The exploration of novel multivariate heterostructures has emerged as a pivotal strategy for developing high-performance electromagnetic wave(EMW)absorption materials.However,the loss mechanism in traditional heterost...The exploration of novel multivariate heterostructures has emerged as a pivotal strategy for developing high-performance electromagnetic wave(EMW)absorption materials.However,the loss mechanism in traditional heterostructures is relatively simple,guided by empirical observations,and is not monotonous.In this work,we presented a novel semiconductor-semiconductor-metal heterostructure sys-tem,Mo-MXene/Mo-metal sulfides(metal=Sn,Fe,Mn,Co,Ni,Zn,and Cu),including semiconductor junctions and Mott-Schottky junctions.By skillfully combining these distinct functional components(Mo-MXene,MoS_(2),metal sulfides),we can engineer a multiple heterogeneous interface with superior absorption capabilities,broad effective absorption bandwidths,and ultrathin matching thickness.The successful establishment of semiconductor-semiconductor-metal heterostructures gives rise to a built-in electric field that intensifies electron transfer,as confirmed by density functional theory,which collaborates with multiple dielectric polarization mechanisms to substantially amplify EMW absorption.We detailed a successful synthesis of a series of Mo-MXene/Mo-metal sulfides featuring both semiconductor-semiconductor and semiconductor-metal interfaces.The achievements were most pronounced in Mo-MXene/Mo-Sn sulfide,which achieved remarkable reflection loss values of-70.6 dB at a matching thickness of only 1.885 mm.Radar cross-section calculations indicate that these MXene/Mo-metal sulfides have tremendous potential in practical military stealth technology.This work marks a departure from conventional component design limitations and presents a novel pathway for the creation of advanced MXene-based composites with potent EMW absorption capabilities.展开更多
Constructing a built-in electric field has emerged as a key strategy for enhancing charge separation and transfer,thereby improving photoelectrochemical performance.Recently,considerable efforts have been devoted to t...Constructing a built-in electric field has emerged as a key strategy for enhancing charge separation and transfer,thereby improving photoelectrochemical performance.Recently,considerable efforts have been devoted to this endeavor.This review systematically summarizes the impact of built-in electric fields on enhancing charge separation and transfer mechanisms,focusing on the modulation of built-in electric fields in terms of depth and orderliness.First,mechanisms and tuning strategies for built-in electric fields are explored.Then,the state-of-the-art works regarding built-in electric fields for modulating charge separation and transfer are summarized and categorized according to surface and interface depth.Finally,current strategies for constructing bulk built-in electric fields in photoelectrodes are explored,and insights into future developments for enhancing charge separation and transfer in high-performance photoelectrochemical applications are provided.展开更多
Lithium sulfur(Li-S)battery is a kind of burgeoning energy storage system with high energy density.However,the electrolyte-soluble intermediate lithium polysulfides(Li PSs)undergo notorious shuttle effect,which seriou...Lithium sulfur(Li-S)battery is a kind of burgeoning energy storage system with high energy density.However,the electrolyte-soluble intermediate lithium polysulfides(Li PSs)undergo notorious shuttle effect,which seriously hinders the commercialization of Li-S batteries.Herein,a unique VSe_(2)/V_(2)C heterostructure with local built-in electric field was rationally engineered from V_(2)C parent via a facile thermal selenization process.It exquisitely synergizes the strong affinity of V_(2)C with the effective electrocatalytic activity of VSe_(2).More importantly,the local built-in electric field at the heterointerface can sufficiently promote the electron/ion transport ability and eventually boost the conversion kinetics of sulfur species.The Li-S battery equipped with VSe_(2)/V_(2)C-CNTs-PP separator achieved an outstanding initial specific capacity of 1439.1 m A h g^(-1)with a high capacity retention of 73%after 100 cycles at0.1 C.More impressively,a wonderful capacity of 571.6 mA h g^(-1)was effectively maintained after 600cycles at 2 C with a capacity decay rate of 0.07%.Even under a sulfur loading of 4.8 mg cm^(-2),areal capacity still can be up to 5.6 m A h cm^(-2).In-situ Raman tests explicitly illustrate the effectiveness of VSe_(2)/V_(2)C-CNTs modifier in restricting Li PSs shuttle.Combined with density functional theory calculations,the underlying mechanism of VSe_(2)/V_(2)C heterostructure for remedying Li PSs shuttling and conversion kinetics was deciphered.The strategy of constructing VSe_(2)/V_(2)C heterocatalyst in this work proposes a universal protocol to design metal selenide-based separator modifier for Li-S battery.Besides,it opens an efficient avenue for the separator engineering of Li-S batteries.展开更多
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 ch...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.展开更多
Recently,the newly synthesized septuple-atomic layer two-dimensional(2D)material MoSi_(2)N_(4)(MSN)has attracted attention worldwide.Our work delves into the effect of vacancies and external electric fields on the ele...Recently,the newly synthesized septuple-atomic layer two-dimensional(2D)material MoSi_(2)N_(4)(MSN)has attracted attention worldwide.Our work delves into the effect of vacancies and external electric fields on the electronic properties of the MSN/graphene(Gr)heterostructure using first-principles calculation.We find that four types of defective structures,N-in,N-out,Si and Mo vacancy defects of monolayer MSN and MSN/Gr heterostructure are stable in air.Moreover,vacancy defects can effectively modulate the charge transfer at the interface of the MSN/Gr heterostructure as well as the work function of the pristine monolayer MSN and MSN/Gr heterostructure.Finally,the application of an external electric field enables the dynamic switching between n-type and p-type Schottky contacts.Our work may offer the possibility of exceeding the capabilities of conventional Schottky diodes based on MSN/Gr heterostructures.展开更多
The practical application of lithium-sulfur(Li-S)batteries is greatly hindered by soluble polysulfides shuttling and sluggish sulfur redox kinetics.Rational design of multifunctional hybrid materials with superior ele...The practical application of lithium-sulfur(Li-S)batteries is greatly hindered by soluble polysulfides shuttling and sluggish sulfur redox kinetics.Rational design of multifunctional hybrid materials with superior electronic conductivity and high electrocatalytic activity,e.g.,heterostructures,is a promising strategy to solve the above obstacles.Herein,a binary metal sulfide MnS-MoS_(2) heterojunction electrocatalyst is first designed for the construction of high-sulfur-loaded and durable Li-S batteries.The MnS-MoS_(2) p-n heterojunction shows a unique structure of MoS_(2) nanosheets decorated with ample MnS nanodots,which contributes to the formation of a strong built-in electric field at the two-phase interface.The MnS-MoS_(2) hybrid host shows strong soluble polysulfide affinity,enhanced electronic conductivity,and exceptional catalytic effect on sulfur reduction.Benefiting from the synergistic effect,the as-derived S/MnS-MoS_(2) cathode delivers a superb rate capability(643 m A h g^(-1)at 6 C)and a durable cyclability(0.048%decay per cycle over 1000 cycles).More impressively,an areal capacity of 9.9 m A h cm^(-2)can be achieved even under an extremely high sulfur loading of 14.7 mg cm^(-2)and a low electrolyte to sulfur ratio of 2.9μL mg^(-1).This work provides an in-depth understanding of the interfacial catalytic effect of binary metal compound heterojunctions on sulfur reaction kinetics.展开更多
