Developing an efficient photocatalyst is the key to realize the practical application of photocatalysis.The S-scheme heterojunction has great potential in photocatalysis due to its unique charge-carrier migration path...Developing an efficient photocatalyst is the key to realize the practical application of photocatalysis.The S-scheme heterojunction has great potential in photocatalysis due to its unique charge-carrier migration pathway,effective light absorption and high redox capacity.However,further enhancing the built-in electric field of the S-scheme,accelerating carrier separation,and achieving higher photocatalytic performance remain unresolved challenges.Herein,based on the continuously adjustable band structure of continuous solid-solution,a novel 0D/2D all solid-solution S-scheme heterojunction with adjustable internal electric field was designed and fabricated by employing a solid-solution of ZnxCd_(1–x)S and Bi_(2)MoyW_(1–y)O_(6)respectively as reduction and oxidation semiconductors.The synergistic optimization of effective light absorption,fast photogenerated carrier separation,and high redox potential leads can be tuned to promote photocatalytic activity.Under visible light,the S-scheme system constructed by Zn_(0.4)Cd_(0.6)S quantum dot(QDs)and Bi_(2)Mo_(0.2)W_(0.8)O_(6)monolayer exhibits a high rate for photocatalytic degradation C_(2)H_(4)(150.6×10^(–3)min^(–1)),which is 16.5 times higher than that of pure Zn_(0.4)Cd_(0.6)S(9.1×10^(–3)min^(–1))and 53.8 times higher than pure Bi_(2)Mo_(0.2)W_(0.8)O_(6)(2.8×10^(–3)min^(–1)).Due to the unique charge-carrier migration pathway,photo-corrosion of Zn_(x)Cd_(1–x)S is further inhibited simultaneously.In-situ irradiation X-ray photoelectron spectroscopy,photoluminescence spectroscopy,time-resolved photoluminescence,transient absorption spectroscopy and electron paramagnetic resonance provide compelling evidence for interfacial charge transfer via S-scheme pathways,while in-situ diffuse reflectance infrared Fourier transform spectroscopy identifies the reaction pathway for C_(2)H_(4)degradation.This novel S-scheme photocatalysts demonstrates excellent performance and potential for the practical application of the fruits and vegetables preservation at room temperatures.展开更多
In this article, distributions of internal stress and internal electric fields around a triple point of ferroelectric polycrystals generated by the spontaneous deformation and spontaneous polarization were investigate...In this article, distributions of internal stress and internal electric fields around a triple point of ferroelectric polycrystals generated by the spontaneous deformation and spontaneous polarization were investigated. It was found that when all three grains consist of a single domain, the internal stresses and the internal electric fields do not vanish. Though it may be determined according to the principle of energy, the spontaneous configuration will not be unique without involving other conditions due to the symmetry of the crystal structure.展开更多
Constructing bismuth oxyhalide solid solutions with a single homogeneous phase have intrigued the research community;however,a deeper understanding of the intrinsic origin for improved bulk-charge separation is still ...Constructing bismuth oxyhalide solid solutions with a single homogeneous phase have intrigued the research community;however,a deeper understanding of the intrinsic origin for improved bulk-charge separation is still unclear.Herein,a series of Bi_(24)O_(31)Cl_(x)Br_(10-x) solid solutions with the same structural characteristics were synthesized by crystal structure regulation.Combining density functional theory calculation,Kelvin probe force microscopy,and zeta potential testing results,an enhanced internal electric field(IEF)intensity between[Bi_(24)O_(31)]and[X]layers was achieved by changing halogen types and ratios.This greatly facilitated bulk-charge separation and transfer efficiency,which is significant for the degradation of phenolic organic pollutants.Owing to the enhanced IEF intensity,the charge carrier density of Bi_(24)O_(31)Cl_(4)Br_(6) was 33.1 and 4.7 times stronger than that of Bi_(24)O_(31)Cl_(10) and Bi_(24)O_(31)Br_(10),respectively.Therefore,Bi24O31Cl4Br6 had an optimal photoactivity for the degradation of bisphenol A,which was 6.21 and 2.71 times higher than those of Bi_(24)O_(31)Cl_(10) and Bi_(24)O_(31)Br_(10),respectively.Thus,this study revealed the intrinsic mechanism of the solid solution strategy for photocatalytic performance enhancement with respect to an IEF.展开更多
Heterojunction photocatalysts have shown considerable activities for organic pollutants degradation.However,the faint connection interface and inferior charge shift efficiency critically block the property of heteroju...Heterojunction photocatalysts have shown considerable activities for organic pollutants degradation.However,the faint connection interface and inferior charge shift efficiency critically block the property of heterojunction photocatalysis.Herein,Bi_(2)O_(2)S/NiFe_(2)O_(4) nanosheets heterojunction with ultrastrong inter-face interaction and high internal electric field are designed by an in-situ growth method.Tentative and theoretical consequences prove that the interfacial interaction and internal electric field not only act as the electron flow bridge but also decrease the electrons shift energy obstacle,thus speeding up electrons transfer and achieving effective spatial electron-hole separation.Therefore,a large amount of·O_(2)^(-)and holes as active species were generated.Remarkably,Bi_(2)O_(2) S/NiFe_(2)O_(4) establishes a considerably boosted photocatalytic performance for tetracycline degradation(0.032 min^(-1)),which is about 14.2-fold and 7.8-fold of the pristine BOS and NFO,respectively.This work provides a promising motivation for modulating charge transfer by interface control and internal electric field to boost photocatalytic performance.展开更多
Conjugated linear polymers are promising metal-free photocatalysts for visible-light-driven photocatalytic water disinfection,but it was still bottlenecked by the insufficient photogenerated charge separation and tran...Conjugated linear polymers are promising metal-free photocatalysts for visible-light-driven photocatalytic water disinfection,but it was still bottlenecked by the insufficient photogenerated charge separation and transport(CST)process.Herein,we obtained the highly crystalline imine-linked conjugated linear poly-mer(ODA-BPAH)with a greatly enhanced CST process.The highly crystalline ODA-BPAH exhibited excel-lent broad-spectrum water disinfection efficiency up to 99.99999%in 1 h,which is among the reported highest of state-of-the-art photocatalysts.The crystallinity of ODA-BPAH was regulated by simply turn-ing the solvent and the experiment results revealed that the ODA-BPAH with high crystallinity exhibited higher internal electric field strength and photocatalytic performance than that with low crystallinity,which indicates that higher crystallinity in linear conjugated polymers contributes to superior CST ef-ficiency as well as the generation of reactive oxygen species.This work highlights the impact of poly-mer crystallinity on the internal electric field and proves that linear poly-imine could be a new type of promising metal-free photocatalyst for water treatment.展开更多
Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a ch...Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a challenge.Herein,cuprous sulfide nanosheets with different Cu vacancy concentration were employed to study IEF modulation and corresponding direct charge transfer.Among the samples,Cu_(1.8)S nanosheets possessed intensified IEF intensity compared with those of Cu_(2)S and Cu_(1.95)S nanosheets,suggesting that an enhanced IEF intensity could be achieved by introducing more Cu vacancies.This intensified IEF of Cu_(1.8)S nanosheets induced numerous photogenerated electrons to migrate to its surface,and the dissociative electrons were then captured by Cu vacancies,resulting in efficient charge separation spatially.In addition,the Cu vacancies on Cu_(1.8)S nanosheets accumulated electrons as active sites to lower the energy barrier of rate-determining step of CO_(2)photoreduction,leading to the selective conversion of CO_(2)to CO.Herein,the manipulation of IEF intensity through Cu vacancy concentration regulation of cuprous sulfide photocatalysts for efficient charge separation has been discussed,providing a scientific strategy to rationally improve photocata lytic performances for solar energy conversion.展开更多
Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen ...Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction(HER).In this study,the intrinsically tunable internal bond electric field(IBEF)at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field(IMEF)induced by the donor-acceptor(D-A)structure for an efficient HER.The aligned orientation of IBEF and IMEF resulted in a remarkable H_(2) evolution rate of 57.3 mmol·g^(-1)·h^(-1)on TNCA,which was approximately 520 times higher than that of TCNA(0.11 mmol·g^(-1)·h^(-1))with the opposing electric field orientation.The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer,kinetically facilitat-ing the migration of photogenerated electrons from D to A.Furthermore,theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only pro-vides a strong driving force for carrier transfer but also effectively hinders the return of free elec-trons to the valence band,improving the utilization of photoelectrons.This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.展开更多
Peroxymonosulfate(PMS)is commonly used in advanced oxidation processes to degrade organic pollutants in wastewater.In this work,to obtain better PMS activation efficiency,Bi_(4)O_(5)Br_(2)/BCZT(BBT)piezoelectric photo...Peroxymonosulfate(PMS)is commonly used in advanced oxidation processes to degrade organic pollutants in wastewater.In this work,to obtain better PMS activation efficiency,Bi_(4)O_(5)Br_(2)/BCZT(BBT)piezoelectric photocatalyst was designed.Abundant active radicals produced by BBT under visible light irradiation and ultrasonic vibration were used to activate PMS,thereby achieving rapid degradation of high concentration pollutants.With the introduction of BCZT,the catalyst has a strong internal electric field and three-dimensional lamellar structure,which promotes the separation and transfer of electrons and holes.It is worth noting that under optimal reaction conditions,the degradation rate of ARB reached 93%by BBT15 within 10 min.The catalytic experiment combined with the piezoelectric performance test results revealed the key role of piezoelectric photocatalytic reaction in PMS activation.This provides an important prospect for PMS to effectively deal with the degradation of high concentrations of organic pollutants.展开更多
Piezo-photocatalysis is an emerging photocatalytic technology in which the piezoelectric electric field drives photogenerated carriers to separate,thereby improving the photocatalytic activity of the catalyst.Herein,s...Piezo-photocatalysis is an emerging photocatalytic technology in which the piezoelectric electric field drives photogenerated carriers to separate,thereby improving the photocatalytic activity of the catalyst.Herein,solid phase and one-step molten salt processes were used to prepare SrBi_(2)Nb_(2)O_(9)(SBN)powders with granular and sheet morphologies,respectively.The influence of micromorphology on the piezo-photocatalytic performances of SBN was determined by degrading ciprofloxacin hydrochloride(CIP).SBN nanosheets demonstrate remarkable piezo-photocatalytic performance,achieving an 89.13%CIP degradation rate in 60 min and an apparent rate constant of 34.73×10^(-3) min^(-1).This performance is approximately 2.65 times higher than that of granular SBN and outperformed many recently reported piezo-photocatalysts under similar experimental conditions.Free radical trapping techniques,electron spin resonance spectroscopy and liquid chromatography-mass spectrometry are utilized to study the potential paths and mechanisms of CIP degradation.Piezoresponse force microscopy and finite element simulation show that the piezo-response of SBN nanosheets is significantly higher than that of granular SBN.SBN nanosheets achieve high degradation efficiency due to their optimized conduction band positions and enhanced piezoelectric effect,facilitated by the two-dimensional nanosheet structures.In this work,the piezoelectric internal electric field of piezoelectric catalysts can be increased by tuning the catalyst morphology,which points to a possible direction for the production of high-performance piezoelectric catalysts.展开更多
We have performed the first-principles calculation to investigate the origins of ferroelectricities and different po- larization behaviours of superlattices BaTiO3/SrTiO3 and PbTiO3/SrTiO3. The density of state （DOS...We have performed the first-principles calculation to investigate the origins of ferroelectricities and different po- larization behaviours of superlattices BaTiO3/SrTiO3 and PbTiO3/SrTiO3. The density of state （DOS） and electronic charge profiles show that there are strong hybridizations between atoms Ti and O and between atoms Pb and O which play very important roles in producing the ferroelectricities of superlattices BaTiO3/SrTiO3 and PbTiO3/SrTiO3. Ow- ing to the decline of internal electric field in SrTiO3 （ST） layer, the tetragonality and polarizations of superlattices decrease with increasing the fraction of SrTiO3 in the superlattices. We find that the polarization of PbTiO3/SrTiO3 is largerthan that of BaTiO3/SrTiO3 at the same ratio of components, because the polarization mismatch between PbTiO3 and SrTiO3 is larger than that between BaTiO3 and SrTiO3. The polarization and tetragonality are en- hanced with respect to those of bulk tetragonal BaTiO3 in the superlattices BaTiO3/SrTiO3, while the polarization and tetragonality are reduced with respect to those of bulk tetragonal PbTiO3 in superlattices PbTiO3/SrTiO3.展开更多
Devising robust S-scheme photocatalysts is of central importance for achieving high-efficient micropollu-tant decontamination.However,the conscious optimization of S-scheme system with high performance remains a prime...Devising robust S-scheme photocatalysts is of central importance for achieving high-efficient micropollu-tant decontamination.However,the conscious optimization of S-scheme system with high performance remains a prime challenge.Herein,carbon quantum dots(CDs)and Mn_(0.5)Cd_(0.5)S(MCS)are mounted on BiOBr(BOB)microspheres,establishing an advanced S-scheme heterojunction with interfacial Bi-S bond.The interfacial Bi-S bonds function as superb channels at atomic-scale to abate the energy barrier for S-scheme charge transportation.Meanwhile,CDs serve as electron collectors to preserve highly reductive electrons from MCS,further augmenting the spatial separation of photo-carriers.Therefore,the optimized CDs/MCS/BOB(MBC)heterojunction manifests significantly strengthened tetracycline hydrochloride(TC)destruction activity and its reaction rate constant is approximately 3.1,2.2,2.1,and 1.5 folds that than that of MCS,BOB,BOB/CDs and MCS/BOB.In addition,MBC exhibits high stability and significant resistance to environmental interferences.The toxicology evaluation confirms the effective abatement of toxicity of TC after treatment.This achievement demonstrates the benefits of CDs-optimized S-scheme photosystems with chemical bonds for photocatalytic water decontamination.展开更多
