The crossmodal interaction of different senses,which is an important basis for learning and memory in the human brain,is highly desired to be mimicked at the device level for developing neuromorphic crossmodal percept...The crossmodal interaction of different senses,which is an important basis for learning and memory in the human brain,is highly desired to be mimicked at the device level for developing neuromorphic crossmodal perception,but related researches are scarce.Here,we demonstrate an optoelectronic synapse for vision-olfactory crossmodal perception based on MXene/violet phosphorus(VP)van der Waals heterojunctions.Benefiting from the efficient separation and transport of photogenerated carriers facilitated by conductive MXene,the photoelectric responsivity of VP is dramatically enhanced by 7 orders of magnitude,reaching up to 7.7 A W^(−1).Excited by ultraviolet light,multiple synaptic functions,including excitatory postsynaptic currents,pairedpulse facilitation,short/long-term plasticity and“learning-experience”behavior,were demonstrated with a low power consumption.Furthermore,the proposed optoelectronic synapse exhibits distinct synaptic behaviors in different gas environments,enabling it to simulate the interaction of visual and olfactory information for crossmodal perception.This work demonstrates the great potential of VP in optoelectronics and provides a promising platform for applications such as virtual reality and neurorobotics.展开更多
Hydrogen evolution reaction(HER)and urea oxidation reaction(UOR)are key reactions of the watercycling associated catalytic process/device.The design of catalysts with a super-hydrophilic/aerophobic structure and optim...Hydrogen evolution reaction(HER)and urea oxidation reaction(UOR)are key reactions of the watercycling associated catalytic process/device.The design of catalysts with a super-hydrophilic/aerophobic structure and optimized electron distribution holds great promise.Here,we have designed a threedimensional(3D)hollow Ni/NiMoN hierarchical structure with arrayed-sheet surface based on a onepot hydrothermal route for efficient urea-assisted HER based on a simple hydrothermal process.The Ni/NiMoN catalyst exhibits super-hydrophilic/aerophobic properties with a small droplet contact angle of 6.07°and an underwater bubble contact angle of 155.7°,thus facilitating an escape of bubbles from the electrodes.Density functional theory calculations and X-ray photoelectron spectroscopy results indicate the optimized electronic structure at the interface of Ni and NiMoN,which can promote the adsorption/desorption of reactants and intermediates.The virtues combining with a large specific surface area endow Ni/NiMoN with efficient catalytic activity of low potentials of 25 mV for HER and 1.33 V for UOR at10 mA cm^(-2).The coupled HER and UOR system demonstrates a low cell voltage of 1.42 V at 10 mA cm^(-2),which is approximately 209 mV lower than water electrolysis.展开更多
Two-dimension(2D)van der Waals heterojunction holds essential promise in achieving high-performance flexible near-infrared(NIR)photodetector.Here,we report the successful fabrication of ZnSb/Ti_(3)C_(2)T_(x)MXene base...Two-dimension(2D)van der Waals heterojunction holds essential promise in achieving high-performance flexible near-infrared(NIR)photodetector.Here,we report the successful fabrication of ZnSb/Ti_(3)C_(2)T_(x)MXene based flexible NIR photodetector array via a facile photolithography technology.The single ZnSb/Ti_(3)C_(2)T_(x)photodetector exhibited a high light-to-dark current ratio of 4.98,fast response/recovery time(2.5/1.3 s)and excellent stability due to the tight connection between 2D ZnSb nanoplates and 2D Ti_(3)C_(2)T_(x)MXene nanoflakes,and the formed 2D van der Waals heterojunction.Thin polyethylene terephthalate(PET)substrate enables the ZnSb/Ti_(3)C_(2)T_(x)photodetector withstand bending such that stable photoelectrical properties with non-obvious change were maintained over 5000 bending cycles.Moreover,the ZnSb/Ti_(3)C_(2)T_(x)photodetectors were integrated into a 26×5 device array,realizing a NIR image sensing application.展开更多
Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well...Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well designed through zeolite-imidazole framework(ZIF-67)carbonization,chemical vapor deposition,and O_(2) plasma treatment.As a result,the threedimensional NHCNBs coupled with NCNTs and unique heterojunction with rich oxygen vacancies reduce the charge transport resistance and accelerate the catalytic reaction rate of the P-Co/CoOV@NHCNB@NCNT,and they display exceedingly good electrocatalytic performance for oxygen reduction reaction(ORR,halfwave potential[EORR,1/2=0.855 V vs.reversible hydrogen electrode])and oxygen evolution reaction(OER,overpotential(η_(OER,10)=377mV@10mA cm^(−2)),which exceeds that of the commercial Pt/C+RuO_(2) and most of the formerly reported electrocatalysts.Impressively,both the aqueous and flexible foldable all-solid-state rechargeable zinc-air batteries(ZABs)assembled with the P-Co/CoOV@NHCNB@NCNT catalyst reveal a large maximum power density and outstanding long-term cycling stability.First-principles density functional theory calculations show that the formation of heterojunctions and oxygen vacancies enhances conductivity,reduces reaction energy barriers,and accelerates reaction kinetics rates.This work opens up a new avenue for the facile construction of highly active,structurally stable,and cost-effective bifunctional catalysts for ZABs.展开更多
In recent years,copper iodide(CuI)is an emerging p-type wide bandgap semiconductor with high intrinsic Hall mobility,high optical absorption and large exciton binding energy.However,the spectral response and the photo...In recent years,copper iodide(CuI)is an emerging p-type wide bandgap semiconductor with high intrinsic Hall mobility,high optical absorption and large exciton binding energy.However,the spectral response and the photoelectric conversion efficiency are limited for CuI-based heterostructure devices,which is related to the difficulty in fabrication of high-quality CuI thin films on other semiconductors.In this study,a p-CuI/n-Si photodiode has been fabricated through a facile solid-phase iodination method.Although the CuI thin film is polycrystalline with obvious structural defects,the CuI/Si diode shows a high weak-light sensitivity and a high rectification ratio of 7.6×10^(4),indicating a good defect tolerance.This is because of the unilateral heterojunction behavior of the formation of the p^(+)n diode.In this work,the mechanism of photocurrent of the p^(+)n diode has been studied comprehensively.Different monochromatic lasers with wavelengths of 400,505,635 and 780 nm have been selected for testing the photoresponse.Under zero-bias voltage,the device is a unilateral heterojunction,and only visible light can be absorbed at the Si side.On the other hand,when a bias voltage of-3 V is applied,the photodiode is switched to a broader“UV-visible”band response mode.Therefore,the detection wavelength range can be switched between the“Visible”and“UV-visible”bands by adjusting the bias voltage.Moreover,the obtained CuI/Si diode was very sensitive to weak light illumination.A very high detectivity of 10^(13)-1014 Jones can be achieved with a power density as low as 0.5μW/cm^(2),which is significantly higher than that of other Cu-based diodes.These findings underscore the high application potential of CuI when integrated with the traditional Si industry.展开更多
