crystal phase particles with nanometer size were successfully precipitated in glass matrix, which was confirmed to be one of indium aluminum zinc oxide compounds (InxAlrZn2O). The presence of aluminum (A1) and indium (In) impurities in the zinc oxides (ZnO) crystal lattice leads to some changes of the carrier concentration in the material and then promote the sharply changes of transmission spectra in IR range wavelength. And subsequently, the IR cut-off edge blue shifted from 5.5 pm in base glass to 3 μm in transparent glass ceramic sample. Furthermore, passive Q switched 1.54 ktm Er glass laser pulses with pulse energy of 10 mJ and pulse width of 800 ns were successfully obtained by using the cobalt doped transparent glass ceramic as a saturable absorber.展开更多
To improve the performance of Ni-Zn ferrites for power field use,the influence of MnO2 additive on the properties of Ni-Zn ferrites was investigated by the conventional powder metallurgy.The results show that MnO2 doe...To improve the performance of Ni-Zn ferrites for power field use,the influence of MnO2 additive on the properties of Ni-Zn ferrites was investigated by the conventional powder metallurgy.The results show that MnO2 does not form a visible second phase in the doping mass fraction range of(0-2.0%).The average grain size,sintering density and real permeability gradually decrease with the increase of the MnO2 content.And the DC resistivity continuously increases with the increase of MnO2 content.The saturation magnetization(magnetic moment in unit mass) first increases slightly when mass fraction of MnO2 is less than 0.4% MnO2,and then gradually decreases with increasing the MnO2 mass fraction due to the exchange interaction of the cations.When the excitation frequency is less than 1 MHz,the power loss(Pcv) continuously increases with increasing the MnO2 content due to the decrease of average grain size.However,when the excitation frequency exceeds 1 MHz,eddy current loss gradually becomes the predominant contribution to Pcv.And the sample with a higher resistivity favors a lower Pcv,except for the sample with 2.0% MnO2.The sample without additive has the best Pcv when worked at frequencies less than 1 MHz;and the sample with 1.6% MnO2 additive has the best Pcv when worked at frequencies higher than 1 MHz.展开更多
Cu-doped TiO2 nanoparticles with different doping contents from 0 to 2.0% (mole fraction) were synthesized through sol-gel method. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and field emissi...Cu-doped TiO2 nanoparticles with different doping contents from 0 to 2.0% (mole fraction) were synthesized through sol-gel method. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscope (FE-SEM) were used to characterize the crystalline structure, chemical valence states and morphology of TiO2 nanoparticles. UV-Vis absorption spectrum was used to measure the optical absorption property of the samples. The photocatalytic performance of the samples was characterized by degrading 20 mg/L methyl orange under UV-Vis irradiation. The results show that the Cu-doped TiO2 nanoparticles exhibit a significant increase in photocatalytic performance over the pure TiO2 nanoparticles, and the TiO2 nanoparticles doped with 1.0% Cu show the best photocatalytic performance. The improvement in photocatalytic performance is attributed to the enhanced light adsorption in UV-Vis range and the decrease of the recombination rate of photoinduced electron-hole oair of the Cu-doped TiO2 nanoparticles.展开更多
Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01~0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of t...Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01~0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of the LiCo 1- x RE x O 2 were investigated by XRD. It was found that the lattice parameters c are increased and the lattice volumes are enlarged compared to that of LiCoO 2. Moreover, the performance of LiCo 1- x RE x O 2 as the cathode material in lithium ion battery is improved, especially LiCo 1- x Y x O 2 and LiCo 1- x La x O 2. The initial charge/discharge capacities of LiCo 0.99 Y 0.01 O 2 and LiCo 0.99 La 0.01 O 2 are 174/154 (mAh·g -1 ) and 159/149 (mAh·g -1 ) respectively, while those for LiCoO 2 working in the same way are only 139/131 (mAh·g -1 ).展开更多
Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibri...Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.展开更多