CuBi_(2)O_(4)(CBO)photocathodes hold significant promise for efficient photoelectrochemical(PEC)water splitting due to their favorable band gap and theoretical onset potential.However,their practical application is hi...CuBi_(2)O_(4)(CBO)photocathodes hold significant promise for efficient photoelectrochemical(PEC)water splitting due to their favorable band gap and theoretical onset potential.However,their practical application is hindered by poor charge separation efficiency.Herein,we introduce a characteristic in-situ solution Fe-doping strategy that markedly improves photoelectrochemical performance of CBO,doubling the photocurrent density and achieving an unprecedented 190 mV anodic shift in the onset potential.By integrating with an electrochemical oxidation post-treatment,a record incident photon-to-current efficiency(IPCE)exceeding 40% at 0.6 V vs.RHE under visible light illumination is achieved.The versatility of the doping strategy is demonstrated across CBO photocathodes synthesized by different methods with various morphologies,grain sizes,and crystallinities.Mechanistic studies reveal that the gradient distribution of Fe^(3+)ions generates an internal electric field that facilitates efficient charge separation and increases acceptor density.The strong Fe-O bonding also enhances structural stability against photoinduced corrosion.Notably,our investigation uncovers the non-temperature-dependent nature of CBO photocurrent,indicating that PEC performance enhancement primarily depends on reducing carrier recombination rather than improving bulk conductivity.This work lays the groundwork for future advancements in water splitting performance of CBO photocathodes,offering a complementary strategy to conventional methods for enhancing charge separation efficiency.展开更多
Aqueous zincion batteries are highly favored for grid-level energy storage owing to their low cost and high safety,but their practical application is limited by slow ion migration.To address this,a strategy has been d...Aqueous zincion batteries are highly favored for grid-level energy storage owing to their low cost and high safety,but their practical application is limited by slow ion migration.To address this,a strategy has been developed to create a cation-accelerating electric field on the surface of the cathode to achieve ultrafast Zn^(2+)diffusion kinetics.By employing electrodeposition to coat MoS_(2)on the surface of BaV_(6)O_(16)·3H_(2)O nanowires,the directional builtin electric field generated at the heterointerface acts as a cation accelerator,continuously accelerating Zn^(2+)diffusion into the active material.The optimized Zn^(2+)diffusion coefficient in CC@BaV-V_(6)O_(16)·3H_(2)@MoS_(2)(7.5×10^(8)cm^(2)s^(-1)) surpasses that of most reported V-based cathodes.Simultaneously,MoS_(2)serving as a cathodic armor extends the cycling life of the Zn-CC@BaV_(6)O_(16)·3H_(2)@MoS_(2)full batteries to over 10000 cycles.This work provides valuable insights into optimizing ion diffusion kinetics for high-performance energy storage devices.展开更多
Devising S-scheme heterostructure is considered as a cutting-edge strategy for advanced photocatalysts with effectively segregated photo-carriers and prominent redox potential for emerging organic pollutants control.H...Devising S-scheme heterostructure is considered as a cutting-edge strategy for advanced photocatalysts with effectively segregated photo-carriers and prominent redox potential for emerging organic pollutants control.Herein,an S-scheme Ag_(2)CO_(3)/C_(3)N_(5) heterojunction photocatalyst was developed via a simple in situ chemical deposition procedure,and further photoreduction operation made metallic Ag(size:3.5–12.5 nm)being in situ formed on Ag_(2)CO_(3)/C_(3)N_(5) for a plasmonic S-scheme Ag/Ag_(2)CO_(3)/C_(3)N_(5) heterojunction photocatalyst.Consequently,Ag/Ag_(2)CO_(3)/C_(3)N_(5) manifests pronouncedly upgraded photocatalytic performance toward oxytetracycline degradation with a superior photoreaction rate constant of 0.0475 min‒1,which is 13.2,3.9 and 2.2 folds that of C_(3)N_(5),Ag_(2)CO_(3),and Ag_(2)CO_(3)/C_(3)N_(5),respectively.As evidenced by comprehensive characterizations and density functional theory calculations,the localized surface plasmon resonance effect of metallic Ag and the unique S-scheme charge transfer mechanism in 0D/0D/2D Ag/Ag_(2)CO_(3)/C_(3)N_(5) collaboratively strengthen the visible-light absorption,and facilitate the effective separation of powerful charge carriers,thereby significantly promoting the generation of reactive species like·OH^(-),h^(+)and·O_(2)^(-)for efficient oxytetracycline destruction.Moreover,four consecutive cycles demonstrate the reusability of Ag/Ag_(2)CO_(3)/C_(3)N_(5).Furthermore,the authentic water purification tests affirm its practical application potential.This work not only provides a candidate strategy for advancing S-scheme heterojunction photocatalysts but also makes a certain contribution to water decontamination.展开更多
The industrial implementation of Solar-driven photocatalysis is hampered by inefficient charge separation,poor reusability and hard retrieval of powdery catalysts.To conquer these drawbacks,a self-floating S-scheme Bi...The industrial implementation of Solar-driven photocatalysis is hampered by inefficient charge separation,poor reusability and hard retrieval of powdery catalysts.To conquer these drawbacks,a self-floating S-scheme Bi_(4)O_(5)Br_(2)/P-doped C_(3)N_(4)/carbon fiber cloth(BB/PN/CC)composed of carbon fibers(CC)as the core and Bi_(4)O_(5)Br_(2)/P-doped C_(3)N_(4)(BB/PN)nanosheets as the shell was constructed as a competent,recyclable cloth-shaped photocatalyst for safe and efficient degradation of aquacultural antibiotics.The BB/PN/CC fabric achieves an exceptional tetracycline degradation rate constant of 0.0118 min‒1,surpassing CN/CC(0.0015 min^(‒1)),BB/CC(0.0066 min^(‒1))and PN/CC(0.0023 min^(‒1))by 6.9,0.8 and 4.1 folds,respectively.Beyond its catalytic prowess,the photocatalyst’s practical superiority is evident in its effortless recovery and environmental adaptability.The superior catalytic effectiveness stems from the S-scheme configuration,which retains the maximum redox capacities of the constituent BB and PN while enabling efficient spatial detachment of photo-carriers.X-ray photoelectron spectroscopy(XPS),in-situ XPS,and electron paramagnetic resonance analyses corroborate the S-scheme mechanism,revealing electron accumulation on PN and hole retention on BB under illumination.Density functional theory calculations further confirm S-scheme interfacial charge redistribution and internal electric field formation.This study advances the design of macroscopic S-scheme heterojunction photocatalysts for sustainable water purification.展开更多
Constructing heterojunction between two semiconductors with matched energy band structure is an effective modification method to obtain excellent photocatalysts.The experimental scheme adopts a simple solvent method t...Constructing heterojunction between two semiconductors with matched energy band structure is an effective modification method to obtain excellent photocatalysts.The experimental scheme adopts a simple solvent method to self-assemble nitrogen doped carbon dots(N-CDs)on the surface of sulfur doped carbon nitride(S-C_(3)N_(4))semiconductor throughπ-πconjugate interaction.Based on this,a novel 0D/2D S-scheme heterojunction N-CDs/S-C_(3)N_(4)hybrid was successfully prepared.The degradation kinetic constants of N-CDs/S-C_(3)N_(4)for rhodamine B(RhB)and p-nitrophenol(PNP)reached 0.23522 and 0.01342 min^(−1),repectively,which were 2.72 and 2.65 times that of S-C_(3)N_(4).The highest photocatalytic hydrogen evolution rate was observed under the simulated sunlight irradiation,which was 2.30 times that of S-C_(3)N_(4).The improvement of photocatalytic performance was mainly based on the formation of the S-scheme heterojunction between S-C_(3)N_(4)and N-CDs.The effects of internal electric field,π-πconjugate interaction and band bending promoted the photogenerated h^(+)and e^(−) with low redox ability to recombine and retained the beneficial h+and e−with strong redox ability,which contributed to the production of more active species of h^(+) and•O_(2)−,therefore the photocatalytic degradation and hydrogen evolution performance were significantly enhanced.展开更多