Charge separation is critical for achieving efficient solar-to-hydrogen conversion,whereas piezoelectric-enhanced photoelectrochemical(PEC)systems can effectively modulate band bending and charge migration.Herein,we d...Charge separation is critical for achieving efficient solar-to-hydrogen conversion,whereas piezoelectric-enhanced photoelectrochemical(PEC)systems can effectively modulate band bending and charge migration.Herein,we design an n-TiO_(2)/Ba TiO_(3)/p-TiO_(2)(TBTm)heterojunction in which the piezoelectric Ba TiO_(3) layer is sandwiched between n-TiO_(2)and p-TiO_(2).The built-in electric field of TBTm can provide a strong driving force to accelerate carrier separation and prolong carrier lifetime.Consequently,the TBT3 achieves a prominent photocurrent density,as high as 2.13 m A cm^(-2)at 1.23 V versus reversible hydrogen electrode(RHE),which is 2.4-and 1.5-times higher than TiO_(2) and TiO_(2)–Ba TiO_(3) heterojunction,respectively.Driven by mechanical deformation,the induced dipole polarization can further regulate built-in electric fields,and the piezoelectric photocurrent density of TBT3-800 is 2.84 times higher than TiO_(2) at 1.23 V vs.RHE due to the construction of piezoelectric-heterostructures.This work provides a piezoelectric polarization strategy for modulating the built-in electric field of heterojunction for PEC system.展开更多
The development of highly active,stable and inexpensive electrocatalysts for hydrogen production by defects and morphology engineering remains a great challenge.Herein,S vacancies-rich Ni_(3)S_(2)@Cu_(2)S nan-otube he...The development of highly active,stable and inexpensive electrocatalysts for hydrogen production by defects and morphology engineering remains a great challenge.Herein,S vacancies-rich Ni_(3)S_(2)@Cu_(2)S nan-otube heterojunction arrays were in-situ grown on copper foam(V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF)for efficient electrocatalytic overall water splitting.With the merits of nanotube arrays and efficient electronic mod-ulation drived by the OD vacancy defect and 2D heterojunction defect,the resultant V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF electrocatalyst exhibits excellent electrocatalytic activity with a low overpotential of 47 mV for the hydrogen evolution reaction(HER)at 10 mA cm^(-2) current density,and 263 mV for the oxygen evolution reaction(OER)at 50 mA cm^(-2) current density,as well as a cell voltage of 1.48 V at 10 mA cm^(-2).Moreover,the nanotube heterojunction arrays endows V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF with outstanding stability in long-term catalytic processes,as confirmed by the continuous chronopotentiom-etry tests at current densities of 10 mA cm^(-2) for 100 h.展开更多
The unique photocatalytic mechanism of S-scheme heterojunction can be used to study new and efficient photocatalysts.By carefully selecting semiconductors for S-scheme heterojunction photocatalysts,it is possible to r...The unique photocatalytic mechanism of S-scheme heterojunction can be used to study new and efficient photocatalysts.By carefully selecting semiconductors for S-scheme heterojunction photocatalysts,it is possible to reduce the rate of photogenerated carrier recombination and increase the conversion efficiency of light into energy.Chalcogenides are a group of compounds that include sulfides and selenides(e.g.,CdS,ZnS,Bi_(2)S_(3),MoS_(2),ZnSe,CdSe,and CuSe).Chalcogenides have attracted considerable attention as heterojunction photocatalysts owing to their narrow bandgap,wide light absorption range,and excellent photoreduction properties.This paper presents a thorough analysis of S-scheme heterojunction photocatalysts based on chalcogenides.Following an introduction to the fundamental characteristics and benefits of S-scheme heterojunction photocatalysts,various chalcogenide-based S-scheme heterojunction photocatalyst synthesis techniques are summarized.These photocatalysts are used in numerous significant photocatalytic reactions,in-cluding the reduction of carbon dioxide,synthesis of hydrogen peroxide,conversion of organic matter,generation of hydrogen from water,nitrogen fixation,degradation of organic pollutants,and sterilization.In addition,cutting-edge characterization techniques,including in situ characterization techniques,are discussed to validate the steady and transient states of photocatalysts with an S-scheme heterojunction.Finally,the design and challenges of chalcogenide-based S-scheme heterojunction photocatalysts are explored and recommended in light of state-of-the-art research.展开更多
Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with...Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with photothermal effect was synthesized by ultrasonic self-assembly combined with calcination.The dark CFO@C absorbed visible light and partly converted into heat to promote the hydrogen evolution reaction.The presence of heterojunctions inhibited the photogenerated electron-hole recombination.The graphite-carbon layer provided a stable channel for electron transfer,and the presence of magnetic CFO made recycle easier.Under the action of photothermal assistance and heterojunction,the hydrogen evolution rate of the optimal CFO@C/CZS was 80.79 mmol g^(-1) h^(-1),which was 2.55 times and 260.61 times of that of pure CZS and CFO@C,respectively.Notably,the composite samples also exhibit excellent stability and a wide range of environmental adaptability.Through experimental tests and first-principles simulation calculation methods,the plausible mechanism of photoactivity enhancement was proposed.This work provided a feasible strategy of photothermal assistance for the development of heterojunction photocatalysts with distinctive hydrogen evolution.展开更多
This study investigates the carrier transport of heterojunction channel in oxide semiconductor thin-film transistor(TFT)using the elevated-metal metal-oxide(EMMO)architecture and indium−zinc oxide(InZnO).The heterojun...This study investigates the carrier transport of heterojunction channel in oxide semiconductor thin-film transistor(TFT)using the elevated-metal metal-oxide(EMMO)architecture and indium−zinc oxide(InZnO).The heterojunction band diagram of InZnO bilayer was modified by the cation composition to form the two-dimensional electron gas(2DEG)at the interface quantum well,as verified using a metal−insulator−semiconductor(MIS)device.Although the 2DEG indeed contributes to a higher mobility than the monolayer channel,the competition and cooperation between the gate field and the built-in field strongly affect such mobility-boosting effect,originating from the carrier inelastic collision at the heterojunction interface and the gate field-induced suppression of quantum well.Benefited from the proper energy-band engineering,a high mobility of 84.3 cm2·V^(−1)·s^(−1),a decent threshold voltage(V_(th))of−6.5 V,and a steep subthreshold swing(SS)of 0.29 V/dec were obtained in InZnO-based heterojunction TFT.展开更多