Cerium-doped titanium dioxide nano-powders were prepared through the sol-gel method and the compound sampies were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV/Vis diffus...Cerium-doped titanium dioxide nano-powders were prepared through the sol-gel method and the compound sampies were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV/Vis diffuse reflectance spectra (DRS). The photocatalytic activity was evaluated by photocatalytic degradation of phenol in water. The results of XRD, TEM, and DRS show that pure TiO2 and Ce-doped TiO2 powder crystallines are a mixture of anatase and rutile ; the doping can retard the development of the grain size of TiO2 and decrease the diameter of TiO2 from more than 20 nm of pure TiO2 to about 10 nm; the doped TiO2 can improve the light absorption of TiO2 and suitable doping content tends to move the DRS spectrum of TiO2 towards visible light, but too much doping is not good for the light absorption ability. The results of the photocatalytic experiments show that doping with Ce content of 0.08% -0.4% can increase the photocatalytic activity of TiO2; however, doping with Ce content of 0.5% -2.5% can significantly decrease the photocatalytic activity of TiO2. The favorite doping content is 0.4% in the range of our experiments.展开更多
Iron(Ⅲ)-doped nanostructure TiO2-coated SiO2 (TiO2/SiO2) particles were prepared using the layer-by-layer assembly technique and their photocatalytic property was studied. TiO2 colloids were synthesized employing...Iron(Ⅲ)-doped nanostructure TiO2-coated SiO2 (TiO2/SiO2) particles were prepared using the layer-by-layer assembly technique and their photocatalytic property was studied. TiO2 colloids were synthesized employing the sol-gel method with TiChas a precursor. The samples were characterized by Fourier transform infrared spectroscopy (FTIR), SEM, EDS, XPS, and XRD. The experimental results show that TiO2 nanopowders on the surface of SiO2 particles are well distributed, the amount of TiO2 is increased with the adding of coating layers, the pure anatase-TiO2 coating layers are synthesized at 500℃, and the photocatalytic activity of Fe^3+-doped TiO2/SiO2 is higher than that of undoped TiO2/SiO2.展开更多
The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,N...The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,Ni,and Cu)doping for modulating the Fermi energy level of Mo2C.The defective energy level facilitates the free water molecule adsorption and,subsequently,promotes the neutral HER efficiency.Specifically,at a current density of 10 mA/cm2,Cu-Mo2C exhibits the best HER performance with an overpotential of 78 mV,followed by Ni-Mo2C,Co-Mo2C,Fe-Mo2C,and bare Mo2C with 90,95,100,and 173 mV,respectively,and the corresponding Tafel slope values are 40,43,42,56,and 102 mV/dec.The modified WF can also lead to an enhanced photocatalytic efficiency owing to the lowered Schottky barrier and excellent carrier transition across the electrocatalyst–solution interface.When coupling the metal-doped Mo2C samples with TiO2,enhanced photocatalytic neutral HER rates are obtained in comparison to the case with bare TiO2.Typically,the HER rates are 521,404,275,224,147,and 112μmol/h for Cu,Ni,Co,Fe,bare Mo2C,and bare TiO2,respectively.Time-resolved photoluminescence spectroscopy(TRPS)and ultrafast transient absorption(TA)measurements are carried out to confirm the recombination and migration of the photogenerated carriers.The fittedτvalues from the TRPS curves are 22.6,20.5,10.1,4.7,4.0,2.5,and 1.9 ns for TiO2,TiO2-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,and TiO2-Pt,respectively.Additionally,the fittedτvalues from the TA results are 31,73,and 105 ps for the TiO2-Mo2C,TiO2-Cu-Mo2C,and TiO2-Pt samples,respectively.This work provides in-depth insights into the WF modulation of an electrocatalyst for improving the HER performance.展开更多
A carbon‐doped TiO2/fly ash support(C‐TiO2/FAS)composite photocatalyst was successfully synthesized through sol impregnation and subsequent carbonization.The carbon dopants were derived from the organic species gene...A carbon‐doped TiO2/fly ash support(C‐TiO2/FAS)composite photocatalyst was successfully synthesized through sol impregnation and subsequent carbonization.The carbon dopants were derived from the organic species generated during the synthesis of the C‐TiO2/FAS composite.A series of analytical techniques,such as scanning electron microscopy(SEM),attenuated total reflection‐Fourier transform infrared(ATR‐FTIR)spectroscopy,X‐ray photoelectron spectroscopy(XPS),and ultraviolet‐visible diffuse reflectance spectroscopy(UV‐Vis DRS),were used to characterize the properties of the prepared samples.The results indicated that C‐TiO2 was successfully coated on the FAS surface.Coupling between C‐TiO2 and FAS resulted in the formation of Si–O–C and Al–O–Ti bonds at their interface.The formation of Si–O–C and Al–O–Ti bonds gave rise to a positive shift of the valence band edge of C‐TiO2 and enhanced its oxidation capability of photogenerated holes as well as photodegradation efficiency of methyl orange.Moreover,the C‐TiO2/FAS photocatalyst exhibited favorable reusability and separability.This work may provide a new route for tuning the electronic band structure of TiO2.展开更多
