Optoelectronic Synapses Based on MXene/Violet Phosphorus van der Waals Heterojunctions for Visual‑Olfactory Crossmodal Perception

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.

Defects and morphology engineering for constructing V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S nanotube heterojunction arrays toward efficient bifunctional electrocatalyst for overall water splitting

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.

Chalcogenide-based S-scheme heterojunction photocatalysts

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 photo-catalysts,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 at-tracted considerable attention as heterojunction photocatalysts owing to their narrow bandgap,wide light absorption range,and excellent photoreduction properties.This paper presents a thor-ough analysis of S-scheme heterojunction photocatalysts based on chalcogenides.Following an introduction to the fundamental characteristics and benefits of S-scheme heterojunction photocata-lysts,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 het-erojunction photocatalysts are explored and recommended in light of state-of-the-art research.

Rational construction of CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S S-scheme heterojunction photocatalyst for extraordinary photothermal-assisted photocatalytic H_(2) evolution

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.

Re-usable Cd_(0.9)Zn_(0.1)S-ZnO@C/PVDF piezo-photocatalytic film with exceptional hydrogen evolution capability triggered by the synergetic advantages of piezoelectricity and S-Scheme heterojunction

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.

Magnetic proximity effect in the two-dimensional ε-Fe_(2)O_(3)/NbSe_(2)heterojunction

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.

Understanding the correlation between energy-state mismatching and open-circuit voltage loss in bulk heterojunction solar cells

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.

Hollow Ni Mo-based nitride heterojunction with super-hydrophilic/aerophobic surface for efficient urea-assisted hydrogen production

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.

Vacancy engineering mediated hollow structured ZnO/ZnS S-scheme heterojunction for highly efficient photocatalytic H2 production

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.

Amplified internal electric field of Cs_(2)CuBr_(4)@WO_(3-x)S-scheme heterojunction for efficient CO_(2)photoreduction

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.

Molten salt construction of core-shell structured S-scheme CuInS_(2)@CoS_(2)heterojunction to boost charge transfer for efficient photocatalytic CO_(2)reduction

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.

Bidirectional rectifier with gate voltage control based on Bi_(2)O_(2)Se/WSe_(2)heterojunction

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.

Modeling and Simulation of Heterojunction Solar Cell with Mono Crystalline Silicon

The monocrystalline silicon is a promising material that could be used in solar cells that convert light into electricity. Although the cost of ordinary silicon (Si) solar cells has decreased significantly over the past two decades, the conversion efficiency of these cells has remained relatively high. While solar cells have a great potential as a device of renewable energy, the high cost they incur per Watt continues to be a significant barrier to their widespread implementation. As a consequence, it is vital to conduct research into alternate materials that may be used in the construction of solar cells. The heterojunction solar cell (HJSC), which is based on n-type zinc oxide (n-ZnO) and p-type silicon (p-Si), is one of the numerous alternatives of the typical Si single homojunction solar cell. There are many deficiencies that can be found in the published research on n-ZnO/p-Si heterojunction solar cell. Inconsistencies in the stated value of open circuit voltage (Voc) of the solar cell are one example of deficiency. The absence of a full theoretical study to evaluate the potential of the solar cell structure is another deficiency that can be found in these researches. A lower value of experimentally obtained VOC in comparison to the theoretical prediction based on the band-gap between n-ZnO and p-Si. There needs to be more consensus among scientists regarding the optimal conditions for the growth of zinc oxide. Many software’s are available for simulating and optimizing the solar cells based on these parameters. For this purpose, in this dissertation, I provide computational results relevant to n-ZnO/p-Si HJSC to overcome deficiencies that have been identified. While modeling and simulating the potential of the solar cell structure with AFORS-HET, it is essential to consider the constraints that exist in the real world. AFORS-HET was explicitly designed to mimic the multilayer solar cell arrangement. In AFORS-HET, we can add up to seven layers for solar cell layout. By using this software, we can figure out the open circuit voltage (VOC), the short circuit current (JSC), the quantum efficiency (QE, %), the heterojunction energy band structure, and the power conversion efficiency (PCE).

ZnSb/Ti_(3)C_(2)T_(x)MXene van der Waals heterojunction for flexible near-infrared photodetector arrays

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.

Improvement of Ga_(2)O_(3)vertical Schottky barrier diode by constructing NiO/Ga_(2)O_(3)heterojunction

The high critical electric field strength of Ga_(2)O_(3)enables higher operating voltages and reduced switching losses in power electronic devices.Suitable Schottky metals and epitaxial films are essential for further enhancing device performance.In this work,the fabrication of vertical Ga_(2)O_(3)barrier diodes with three different barrier metals was carried out on an n--Ga_(2)O_(3)homogeneous epitaxial film deposited on an n+-β-Ga_(2)O_(3)substrate by metal-organic chemical vapor deposition,excluding the use of edge terminals.The ideal factor,barrier height,specific on-resistance,and breakdown voltage characteristics of all devices were investigated at room temperature.In addition,the vertical Ga_(2)O_(3)barrier diodes achieve a higher breakdown volt-age and exhibit a reverse leakage as low as 4.82×10^(-8)A/cm^(2)by constructing a NiO/Ga_(2)O_(3)heterojunction.Therefore,Ga_(2)O_(3)power detailed investigations into Schottky barrier metal and NiO/Ga_(2)O_(3)heterojunction of Ga_(2)O_(3)homogeneous epitaxial films are of great research potential in high-efficiency,high-power,and high-reliability applications.