The recombination of photogenerated electrons and holes is a crucial factor limiting photocatalytic H_(2)evolution.The S-scheme ZnWO_(4)-ZnIn_(2)S_(4)heterojunction with 2D coupling interfaces was successfully synthes...The recombination of photogenerated electrons and holes is a crucial factor limiting photocatalytic H_(2)evolution.The S-scheme ZnWO_(4)-ZnIn_(2)S_(4)heterojunction with 2D coupling interfaces was successfully synthesized using a simple solvothermal method.An effective S-scheme interfacial charge migration route at the S-scheme heterogeneous interface was determined by energy band structure analyses(such as UPS,Mott-Schottky and XPS plots),which facilitates the separation of photoexcited carriers.It is worth noting that the optimal ZnWO_(4)-ZnIn_(2)S_(4)composite has an H_(2)evolution activity of 4925.3μmol g^(-1)h^(-1)with favourable photostability and stability.Meanwhile,the ZnWO_(4)-Zn In_(2)S_(4)heterojunction exhibits the maximum optical response value(2.8 m A cm-2)in the initial stage,effectively promoting the separation and migration of photogenerated carriers.The establishment of the built-in electric field direction at the interface can effectively promote the space charge separation between the ZnWO_(4)and ZnIn_(2)S_(4)nanosheets,which is favorable to the photocatalytic H_(2)evolution.This work provides valuable guidance for designing S-scheme heterojunction photocatalysts composed of two n-type semiconductors for energy and environmental applications.The recombination of photogenerated electrons and holes is a crucial factor limiting photocatalytic H_(2)evolution.The S-scheme ZnWO_(4)-ZnIn_(2)S_(4)heterojunction with 2D coupling interfaces was successfully synthesized using a simple solvothermal method.An effective S-scheme interfacial charge migration route at the S-scheme heterogeneous interface was determined by energy band structure analyses(such as UPS,Mott-Schottky and XPS plots),which facilitates the separation of photoexcited carriers.It is worth noting that the optimal ZnWO_(4)-ZnIn_(2)S_(4)composite has an H_(2)evolution activity of 4925.3μmol g^(-1)h^(-1)with favourable photostability and stability.Meanwhile,the ZnWO_(4)-ZnIn_(2)S_(4)heterojunction exhibits the maximum optical response value(2.8 m A cm-2)in the initial stage,effectively promoting the separation and migration of photogenerated carriers.The establishment of the built-in electric field direction at the interface can effectively promote the space charge separation between the ZnWO_(4)and Zn In_(2)S_(4)nanosheets,which is favorable to the photocatalytic H_(2)evolution.This work provides valuable guidance for designing S-scheme heterojunction photocatalysts composed of two n-type semiconductors for energy and environmental applications.展开更多
In this work,a novel NiP_(2)/g-C_(3)N_(4)heterojunction via homogeneous precipitation method assisted by thermal phosphorization reaction was designed and constructed,and the optimized sample showed the excellent phot...In this work,a novel NiP_(2)/g-C_(3)N_(4)heterojunction via homogeneous precipitation method assisted by thermal phosphorization reaction was designed and constructed,and the optimized sample showed the excellent photocatalytic H_(2)evolution activity under visible-light irradiation,which was nearly 112 times higher than that of pristine g-C_(3)N_(4)sample.Experimental characterizations and DFT calculations demonstrated that the NiP_(2)nanoparticles covered on the g-C_(3)N_(4)surface can form a built-in electric field at the interface to accelerate the transfer of photoexcited electrons from g-C_(3)N_(4)to NiP_(2),crucial for hindering the recombination of electron-hole pairs.Moreover,the energy barrier of hydrogen evolution reaction can also vastly reduce when combined NiP_(2)and g-C_(3)N_(4)to construct NiP_(2)/g-C_(3)N_(4)heterojunction.This work represents a method through combing experimental and theoretical tools to thoroughly investigate the mechanism of photocatalytic process.展开更多
Stable potassium metal batteries(PMBs)are promising candidates for electrical energy storage due to their ability to reversibly store electrical energy at a low cost.However,dendritic growth and large volume changes h...Stable potassium metal batteries(PMBs)are promising candidates for electrical energy storage due to their ability to reversibly store electrical energy at a low cost.However,dendritic growth and large volume changes hinder their practical application.Here,referring to the morphology and structure of a virus,a bionic virus-like-carbon microsphere(BVC)was designed as the anode host for a PMB.A BVC with a three-dimensional structure can not only control the electric field,which can suppress dendrite formation,but can also provide a larger space to accommodate the volume change during the cycle progress.The designed potassium(K)metal anode exhibits excellent cycle life and stability(during 1800 h of repeated plating/stripping of K at a current density of 0.1 mA cm−2,K-BVC can realize a very stable K metal anode with low voltage hysteresis).Stable cyclability and improved rate capability can be realized in a full cell using Prussian blue over 400 cycles.This research provides a new idea for the development of stable K metal anodes and may pave the way for the practical application of next-generation metal batteries.展开更多
Heteroatom doping has emerged as a prevailing strategy to enhance the storage of sodium ions in carbon materials.However,the underlying mechanism governing the performance enhancement remains undisclosed.Herein,we fab...Heteroatom doping has emerged as a prevailing strategy to enhance the storage of sodium ions in carbon materials.However,the underlying mechanism governing the performance enhancement remains undisclosed.Herein,we fabricated N/S co-doped carbon beaded fibers(S-N-CBFs),which exhibited glorious rate performance and durableness in Na+storage,showcasing no obvious capacity decay even after 3500 cycles.Furthermore,when used as anodes in sodium-ion capacitors,the S-N-CBFs delivered exceptional results,boasting a high energy density of 225 Wh·kg^(-1),superior power output of 22500 W·kg^(-1),and outstanding cycling stability with a capacity attenuation of merely 0.014%per cycle after 4000 cycles at 2 A·g^(-1).Mechanistic investigations revealed that the incorporation of both pyridinic N and pyrrolic N into the carbon matrix of S-N-CBFs induced internal electric fields(IEFs),with the former IEF being stronger than the latter,in conjunction with the doped S atom.Density functional theory calculations further unveiled that the intensity of the IEF directly influenced the adsorption of Na+,thereby resulting in the exceptional performances of S-N-CBFs as sodium-ion storage materials.This work uncovers the pivotal role of IEF in regulating the electronic structure of carbon materials and enhancing their Na^(+)storage capabilities,providing valuable insights for the development of more advanced electrode materials.展开更多
文摘Developing an efficient photocatalyst is the key to realize the practical application of photocatalysis.The S-scheme heterojunction has great potential in photocatalysis due to its unique charge-carrier migration pathway,effective light absorption and high redox capacity.However,further enhancing the built-in electric field of the S-scheme,accelerating carrier separation,and achieving higher photocatalytic performance remain unresolved challenges.Herein,based on the continuously adjustable band structure of continuous solid-solution,a novel 0D/2D all solid-solution S-scheme heterojunction with adjustable internal electric field was designed and fabricated by employing a solid-solution of ZnxCd_(1–x)S and Bi_(2)MoyW_(1–y)O_(6)respectively as reduction and oxidation semiconductors.The synergistic optimization of effective light absorption,fast photogenerated carrier separation,and high redox potential leads can be tuned to promote photocatalytic activity.Under visible light,the S-scheme system constructed by Zn_(0.4)Cd_(0.6)S quantum dot(QDs)and Bi_(2)Mo_(0.2)W_(0.8)O_(6)monolayer exhibits a high rate for photocatalytic degradation C_(2)H_(4)(150.6×10^(–3)min^(–1)),which is 16.5 times higher than that of pure Zn_(0.4)Cd_(0.6)S(9.1×10^(–3)min^(–1))and 53.8 times higher than pure Bi_(2)Mo_(0.2)W_(0.8)O_(6)(2.8×10^(–3)min^(–1)).Due to the unique charge-carrier migration pathway,photo-corrosion of Zn_(x)Cd_(1–x)S is further inhibited simultaneously.In-situ irradiation X-ray photoelectron spectroscopy,photoluminescence spectroscopy,time-resolved photoluminescence,transient absorption spectroscopy and electron paramagnetic resonance provide compelling evidence for interfacial charge transfer via S-scheme pathways,while in-situ diffuse reflectance infrared Fourier transform spectroscopy identifies the reaction pathway for C_(2)H_(4)degradation.This novel S-scheme photocatalysts demonstrates excellent performance and potential for the practical application of the fruits and vegetables preservation at room temperatures.