基金Project supported by the National Key Research and Development Program of China (Grant Nos.2020YFF01014706 and 2017YFC0601901)the National Natural Science Foundation of China (Grant Nos.61571019 and 52177026)。
文摘Josephson junction plays a key role not only in studying the basic physics of unconventional iron-based superconductors but also in realizing practical application of thin-film based devices,therefore the preparation of high-quality iron pnictide Josephson junctions is of great importance.In this work,we have successfully fabricated Josephson junctions from Co-doped BaFe_(2)As_(2)thin films using a direct junction fabrication technique which utilizes high energy focused helium ion beam(FHIB).The electrical transport properties were investigated for junctions fabricated with various He^(+)irradiation doses.The junctions show sharp superconducting transition around 24 K with a narrow transition width of 2.5 K,and a dose correlated foot-structure resistance which corresponds to the effective tuning of junction properties by He^(+)irradiation.Significant J_c suppression by more than two orders of magnitude can be achieved by increasing the He^(+)irradiation dose,which is advantageous for the realization of low noise ion pnictide thin film devices.Clear Shapiro steps are observed under 10 GHz microwave irradiation.The above results demonstrate the successful fabrication of high quality and controllable Co-doped BaFe_(2)As_(2)Josephson junction with high reproducibility using the FHIB technique,laying the foundation for future investigating the mechanism of iron-based superconductors,and also the further implementation in various superconducting electronic devices.
基金financially supported by the Technion V.P.for Research Fund(No.2023320)。
文摘The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures.Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9-x(SDC)containing a fixed valence dopant Sm3+are very different from those published for Pr0.1Ce0.9O_(2)-x(PCO) with the variable valence dopant Pr4+/Pr3+being reduced under milder conditions.The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO.It leads to the following predictions:the highly reduced surface of SDC is metallic and neutral,the metallic surface electron density of state is gs=0.9×10^(38)J-1·m^(-2)(1.4×1015eV^(-1)·cm^(-2)),the electron effective mass is meff,s=3.3me,and the phase diagram of the reduced surface has theα(fcc)structure as in the bulk.In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting.The surface of PCO maintains high Pr^(3+) defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk.The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO_(2) are reviewed,as well as the key theoretical considerations applied in coping with this problem.For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.
基金National Natural Science Foundation of China,Grant/Award Number:NSFC‐U1904215National Research Foundation of Korea,Grant/Award Number:2021R1A2C2012127。
文摘Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)nanoflakes for hydrogen evolution reaction(HER).The doping of MoS_(2)with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics,which significantly enhances its electrical conductivity and structural stability,which are verified by various characterization tools,including X‐ray photoelectron spectroscopy,high‐resolution transmission electron microscopy,X‐ray absorption near‐edge spectroscopy,and extended X‐ray absorption fine structure.Moreover,the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites,which remarkably enhance its HER activity.The optimized P‐BMS electrocatalysts exhibit low overpotentials(60 and 72 mV at 10 mA cm^(−2))in H_(2)SO_(4)(0.5 M)and KOH(1.0 M),respectively.The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques.This study has shown that phase engineering is a promising strategy for enhancing the H*adsorption of metal sulfides.
基金supported by the National Natural Science Foundation of China (Grant No. 12304072)Program for Science and Technology Innovation Team in Zhejiang (Grant No. 2021R01004)+1 种基金Natural Science Foundation of Ningbo(Grant No. 2021J121)supported by the User Experiment Assist System of Shanghai Synchrotron Radiation Facility (SSRF)。
文摘Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_(1)2_(1)2_(1).Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.