To overcome the serious technological issues affecting lithium-sulfur(Li-S) batteries,such as sluggish sulfur redox kinetics and the detrimental shuttle effect,heterostructure engineering has been investigated as a st...To overcome the serious technological issues affecting lithium-sulfur(Li-S) batteries,such as sluggish sulfur redox kinetics and the detrimental shuttle effect,heterostructure engineering has been investigated as a strategy to effectively capture soluble lithium polysulfide intermediates and promote their conversion reaction by integrating highly polar metal oxides with catalytically active metals sulfides.However,to fully exploit the outstanding properties of heterostructure-based composites,their detailed structure and interfacial contacts should be designed rationally.Herein,optimally arranged TiO_(2)and MoS_(2)-based heterostructures(TiO_(2)@MoS_(2)) are fabricated on carbon cloth as a multifunctional interlayer to efficiently trap polysulfide intermediates and accelerate their redox kinetics.Owing to the synergistic effects between TiO_(2)and MoS_(2)and the uniform heterointerface distribution that induces the ideally oriented built-in electric field,Li-S batteries with TiO_(2)@MoS_(2)interlayers exhibit high rate capability(601 mA h g^(-1)at 5 C),good cycling stability(capacity-fade rate of 0.067% per cycle over 500 cycles at2 C),and satisfactory areal capacity(5.2 mA h cm^(-2)) under an increased sulfur loading of 5.2 mg cm^(-2).Moreover,by comparing with a MoS_(2)@TiO_(2)interlayer composed of reversely arranged heterostructures,the effect of the built-in electric field’s direction on the electrocatalytic reactions of polysulfide intermediates is thoroughly investigated for the first time.The superior electrocatalytic activities of the rationally arranged TiO_(2)@MoS_(2)interlayer demonstrate the importance of optimizing the built-in electric field of heterostructures for producing high-performance Li-S batteries.展开更多
The shuttle effect of polysulfides is a major challenge for the commercialization of lithium-sulfur battery.The systematic modification of separators has the potential to solve these problems by enhancing the adsorpti...The shuttle effect of polysulfides is a major challenge for the commercialization of lithium-sulfur battery.The systematic modification of separators has the potential to solve these problems by enhancing the adsorption and catalytic conversion of polysulfides.Herein,strong internal electric field bismuth oxycarbonate(Bi_(2)O_(2)CO_(3))nanoflowers decorated conductive carbon(DC+BOC)is proposed to be systematically modified on separator.This intermediate layer not only possesses a strong affinity for polysulfides,but also promotes the conversion of polysulfides and induces the formation of a stable solid electrolyte interphase(SEI)layer,thereby improving the rate performance and cycling stability of the battery.As expected,the modified membrane achieved a high specific capacity of 713 mA h g^(-1) at 5 C.At 1 C,high reversibility of 719 mA h g^(-1) was achieved after 550 cycles with only 0.044%decay per cycle.More importantly,under the sulfur loading of 5.1 mg cm^(-2),the area specific capacity remained at4.1 mA h cm^(-2) after 200 cycles,and the attenuation rate per cycle was only 0,056%.This work provides a new strategy to overcome the shuttle effect of polysulfide,and shows great potential in the application of high-performance lithium-sulfur batteries.展开更多
Ultraviolet(UV)photodetectors are extensively adopted in the fields of the Internet of Things,optical communications and imaging.Nowadays,with broadening the application scope of UV photodetectors,developing integrate...Ultraviolet(UV)photodetectors are extensively adopted in the fields of the Internet of Things,optical communications and imaging.Nowadays,with broadening the application scope of UV photodetectors,developing integrated devices with more functionalities rather than basic photo-detecting ability are highly required and have been triggered ever-growing interest in scientific and industrial communities.Ferroelectric thin films have become a potential candidate in the field of UV detection due to their wide bandgap and unique photovoltaic characteristics.Additionally,ferroelectric thin films perform excellent dielectric,piezoelectric,pyroelectric,acousto-optic effects,etc.,which can satisfy the demand for the diversified development of UV detectors.In this review,according to the different roles of ferroelectric thin films in the device,the UV photodetectors based on ferroelectric films are classified into ferroelectric depolarization field driven type,ferroelectric depolarization field and built-in electric field co-driven type,and ferroelectric field enhanced type.These three types of ferroelectric UV photodetectors have great potential and are expected to promote the development of a new generation of UV detection technology.At the end of the paper,the advantages and challenges of three types of ferroelectric UV photodetectors are summarized,and the possible development direction in the future is proposed.展开更多
Exploiting high-rate anode materials with fast K+diffusion is intriguing for the development of advanced potassium-ion batteries(KIBs)but remains unrealized.Here,heterostructure engineering is proposed to construct th...Exploiting high-rate anode materials with fast K+diffusion is intriguing for the development of advanced potassium-ion batteries(KIBs)but remains unrealized.Here,heterostructure engineering is proposed to construct the dual transition metal tellurides(CoTe_(2)/ZnTe),which are anchored onto two-dimensional(2D)Ti_(3)C_(2)T_(x)MXene nanosheets.Various theoretical modeling and experimental findings reveal that heterostructure engineering can regulate the electronic structures of CoTe_(2)/ZnTe interfaces,improving K+diffusion and adsorption.In addition,the different work functions between CoTe_(2)/ZnTe induce a robust built-in electric field at the CoTe_(2)/ZnTe interface,providing a strong driving force to facilitate charge transport.Moreover,the conductive and elastic Ti_(3)C_(2)T_(x)can effectively promote electrode conductivity and alleviate the volume change of CoTe_(2)/ZnTe heterostructures upon cycling.Owing to these merits,the resulting CoTe_(2)/ZnTe/Ti_(3)C_(2)T_(x)(CZT)exhibit excellent rate capability(137.0 mAh g^(-1)at 10 A g^(-1))and cycling stability(175.3 mAh g^(-1)after 4000 cycles at 3.0 A g^(-1),with a high capacity retention of 89.4%).More impressively,the CZT-based full cells demonstrate high energy density(220.2 Wh kg^(-1))and power density(837.2 W kg^(-1)).This work provides a general and effective strategy by integrating heterostructure engineering and 2D material nanocompositing for designing advanced high-rate anode materials for next-generation KIBs.展开更多