基金National Natural Science Foundation of China(No.19672053)Special Funds for Doctoral Programs(No.96061305)
文摘In this article, distributions of internal stress and internal electric fields around a triple point of ferroelectric polycrystals generated by the spontaneous deformation and spontaneous polarization were investigated. It was found that when all three grains consist of a single domain, the internal stresses and the internal electric fields do not vanish. Though it may be determined according to the principle of energy, the spontaneous configuration will not be unique without involving other conditions due to the symmetry of the crystal structure.
文摘Constructing bismuth oxyhalide solid solutions with a single homogeneous phase have intrigued the research community;however,a deeper understanding of the intrinsic origin for improved bulk-charge separation is still unclear.Herein,a series of Bi_(24)O_(31)Cl_(x)Br_(10-x) solid solutions with the same structural characteristics were synthesized by crystal structure regulation.Combining density functional theory calculation,Kelvin probe force microscopy,and zeta potential testing results,an enhanced internal electric field(IEF)intensity between[Bi_(24)O_(31)]and[X]layers was achieved by changing halogen types and ratios.This greatly facilitated bulk-charge separation and transfer efficiency,which is significant for the degradation of phenolic organic pollutants.Owing to the enhanced IEF intensity,the charge carrier density of Bi_(24)O_(31)Cl_(4)Br_(6) was 33.1 and 4.7 times stronger than that of Bi_(24)O_(31)Cl_(10) and Bi_(24)O_(31)Br_(10),respectively.Therefore,Bi24O31Cl4Br6 had an optimal photoactivity for the degradation of bisphenol A,which was 6.21 and 2.71 times higher than those of Bi_(24)O_(31)Cl_(10) and Bi_(24)O_(31)Br_(10),respectively.Thus,this study revealed the intrinsic mechanism of the solid solution strategy for photocatalytic performance enhancement with respect to an IEF.
基金the financial support by the National Natural Science Foundation of China as general projects(Grant Nos.51779068,52070066,52211530084,42277059,and 22006029)Tianjin Commission of Science and Technology as key technologies R&D projects(No.21YFSNSN00250)+1 种基金Doctoral Inno-vation Project of Hebei Province(CXZZBS2023031)the Royal Society/International Exchanges 2021 Cost Share/NSFC(Grant No.IEC\NSFC\211142).
文摘Heterojunction photocatalysts have shown considerable activities for organic pollutants degradation.However,the faint connection interface and inferior charge shift efficiency critically block the property of heterojunction photocatalysis.Herein,Bi_(2)O_(2)S/NiFe_(2)O_(4) nanosheets heterojunction with ultrastrong inter-face interaction and high internal electric field are designed by an in-situ growth method.Tentative and theoretical consequences prove that the interfacial interaction and internal electric field not only act as the electron flow bridge but also decrease the electrons shift energy obstacle,thus speeding up electrons transfer and achieving effective spatial electron-hole separation.Therefore,a large amount of·O_(2)^(-)and holes as active species were generated.Remarkably,Bi_(2)O_(2) S/NiFe_(2)O_(4) establishes a considerably boosted photocatalytic performance for tetracycline degradation(0.032 min^(-1)),which is about 14.2-fold and 7.8-fold of the pristine BOS and NFO,respectively.This work provides a promising motivation for modulating charge transfer by interface control and internal electric field to boost photocatalytic performance.
基金This work was financially supported by the Liaoning Revital-ization Talents Program(No.1808013)the Shenyang National Laboratory for Materials Science.The authors thank Mr.Long Guan and Mr.Zhiyong Yang from Shenyang Dequan Instrument and Equipment Sales Co.,Ltd.for the Fluorescence microscope analysis and Mr.Jilong Gao from Shiyanjia Lab(www.shiyanjia.com)for the ss NMR analysis.
文摘Conjugated linear polymers are promising metal-free photocatalysts for visible-light-driven photocatalytic water disinfection,but it was still bottlenecked by the insufficient photogenerated charge separation and transport(CST)process.Herein,we obtained the highly crystalline imine-linked conjugated linear poly-mer(ODA-BPAH)with a greatly enhanced CST process.The highly crystalline ODA-BPAH exhibited excel-lent broad-spectrum water disinfection efficiency up to 99.99999%in 1 h,which is among the reported highest of state-of-the-art photocatalysts.The crystallinity of ODA-BPAH was regulated by simply turn-ing the solvent and the experiment results revealed that the ODA-BPAH with high crystallinity exhibited higher internal electric field strength and photocatalytic performance than that with low crystallinity,which indicates that higher crystallinity in linear conjugated polymers contributes to superior CST ef-ficiency as well as the generation of reactive oxygen species.This work highlights the impact of poly-mer crystallinity on the internal electric field and proves that linear poly-imine could be a new type of promising metal-free photocatalyst for water treatment.
基金supported by the National Natural Science Foundation of China(52200123)the Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education(GCP2022007)the Scientific Research and Innovation Team Program of Sichuan University of Science and Engineering(SUSE652A014)。
文摘Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a challenge.Herein,cuprous sulfide nanosheets with different Cu vacancy concentration were employed to study IEF modulation and corresponding direct charge transfer.Among the samples,Cu_(1.8)S nanosheets possessed intensified IEF intensity compared with those of Cu_(2)S and Cu_(1.95)S nanosheets,suggesting that an enhanced IEF intensity could be achieved by introducing more Cu vacancies.This intensified IEF of Cu_(1.8)S nanosheets induced numerous photogenerated electrons to migrate to its surface,and the dissociative electrons were then captured by Cu vacancies,resulting in efficient charge separation spatially.In addition,the Cu vacancies on Cu_(1.8)S nanosheets accumulated electrons as active sites to lower the energy barrier of rate-determining step of CO_(2)photoreduction,leading to the selective conversion of CO_(2)to CO.Herein,the manipulation of IEF intensity through Cu vacancy concentration regulation of cuprous sulfide photocatalysts for efficient charge separation has been discussed,providing a scientific strategy to rationally improve photocata lytic performances for solar energy conversion.