基金National Natural Science Foundation of China,Grant/Award Number:51971065Innovation Program of Shanghai Municipal Education Commission,Grant/Award Number:2019-01-07-00-07-E00028。
文摘SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish reaction kinetics,low electronic conductivity,and large volume changes during charge and discharge hinder the practical applications of SnO_(2)-based electrodes for SIBs and PIBs.Engineering rational structures with fast charge/ion transfer and robust stability is important to overcoming these challenges.Herein,S-doped SnO_(2)(S-SnO_(2))quantum dots(QDs)(≈3 nm)encapsulated in an N,S codoped carbon fiber networks(S-SnO_(2)-CFN)are rationally fabricated using a sequential freeze-drying,calcination,and S-doping strategy.Experimental analysis and density functional theory calculations reveal that the integration of S-SnO_(2) QDs with N,S codoped carbon fiber network remarkably decreases the adsorption energies of Na/K atoms in the interlayer of SnO_(2)-CFN,and the S doping can increase the conductivity of SnO_(2),thereby enhancing the ion transfer kinetics.The synergistic interaction between S-SnO_(2) QDs and N,S codoped carbon fiber network results in a composite with fast Na+/K+storage and extraordinary long-term cyclability.Specifically,the S-SnO_(2)-CFN delivers high rate capacities of 141.0 mAh g^(−1) at 20 A g^(−1) in SIBs and 102.8 mAh g^(−1) at 10 A g^(−1) in PIBs.Impressively,it delivers ultra-stable sodium storage up to 10,000 cycles at 5 A g^(−1) and potassium storage up to 5000 cycles at 2 A g^(−1).This study provides insights into constructing metal oxide-based carbon fiber network structures for high-performance electrochemical energy storage and conversion devices.
文摘Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation of charges,resulting in poor photocatalytic activity.In the present study,we successfully synthesize SrTaO_(2)N photocatalyst with low density of defect states,uniform morphology and particle size by flux-assisted one-pot nitridation combined with Mg doping.Some important parameters,such as the size of unit cell,the content of nitrogen,and microstructure,prove the successful doping of Mg.The defect-related carrier recombination has been significantly reduced by Mg doping,which effectively promotes the charge separation.Moreover,Mg doping induces a change of the band edge,which makes proton reduction have a stronger driving force.After modifying with the core/shell-structured Pt/Cr_(2)O_(3)cocatalyst,the H_(2)evolution activity of the optimized SrTaO_(2)N:Mg is 10 times that of the undoped SrTaO_(2)N,with an impressive apparent quantum yield of 1.51%at 420 nm.By coupling with Au-FeCoO_(x)modified BiVO_(4)as an O_(2)-evolution photocatalyst and[Fe(CN)_(6)]_(3)−/[Fe(CN)_(6)]_(4)−as the redox couple,a redox-based Z-scheme overall water splitting system is successfully constructed with an apparent quantum yield of 1.36%at 420 nm.This work provides an alternative way to prepare oxynitride semiconductors with reduced defects to promote the conversion of solar energy.
基金the National Natural Science Foundation of China(No.51372044)the Guangxi Distinguished Experts Special Fund,Guangxi Natural Science Foundation(No.2014GXNSFFA118004)the Improving the Basic Ability of Young and Middle-aged University Teachers in Guangxi(No.KY2016YB185)
文摘Nano-spherical Co^(2+)-doped FeS_2 was synthesized through a simple solvothermal method. The products were investigated using XRD, FE-SEM, BET, ICP, EDS, TEM, HRTEM, XPS, and UV-vis spectroscopy. The results indicated that Co^(2+) ion could change the particle nucleation process and inhibited the particle growth of FeS_2. In addition, when the content of doped Co^(2+) was 15%, the degradation efficiency of methylene blue(MB) achieved 60.72% after 210 min irradiation, which increased by 52.01% than that of the undoped FeS_2. Moreover, comparison experiments also demonstrated that the M(M=Co^2+,Co^2+/Ni^2+)-doped FeS_2 photocatalytic activity efficiency sequence was Co^(2+) 〉 Ni^(2+)〉Co^(2+)/Ni^(2+). This is ascribed to the fact that the Co^(2+) doping could induce the absorption edge shifting into the visible-light region and increased the surface area of the samples. The effect mechanisms of M-doping on the band gap and the photocatalytic activity of FeS_2 were also discussed.