Due to their high electrical conductivity and layered structure,two dimensional MXene materials are re⁃garded as promising candidates for energy storage applications.However,the relatively low stability and specific c...Due to their high electrical conductivity and layered structure,two dimensional MXene materials are re⁃garded as promising candidates for energy storage applications.However,the relatively low stability and specific ca⁃pacity of MXene materials limit their further utilization.In this study,these issues are addressed using a heterostruc⁃ture strategy via a one-step selenization method to form Mo_(2)C@MoSe_(2).Synchrotron radiation X-ray spectroscopic and high-resolution transmission electron microscopy(HRTEM)characterizations revealed the heterostructure consisting of in-situ grown MoSe_(2)on Mo_(2)C MXene.Electrochemical tests proved the heterojunction electrode’s superior rate perfor⁃mance of 289.06 mAh·g^(-1)at a high current density of 5 A·g^(-1)and long cycling stability of 550 mAh·g^(-1)after 900 cycles at 1 A·g^(-1).This work highlights the useful X-ray spectroscopic analysis to directly elucidate the heterojunction structure,providing an effective reference method for probing heterostructures.展开更多
Piezoelectric materials have advantages of fine-tuning photocatalytic performance through harvesting mechanical energy and open a new avenue in facilitating green catalytic reaction.Herein,polyvinylidene fluoride(PVDF...Piezoelectric materials have advantages of fine-tuning photocatalytic performance through harvesting mechanical energy and open a new avenue in facilitating green catalytic reaction.Herein,polyvinylidene fluoride(PVDF),a flexible piezoelectric material,was introduced to synthesize a novel Cd_(0.9)Zn_(0.1)S-ZnO@C/PVDF(CZS-ZO@C/PVDF)piezo-photocatalytic film by spin coating and immersion phase conversion method.Benefiting from the piezoelectricity of PVDF and the internal electric field(IEF)of CZS-ZO@C Step-scheme(S-Scheme)heterojunction,CZS-ZO@C/PVDF was able to induce a hydrogen generation rate of 34.9 mmol g^(−1)h^(−1)activated by ultrasound and visible light(U-L),which is∼17.5 times of Cd_(0.9)Zn_(0.1)S/PVDF(CZS/PVDF)and∼7.4 times of the photocatalysis rate activated by visible light only(L).Piezoelectric measurements and COMSOL simulation illustrated the excellent piezoelectricity of CZS-ZO@C/PVDF film,which exhibits a piezoelectric coefficient(d33)of 9.9 pm V−1 and a piezoelectric potential of 874 mV(under 0.5 MPa).The reaction mechanism for the exceptional piezo-photocatalytic performance was finally disclosed through density functional theory(DFT)calculation and electrochemical tests.This study enriches the application scope of piezoelectric materials in sustainable energy catalysis and provides a new direction to develop efficient piezoelectric photocatalysts.展开更多
Two-dimensional(2D)magnet/superconductor heterostructures can promote the design of artificial materials for exploring 2D physics and device applications by exotic proximity effects.However,plagued by the low Curie te...Two-dimensional(2D)magnet/superconductor heterostructures can promote the design of artificial materials for exploring 2D physics and device applications by exotic proximity effects.However,plagued by the low Curie temperature and instability in air,it is hard to realize practical applications for the reported layered magnetic materials at present.In this paper,we developed a space-confined chemical vapor deposition method to synthesize ultrathin air-stable ε-Fe_(2)O_(3) nanosheets with Curie temperature above 350 K.The ε-Fe_(2)O_(3)/NbSe_(2) heterojunction was constructed to study the magnetic proximity effect on the superconductivity of the NbSe_(2) multilayer.The electrical transport results show that the subtle proximity effect can modulate the interfacial spin–orbit interaction while undegrading the superconducting critical parameters.Our work paves the way to construct 2D heterojunctions with ultrathin nonlayered materials and layered van der Waals(vdW)materials for exploring new physical phenomena.展开更多
Photoinduced intermolecular charge transfer(PICT)determines the voltage loss in bulk heterojunction(BHJ)organic photovoltaics(OPVs),and this voltage loss can be minimized by inducing efficient PICT,which requires ener...Photoinduced intermolecular charge transfer(PICT)determines the voltage loss in bulk heterojunction(BHJ)organic photovoltaics(OPVs),and this voltage loss can be minimized by inducing efficient PICT,which requires energy-state matching between the donor and acceptor at the BHJ interfaces.Thus,both geometrically and energetically accessible delocalized state matching at the hot energy level is crucial for achieving efficient PICT.In this study,an effective method for quantifying the hot state matching of OPVs was developed.The degree of energy-state matching between the electron donor and acceptor at BHJ interfaces was quantified using a mismatching factor(MF)calculated from the modified optical density of the BHJ.Furthermore,the correlation between the open-circuit voltage(Voc)of the OPV device and energy-state matching at the BHJ interface was investigated using the calculated MF.The OPVs with small absolute MF values exhibited high Voc values.This result clearly indicates that the energy-state matching between the donor and acceptor is crucial for achieving a high Voc in OPVs.Because the MF indicates the degree of energy-state matching,which is a critical factor for suppressing energy loss,it can be used to estimate the Voc loss in OPVs.展开更多
Extending the ionic conductivity is the pre-requisite of electrolytes in fuel cell technology for high-electrochemical performance.In this regard,the introduction of semiconductor-oxide materials and the approach of h...Extending the ionic conductivity is the pre-requisite of electrolytes in fuel cell technology for high-electrochemical performance.In this regard,the introduction of semiconductor-oxide materials and the approach of heterostructure formation by modulating energy bands to enhance ionic conduction acting as an electrolyte in fuel cell-device.Semiconductor(n-type;SnO_(2))plays a key role by introducing into p-type SrFe_(0.2)Ti_(0.8)O_(3-δ)(SFT)semiconductor perovskite materials to construct p-n heterojunction for high ionic conductivity.Therefore,two different composites of SFT and SnO_(2)are constructed by gluing p-and n-type SFT-SnO_(2),where the optimal composition of SFT-SnO_(2)(6∶4)heterostructure electrolyte-based fuel cell achieved excellent ionic conductivity 0.24 S cm^(-1)with power-output of 1004 mW cm^(-2)and high OCV 1.12 V at a low operational temperature of 500℃.The high power-output and significant ionic conductivity with durable operation of 54 h are accredited to SFT-SnO_(2)heterojunction formation including interfacial conduction assisted by a built-in electric field in fuel cell device.Moreover,the fuel conversion efficiency and considerable Faradaic efficiency reveal the compatibility of SFT-SnO_(2)heterostructure electrolyte and ruled-out short-circuiting issue.Further,the first principle calculation provides sufficient information on structure optimization and energy-band structure modulation of SFT-SnO_(2).This strategy will provide new insight into semiconductor-based fuel cell technology to design novel electrolytes.展开更多