Rapid technological development and population growth are responsible for a series of imminent environmental problems and an ineluctable energy crisis.The application of semiconductor nanomaterials in photocatalysis o...Rapid technological development and population growth are responsible for a series of imminent environmental problems and an ineluctable energy crisis.The application of semiconductor nanomaterials in photocatalysis or photoelectrocatalysis(PEC)for either the degradation of contaminants in the environment or the generation of hydrogen as clean fuel is an effective approach to alleviate these problems.However,the efficiency of such processes remains suboptimal for real applications.Reasonable construction of a built-in electric field is considered to efficiently enhance carrier separation and reduce carrier recombination to improve catalytic performance.In the past decade,as a new method to enhance the built-in electric field,the piezoelectric effect from piezoelectric materials has been extensively studied.In this review,we provide an overview of the properties of piezoelectric materials and the mechanisms of piezoelectricity and ferroelectricity for a built-in electric field.Then,piezoelectric and ferroelectric polarization regulated built-in electric fields that mediate catalysis are discussed.Furthermore,the applications of piezoelectric semiconductor materials are also highlighted,including degradation of pollutants,bacteria disinfection,water splitting for H2 generation,and organic synthesis.We conclude by discussing the challenges in the field and the exciting opportunities to further improve piezo-catalytic efficiency.展开更多
The cyclotron mass of magnetopolarons in wurtzite InxGa1-xN/GaN quantum well is studied in the presence of an external magnetic field by using the Larsen perturbation method. The effects of the built-in electric field...The cyclotron mass of magnetopolarons in wurtzite InxGa1-xN/GaN quantum well is studied in the presence of an external magnetic field by using the Larsen perturbation method. The effects of the built-in electric field and different phonon modes including interface, confined and half-space phonon modes are considered in our calculation. The results for a zinc-blende quantum well are also given for comparison. It is found that the main contribution to the transition energy comes from half-space and interface phonon modes when the well width is very small while the confined modes play a more important role in a wider well due to the location of the electron wave function. As the well width increases, the cyclotron mass of magnetopolarons first increases to a maximum and then decreases either with or without the built-in electric field in the wurtzite structure and the built-in electric field slightly reduces the cyclotron mass. The variation of cyclotron mass in a zinc-blende structure is similar to that in a wurtzite structure. With the increase of external magnetic field, the cyclotron mass of polarons almost linearly increases. The cyclotron frequency of magnetopolarons is also discussed.展开更多
Developing highly efficient,durable,and non-noble electrocatalysts for the sluggish anodic oxygen evolution reaction(OER)is the pivotal for meeting the practical demand in water splitting.However,the current transitio...Developing highly efficient,durable,and non-noble electrocatalysts for the sluggish anodic oxygen evolution reaction(OER)is the pivotal for meeting the practical demand in water splitting.However,the current transition-metal electrocatalysts still suffer from low activity and durability on account of poor interfacial reaction kinetics.In this work,a facile solid-state synthesis strategy is developed to construct transition-metal sulfides heterostructures(denoted as MS_(2)/NiS_(2),M=Mo or W)for boosting OER electrocatalysis.As a result,MoS2/NiS2 and WS2/NiS2 show lower overpotentials of 300 mV and 320 mV to achieve the current density of 10 mA·cm^(-2),and smaller Tafel slopes of 60 mV.dec^(-1) and 83 mV.dec^(-1)in 1 mol·L^(-1) KOH,respectively,in comparison with the single MoS2,WS2,NiS2,as well as even the benchmark RuO2.The experiments reveal that the designed heterostructures have strong electronic interactions and spontaneously develop a built-in electric field at the heterointerface with uneven charge distribution based on the difference of band structures,which promote interfacial charge transfer,improve absorptivity of OH-,and modulate the energy level more comparable to the OER.Thus,the designed transition-metal sulfides heterostructures exhibit a remarkably high electrocatalytic activity for OER.This study provides a simple strategy to manipulate the heterostructure interface via an energy level engineering method for OER and can be extended to fabricate other heterostructures for various energy-related applications.展开更多
S-scheme possesses superior redox capabilities compared with the II-scheme,providing an effective method to solve the innate defects of g-C_(3)N_(4)(CN).In this study,S-doped g-C_(3)N_(4)/g-C_(3)N_(4)(SCN-tm/CN)S-sche...S-scheme possesses superior redox capabilities compared with the II-scheme,providing an effective method to solve the innate defects of g-C_(3)N_(4)(CN).In this study,S-doped g-C_(3)N_(4)/g-C_(3)N_(4)(SCN-tm/CN)S-scheme homojunction was constructed by rationally integrating morphology control with interfacial engineering to enhance the photocatalytic hydrogen evolution performance.In-situ Kelvin probe force microscopy(KPFM)confirms the transport of photo-generated electrons from CN to SCN.Density functional theory(DFT)calculations reveal that the generation of a built-in electric field between SCN and CN enables the carrier separation to be more efficient and effective.Femtosecond transient absorption spectrum(fs-TAS)indicates prolonged lifetimes of SCN-tm/CN_(3)(τ1:9.7,τ2:110,andτ3:1343.5 ps)in comparison to those of CN(τ1:4.86,τ2:55.2,andτ3:927 ps),signifying that the construction of homojunction promotes the separation and transport of electron hole pairs,thus favoring the photocatalytic process.Under visible light irradiation,the optimized SCN-tm/CN_(3)exhibits excellent photocatalytic activity with the hydrogen evolution rate of 5407.3μmol·g^(−1)·h^(−1),which is 20.4 times higher than that of CN(265.7μmol·g^(−1)·h^(−1)).Moreover,the homojunction also displays an apparent quantum efficiency of 26.8%at 435 nm as well as ultra-long and ultra-stable cycle ability.This work offers a new strategy to construct highly efficient photocatalysts based on the metal-free conjugated polymeric CN for realizing solar energy conversion.展开更多
Achieving a high carrier migration efficiency by constructing built-in electric field is one of the promising approaches for promoting photocatalytic activity. Herein, we have designed a donor-acceptor(D-A) crystallin...Achieving a high carrier migration efficiency by constructing built-in electric field is one of the promising approaches for promoting photocatalytic activity. Herein, we have designed a donor-acceptor(D-A) crystalline carbon nitride(APMCN) with 4-amino-2,6-dihydroxypyrimidine(AP) as electron donor, in which the pyrimidine ring was well embedded in the heptazine ring via hydrogen-bonding effect during hydrothermal process. The APMCN shows superior charge-transfer due to giant built-in electric field(5.94times higher than pristine carbon nitride), thereby exhibiting excellent photocatalytic H_(2) evolution rate(1350 μmol/h) with a high AQY(62.8%) at 400 nm. Mechanistic analysis based on detailed experimental investigation together with theoretical analysis reveals that the excellent photocatalytic activity is attributed to the promoted charge separation by the giant internal electric field originated from the D–A structure.展开更多