基金the National Natrural Science Foundation of China(Nos. 50902137 and 60937003)
文摘The preparation and characteristics of a new transparent glass ceramic were described. Crystal phase particles with nanometer size were successfully precipitated in glass matrix, which was confirmed to be one of indium aluminum zinc oxide compounds (InxAlrZn2O). The presence of aluminum (A1) and indium (In) impurities in the zinc oxides (ZnO) crystal lattice leads to some changes of the carrier concentration in the material and then promote the sharply changes of transmission spectra in IR range wavelength. And subsequently, the IR cut-off edge blue shifted from 5.5 pm in base glass to 3 μm in transparent glass ceramic sample. Furthermore, passive Q switched 1.54 ktm Er glass laser pulses with pulse energy of 10 mJ and pulse width of 800 ns were successfully obtained by using the cobalt doped transparent glass ceramic as a saturable absorber.
基金Projects(50702011,60721001)supported by the National Natural Science Foundation of China
文摘To improve the performance of Ni-Zn ferrites for power field use,the influence of MnO2 additive on the properties of Ni-Zn ferrites was investigated by the conventional powder metallurgy.The results show that MnO2 does not form a visible second phase in the doping mass fraction range of(0-2.0%).The average grain size,sintering density and real permeability gradually decrease with the increase of the MnO2 content.And the DC resistivity continuously increases with the increase of MnO2 content.The saturation magnetization(magnetic moment in unit mass) first increases slightly when mass fraction of MnO2 is less than 0.4% MnO2,and then gradually decreases with increasing the MnO2 mass fraction due to the exchange interaction of the cations.When the excitation frequency is less than 1 MHz,the power loss(Pcv) continuously increases with increasing the MnO2 content due to the decrease of average grain size.However,when the excitation frequency exceeds 1 MHz,eddy current loss gradually becomes the predominant contribution to Pcv.And the sample with a higher resistivity favors a lower Pcv,except for the sample with 2.0% MnO2.The sample without additive has the best Pcv when worked at frequencies less than 1 MHz;and the sample with 1.6% MnO2 additive has the best Pcv when worked at frequencies higher than 1 MHz.
基金Project(2010CB631001)supported by the National Basic Research Program of ChinaProject(50871046)supported by the National Natural Science Foundation of China
文摘Cu-doped TiO2 nanoparticles with different doping contents from 0 to 2.0% (mole fraction) were synthesized through sol-gel method. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscope (FE-SEM) were used to characterize the crystalline structure, chemical valence states and morphology of TiO2 nanoparticles. UV-Vis absorption spectrum was used to measure the optical absorption property of the samples. The photocatalytic performance of the samples was characterized by degrading 20 mg/L methyl orange under UV-Vis irradiation. The results show that the Cu-doped TiO2 nanoparticles exhibit a significant increase in photocatalytic performance over the pure TiO2 nanoparticles, and the TiO2 nanoparticles doped with 1.0% Cu show the best photocatalytic performance. The improvement in photocatalytic performance is attributed to the enhanced light adsorption in UV-Vis range and the decrease of the recombination rate of photoinduced electron-hole oair of the Cu-doped TiO2 nanoparticles.
文摘Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01~0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of the LiCo 1- x RE x O 2 were investigated by XRD. It was found that the lattice parameters c are increased and the lattice volumes are enlarged compared to that of LiCoO 2. Moreover, the performance of LiCo 1- x RE x O 2 as the cathode material in lithium ion battery is improved, especially LiCo 1- x Y x O 2 and LiCo 1- x La x O 2. The initial charge/discharge capacities of LiCo 0.99 Y 0.01 O 2 and LiCo 0.99 La 0.01 O 2 are 174/154 (mAh·g -1 ) and 159/149 (mAh·g -1 ) respectively, while those for LiCoO 2 working in the same way are only 139/131 (mAh·g -1 ).
基金financially supported by the National Natural Science Foundation of China(No.51904250)the China Postdoctoral Science Foundation(No.2021M692254)+2 种基金the Sichuan Science and Technology Program(No.2022YFG0098)the Fundamental Research Funds for the Central Universities(Nos.2021CDSN-02,2022SCU12002,2022CDZG-17,2022CDSN-08,2022CDZG-9)the Hohhot Science and Technology Program(No.2023-Jie Bang Gua Shuai-Gao-3)。
文摘Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.