Utilizing sunlight to convert CO_(2) into chemical fuels could address the greenhouse effect and fossil fuel crisis,Heterojunction structure catalysts with oxygen vacancy are attractive in the field of photocatalytic ...Utilizing sunlight to convert CO_(2) into chemical fuels could address the greenhouse effect and fossil fuel crisis,Heterojunction structure catalysts with oxygen vacancy are attractive in the field of photocatalytic CO_(2) conversion.Herein,a modified TiO_(2)/In_(2)O_(3)(R-P2 5/In_(2)O_(3-x)) type Ⅱ heterojunction composite with oxygen vacancies is designed for photocatalytic CO_(2) reduction,which exhibits excellent CO_(2) reduction activity,with a C_(2) selectivity of 56.66%(in terms of R_(electron)).In situ Fourier-transform infrared spectroscopy(DRIFTS) and time-resolved photoluminescence(TR-PL) spectroscopy are used to reveal the intermediate formation of the photocatalytic mechanism and photogenerated electron lifetime,respectively.The experimental characterizations reveal that the R-P25/In_(2)O_(3-x) composite shows a remarkable behavior for coupling C-C bonds.Besides,efficient charge separation contributes to the improved CO_(2) conversion performance of photocatalysts.This work introduces a type Ⅱ heterojunction composite photocatalyst,which promotes understanding the CO_(2) reduction mechanisms on heterojunction composites and is valuable for the development of photocatalysts.展开更多
Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme hetero...Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.展开更多
Heterojunction construction,especially S-scheme heterojunction,represents an efficient universal strategy to achieve high-performance photocatalytic materials.For further performance stimulation of these well-designed...Heterojunction construction,especially S-scheme heterojunction,represents an efficient universal strategy to achieve high-performance photocatalytic materials.For further performance stimulation of these well-designed heterojunctions,modulating the interfacial internal electric field(IEF)to steer dynamic charge transfer represents a promising approach.Herein,we realized the precise regulation of Fermi level(E_(F))of the oxidation semiconductor(mesoporous WO_(3-x))by tailoring the concentration of oxygen vacancies(V_(O)),maximizing the IEF intensity in Cs_(2)CuBr_(4)@WO_(3-x)(CCB@WO_(3-x))S-scheme heterojunction.The augmented IEF affords a robust driving force for directional electron delivery,leading to boosted charge separation.Hence,the developed CCB@WO_(3-x)S-scheme heterojunction demonstrated outstanding photocatalytic CO_(2)reduction performance,with the electron consumption rate(Relectron)up to 390.34μmol g^(-1)h^(-1),which is 3.28 folds higher than that of pure CCB.An in-depth analysis of the S-scheme electron transfer mode was presented via theoretical investigations,electron spin resonance(ESR),photo-irradiated Kelvin probe force microscopy(KPFM),and in-situ X-ray photoelectron spectroscopy(XPS).Finally,the CO_(2)photoconversion route was explored in detail using in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and DFT theoretical calculations.展开更多
Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-mat...Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-matched S-scheme heterostructure and establishing a robust built-in electric field emerge as pivotal strategies.In pursuit of this goal,a core-shell structured CuInS_(2)@CoS_(2)S-scheme heterojunction was meticulously engineered through a two-step molten salt method.This approach over the CuInS_(2)-based composites produced an internal electric field owing to the disparity be-tween the Fermi levels of CoS_(2) and CuInS_(2) at their interface.Consequently,the electric field facili-tated the directed migration of charges and the proficient separation of photoinduced carriers.The resulting CuInS_(2)@CoS_(2) heterostructure exhibited remarkable CO_(2) photoreduction performance,which was 21.7 and 26.5 times that of pure CuInS_(2) and CoS_(2),respectively.The S-scheme heterojunc-tion photogenerated charge transfer mechanism was validated through a series of rigorous anal-yses,including in situ irradiation X-ray photoelectron spectroscopy,work function calculations,and differential charge density examinations.Furthermore,in situ infrared spectroscopy and density functional theory calculations corroborated the fact that the CuInS_(2)@CoS_(2) heterojunction substan-tially lowered the formation energy of *COOH and *CO.This study demonstrates the application potential of S-scheme heterojunctions fabricated via the molten salt method in the realm of ad-dressing carbon-related environmental issues.展开更多
Two-dimensional(2D)WSe_(2)has received increasing attention due to its unique optical properties and bipolar behavior.Several WSe_(2)-based heterojunctions exhibit bidirectional rectification characteristics,but most ...Two-dimensional(2D)WSe_(2)has received increasing attention due to its unique optical properties and bipolar behavior.Several WSe_(2)-based heterojunctions exhibit bidirectional rectification characteristics,but most devices have a lower rectification ratio.In this work,the Bi_(2)O_(2)Se/WSe_(2)heterojunction prepared by us has a typeⅡband alignment,which can vastly suppress the channel current through the interface barrier so that the Bi_(2)O_(2)Se/WSe_(2)heterojunction device has a large rectification ratio of about 10^(5).Meanwhile,under different gate voltage modulation,the current on/off ratio of the device changes by nearly five orders of magnitude,and the maximum current on/off ratio is expected to be achieved 106.The photocurrent measurement reveals the behavior of recombination and space charge confinement,further verifying the bidirectional rectification behavior of heterojunctions,and it also exhibits excellent performance in light response.In the future,Bi_(2)O_(2)Se/WSe_(2)heterojunction field-effect transistors have great potential to reduce the volume of integrated circuits as a bidirectional controlled switching device.展开更多
基金supported by National Natural Science Foundation of China(No.51902250).