文摘Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction(HER).In this study,the intrinsically tunable internal bond electric field(IBEF)at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field(IMEF)induced by the donor-acceptor(D-A)structure for an efficient HER.The aligned orientation of IBEF and IMEF resulted in a remarkable H_(2) evolution rate of 57.3 mmol·g^(-1)·h^(-1)on TNCA,which was approximately 520 times higher than that of TCNA(0.11 mmol·g^(-1)·h^(-1))with the opposing electric field orientation.The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer,kinetically facilitat-ing the migration of photogenerated electrons from D to A.Furthermore,theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only pro-vides a strong driving force for carrier transfer but also effectively hinders the return of free elec-trons to the valence band,improving the utilization of photoelectrons.This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.
基金financially supported by the National Natural Science Foundation of China(No.51302061)Natural Science Foundation of Hebei Province(No.E2020201021 and E2023201019)+4 种基金Industry-University-Research Cooperation Major Projects of Shijiazhuang(No.241130477A)Research Innovation Team of College of Chemistry and Environmental Science of Hebei University(No.hxkytd2102)Industry-University-research Cooperation Project of Colleges and Universities in Hebei Province(No.CXZX2025016)Hebei Province Innovation Capability Enhancement Plan Project(No.22567620H)Bintuan Science and Technology Program(Nos.2020DB002 and 2022DB009)。
文摘Peroxymonosulfate(PMS)is commonly used in advanced oxidation processes to degrade organic pollutants in wastewater.In this work,to obtain better PMS activation efficiency,Bi_(4)O_(5)Br_(2)/BCZT(BBT)piezoelectric photocatalyst was designed.Abundant active radicals produced by BBT under visible light irradiation and ultrasonic vibration were used to activate PMS,thereby achieving rapid degradation of high concentration pollutants.With the introduction of BCZT,the catalyst has a strong internal electric field and three-dimensional lamellar structure,which promotes the separation and transfer of electrons and holes.It is worth noting that under optimal reaction conditions,the degradation rate of ARB reached 93%by BBT15 within 10 min.The catalytic experiment combined with the piezoelectric performance test results revealed the key role of piezoelectric photocatalytic reaction in PMS activation.This provides an important prospect for PMS to effectively deal with the degradation of high concentrations of organic pollutants.
基金funded by the National Natural Science Foundation of China(22272057)Natural Science Foundation of Guangdong Province(2019A1515012129)Science and Technology Planning Project of Guangzhou City(202002030420).
文摘Piezo-photocatalysis is an emerging photocatalytic technology in which the piezoelectric electric field drives photogenerated carriers to separate,thereby improving the photocatalytic activity of the catalyst.Herein,solid phase and one-step molten salt processes were used to prepare SrBi_(2)Nb_(2)O_(9)(SBN)powders with granular and sheet morphologies,respectively.The influence of micromorphology on the piezo-photocatalytic performances of SBN was determined by degrading ciprofloxacin hydrochloride(CIP).SBN nanosheets demonstrate remarkable piezo-photocatalytic performance,achieving an 89.13%CIP degradation rate in 60 min and an apparent rate constant of 34.73×10^(-3) min^(-1).This performance is approximately 2.65 times higher than that of granular SBN and outperformed many recently reported piezo-photocatalysts under similar experimental conditions.Free radical trapping techniques,electron spin resonance spectroscopy and liquid chromatography-mass spectrometry are utilized to study the potential paths and mechanisms of CIP degradation.Piezoresponse force microscopy and finite element simulation show that the piezo-response of SBN nanosheets is significantly higher than that of granular SBN.SBN nanosheets achieve high degradation efficiency due to their optimized conduction band positions and enhanced piezoelectric effect,facilitated by the two-dimensional nanosheet structures.In this work,the piezoelectric internal electric field of piezoelectric catalysts can be increased by tuning the catalyst morphology,which points to a possible direction for the production of high-performance piezoelectric catalysts.
基金Project supported by the National Natural Science Foundation of China （Grant Nos 10572155, 10172030 and 50232030）.
文摘We have performed the first-principles calculation to investigate the origins of ferroelectricities and different po- larization behaviours of superlattices BaTiO3/SrTiO3 and PbTiO3/SrTiO3. The density of state （DOS） and electronic charge profiles show that there are strong hybridizations between atoms Ti and O and between atoms Pb and O which play very important roles in producing the ferroelectricities of superlattices BaTiO3/SrTiO3 and PbTiO3/SrTiO3. Ow- ing to the decline of internal electric field in SrTiO3 （ST） layer, the tetragonality and polarizations of superlattices decrease with increasing the fraction of SrTiO3 in the superlattices. We find that the polarization of PbTiO3/SrTiO3 is largerthan that of BaTiO3/SrTiO3 at the same ratio of components, because the polarization mismatch between PbTiO3 and SrTiO3 is larger than that between BaTiO3 and SrTiO3. The polarization and tetragonality are en- hanced with respect to those of bulk tetragonal BaTiO3 in the superlattices BaTiO3/SrTiO3, while the polarization and tetragonality are reduced with respect to those of bulk tetragonal PbTiO3 in superlattices PbTiO3/SrTiO3.
基金supported by the NSFC-Zhejiang Joint Fund for Integration of Industrialization and Diversification(No.U1809214)the Natural Science Foundation of Zhejiang Province(Nos.LTGN23E080001 and LY20E080014)+1 种基金the Science and Technology Project of Zhoushan(No.2022C41011)the National Natural Science Foundation of China(No.22201251).
文摘Devising robust S-scheme photocatalysts is of central importance for achieving high-efficient micropollu-tant decontamination.However,the conscious optimization of S-scheme system with high performance remains a prime challenge.Herein,carbon quantum dots(CDs)and Mn_(0.5)Cd_(0.5)S(MCS)are mounted on BiOBr(BOB)microspheres,establishing an advanced S-scheme heterojunction with interfacial Bi-S bond.The interfacial Bi-S bonds function as superb channels at atomic-scale to abate the energy barrier for S-scheme charge transportation.Meanwhile,CDs serve as electron collectors to preserve highly reductive electrons from MCS,further augmenting the spatial separation of photo-carriers.Therefore,the optimized CDs/MCS/BOB(MBC)heterojunction manifests significantly strengthened tetracycline hydrochloride(TC)destruction activity and its reaction rate constant is approximately 3.1,2.2,2.1,and 1.5 folds that than that of MCS,BOB,BOB/CDs and MCS/BOB.In addition,MBC exhibits high stability and significant resistance to environmental interferences.The toxicology evaluation confirms the effective abatement of toxicity of TC after treatment.This achievement demonstrates the benefits of CDs-optimized S-scheme photosystems with chemical bonds for photocatalytic water decontamination.