Co/CoO heterojunction rich in oxygen vacancies introduced by O2 plasma embedded in mesoporous walls of carbon nanoboxes covered with carbon nanotubes for rechargeable zinc-air battery

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.

Interfacial built-in electric field and crosslinking pathways enabling WS_(2)/Ti_(3)C_(2)T_(x) heterojunction with robust sodium storage at low temperature

Developing efficient energy storage for sodium-ion batteries(SIBs)by creating high-performance heterojunctions and understanding their interfacial interaction at the atomic/molecular level holds promise but is also challenging.Besides,sluggish reaction kinetics at low temperatures restrict the operation of SIBs in cold climates.Herein,cross-linking nanoarchitectonics of WS_(2)/Ti_(3)C_(2)T_(x) heterojunction,featuring built-in electric field(BIEF),have been developed,employing as a model to reveal the positive effect of heterojunction design and BIEF for modifying the reaction kinetics and electrochemical activity.Particularly,the theoretical analysis manifests the discrepancy in work functions leads to the electronic flow from the electron-rich Ti_(3)C_(2)T_(x) to layered WS_(2),spontaneously forming the BIEF and“ion reservoir”at the heterogeneous interface.Besides,the generation of cross-linking pathways further promotes the transportation of electrons/ions,which guarantees rapid diffusion kinetics and excellent structure coupling.Consequently,superior sodium storage performance is obtained for the WS_(2)/Ti_(3)C_(2)T_(x) heterojunction,with only 0.2%decay per cycle at 5.0 A g^(-1)(25℃)up to 1000 cycles and a high capacity of 293.5 mA h g^(-1)(0.1A g^(-1)after 100 cycles)even at-20℃.Importantly,the spontaneously formed BIEF,accompanied by“ion reservoir”,in heterojunction provides deep understandings of the correlation between structure fabricated and performance obtained.

Facile preparation of Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3) heterojunction for enhanced performance in catalytic nitrogen fixation via photocatalysis and piezo-photocatalysis

In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)and the Ag_(2)S content were optimized. The best 0.5% Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3)(KTN) sample presents an enhanced photocatalytic performance in ammonia synthesis than KTN and Ag_(2)S. Under simulated sunlight, the NH_(3)generation rate of 0.5% Ag_(2)S/KTN reaches 2.0 times that of pure KTN. Under visible light, the reaction rate ratio of the two catalysts is 6.0.XRD, XPS, and TEM analysis revealed that Ag2S was intimately decorated on the KTN nanocubes surface, which promoted the electron transfer between the two semiconductors. The band structure investigation indicated that the Ag_(2)S/KTN heterojunction established a type-Ⅱ band alignment with intimate contact, thus realizing the effective transfer and separation of photogenerated carriers. The change in charge separation was considered as the main reason for the enhanced photocatalytic performance. Interestingly, the Ag_(2)S/KTN composite exhibited higher NH3generation performance under the combined action of ultrasonic vibration and simulated sunlight. The enhanced piezo-photocatalytic performance can be ascribed that the piezoelectric effect of KTN improved the bulk separation of charge carriers in KTN. This study not only provides a potential catalyst for photocatalytic nitrogen fixation but also shows new ideas for the design of highly efficient catalysts via semiconductor modification and external field coupling.

Engineering homotype heterojunctions in hard carbon to induce stable solid electrolyte interfaces for sodium-ion batteries

Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this paper,homotype heterojunctions are designed on HC to induce the generation of stable solid electrolyte interfaces,which can effectively increase the ICE of HC from 64.7%to 81.1%.The results show that using a simple surface engineering strategy to construct a homotypic amorphous Al_(2)O_(3) layer on the HC could shield the active sites,and further inhibit electrolyte decomposition and side effects occurrence.Particularly,due to the suppression of continuous decomposition of NaPF 6 in ester-based electrolytes,the accumulation of NaF could be reduced,leading to the formation of thinner and denser solid electrolyte interface films and a decrease in the interface resistance.The HC anode can not only improve the ICE but elevate its sodium storage performance based on this homotype heterojunction composed of HC and Al_(2)O_(3).The optimized HC anode exhibits an outstanding reversible capacity of 321.5mAhg^(−1) at 50mAg^(−1).The cycling stability is also improved effectively,and the capacity retention rate is 86.9%after 2000 cycles at 1Ag^(−1) while that of the untreated HC is only 52.6%.More importantly,the improved sodium storage behaviors are explained by electrochemical kinetic analysis.

Metal-Free 2D/2D van der Waals Heterojunction Based on Covalent Organic Frameworks for Highly Efficient Solar Energy Catalysis

Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate.Herein,a novel metal-free 2D/2D van der Waals heterojunction,composed of a two-dimensional(2D)COF with ketoenamine linkage(TpPa-1-COF)and 2D defective hexagonal boron nitride(h-BN),is successfully constructed through in situ solvothermal method.Benefitting from the presence of VDW heterojunction,larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN,which make contributions to promoting charge car-riers separation.The introduced defects can also endow the h-BN with porous structure,thus providing more reactive sites.Moreover,the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN,which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF,and suppress electron backflow,corroborated by experimental and density functional theory calculations results.Accordingly,the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays out-standing solar energy catalytic activity for water splitting without co-catalysts,and the H_(2) evolution rate can reach up to 3.15 mmol g^(−1) h^(−1),which is about 67 times greater than that of pristine TpPa-1-COF,also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date.In particular,it is the first work for constructing COFs-based heterojunctions with the help of h-BN,which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H_(2) evolution.