文摘The crossmodal interaction of different senses,which is an important basis for learning and memory in the human brain,is highly desired to be mimicked at the device level for developing neuromorphic crossmodal perception,but related researches are scarce.Here,we demonstrate an optoelectronic synapse for vision-olfactory crossmodal perception based on MXene/violet phosphorus(VP)van der Waals heterojunctions.Benefiting from the efficient separation and transport of photogenerated carriers facilitated by conductive MXene,the photoelectric responsivity of VP is dramatically enhanced by 7 orders of magnitude,reaching up to 7.7 A W^(−1).Excited by ultraviolet light,multiple synaptic functions,including excitatory postsynaptic currents,pairedpulse facilitation,short/long-term plasticity and“learning-experience”behavior,were demonstrated with a low power consumption.Furthermore,the proposed optoelectronic synapse exhibits distinct synaptic behaviors in different gas environments,enabling it to simulate the interaction of visual and olfactory information for crossmodal perception.This work demonstrates the great potential of VP in optoelectronics and provides a promising platform for applications such as virtual reality and neurorobotics.
基金financially supported by the National Key R&D Program of China(2022YFA1503003)the National Natural Science Foundation of China(91961111,22271081)+3 种基金the Natural Science Foundation of Heilongjiang Province(ZD2021B003)the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(UNPYSCT-2020004)The Basic Research Fund of Heilongjiang University in Heilongjiang Province(2021-KYYWF-0039)the Heilongjiang University Excellent Youth Foundation。
文摘Hydrogen evolution reaction(HER)and urea oxidation reaction(UOR)are key reactions of the watercycling associated catalytic process/device.The design of catalysts with a super-hydrophilic/aerophobic structure and optimized electron distribution holds great promise.Here,we have designed a threedimensional(3D)hollow Ni/NiMoN hierarchical structure with arrayed-sheet surface based on a onepot hydrothermal route for efficient urea-assisted HER based on a simple hydrothermal process.The Ni/NiMoN catalyst exhibits super-hydrophilic/aerophobic properties with a small droplet contact angle of 6.07°and an underwater bubble contact angle of 155.7°,thus facilitating an escape of bubbles from the electrodes.Density functional theory calculations and X-ray photoelectron spectroscopy results indicate the optimized electronic structure at the interface of Ni and NiMoN,which can promote the adsorption/desorption of reactants and intermediates.The virtues combining with a large specific surface area endow Ni/NiMoN with efficient catalytic activity of low potentials of 25 mV for HER and 1.33 V for UOR at10 mA cm^(-2).The coupled HER and UOR system demonstrates a low cell voltage of 1.42 V at 10 mA cm^(-2),which is approximately 209 mV lower than water electrolysis.
基金supported by National Natural Science Foundation of China(51672308,51972025,61888102,and 62004187).
文摘Two-dimension(2D)van der Waals heterojunction holds essential promise in achieving high-performance flexible near-infrared(NIR)photodetector.Here,we report the successful fabrication of ZnSb/Ti_(3)C_(2)T_(x)MXene based flexible NIR photodetector array via a facile photolithography technology.The single ZnSb/Ti_(3)C_(2)T_(x)photodetector exhibited a high light-to-dark current ratio of 4.98,fast response/recovery time(2.5/1.3 s)and excellent stability due to the tight connection between 2D ZnSb nanoplates and 2D Ti_(3)C_(2)T_(x)MXene nanoflakes,and the formed 2D van der Waals heterojunction.Thin polyethylene terephthalate(PET)substrate enables the ZnSb/Ti_(3)C_(2)T_(x)photodetector withstand bending such that stable photoelectrical properties with non-obvious change were maintained over 5000 bending cycles.Moreover,the ZnSb/Ti_(3)C_(2)T_(x)photodetectors were integrated into a 26×5 device array,realizing a NIR image sensing application.
基金the support from the Zhejiang Provincial Natural Science Foundation (No.LR22E070001),the National Natural Science Foundation of China (Nos.12275239 and 11975205)the Guangdong Basic and Applied Basic Research Foundation (No.2020B1515120048).
文摘Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well designed through zeolite-imidazole framework(ZIF-67)carbonization,chemical vapor deposition,and O_(2) plasma treatment.As a result,the threedimensional NHCNBs coupled with NCNTs and unique heterojunction with rich oxygen vacancies reduce the charge transport resistance and accelerate the catalytic reaction rate of the P-Co/CoOV@NHCNB@NCNT,and they display exceedingly good electrocatalytic performance for oxygen reduction reaction(ORR,halfwave potential[EORR,1/2=0.855 V vs.reversible hydrogen electrode])and oxygen evolution reaction(OER,overpotential(η_(OER,10)=377mV@10mA cm^(−2)),which exceeds that of the commercial Pt/C+RuO_(2) and most of the formerly reported electrocatalysts.Impressively,both the aqueous and flexible foldable all-solid-state rechargeable zinc-air batteries(ZABs)assembled with the P-Co/CoOV@NHCNB@NCNT catalyst reveal a large maximum power density and outstanding long-term cycling stability.First-principles density functional theory calculations show that the formation of heterojunctions and oxygen vacancies enhances conductivity,reduces reaction energy barriers,and accelerates reaction kinetics rates.This work opens up a new avenue for the facile construction of highly active,structurally stable,and cost-effective bifunctional catalysts for ZABs.
基金National Natural Science Foundation of China(62074056)Fundamental Research Funds for the Central Universities。
文摘In recent years,copper iodide(CuI)is an emerging p-type wide bandgap semiconductor with high intrinsic Hall mobility,high optical absorption and large exciton binding energy.However,the spectral response and the photoelectric conversion efficiency are limited for CuI-based heterostructure devices,which is related to the difficulty in fabrication of high-quality CuI thin films on other semiconductors.In this study,a p-CuI/n-Si photodiode has been fabricated through a facile solid-phase iodination method.Although the CuI thin film is polycrystalline with obvious structural defects,the CuI/Si diode shows a high weak-light sensitivity and a high rectification ratio of 7.6×10^(4),indicating a good defect tolerance.This is because of the unilateral heterojunction behavior of the formation of the p^(+)n diode.In this work,the mechanism of photocurrent of the p^(+)n diode has been studied comprehensively.Different monochromatic lasers with wavelengths of 400,505,635 and 780 nm have been selected for testing the photoresponse.Under zero-bias voltage,the device is a unilateral heterojunction,and only visible light can be absorbed at the Si side.On the other hand,when a bias voltage of-3 V is applied,the photodiode is switched to a broader“UV-visible”band response mode.Therefore,the detection wavelength range can be switched between the“Visible”and“UV-visible”bands by adjusting the bias voltage.Moreover,the obtained CuI/Si diode was very sensitive to weak light illumination.A very high detectivity of 10^(13)-1014 Jones can be achieved with a power density as low as 0.5μW/cm^(2),which is significantly higher than that of other Cu-based diodes.These findings underscore the high application potential of CuI when integrated with the traditional Si industry.