文摘Cerium-doped titanium dioxide nano-powders were prepared through the sol-gel method and the compound sampies were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV/Vis diffuse reflectance spectra (DRS). The photocatalytic activity was evaluated by photocatalytic degradation of phenol in water. The results of XRD, TEM, and DRS show that pure TiO2 and Ce-doped TiO2 powder crystallines are a mixture of anatase and rutile ; the doping can retard the development of the grain size of TiO2 and decrease the diameter of TiO2 from more than 20 nm of pure TiO2 to about 10 nm; the doped TiO2 can improve the light absorption of TiO2 and suitable doping content tends to move the DRS spectrum of TiO2 towards visible light, but too much doping is not good for the light absorption ability. The results of the photocatalytic experiments show that doping with Ce content of 0.08% -0.4% can increase the photocatalytic activity of TiO2; however, doping with Ce content of 0.5% -2.5% can significantly decrease the photocatalytic activity of TiO2. The favorite doping content is 0.4% in the range of our experiments.
基金the Nationnal Natural Science Foundation of China (No. 50342016).
文摘Iron(Ⅲ)-doped nanostructure TiO2-coated SiO2 (TiO2/SiO2) particles were prepared using the layer-by-layer assembly technique and their photocatalytic property was studied. TiO2 colloids were synthesized employing the sol-gel method with TiChas a precursor. The samples were characterized by Fourier transform infrared spectroscopy (FTIR), SEM, EDS, XPS, and XRD. The experimental results show that TiO2 nanopowders on the surface of SiO2 particles are well distributed, the amount of TiO2 is increased with the adding of coating layers, the pure anatase-TiO2 coating layers are synthesized at 500℃, and the photocatalytic activity of Fe^3+-doped TiO2/SiO2 is higher than that of undoped TiO2/SiO2.
文摘The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,Ni,and Cu)doping for modulating the Fermi energy level of Mo2C.The defective energy level facilitates the free water molecule adsorption and,subsequently,promotes the neutral HER efficiency.Specifically,at a current density of 10 mA/cm2,Cu-Mo2C exhibits the best HER performance with an overpotential of 78 mV,followed by Ni-Mo2C,Co-Mo2C,Fe-Mo2C,and bare Mo2C with 90,95,100,and 173 mV,respectively,and the corresponding Tafel slope values are 40,43,42,56,and 102 mV/dec.The modified WF can also lead to an enhanced photocatalytic efficiency owing to the lowered Schottky barrier and excellent carrier transition across the electrocatalyst–solution interface.When coupling the metal-doped Mo2C samples with TiO2,enhanced photocatalytic neutral HER rates are obtained in comparison to the case with bare TiO2.Typically,the HER rates are 521,404,275,224,147,and 112μmol/h for Cu,Ni,Co,Fe,bare Mo2C,and bare TiO2,respectively.Time-resolved photoluminescence spectroscopy(TRPS)and ultrafast transient absorption(TA)measurements are carried out to confirm the recombination and migration of the photogenerated carriers.The fittedτvalues from the TRPS curves are 22.6,20.5,10.1,4.7,4.0,2.5,and 1.9 ns for TiO2,TiO2-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,and TiO2-Pt,respectively.Additionally,the fittedτvalues from the TA results are 31,73,and 105 ps for the TiO2-Mo2C,TiO2-Cu-Mo2C,and TiO2-Pt samples,respectively.This work provides in-depth insights into the WF modulation of an electrocatalyst for improving the HER performance.
文摘A carbon‐doped TiO2/fly ash support(C‐TiO2/FAS)composite photocatalyst was successfully synthesized through sol impregnation and subsequent carbonization.The carbon dopants were derived from the organic species generated during the synthesis of the C‐TiO2/FAS composite.A series of analytical techniques,such as scanning electron microscopy(SEM),attenuated total reflection‐Fourier transform infrared(ATR‐FTIR)spectroscopy,X‐ray photoelectron spectroscopy(XPS),and ultraviolet‐visible diffuse reflectance spectroscopy(UV‐Vis DRS),were used to characterize the properties of the prepared samples.The results indicated that C‐TiO2 was successfully coated on the FAS surface.Coupling between C‐TiO2 and FAS resulted in the formation of Si–O–C and Al–O–Ti bonds at their interface.The formation of Si–O–C and Al–O–Ti bonds gave rise to a positive shift of the valence band edge of C‐TiO2 and enhanced its oxidation capability of photogenerated holes as well as photodegradation efficiency of methyl orange.Moreover,the C‐TiO2/FAS photocatalyst exhibited favorable reusability and separability.This work may provide a new route for tuning the electronic band structure of TiO2.