Employing the alkaline water electrolysis system to generate hydrogen holds great prospects but still poses significant challenges,particularly for the construction of hydrogen evolution reaction(HER)catalysts operati...Employing the alkaline water electrolysis system to generate hydrogen holds great prospects but still poses significant challenges,particularly for the construction of hydrogen evolution reaction(HER)catalysts operating at ampere-level current density.Herein,the unique Ru and RuP_(2)dual nano-islands are deliberately implanted on N-doped carbon substrate(denoted as Ru-RuP_(2)/NC),in which a built-in electric field(BEF)is spontaneously generated between Ru-RuP_(2)dual nano-islands driven by their work function difference.Experimental and theoretical results unveil that such constructed BEF could serve as the driving force for triggering fast hydrogen spillover process on bridged Ru-RuP_(2)dual nano-islands,which could invalidate the inhibitory effect of high hydrogen coverage at ampere-level current density,and synchronously speed up the water dissociation on Ru nano-islands and hydrogen adsorption/desorption on RuP_(2)nano-islands through hydrogen spillover process.As a result,the Ru-RuP_(2)/NC affords an ultra-low overpotential of 218 mV to achieve 1.0 A·cm^(−2)along with the superior stability over 1000 h,holding the great promising prospect in practical applications at ampere-level current density.More importantly,this work is the first to advance the scientific understanding of the relationship between the constructed BEF and hydrogen spillover process,which could be enlightening for the rational design of the cost-effective alkaline HER catalysts at ampere-level current density.展开更多
At present,industrial synthetic ammonia was still obtained through the Hubble-Bosch process,with large energy consumption.It is a research hotspot to realize green synthetic ammonia by using solar energy.The difficult...At present,industrial synthetic ammonia was still obtained through the Hubble-Bosch process,with large energy consumption.It is a research hotspot to realize green synthetic ammonia by using solar energy.The difficulty of photocatalytic ammonia synthesis was that the photo-excited electrons have not enough energy to active N≡N.In this study,Ti was doped into BiOBr by one-step hydrothermal method,which was oxidized into TiO_(2)when the doping amount reaches the maximum,in situ forming Ti_(0.31)B_(0.69)OB/TiO_(2)composites.Benefiting from the synergistic effect of Ti doping and S-scheme heterojunction,the synthetic ammonia efficiency of Ti_(0.31)B_(0.69)OB/TiO_(2)-11.96 reached 1.643 mmol·g_(cat)^(-1)at mild conditions and without hole scavenger for up to 7 h,the efficiency of synthetic ammonia is 115 times,10.5 times and 3.3 times of that of BiOBr,Ti_(0.31)B_(0.69)OB and TiO_(2),respectively.Specifically,DFT calculation confirms that Ti doping accurately refine the electronic structure of BiOBr,facilitate nitrogen adsorption activation and reduce hydrogenation reaction energy barrier,thus accelerating the reaction kinetics of photocatalytic nitrogen reduction(NRR),Meanwhile,constructing S-scheme heterojunction boosts the separation and transfer of photogenerated electron-hole pairs,improving the reduction ability of electrons in the conduction band of TiO_(2)and the oxidation ability of holes in the valence band of Ti_(0.31)B_(0.69)OB.展开更多
Lead-free tin perovskite solar cells(PSCs)have undergone rapid development in recent years and are regarded as a promising ecofriendly photovoltaic technology.However,a strategy to suppress charge recombination via a ...Lead-free tin perovskite solar cells(PSCs)have undergone rapid development in recent years and are regarded as a promising ecofriendly photovoltaic technology.However,a strategy to suppress charge recombination via a built-in electric field inside a tin perovskite crystal is still lacking.In the present study,a formamidinium tin iodide(FASnI;)perovskite absorber with a vertical Sn;gradient was fabricated using a Lewis base-assisted recrystallization method to enhance the built-in electric field and minimize the bulk recombination loss inside the tin perovskites.Depth-dependent X-ray photoelectron spectroscopy revealed that the Fermi level upshifts with an increase in Sn;content from the bottom to the top in this heterogeneous FASnI;film,which generates an additional electric field to prevent the trapping of photo-induced electrons and holes.Consequently,the Sn;-gradient FASnI;absorber exhibits a promising efficiency of 13.82%for inverted tin PSCs with an open-circuit voltage increase of 130 mV,and the optimized cell maintains over 13%efficiency after continuous operation under 1-sun illumination for 1,000 h.展开更多
For cases in which a robot with installed solar cells and a sensor operates in a nuclear reactor building or in space for extravehicular activity, we require elastic and extensible solar cells. More than two different...For cases in which a robot with installed solar cells and a sensor operates in a nuclear reactor building or in space for extravehicular activity, we require elastic and extensible solar cells. More than two different types of sensing are also required, minimally with photovoltaics and built-in electricity. Magnetic compound fluid (MCF) rubber solar cells are made of rubber, so they are elastic and extensible as well as sensitive. To achieve flexibility and an effective photovoltaic effect, MCF rubber solar cells must include both soluble and insoluble rubbers, Fe<sub>3</sub>O<sub>4</sub>, TiO<sub>2</sub>, Na<sub>2</sub>WO<sub>4</sub>∙2H<sub>2</sub>O, etc. On the basis of this constitution, we propose a consummate fabrication process for MCF rubber solar cells. The characteristics of these cells result from the semiconductor-like role of the molecules of TiO<sub>2</sub>, Fe<sub>3</sub>O<sub>4</sub>, Ni, Na<sub>2</sub>WO<sub>4</sub>∙2H<sub>2</sub>O, polydimethylsiloxane (PDMS), natural rubber (NR), oleic acid, polyvinyl alcohol (PVA), water and magnetic cluster involved in the MCF rubber. Their tendencies can be deduced by synthesizing knowledge about the enhancement of the reverse-bias saturation current <em>I</em><sub><em>S</em></sub> and the diode ideality factor <em>N</em>, with conventional knowledge about the semiconductor affected by <em>γ</em>-irradiation and the attenuation of the photon energy of <em>γ</em>-rays.展开更多
The strong intrinsic Coulomb interactions of Frenkel excitons in crystalline carbon nitride(CCN) greatly limits their dissociation into electrons and holes, resulting in unsatisfactory charges separation and photocata...The strong intrinsic Coulomb interactions of Frenkel excitons in crystalline carbon nitride(CCN) greatly limits their dissociation into electrons and holes, resulting in unsatisfactory charges separation and photocatalytic efficiency. Herein, we propose a strategy to facilitate excitons dissociation by molecular regulation induced built-in electric field(BIEF). The electron-rich pyrimidine-ring into CCN changes the charge density distribution over heptazine-rings to induce BIEF between melon chains. Such BIEF is sufficient to overcome the considerable exciton binding energy(EBE) and reduce it from 38.4 meV to 16.4 meV,increasing the excitons dissociation efficiency(EDE) from 21.5% to 51.9%. Our results establish a strategy to facilitate excitons dissociation through molecular regulation induced BIEF, targeting the intrinsic high EBE and low EDE of polymer photocatalysts.展开更多
基金supported by the National Natural Science Foundation of China(No.22269010,52231007,12327804,T2321003,22088101)the Jiangxi Provincial Natural Science Foundation(No.20224BAB214021)+1 种基金the Major Research Program of Jingdezhen Ceramic Industry(No.2023ZDGG002)the Ministry of Science and Technology of China(973 Project No.2021YFA1200600).