基金the support from the National Natural Science Foundation of China(22222808,21978200,22161142002)the Joint Research Programs of National Natural Science Foundation of China and Pakistan Science Foundation(PSF-NSFC-IV/Phy/P-PU(31))the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Charge separation is critical for achieving efficient solar-to-hydrogen conversion,whereas piezoelectric-enhanced photoelectrochemical(PEC)systems can effectively modulate band bending and charge migration.Herein,we design an n-TiO_(2)/Ba TiO_(3)/p-TiO_(2)(TBTm)heterojunction in which the piezoelectric Ba TiO_(3) layer is sandwiched between n-TiO_(2)and p-TiO_(2).The built-in electric field of TBTm can provide a strong driving force to accelerate carrier separation and prolong carrier lifetime.Consequently,the TBT3 achieves a prominent photocurrent density,as high as 2.13 m A cm^(-2)at 1.23 V versus reversible hydrogen electrode(RHE),which is 2.4-and 1.5-times higher than TiO_(2) and TiO_(2)–Ba TiO_(3) heterojunction,respectively.Driven by mechanical deformation,the induced dipole polarization can further regulate built-in electric fields,and the piezoelectric photocurrent density of TBT3-800 is 2.84 times higher than TiO_(2) at 1.23 V vs.RHE due to the construction of piezoelectric-heterostructures.This work provides a piezoelectric polarization strategy for modulating the built-in electric field of heterojunction for PEC system.
基金supported by the National Natural Science Foundation of China under Grant No.52072196,52002200,52102106,52202262,22379081,22379080Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant No.ZR2020zD09the Natural Science Foundation of Shandong Province under Grant No.ZR2020QE063,ZR202108180009,ZR2023QE059.
文摘The development of highly active,stable and inexpensive electrocatalysts for hydrogen production by defects and morphology engineering remains a great challenge.Herein,S vacancies-rich Ni_(3)S_(2)@Cu_(2)S nan-otube heterojunction arrays were in-situ grown on copper foam(V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF)for efficient electrocatalytic overall water splitting.With the merits of nanotube arrays and efficient electronic mod-ulation drived by the OD vacancy defect and 2D heterojunction defect,the resultant V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF electrocatalyst exhibits excellent electrocatalytic activity with a low overpotential of 47 mV for the hydrogen evolution reaction(HER)at 10 mA cm^(-2) current density,and 263 mV for the oxygen evolution reaction(OER)at 50 mA cm^(-2) current density,as well as a cell voltage of 1.48 V at 10 mA cm^(-2).Moreover,the nanotube heterojunction arrays endows V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF with outstanding stability in long-term catalytic processes,as confirmed by the continuous chronopotentiom-etry tests at current densities of 10 mA cm^(-2) for 100 h.
文摘The unique photocatalytic mechanism of S-scheme heterojunction can be used to study new and efficient photocatalysts.By carefully selecting semiconductors for S-scheme heterojunction photocatalysts,it is possible to reduce the rate of photogenerated carrier recombination and increase the conversion efficiency of light into energy.Chalcogenides are a group of compounds that include sulfides and selenides(e.g.,CdS,ZnS,Bi_(2)S_(3),MoS_(2),ZnSe,CdSe,and CuSe).Chalcogenides have attracted considerable attention as heterojunction photocatalysts owing to their narrow bandgap,wide light absorption range,and excellent photoreduction properties.This paper presents a thorough analysis of S-scheme heterojunction photocatalysts based on chalcogenides.Following an introduction to the fundamental characteristics and benefits of S-scheme heterojunction photocatalysts,various chalcogenide-based S-scheme heterojunction photocatalyst synthesis techniques are summarized.These photocatalysts are used in numerous significant photocatalytic reactions,in-cluding the reduction of carbon dioxide,synthesis of hydrogen peroxide,conversion of organic matter,generation of hydrogen from water,nitrogen fixation,degradation of organic pollutants,and sterilization.In addition,cutting-edge characterization techniques,including in situ characterization techniques,are discussed to validate the steady and transient states of photocatalysts with an S-scheme heterojunction.Finally,the design and challenges of chalcogenide-based S-scheme heterojunction photocatalysts are explored and recommended in light of state-of-the-art research.
基金supported by the Shandong Provincial Natural Science Foundation(ZR2022ME179,ZR2021QE086)the Shandong Provincial Key Research and Development Program(Public Welfare Science and Technology Research)(2019GGX103010)+2 种基金the Science and Technology Planning Project of Higher School in Shandong Province(J18KA243)the Liaocheng Key Research and Development Program(Policy guidance category)(2022YDSF90)the Liaocheng University High-level Talents&PhD Research Startup Foundation(318051619)。
文摘Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with photothermal effect was synthesized by ultrasonic self-assembly combined with calcination.The dark CFO@C absorbed visible light and partly converted into heat to promote the hydrogen evolution reaction.The presence of heterojunctions inhibited the photogenerated electron-hole recombination.The graphite-carbon layer provided a stable channel for electron transfer,and the presence of magnetic CFO made recycle easier.Under the action of photothermal assistance and heterojunction,the hydrogen evolution rate of the optimal CFO@C/CZS was 80.79 mmol g^(-1) h^(-1),which was 2.55 times and 260.61 times of that of pure CZS and CFO@C,respectively.Notably,the composite samples also exhibit excellent stability and a wide range of environmental adaptability.Through experimental tests and first-principles simulation calculation methods,the plausible mechanism of photoactivity enhancement was proposed.This work provided a feasible strategy of photothermal assistance for the development of heterojunction photocatalysts with distinctive hydrogen evolution.
基金supported by National Key Research and Development Program(2021YFB3600802)Shenzhen Municipal Scientific Program(JSGG20220831103803007,SGDX20211123145404006)Guangdong Basic and Applied Basic Research Foundation(2022A1515110029)
文摘This study investigates the carrier transport of heterojunction channel in oxide semiconductor thin-film transistor(TFT)using the elevated-metal metal-oxide(EMMO)architecture and indium−zinc oxide(InZnO).The heterojunction band diagram of InZnO bilayer was modified by the cation composition to form the two-dimensional electron gas(2DEG)at the interface quantum well,as verified using a metal−insulator−semiconductor(MIS)device.Although the 2DEG indeed contributes to a higher mobility than the monolayer channel,the competition and cooperation between the gate field and the built-in field strongly affect such mobility-boosting effect,originating from the carrier inelastic collision at the heterojunction interface and the gate field-induced suppression of quantum well.Benefited from the proper energy-band engineering,a high mobility of 84.3 cm2·V^(−1)·s^(−1),a decent threshold voltage(V_(th))of−6.5 V,and a steep subthreshold swing(SS)of 0.29 V/dec were obtained in InZnO-based heterojunction TFT.