基金financial support by the National Natural Science Foundation of China(NSFC,Grant No.22379153 and 22109128)the Ningbo Key Research and Development Project(2023Z147)the Ningbo 3315 Program。
文摘CuBi_(2)O_(4)(CBO)photocathodes hold significant promise for efficient photoelectrochemical(PEC)water splitting due to their favorable band gap and theoretical onset potential.However,their practical application is hindered by poor charge separation efficiency.Herein,we introduce a characteristic in-situ solution Fe-doping strategy that markedly improves photoelectrochemical performance of CBO,doubling the photocurrent density and achieving an unprecedented 190 mV anodic shift in the onset potential.By integrating with an electrochemical oxidation post-treatment,a record incident photon-to-current efficiency(IPCE)exceeding 40% at 0.6 V vs.RHE under visible light illumination is achieved.The versatility of the doping strategy is demonstrated across CBO photocathodes synthesized by different methods with various morphologies,grain sizes,and crystallinities.Mechanistic studies reveal that the gradient distribution of Fe^(3+)ions generates an internal electric field that facilitates efficient charge separation and increases acceptor density.The strong Fe-O bonding also enhances structural stability against photoinduced corrosion.Notably,our investigation uncovers the non-temperature-dependent nature of CBO photocurrent,indicating that PEC performance enhancement primarily depends on reducing carrier recombination rather than improving bulk conductivity.This work lays the groundwork for future advancements in water splitting performance of CBO photocathodes,offering a complementary strategy to conventional methods for enhancing charge separation efficiency.
基金National Natural Science Foundation of China (61761047 and 41876055)Program for Innovative Research Team (in Science and Technology) in University of Yunnan Province。
文摘Aqueous zincion batteries are highly favored for grid-level energy storage owing to their low cost and high safety,but their practical application is limited by slow ion migration.To address this,a strategy has been developed to create a cation-accelerating electric field on the surface of the cathode to achieve ultrafast Zn^(2+)diffusion kinetics.By employing electrodeposition to coat MoS_(2)on the surface of BaV_(6)O_(16)·3H_(2)O nanowires,the directional builtin electric field generated at the heterointerface acts as a cation accelerator,continuously accelerating Zn^(2+)diffusion into the active material.The optimized Zn^(2+)diffusion coefficient in CC@BaV-V_(6)O_(16)·3H_(2)@MoS_(2)(7.5×10^(8)cm^(2)s^(-1)) surpasses that of most reported V-based cathodes.Simultaneously,MoS_(2)serving as a cathodic armor extends the cycling life of the Zn-CC@BaV_(6)O_(16)·3H_(2)@MoS_(2)full batteries to over 10000 cycles.This work provides valuable insights into optimizing ion diffusion kinetics for high-performance energy storage devices.
文摘Devising S-scheme heterostructure is considered as a cutting-edge strategy for advanced photocatalysts with effectively segregated photo-carriers and prominent redox potential for emerging organic pollutants control.Herein,an S-scheme Ag_(2)CO_(3)/C_(3)N_(5) heterojunction photocatalyst was developed via a simple in situ chemical deposition procedure,and further photoreduction operation made metallic Ag(size:3.5–12.5 nm)being in situ formed on Ag_(2)CO_(3)/C_(3)N_(5) for a plasmonic S-scheme Ag/Ag_(2)CO_(3)/C_(3)N_(5) heterojunction photocatalyst.Consequently,Ag/Ag_(2)CO_(3)/C_(3)N_(5) manifests pronouncedly upgraded photocatalytic performance toward oxytetracycline degradation with a superior photoreaction rate constant of 0.0475 min‒1,which is 13.2,3.9 and 2.2 folds that of C_(3)N_(5),Ag_(2)CO_(3),and Ag_(2)CO_(3)/C_(3)N_(5),respectively.As evidenced by comprehensive characterizations and density functional theory calculations,the localized surface plasmon resonance effect of metallic Ag and the unique S-scheme charge transfer mechanism in 0D/0D/2D Ag/Ag_(2)CO_(3)/C_(3)N_(5) collaboratively strengthen the visible-light absorption,and facilitate the effective separation of powerful charge carriers,thereby significantly promoting the generation of reactive species like·OH^(-),h^(+)and·O_(2)^(-)for efficient oxytetracycline destruction.Moreover,four consecutive cycles demonstrate the reusability of Ag/Ag_(2)CO_(3)/C_(3)N_(5).Furthermore,the authentic water purification tests affirm its practical application potential.This work not only provides a candidate strategy for advancing S-scheme heterojunction photocatalysts but also makes a certain contribution to water decontamination.
文摘The industrial implementation of Solar-driven photocatalysis is hampered by inefficient charge separation,poor reusability and hard retrieval of powdery catalysts.To conquer these drawbacks,a self-floating S-scheme Bi_(4)O_(5)Br_(2)/P-doped C_(3)N_(4)/carbon fiber cloth(BB/PN/CC)composed of carbon fibers(CC)as the core and Bi_(4)O_(5)Br_(2)/P-doped C_(3)N_(4)(BB/PN)nanosheets as the shell was constructed as a competent,recyclable cloth-shaped photocatalyst for safe and efficient degradation of aquacultural antibiotics.The BB/PN/CC fabric achieves an exceptional tetracycline degradation rate constant of 0.0118 min‒1,surpassing CN/CC(0.0015 min^(‒1)),BB/CC(0.0066 min^(‒1))and PN/CC(0.0023 min^(‒1))by 6.9,0.8 and 4.1 folds,respectively.Beyond its catalytic prowess,the photocatalyst’s practical superiority is evident in its effortless recovery and environmental adaptability.The superior catalytic effectiveness stems from the S-scheme configuration,which retains the maximum redox capacities of the constituent BB and PN while enabling efficient spatial detachment of photo-carriers.X-ray photoelectron spectroscopy(XPS),in-situ XPS,and electron paramagnetic resonance analyses corroborate the S-scheme mechanism,revealing electron accumulation on PN and hole retention on BB under illumination.Density functional theory calculations further confirm S-scheme interfacial charge redistribution and internal electric field formation.This study advances the design of macroscopic S-scheme heterojunction photocatalysts for sustainable water purification.
基金support from the National Natural Science Foundation of China (Nos. 51962023, 51772139)the Natural Science Foundation of Jiangxi Province, China (No. 20192ACBL21047, 20212BAB204045)+1 种基金the Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle (Nanchang Hangkong University) (No. ES202002077)the 2019 Project of Liaoning Education Department (No. 2019LNJC20)
文摘Constructing heterojunction between two semiconductors with matched energy band structure is an effective modification method to obtain excellent photocatalysts.The experimental scheme adopts a simple solvent method to self-assemble nitrogen doped carbon dots(N-CDs)on the surface of sulfur doped carbon nitride(S-C_(3)N_(4))semiconductor throughπ-πconjugate interaction.Based on this,a novel 0D/2D S-scheme heterojunction N-CDs/S-C_(3)N_(4)hybrid was successfully prepared.The degradation kinetic constants of N-CDs/S-C_(3)N_(4)for rhodamine B(RhB)and p-nitrophenol(PNP)reached 0.23522 and 0.01342 min^(−1),repectively,which were 2.72 and 2.65 times that of S-C_(3)N_(4).The highest photocatalytic hydrogen evolution rate was observed under the simulated sunlight irradiation,which was 2.30 times that of S-C_(3)N_(4).The improvement of photocatalytic performance was mainly based on the formation of the S-scheme heterojunction between S-C_(3)N_(4)and N-CDs.The effects of internal electric field,π-πconjugate interaction and band bending promoted the photogenerated h^(+)and e^(−) with low redox ability to recombine and retained the beneficial h+and e−with strong redox ability,which contributed to the production of more active species of h^(+) and•O_(2)−,therefore the photocatalytic degradation and hydrogen evolution performance were significantly enhanced.