文摘The exploration of novel multivariate heterostructures has emerged as a pivotal strategy for developing high-performance electromagnetic wave(EMW)absorption materials.However,the loss mechanism in traditional heterostructures is relatively simple,guided by empirical observations,and is not monotonous.In this work,we presented a novel semiconductor-semiconductor-metal heterostructure sys-tem,Mo-MXene/Mo-metal sulfides(metal=Sn,Fe,Mn,Co,Ni,Zn,and Cu),including semiconductor junctions and Mott-Schottky junctions.By skillfully combining these distinct functional components(Mo-MXene,MoS_(2),metal sulfides),we can engineer a multiple heterogeneous interface with superior absorption capabilities,broad effective absorption bandwidths,and ultrathin matching thickness.The successful establishment of semiconductor-semiconductor-metal heterostructures gives rise to a built-in electric field that intensifies electron transfer,as confirmed by density functional theory,which collaborates with multiple dielectric polarization mechanisms to substantially amplify EMW absorption.We detailed a successful synthesis of a series of Mo-MXene/Mo-metal sulfides featuring both semiconductor-semiconductor and semiconductor-metal interfaces.The achievements were most pronounced in Mo-MXene/Mo-Sn sulfide,which achieved remarkable reflection loss values of-70.6 dB at a matching thickness of only 1.885 mm.Radar cross-section calculations indicate that these MXene/Mo-metal sulfides have tremendous potential in practical military stealth technology.This work marks a departure from conventional component design limitations and presents a novel pathway for the creation of advanced MXene-based composites with potent EMW absorption capabilities.
基金financially supported by the Industrial Technology Innovation Program of IMAST(No.2023JSYD 01003)the National Natural Science Foundation of China(Nos.52104292 and U2341209)。
文摘Constructing a built-in electric field has emerged as a key strategy for enhancing charge separation and transfer,thereby improving photoelectrochemical performance.Recently,considerable efforts have been devoted to this endeavor.This review systematically summarizes the impact of built-in electric fields on enhancing charge separation and transfer mechanisms,focusing on the modulation of built-in electric fields in terms of depth and orderliness.First,mechanisms and tuning strategies for built-in electric fields are explored.Then,the state-of-the-art works regarding built-in electric fields for modulating charge separation and transfer are summarized and categorized according to surface and interface depth.Finally,current strategies for constructing bulk built-in electric fields in photoelectrodes are explored,and insights into future developments for enhancing charge separation and transfer in high-performance photoelectrochemical applications are provided.
基金supported by the National Natural Science Foundation of China(No.52072099)the Joint Guidance Project of the Natural Science Foundation of Heilongjiang Province,China(No.LH2022E093)the Team Program of the Natural Science Foundation of Heilongjiang Province,China(No.TD2021E005)。
文摘Lithium sulfur(Li-S)battery is a kind of burgeoning energy storage system with high energy density.However,the electrolyte-soluble intermediate lithium polysulfides(Li PSs)undergo notorious shuttle effect,which seriously hinders the commercialization of Li-S batteries.Herein,a unique VSe_(2)/V_(2)C heterostructure with local built-in electric field was rationally engineered from V_(2)C parent via a facile thermal selenization process.It exquisitely synergizes the strong affinity of V_(2)C with the effective electrocatalytic activity of VSe_(2).More importantly,the local built-in electric field at the heterointerface can sufficiently promote the electron/ion transport ability and eventually boost the conversion kinetics of sulfur species.The Li-S battery equipped with VSe_(2)/V_(2)C-CNTs-PP separator achieved an outstanding initial specific capacity of 1439.1 m A h g^(-1)with a high capacity retention of 73%after 100 cycles at0.1 C.More impressively,a wonderful capacity of 571.6 mA h g^(-1)was effectively maintained after 600cycles at 2 C with a capacity decay rate of 0.07%.Even under a sulfur loading of 4.8 mg cm^(-2),areal capacity still can be up to 5.6 m A h cm^(-2).In-situ Raman tests explicitly illustrate the effectiveness of VSe_(2)/V_(2)C-CNTs modifier in restricting Li PSs shuttle.Combined with density functional theory calculations,the underlying mechanism of VSe_(2)/V_(2)C heterostructure for remedying Li PSs shuttling and conversion kinetics was deciphered.The strategy of constructing VSe_(2)/V_(2)C heterocatalyst in this work proposes a universal protocol to design metal selenide-based separator modifier for Li-S battery.Besides,it opens an efficient avenue for the separator engineering of Li-S batteries.
基金supported by the faculty startup funds from the Yangzhou Universitythe Natural Science Foundation of Jiangsu Province(BK20210821)+1 种基金the National Natural Science Foundation of China(22102141)the Lvyangjinfeng Talent Program of Yangzhou。
文摘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.
基金Project supported by the Industry and Education Combination Innovation Platform of Intelligent Manufacturing and Graduate Joint Training Base at Guizhou University(Grant No.2020-520000-83-01-324061)the National Natural Science Foundation of China(Grant No.61264004)the High-level Creative Talent Training Program in Guizhou Province of China(Grant No.[2015]4015).
文摘Recently,the newly synthesized septuple-atomic layer two-dimensional(2D)material MoSi_(2)N_(4)(MSN)has attracted attention worldwide.Our work delves into the effect of vacancies and external electric fields on the electronic properties of the MSN/graphene(Gr)heterostructure using first-principles calculation.We find that four types of defective structures,N-in,N-out,Si and Mo vacancy defects of monolayer MSN and MSN/Gr heterostructure are stable in air.Moreover,vacancy defects can effectively modulate the charge transfer at the interface of the MSN/Gr heterostructure as well as the work function of the pristine monolayer MSN and MSN/Gr heterostructure.Finally,the application of an external electric field enables the dynamic switching between n-type and p-type Schottky contacts.Our work may offer the possibility of exceeding the capabilities of conventional Schottky diodes based on MSN/Gr heterostructures.
基金financial support from the National Natural Science Foundation of China (NSFC,21875155,22032004)the support of the National Key Research and Development Program of China (2021YFA1201502)the support of the Nanqiang Young Top-notch Talent Fellowship in Xiamen University。
文摘The practical application of lithium-sulfur(Li-S)batteries is greatly hindered by soluble polysulfides shuttling and sluggish sulfur redox kinetics.Rational design of multifunctional hybrid materials with superior electronic conductivity and high electrocatalytic activity,e.g.,heterostructures,is a promising strategy to solve the above obstacles.Herein,a binary metal sulfide MnS-MoS_(2) heterojunction electrocatalyst is first designed for the construction of high-sulfur-loaded and durable Li-S batteries.The MnS-MoS_(2) p-n heterojunction shows a unique structure of MoS_(2) nanosheets decorated with ample MnS nanodots,which contributes to the formation of a strong built-in electric field at the two-phase interface.The MnS-MoS_(2) hybrid host shows strong soluble polysulfide affinity,enhanced electronic conductivity,and exceptional catalytic effect on sulfur reduction.Benefiting from the synergistic effect,the as-derived S/MnS-MoS_(2) cathode delivers a superb rate capability(643 m A h g^(-1)at 6 C)and a durable cyclability(0.048%decay per cycle over 1000 cycles).More impressively,an areal capacity of 9.9 m A h cm^(-2)can be achieved even under an extremely high sulfur loading of 14.7 mg cm^(-2)and a low electrolyte to sulfur ratio of 2.9μL mg^(-1).This work provides an in-depth understanding of the interfacial catalytic effect of binary metal compound heterojunctions on sulfur reaction kinetics.