基金National Key Research and Development Program of China(2020YFA0405800)National Natural Science Foundation of China(12322515,U23A20121,12225508)+2 种基金Youth Innovation Promotion Association of CAS(2022457)National Postdoctoral Program for Innovative Talents(BX20230346)China Postdoctoral Science Foundation(2023M743365)。
文摘Due to their high electrical conductivity and layered structure,two dimensional MXene materials are re⁃garded as promising candidates for energy storage applications.However,the relatively low stability and specific ca⁃pacity of MXene materials limit their further utilization.In this study,these issues are addressed using a heterostruc⁃ture strategy via a one-step selenization method to form Mo_(2)C@MoSe_(2).Synchrotron radiation X-ray spectroscopic and high-resolution transmission electron microscopy(HRTEM)characterizations revealed the heterostructure consisting of in-situ grown MoSe_(2)on Mo_(2)C MXene.Electrochemical tests proved the heterojunction electrode’s superior rate perfor⁃mance of 289.06 mAh·g^(-1)at a high current density of 5 A·g^(-1)and long cycling stability of 550 mAh·g^(-1)after 900 cycles at 1 A·g^(-1).This work highlights the useful X-ray spectroscopic analysis to directly elucidate the heterojunction structure,providing an effective reference method for probing heterostructures.
基金supported by the Shandong Provincial Natural Science Foundation,China(ZR2022ME179,ZR2021ME046).
文摘Piezoelectric materials have advantages of fine-tuning photocatalytic performance through harvesting mechanical energy and open a new avenue in facilitating green catalytic reaction.Herein,polyvinylidene fluoride(PVDF),a flexible piezoelectric material,was introduced to synthesize a novel Cd_(0.9)Zn_(0.1)S-ZnO@C/PVDF(CZS-ZO@C/PVDF)piezo-photocatalytic film by spin coating and immersion phase conversion method.Benefiting from the piezoelectricity of PVDF and the internal electric field(IEF)of CZS-ZO@C Step-scheme(S-Scheme)heterojunction,CZS-ZO@C/PVDF was able to induce a hydrogen generation rate of 34.9 mmol g^(−1)h^(−1)activated by ultrasound and visible light(U-L),which is∼17.5 times of Cd_(0.9)Zn_(0.1)S/PVDF(CZS/PVDF)and∼7.4 times of the photocatalysis rate activated by visible light only(L).Piezoelectric measurements and COMSOL simulation illustrated the excellent piezoelectricity of CZS-ZO@C/PVDF film,which exhibits a piezoelectric coefficient(d33)of 9.9 pm V−1 and a piezoelectric potential of 874 mV(under 0.5 MPa).The reaction mechanism for the exceptional piezo-photocatalytic performance was finally disclosed through density functional theory(DFT)calculation and electrochemical tests.This study enriches the application scope of piezoelectric materials in sustainable energy catalysis and provides a new direction to develop efficient piezoelectric photocatalysts.
基金The work is supported by the National Key Research and Development Program of China(Grant No.2022YFA1204104)the National Natural Science Foundation of China(Grant No.61888102)the Chinese Academy of Sciences(Grant Nos.ZDBS-SSW-WHC001 and XDB33030100).
文摘Two-dimensional(2D)magnet/superconductor heterostructures can promote the design of artificial materials for exploring 2D physics and device applications by exotic proximity effects.However,plagued by the low Curie temperature and instability in air,it is hard to realize practical applications for the reported layered magnetic materials at present.In this paper,we developed a space-confined chemical vapor deposition method to synthesize ultrathin air-stable ε-Fe_(2)O_(3) nanosheets with Curie temperature above 350 K.The ε-Fe_(2)O_(3)/NbSe_(2) heterojunction was constructed to study the magnetic proximity effect on the superconductivity of the NbSe_(2) multilayer.The electrical transport results show that the subtle proximity effect can modulate the interfacial spin–orbit interaction while undegrading the superconducting critical parameters.Our work paves the way to construct 2D heterojunctions with ultrathin nonlayered materials and layered van der Waals(vdW)materials for exploring new physical phenomena.
基金National Research Foundation of Korea,Grant/Award Number:2022R1A6A1A03051158BrainLink Program,Grant/Award Number:2022H1D3A3A01077343Nano Material Technology Development Program,Grant/Award Number:2021M3H4A1A02057007。
文摘Photoinduced intermolecular charge transfer(PICT)determines the voltage loss in bulk heterojunction(BHJ)organic photovoltaics(OPVs),and this voltage loss can be minimized by inducing efficient PICT,which requires energy-state matching between the donor and acceptor at the BHJ interfaces.Thus,both geometrically and energetically accessible delocalized state matching at the hot energy level is crucial for achieving efficient PICT.In this study,an effective method for quantifying the hot state matching of OPVs was developed.The degree of energy-state matching between the electron donor and acceptor at BHJ interfaces was quantified using a mismatching factor(MF)calculated from the modified optical density of the BHJ.Furthermore,the correlation between the open-circuit voltage(Voc)of the OPV device and energy-state matching at the BHJ interface was investigated using the calculated MF.The OPVs with small absolute MF values exhibited high Voc values.This result clearly indicates that the energy-state matching between the donor and acceptor is crucial for achieving a high Voc in OPVs.Because the MF indicates the degree of energy-state matching,which is a critical factor for suppressing energy loss,it can be used to estimate the Voc loss in OPVs.