基金financially supported by the framework of the Young Taishan Scholars Program of Shandong Province(No.tsqn.201909026)the Natural Science Foundation of Jiangsu Province(No.BK20200237)+2 种基金the Youth Interdisciplinary Science and Innovative Research Groups of Shandong University(No.2020QNQT014)the Shandong University Future Youth Grant Program(No.61440089964189)the National Natural Science Foundation of China(No.21975084)for their support。
文摘The recombination of photogenerated electrons and holes is a crucial factor limiting photocatalytic H_(2)evolution.The S-scheme ZnWO_(4)-ZnIn_(2)S_(4)heterojunction with 2D coupling interfaces was successfully synthesized using a simple solvothermal method.An effective S-scheme interfacial charge migration route at the S-scheme heterogeneous interface was determined by energy band structure analyses(such as UPS,Mott-Schottky and XPS plots),which facilitates the separation of photoexcited carriers.It is worth noting that the optimal ZnWO_(4)-ZnIn_(2)S_(4)composite has an H_(2)evolution activity of 4925.3μmol g^(-1)h^(-1)with favourable photostability and stability.Meanwhile,the ZnWO_(4)-Zn In_(2)S_(4)heterojunction exhibits the maximum optical response value(2.8 m A cm-2)in the initial stage,effectively promoting the separation and migration of photogenerated carriers.The establishment of the built-in electric field direction at the interface can effectively promote the space charge separation between the ZnWO_(4)and ZnIn_(2)S_(4)nanosheets,which is favorable to the photocatalytic H_(2)evolution.This work provides valuable guidance for designing S-scheme heterojunction photocatalysts composed of two n-type semiconductors for energy and environmental applications.The recombination of photogenerated electrons and holes is a crucial factor limiting photocatalytic H_(2)evolution.The S-scheme ZnWO_(4)-ZnIn_(2)S_(4)heterojunction with 2D coupling interfaces was successfully synthesized using a simple solvothermal method.An effective S-scheme interfacial charge migration route at the S-scheme heterogeneous interface was determined by energy band structure analyses(such as UPS,Mott-Schottky and XPS plots),which facilitates the separation of photoexcited carriers.It is worth noting that the optimal ZnWO_(4)-ZnIn_(2)S_(4)composite has an H_(2)evolution activity of 4925.3μmol g^(-1)h^(-1)with favourable photostability and stability.Meanwhile,the ZnWO_(4)-ZnIn_(2)S_(4)heterojunction exhibits the maximum optical response value(2.8 m A cm-2)in the initial stage,effectively promoting the separation and migration of photogenerated carriers.The establishment of the built-in electric field direction at the interface can effectively promote the space charge separation between the ZnWO_(4)and Zn In_(2)S_(4)nanosheets,which is favorable to the photocatalytic H_(2)evolution.This work provides valuable guidance for designing S-scheme heterojunction photocatalysts composed of two n-type semiconductors for energy and environmental applications.
基金supported by the National Natural Science Foundation of China(Grant Nos.U1862105,22108214,22050410267)Natural Science Basic Research Plan in Shaanxi Province of China(Grant Nos.2017JZ001,2018KJXX-008)+3 种基金Fundamental Research Funds for the Central Universities(Grant No.cxtd2017004)China Postdoctoral Science Foundation(Grant No.2021TQ0262)the Promotion Plan for Young People of Shaanxi Association for Science and Technology(20210605)K.C.Wong Education Foundation,Hong Kong,China。
文摘In this work,a novel NiP_(2)/g-C_(3)N_(4)heterojunction via homogeneous precipitation method assisted by thermal phosphorization reaction was designed and constructed,and the optimized sample showed the excellent photocatalytic H_(2)evolution activity under visible-light irradiation,which was nearly 112 times higher than that of pristine g-C_(3)N_(4)sample.Experimental characterizations and DFT calculations demonstrated that the NiP_(2)nanoparticles covered on the g-C_(3)N_(4)surface can form a built-in electric field at the interface to accelerate the transfer of photoexcited electrons from g-C_(3)N_(4)to NiP_(2),crucial for hindering the recombination of electron-hole pairs.Moreover,the energy barrier of hydrogen evolution reaction can also vastly reduce when combined NiP_(2)and g-C_(3)N_(4)to construct NiP_(2)/g-C_(3)N_(4)heterojunction.This work represents a method through combing experimental and theoretical tools to thoroughly investigate the mechanism of photocatalytic process.
基金the National Nature Science Foundation of China(U20A20247 and 51922038).
文摘Stable potassium metal batteries(PMBs)are promising candidates for electrical energy storage due to their ability to reversibly store electrical energy at a low cost.However,dendritic growth and large volume changes hinder their practical application.Here,referring to the morphology and structure of a virus,a bionic virus-like-carbon microsphere(BVC)was designed as the anode host for a PMB.A BVC with a three-dimensional structure can not only control the electric field,which can suppress dendrite formation,but can also provide a larger space to accommodate the volume change during the cycle progress.The designed potassium(K)metal anode exhibits excellent cycle life and stability(during 1800 h of repeated plating/stripping of K at a current density of 0.1 mA cm−2,K-BVC can realize a very stable K metal anode with low voltage hysteresis).Stable cyclability and improved rate capability can be realized in a full cell using Prussian blue over 400 cycles.This research provides a new idea for the development of stable K metal anodes and may pave the way for the practical application of next-generation metal batteries.
基金the National Natural Science Foundation of China(No.22138013).
文摘Heteroatom doping has emerged as a prevailing strategy to enhance the storage of sodium ions in carbon materials.However,the underlying mechanism governing the performance enhancement remains undisclosed.Herein,we fabricated N/S co-doped carbon beaded fibers(S-N-CBFs),which exhibited glorious rate performance and durableness in Na+storage,showcasing no obvious capacity decay even after 3500 cycles.Furthermore,when used as anodes in sodium-ion capacitors,the S-N-CBFs delivered exceptional results,boasting a high energy density of 225 Wh·kg^(-1),superior power output of 22500 W·kg^(-1),and outstanding cycling stability with a capacity attenuation of merely 0.014%per cycle after 4000 cycles at 2 A·g^(-1).Mechanistic investigations revealed that the incorporation of both pyridinic N and pyrrolic N into the carbon matrix of S-N-CBFs induced internal electric fields(IEFs),with the former IEF being stronger than the latter,in conjunction with the doped S atom.Density functional theory calculations further unveiled that the intensity of the IEF directly influenced the adsorption of Na+,thereby resulting in the exceptional performances of S-N-CBFs as sodium-ion storage materials.This work uncovers the pivotal role of IEF in regulating the electronic structure of carbon materials and enhancing their Na^(+)storage capabilities,providing valuable insights for the development of more advanced electrode materials.