基金supported by the National R&D Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (2018M3D1A1058793 and 2021R1A3B1068920)supported by the Creative Materials Discovery Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (2018M3D1A1058744)the Yonsei Signature Research Cluster Program of 2021 (2021-22-0002)。
文摘To overcome the serious technological issues affecting lithium-sulfur(Li-S) batteries,such as sluggish sulfur redox kinetics and the detrimental shuttle effect,heterostructure engineering has been investigated as a strategy to effectively capture soluble lithium polysulfide intermediates and promote their conversion reaction by integrating highly polar metal oxides with catalytically active metals sulfides.However,to fully exploit the outstanding properties of heterostructure-based composites,their detailed structure and interfacial contacts should be designed rationally.Herein,optimally arranged TiO_(2)and MoS_(2)-based heterostructures(TiO_(2)@MoS_(2)) are fabricated on carbon cloth as a multifunctional interlayer to efficiently trap polysulfide intermediates and accelerate their redox kinetics.Owing to the synergistic effects between TiO_(2)and MoS_(2)and the uniform heterointerface distribution that induces the ideally oriented built-in electric field,Li-S batteries with TiO_(2)@MoS_(2)interlayers exhibit high rate capability(601 mA h g^(-1)at 5 C),good cycling stability(capacity-fade rate of 0.067% per cycle over 500 cycles at2 C),and satisfactory areal capacity(5.2 mA h cm^(-2)) under an increased sulfur loading of 5.2 mg cm^(-2).Moreover,by comparing with a MoS_(2)@TiO_(2)interlayer composed of reversely arranged heterostructures,the effect of the built-in electric field’s direction on the electrocatalytic reactions of polysulfide intermediates is thoroughly investigated for the first time.The superior electrocatalytic activities of the rationally arranged TiO_(2)@MoS_(2)interlayer demonstrate the importance of optimizing the built-in electric field of heterostructures for producing high-performance Li-S batteries.
基金financially sponsored by the National Natural Science Foundation of China(51872208 and 52072273)the Zhejiang Provincial Special Support Program for High-level Talents(2019R52042)。
文摘The shuttle effect of polysulfides is a major challenge for the commercialization of lithium-sulfur battery.The systematic modification of separators has the potential to solve these problems by enhancing the adsorption and catalytic conversion of polysulfides.Herein,strong internal electric field bismuth oxycarbonate(Bi_(2)O_(2)CO_(3))nanoflowers decorated conductive carbon(DC+BOC)is proposed to be systematically modified on separator.This intermediate layer not only possesses a strong affinity for polysulfides,but also promotes the conversion of polysulfides and induces the formation of a stable solid electrolyte interphase(SEI)layer,thereby improving the rate performance and cycling stability of the battery.As expected,the modified membrane achieved a high specific capacity of 713 mA h g^(-1) at 5 C.At 1 C,high reversibility of 719 mA h g^(-1) was achieved after 550 cycles with only 0.044%decay per cycle.More importantly,under the sulfur loading of 5.1 mg cm^(-2),the area specific capacity remained at4.1 mA h cm^(-2) after 200 cycles,and the attenuation rate per cycle was only 0,056%.This work provides a new strategy to overcome the shuttle effect of polysulfide,and shows great potential in the application of high-performance lithium-sulfur batteries.
基金supported by the Guang Dong Basic and Applied Basic Research Foundation,China(2021B1515120025)。
文摘Ultraviolet(UV)photodetectors are extensively adopted in the fields of the Internet of Things,optical communications and imaging.Nowadays,with broadening the application scope of UV photodetectors,developing integrated devices with more functionalities rather than basic photo-detecting ability are highly required and have been triggered ever-growing interest in scientific and industrial communities.Ferroelectric thin films have become a potential candidate in the field of UV detection due to their wide bandgap and unique photovoltaic characteristics.Additionally,ferroelectric thin films perform excellent dielectric,piezoelectric,pyroelectric,acousto-optic effects,etc.,which can satisfy the demand for the diversified development of UV detectors.In this review,according to the different roles of ferroelectric thin films in the device,the UV photodetectors based on ferroelectric films are classified into ferroelectric depolarization field driven type,ferroelectric depolarization field and built-in electric field co-driven type,and ferroelectric field enhanced type.These three types of ferroelectric UV photodetectors have great potential and are expected to promote the development of a new generation of UV detection technology.At the end of the paper,the advantages and challenges of three types of ferroelectric UV photodetectors are summarized,and the possible development direction in the future is proposed.
基金The authors thank the financial support from the National Natural Science Foundation of China(No.52201242 and 52250010)Natural Science Foundation of Jiangsu Province(No.BK20200386)+1 种基金Young Elite Scientists Sponsorship Program by CAST(No.2021QNRC001)the Fundamental Research Funds for the Central Universities(No.2242022R40018).
文摘Exploiting high-rate anode materials with fast K+diffusion is intriguing for the development of advanced potassium-ion batteries(KIBs)but remains unrealized.Here,heterostructure engineering is proposed to construct the dual transition metal tellurides(CoTe_(2)/ZnTe),which are anchored onto two-dimensional(2D)Ti_(3)C_(2)T_(x)MXene nanosheets.Various theoretical modeling and experimental findings reveal that heterostructure engineering can regulate the electronic structures of CoTe_(2)/ZnTe interfaces,improving K+diffusion and adsorption.In addition,the different work functions between CoTe_(2)/ZnTe induce a robust built-in electric field at the CoTe_(2)/ZnTe interface,providing a strong driving force to facilitate charge transport.Moreover,the conductive and elastic Ti_(3)C_(2)T_(x)can effectively promote electrode conductivity and alleviate the volume change of CoTe_(2)/ZnTe heterostructures upon cycling.Owing to these merits,the resulting CoTe_(2)/ZnTe/Ti_(3)C_(2)T_(x)(CZT)exhibit excellent rate capability(137.0 mAh g^(-1)at 10 A g^(-1))and cycling stability(175.3 mAh g^(-1)after 4000 cycles at 3.0 A g^(-1),with a high capacity retention of 89.4%).More impressively,the CZT-based full cells demonstrate high energy density(220.2 Wh kg^(-1))and power density(837.2 W kg^(-1)).This work provides a general and effective strategy by integrating heterostructure engineering and 2D material nanocompositing for designing advanced high-rate anode materials for next-generation KIBs.