基金supported by the National Natural Science Foundation of China(Grant No.32250410309 and 52105582)Natural Science Foundation of Guangdong Province(Grant No.2022A1515010894 and 2022B0303040002)+1 种基金Fundamental Research Foundation of Shenzhen(JCYJ20210324095210030 and JCYJ20220818095810023)Shenzhen-Hong Kong-Macao S&T Program(Category C:SGDX20210823103200004)
文摘Extending the ionic conductivity is the pre-requisite of electrolytes in fuel cell technology for high-electrochemical performance.In this regard,the introduction of semiconductor-oxide materials and the approach of heterostructure formation by modulating energy bands to enhance ionic conduction acting as an electrolyte in fuel cell-device.Semiconductor(n-type;SnO_(2))plays a key role by introducing into p-type SrFe_(0.2)Ti_(0.8)O_(3-δ)(SFT)semiconductor perovskite materials to construct p-n heterojunction for high ionic conductivity.Therefore,two different composites of SFT and SnO_(2)are constructed by gluing p-and n-type SFT-SnO_(2),where the optimal composition of SFT-SnO_(2)(6∶4)heterostructure electrolyte-based fuel cell achieved excellent ionic conductivity 0.24 S cm^(-1)with power-output of 1004 mW cm^(-2)and high OCV 1.12 V at a low operational temperature of 500℃.The high power-output and significant ionic conductivity with durable operation of 54 h are accredited to SFT-SnO_(2)heterojunction formation including interfacial conduction assisted by a built-in electric field in fuel cell device.Moreover,the fuel conversion efficiency and considerable Faradaic efficiency reveal the compatibility of SFT-SnO_(2)heterostructure electrolyte and ruled-out short-circuiting issue.Further,the first principle calculation provides sufficient information on structure optimization and energy-band structure modulation of SFT-SnO_(2).This strategy will provide new insight into semiconductor-based fuel cell technology to design novel electrolytes.
基金National Research Foundation (NRF) of Korea grant funded by the Korea Government (MSIT) (NRF-2022R1A2C2093415)partially funding from the Circle Foundation (Republic of Korea) (Grant Number: 2023 TCF Innovative Science Project-03))partially Korea Basic Science Institute (National Research Facilities and Equipment Center) grant funded by the Ministry of Education (2022R1A6C101A751)。
文摘Utilizing sunlight to convert CO_(2) into chemical fuels could address the greenhouse effect and fossil fuel crisis,Heterojunction structure catalysts with oxygen vacancy are attractive in the field of photocatalytic CO_(2) conversion.Herein,a modified TiO_(2)/In_(2)O_(3)(R-P2 5/In_(2)O_(3-x)) type Ⅱ heterojunction composite with oxygen vacancies is designed for photocatalytic CO_(2) reduction,which exhibits excellent CO_(2) reduction activity,with a C_(2) selectivity of 56.66%(in terms of R_(electron)).In situ Fourier-transform infrared spectroscopy(DRIFTS) and time-resolved photoluminescence(TR-PL) spectroscopy are used to reveal the intermediate formation of the photocatalytic mechanism and photogenerated electron lifetime,respectively.The experimental characterizations reveal that the R-P25/In_(2)O_(3-x) composite shows a remarkable behavior for coupling C-C bonds.Besides,efficient charge separation contributes to the improved CO_(2) conversion performance of photocatalysts.This work introduces a type Ⅱ heterojunction composite photocatalyst,which promotes understanding the CO_(2) reduction mechanisms on heterojunction composites and is valuable for the development of photocatalysts.
文摘Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.
基金This work was financially supported by the National Natural Science Foundation of China(51972213)Natural Science Foundation of Shanghai(22ZR1460700).
文摘Heterojunction construction,especially S-scheme heterojunction,represents an efficient universal strategy to achieve high-performance photocatalytic materials.For further performance stimulation of these well-designed heterojunctions,modulating the interfacial internal electric field(IEF)to steer dynamic charge transfer represents a promising approach.Herein,we realized the precise regulation of Fermi level(E_(F))of the oxidation semiconductor(mesoporous WO_(3-x))by tailoring the concentration of oxygen vacancies(V_(O)),maximizing the IEF intensity in Cs_(2)CuBr_(4)@WO_(3-x)(CCB@WO_(3-x))S-scheme heterojunction.The augmented IEF affords a robust driving force for directional electron delivery,leading to boosted charge separation.Hence,the developed CCB@WO_(3-x)S-scheme heterojunction demonstrated outstanding photocatalytic CO_(2)reduction performance,with the electron consumption rate(Relectron)up to 390.34μmol g^(-1)h^(-1),which is 3.28 folds higher than that of pure CCB.An in-depth analysis of the S-scheme electron transfer mode was presented via theoretical investigations,electron spin resonance(ESR),photo-irradiated Kelvin probe force microscopy(KPFM),and in-situ X-ray photoelectron spectroscopy(XPS).Finally,the CO_(2)photoconversion route was explored in detail using in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and DFT theoretical calculations.
文摘Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-matched S-scheme heterostructure and establishing a robust built-in electric field emerge as pivotal strategies.In pursuit of this goal,a core-shell structured CuInS_(2)@CoS_(2)S-scheme heterojunction was meticulously engineered through a two-step molten salt method.This approach over the CuInS_(2)-based composites produced an internal electric field owing to the disparity be-tween the Fermi levels of CoS_(2) and CuInS_(2) at their interface.Consequently,the electric field facili-tated the directed migration of charges and the proficient separation of photoinduced carriers.The resulting CuInS_(2)@CoS_(2) heterostructure exhibited remarkable CO_(2) photoreduction performance,which was 21.7 and 26.5 times that of pure CuInS_(2) and CoS_(2),respectively.The S-scheme heterojunc-tion photogenerated charge transfer mechanism was validated through a series of rigorous anal-yses,including in situ irradiation X-ray photoelectron spectroscopy,work function calculations,and differential charge density examinations.Furthermore,in situ infrared spectroscopy and density functional theory calculations corroborated the fact that the CuInS_(2)@CoS_(2) heterojunction substan-tially lowered the formation energy of *COOH and *CO.This study demonstrates the application potential of S-scheme heterojunctions fabricated via the molten salt method in the realm of ad-dressing carbon-related environmental issues.
基金This work was supported by the National Natural Science Foundation of China(61704054,92161115,62374099,and 62022047)the Fundamental Research Funds for the Central Universities(JB2020MS042 and JB2019MS051).
文摘Two-dimensional(2D)WSe_(2)has received increasing attention due to its unique optical properties and bipolar behavior.Several WSe_(2)-based heterojunctions exhibit bidirectional rectification characteristics,but most devices have a lower rectification ratio.In this work,the Bi_(2)O_(2)Se/WSe_(2)heterojunction prepared by us has a typeⅡband alignment,which can vastly suppress the channel current through the interface barrier so that the Bi_(2)O_(2)Se/WSe_(2)heterojunction device has a large rectification ratio of about 10^(5).Meanwhile,under different gate voltage modulation,the current on/off ratio of the device changes by nearly five orders of magnitude,and the maximum current on/off ratio is expected to be achieved 106.The photocurrent measurement reveals the behavior of recombination and space charge confinement,further verifying the bidirectional rectification behavior of heterojunctions,and it also exhibits excellent performance in light response.In the future,Bi_(2)O_(2)Se/WSe_(2)heterojunction field-effect transistors have great potential to reduce the volume of integrated circuits as a bidirectional controlled switching device.