基金supported by the Youth Innovation Promotion Association of the Chinese Academy of Sciences(2015023)National Natural Science Foundation of China(81471784,51802115)+3 种基金Natural Science Foundation of Beijing(2172058)Natural Science Foundation of Shandong Province(ZR2018BEM010,ZR2019YQ21)Major Program of Shandong Province Natural Science Foundation(ZR2018ZC0843)Scientific and Technology Project of University of Jinan(XKY1923)~~
文摘Rapid technological development and population growth are responsible for a series of imminent environmental problems and an ineluctable energy crisis.The application of semiconductor nanomaterials in photocatalysis or photoelectrocatalysis(PEC)for either the degradation of contaminants in the environment or the generation of hydrogen as clean fuel is an effective approach to alleviate these problems.However,the efficiency of such processes remains suboptimal for real applications.Reasonable construction of a built-in electric field is considered to efficiently enhance carrier separation and reduce carrier recombination to improve catalytic performance.In the past decade,as a new method to enhance the built-in electric field,the piezoelectric effect from piezoelectric materials has been extensively studied.In this review,we provide an overview of the properties of piezoelectric materials and the mechanisms of piezoelectricity and ferroelectricity for a built-in electric field.Then,piezoelectric and ferroelectric polarization regulated built-in electric fields that mediate catalysis are discussed.Furthermore,the applications of piezoelectric semiconductor materials are also highlighted,including degradation of pollutants,bacteria disinfection,water splitting for H2 generation,and organic synthesis.We conclude by discussing the challenges in the field and the exciting opportunities to further improve piezo-catalytic efficiency.
基金Project supported by the National Natural Science Foundation of China (Grant No. 10964007)the Natural Science Foundation of Inner Mongolia,China (Grant No. 2009MS0110)
文摘The cyclotron mass of magnetopolarons in wurtzite InxGa1-xN/GaN quantum well is studied in the presence of an external magnetic field by using the Larsen perturbation method. The effects of the built-in electric field and different phonon modes including interface, confined and half-space phonon modes are considered in our calculation. The results for a zinc-blende quantum well are also given for comparison. It is found that the main contribution to the transition energy comes from half-space and interface phonon modes when the well width is very small while the confined modes play a more important role in a wider well due to the location of the electron wave function. As the well width increases, the cyclotron mass of magnetopolarons first increases to a maximum and then decreases either with or without the built-in electric field in the wurtzite structure and the built-in electric field slightly reduces the cyclotron mass. The variation of cyclotron mass in a zinc-blende structure is similar to that in a wurtzite structure. With the increase of external magnetic field, the cyclotron mass of polarons almost linearly increases. The cyclotron frequency of magnetopolarons is also discussed.
基金supported by the National Natural Science Foun-dation of China(21922814,22138012,21961160745,21921005,22178349,22078333,22108281 and 31961133019)Excellent Member in Youth Innovation Promotion Association,Chinese Academy of Sciences(Y202014)Shandong Energy Institute(Grant Number SEI 1202133).
文摘Developing highly efficient,durable,and non-noble electrocatalysts for the sluggish anodic oxygen evolution reaction(OER)is the pivotal for meeting the practical demand in water splitting.However,the current transition-metal electrocatalysts still suffer from low activity and durability on account of poor interfacial reaction kinetics.In this work,a facile solid-state synthesis strategy is developed to construct transition-metal sulfides heterostructures(denoted as MS_(2)/NiS_(2),M=Mo or W)for boosting OER electrocatalysis.As a result,MoS2/NiS2 and WS2/NiS2 show lower overpotentials of 300 mV and 320 mV to achieve the current density of 10 mA·cm^(-2),and smaller Tafel slopes of 60 mV.dec^(-1) and 83 mV.dec^(-1)in 1 mol·L^(-1) KOH,respectively,in comparison with the single MoS2,WS2,NiS2,as well as even the benchmark RuO2.The experiments reveal that the designed heterostructures have strong electronic interactions and spontaneously develop a built-in electric field at the heterointerface with uneven charge distribution based on the difference of band structures,which promote interfacial charge transfer,improve absorptivity of OH-,and modulate the energy level more comparable to the OER.Thus,the designed transition-metal sulfides heterostructures exhibit a remarkably high electrocatalytic activity for OER.This study provides a simple strategy to manipulate the heterostructure interface via an energy level engineering method for OER and can be extended to fabricate other heterostructures for various energy-related applications.
基金the Natural Science Foundation of Henan(No.232300421361)the National Natural Science Foundation of China(Nos.21671176 and 21001096).
文摘S-scheme possesses superior redox capabilities compared with the II-scheme,providing an effective method to solve the innate defects of g-C_(3)N_(4)(CN).In this study,S-doped g-C_(3)N_(4)/g-C_(3)N_(4)(SCN-tm/CN)S-scheme homojunction was constructed by rationally integrating morphology control with interfacial engineering to enhance the photocatalytic hydrogen evolution performance.In-situ Kelvin probe force microscopy(KPFM)confirms the transport of photo-generated electrons from CN to SCN.Density functional theory(DFT)calculations reveal that the generation of a built-in electric field between SCN and CN enables the carrier separation to be more efficient and effective.Femtosecond transient absorption spectrum(fs-TAS)indicates prolonged lifetimes of SCN-tm/CN_(3)(τ1:9.7,τ2:110,andτ3:1343.5 ps)in comparison to those of CN(τ1:4.86,τ2:55.2,andτ3:927 ps),signifying that the construction of homojunction promotes the separation and transport of electron hole pairs,thus favoring the photocatalytic process.Under visible light irradiation,the optimized SCN-tm/CN_(3)exhibits excellent photocatalytic activity with the hydrogen evolution rate of 5407.3μmol·g^(−1)·h^(−1),which is 20.4 times higher than that of CN(265.7μmol·g^(−1)·h^(−1)).Moreover,the homojunction also displays an apparent quantum efficiency of 26.8%at 435 nm as well as ultra-long and ultra-stable cycle ability.This work offers a new strategy to construct highly efficient photocatalysts based on the metal-free conjugated polymeric CN for realizing solar energy conversion.
基金supported by the Basic Science Center Program for Ordered Energy Conversion of the National Natural Science Foundation of China (No.51888103)the National Natural Science Foundation of China (Nos.52376209 and 52172248)+1 种基金China Postdoctoral Science Foundation (Nos.2020M673386 and 2020T130503)China Fundamental Research Funds for the Central Universities。
文摘Achieving a high carrier migration efficiency by constructing built-in electric field is one of the promising approaches for promoting photocatalytic activity. Herein, we have designed a donor-acceptor(D-A) crystalline carbon nitride(APMCN) with 4-amino-2,6-dihydroxypyrimidine(AP) as electron donor, in which the pyrimidine ring was well embedded in the heptazine ring via hydrogen-bonding effect during hydrothermal process. The APMCN shows superior charge-transfer due to giant built-in electric field(5.94times higher than pristine carbon nitride), thereby exhibiting excellent photocatalytic H_(2) evolution rate(1350 μmol/h) with a high AQY(62.8%) at 400 nm. Mechanistic analysis based on detailed experimental investigation together with theoretical analysis reveals that the excellent photocatalytic activity is attributed to the promoted charge separation by the giant internal electric field originated from the D–A structure.
基金the National Natural Science Foundation of China(Nos.22279124 and 52261145700)Shandong Province Natural Science Foundation(No.ZR2022ZD30)National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(Nos.NRF-2020R1A2C3004146 and RS-2023-00235596).
文摘Employing the alkaline water electrolysis system to generate hydrogen holds great prospects but still poses significant challenges,particularly for the construction of hydrogen evolution reaction(HER)catalysts operating at ampere-level current density.Herein,the unique Ru and RuP_(2)dual nano-islands are deliberately implanted on N-doped carbon substrate(denoted as Ru-RuP_(2)/NC),in which a built-in electric field(BEF)is spontaneously generated between Ru-RuP_(2)dual nano-islands driven by their work function difference.Experimental and theoretical results unveil that such constructed BEF could serve as the driving force for triggering fast hydrogen spillover process on bridged Ru-RuP_(2)dual nano-islands,which could invalidate the inhibitory effect of high hydrogen coverage at ampere-level current density,and synchronously speed up the water dissociation on Ru nano-islands and hydrogen adsorption/desorption on RuP_(2)nano-islands through hydrogen spillover process.As a result,the Ru-RuP_(2)/NC affords an ultra-low overpotential of 218 mV to achieve 1.0 A·cm^(−2)along with the superior stability over 1000 h,holding the great promising prospect in practical applications at ampere-level current density.More importantly,this work is the first to advance the scientific understanding of the relationship between the constructed BEF and hydrogen spillover process,which could be enlightening for the rational design of the cost-effective alkaline HER catalysts at ampere-level current density.
基金financially supported by the National Natural Science Foundation of China(Nos.22168040 and 22162025)the Project of Science&Technology Office of Shannxi Province(No.2022JM-062)。
文摘At present,industrial synthetic ammonia was still obtained through the Hubble-Bosch process,with large energy consumption.It is a research hotspot to realize green synthetic ammonia by using solar energy.The difficulty of photocatalytic ammonia synthesis was that the photo-excited electrons have not enough energy to active N≡N.In this study,Ti was doped into BiOBr by one-step hydrothermal method,which was oxidized into TiO_(2)when the doping amount reaches the maximum,in situ forming Ti_(0.31)B_(0.69)OB/TiO_(2)composites.Benefiting from the synergistic effect of Ti doping and S-scheme heterojunction,the synthetic ammonia efficiency of Ti_(0.31)B_(0.69)OB/TiO_(2)-11.96 reached 1.643 mmol·g_(cat)^(-1)at mild conditions and without hole scavenger for up to 7 h,the efficiency of synthetic ammonia is 115 times,10.5 times and 3.3 times of that of BiOBr,Ti_(0.31)B_(0.69)OB and TiO_(2),respectively.Specifically,DFT calculation confirms that Ti doping accurately refine the electronic structure of BiOBr,facilitate nitrogen adsorption activation and reduce hydrogenation reaction energy barrier,thus accelerating the reaction kinetics of photocatalytic nitrogen reduction(NRR),Meanwhile,constructing S-scheme heterojunction boosts the separation and transfer of photogenerated electron-hole pairs,improving the reduction ability of electrons in the conduction band of TiO_(2)and the oxidation ability of holes in the valence band of Ti_(0.31)B_(0.69)OB.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.11834011 and 12074245)The work performed at the University of Tokyo was supported by JSPS KAKENHI Grant Number 21H02040 and the New Energy and Industrial Technology Development Organization(NEDO)+1 种基金T.W.,G.T.,L.K.O.,and Y.B.Q.acknowledge the support from the Energy Materials and Surface Sciences Unit of the Okinawa Institute of Science and Technology Graduate University.We thank Mrs Miwako Furue and Dr.Haibin Wang at the University of Tokyo for the GIXRD and EDS measurementsOpen access funding provided by Shanghai Jiao Tong University
文摘Lead-free tin perovskite solar cells(PSCs)have undergone rapid development in recent years and are regarded as a promising ecofriendly photovoltaic technology.However,a strategy to suppress charge recombination via a built-in electric field inside a tin perovskite crystal is still lacking.In the present study,a formamidinium tin iodide(FASnI;)perovskite absorber with a vertical Sn;gradient was fabricated using a Lewis base-assisted recrystallization method to enhance the built-in electric field and minimize the bulk recombination loss inside the tin perovskites.Depth-dependent X-ray photoelectron spectroscopy revealed that the Fermi level upshifts with an increase in Sn;content from the bottom to the top in this heterogeneous FASnI;film,which generates an additional electric field to prevent the trapping of photo-induced electrons and holes.Consequently,the Sn;-gradient FASnI;absorber exhibits a promising efficiency of 13.82%for inverted tin PSCs with an open-circuit voltage increase of 130 mV,and the optimized cell maintains over 13%efficiency after continuous operation under 1-sun illumination for 1,000 h.
文摘For cases in which a robot with installed solar cells and a sensor operates in a nuclear reactor building or in space for extravehicular activity, we require elastic and extensible solar cells. More than two different types of sensing are also required, minimally with photovoltaics and built-in electricity. Magnetic compound fluid (MCF) rubber solar cells are made of rubber, so they are elastic and extensible as well as sensitive. To achieve flexibility and an effective photovoltaic effect, MCF rubber solar cells must include both soluble and insoluble rubbers, Fe<sub>3</sub>O<sub>4</sub>, TiO<sub>2</sub>, Na<sub>2</sub>WO<sub>4</sub>∙2H<sub>2</sub>O, etc. On the basis of this constitution, we propose a consummate fabrication process for MCF rubber solar cells. The characteristics of these cells result from the semiconductor-like role of the molecules of TiO<sub>2</sub>, Fe<sub>3</sub>O<sub>4</sub>, Ni, Na<sub>2</sub>WO<sub>4</sub>∙2H<sub>2</sub>O, polydimethylsiloxane (PDMS), natural rubber (NR), oleic acid, polyvinyl alcohol (PVA), water and magnetic cluster involved in the MCF rubber. Their tendencies can be deduced by synthesizing knowledge about the enhancement of the reverse-bias saturation current <em>I</em><sub><em>S</em></sub> and the diode ideality factor <em>N</em>, with conventional knowledge about the semiconductor affected by <em>γ</em>-irradiation and the attenuation of the photon energy of <em>γ</em>-rays.
基金jointly supported by the Natural Science Foundation of China(Nos.51874199,22078200,22102103)the grant from SZIIT(No.SZIIT2022KJ026)+1 种基金Guangdong Basic and Applied Basic Research Foundation(Nos.2019A1515111021,2021A1515010162)Shenzhen Innovation Program(No.JCYJ20170818142642395)。
文摘The strong intrinsic Coulomb interactions of Frenkel excitons in crystalline carbon nitride(CCN) greatly limits their dissociation into electrons and holes, resulting in unsatisfactory charges separation and photocatalytic efficiency. Herein, we propose a strategy to facilitate excitons dissociation by molecular regulation induced built-in electric field(BIEF). The electron-rich pyrimidine-ring into CCN changes the charge density distribution over heptazine-rings to induce BIEF between melon chains. Such BIEF is sufficient to overcome the considerable exciton binding energy(EBE) and reduce it from 38.4 meV to 16.4 meV,increasing the excitons dissociation efficiency(EDE) from 21.5% to 51.9%. Our results establish a strategy to facilitate excitons dissociation through molecular regulation induced BIEF, targeting the intrinsic high EBE and low EDE of polymer photocatalysts.