The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor ...The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor featuring a broad spectral absorption range,is successfully employed as the electron acceptor to combine with CdS for constructing a S-scheme heterojunction.The optimized photocatalyst(CdSCuO2∶1)delivers an exceptional hydrogen evolution rate of 18.89 mmol/(g·h),4.15-fold higher compared with bare CdS.X-ray photoelectron spectroscopy(XPS)and ultraviolet-visible diffuse reflection absorption spectroscopy(UV-vis DRS)confirmed the S-scheme band structure of the composites.Moreover,the surface photovoltage(SPV)and electron paramagnetic resonance(EPR)indicated that the photogenerated electrons and photogenerated holes of CdS-CuO2∶1 were respectively transferred to the conduction band(CB)of CdS with a higher reduction potential and the valence band(VB)of CuO with a higher oxidation potential under illumination,as expected for the S-scheme mechanism.Density-functional-theory calculations of the electron density difference(EDD)disclose an interfacial electric field oriented from CdS to CuO.This built-in field suppresses charge recombination and accelerates carrier migration,rationalizing the markedly enhanced PHE activity.This study offers a novel strategy for designing S-scheme heterojunctions with high light harvesting and charge utilization toward sustainable solar-tohydrogen conversion.展开更多
Photo-assisted lithium–sulfur batteries(PALSBs)offer an eco-friendly solution to address the issue of sluggish reaction kinetics of conventional LSBs.However,designing an efficient photoelectrode for practical implem...Photo-assisted lithium–sulfur batteries(PALSBs)offer an eco-friendly solution to address the issue of sluggish reaction kinetics of conventional LSBs.However,designing an efficient photoelectrode for practical implementation remains a significant challenge.Herein,we construct a free-standing polymer–inorganic hybrid photoelectrode with a direct Z-scheme heterostructure to develop high-efficiency PALSBs.Specifically,polypyrrole(PPy)is in situ vapor-phase polymerized on the surface of N-doped TiO_(2) nanorods supported on carbon cloth(N-TiO_(2)/CC),thereby forming a well-defined p–n heterojunction.This architecture efficiently facilitates the carrier separation of photo-generated electron–hole pairs and significantly enhances carrier transport by creating a built-in electric field.Thus,the PPy@N-TiO_(2)/CC can simultaneously act as a photocatalyst and an electrocatalyst to accelerate the reduction and evolution of sulfur,enabling ultrafast sulfur redox dynamics,as convincingly validated by both theoretical simulations and experimental results.Consequently,the PPy@N-TiO_(2)/CC PALSB achieves a high discharge capacity of 1653 mAh g^(−1),reaching 98.7%of the theoretical value.Furthermore,5 h of photo-charging without external voltage enables the PALSB to deliver a discharge capacity of 333 mAh g^(−1),achieving dual-mode energy harvesting capabilities.This work successfully integrates solar energy conversion and storage within a rechargeable battery system,providing a promising strategy for sustainable energy storage technologies.展开更多
Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchan...Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchange strategy for the in-situ growth of BiVO_(4) on an InVO_(4) substrate to generate a Z-scheme heterojunction of InVO_(4)/BiVO_(4) .This in-situ partial transformation approach endows the InVO_(4)/BiVO_(4) heterojunction with a tightly connected interface,resulting in a significant improvement in charge separation efficiency between InVO_(4) and BiVO_(4).Moreover,the construction of the heterojunction reduces the formation energy barrier of the ^(*)COOH intermediate during the photoreduction of CO_(2) and increases the desorption energy barrier of the ^(*)CO intermediate,facilitating the deep reduction of ^(*)CO.Consequently,the InVO_(4)/BiVO_(4) heterojunction is capable of photocatalytic CO_(2) reduction to CH_(3)OH with high efficiency and selectivity.Under conditions where water serves as the electron source and a light intensity of 100 m W/cm^(2),the yield of CH_(3)OH reaches 130.5 μmol g^(-1)h^(-1) with a selectivity of 92 %,outperforming photocatalysts reported under similar conditions.展开更多
The rapid recombination of photogenerated charge carriers and the poor stability of metal sulfides remain bottlenecks limiting their practical applications. In this study, sulfur vacancies were introduced into an S-sc...The rapid recombination of photogenerated charge carriers and the poor stability of metal sulfides remain bottlenecks limiting their practical applications. In this study, sulfur vacancies were introduced into an S-scheme AgIn_(5)S_(8)/Bi_(2)S_(3) heterojunction via an in situ hydrothermal method. The sulfur vacancies induced charge density redistribution within the heterojunction and generated efficient active sites for electrons, thereby creating a localized electron-rich environment. The synergistic effects of the sulfur vacancies, internal electric field, and defect energy levels accelerated the separation and transfer of photogenerated charge carriers via the S-scheme pathway, thereby enhancing the visible-light photocatalytic performance, by achieving a Cr(Ⅵ) reduction efficiency of 99.6%. More importantly, the long-term stability and excellent anti-interference capability of the S-scheme AgIn_(5)S_(8)/Bi_(2)S_(3) heterojunction demonstrate its practical application potential, achieving 98.9% Cr(Ⅵ) removal from real electroplating wastewater and meeting discharge standards. This work provides a theoretical basis for constructing highly-catalytic S-scheme heterojunctions and serves as a promising solution for Cr(VI)-containing electroplating wastewater treatment.展开更多
Semi-transparent organic photovoltaics(ST-OPVs)have great potential for photovoltaic building integration and agricultural greenhouse energy.However,the mutually constraining relationship between average visible trans...Semi-transparent organic photovoltaics(ST-OPVs)have great potential for photovoltaic building integration and agricultural greenhouse energy.However,the mutually constraining relationship between average visible transmittance(AVT)and power conversion efficiency(PCE)remains a key issue of STOPVs.Herein,we innovatively applied a surface texturization strategy by integrating with a pseudo-planar heterojunction(PPHJ)structure to fabricate ST-OPVs,which possess outstanding photoelectric conversion and light management capability.The textured active layer performs significantly improved light capture capability and reduced optical loss due to that the micro-patterned arrays can deflect incident light multiple times.Moreover,the surface texturization strategy can enhance the crystallinity of the active layer and precisely control donor/acceptor inter-penetration,which magnifies exciton dissociation interface and forms ordered carrier dynamics.Consequently,the textured opaque device via blade-coating performs a record PCE of 19.17%(certified 19.02%)and the semi-transparent device achieves one of the highest light utilization efficiency(LUE)of 5.54%with prominent PCE(14.40%)and AVT(38.43%).Most importantly,the excellent thermal insulation performance and color rendering index of ST-OPVs are fitting for the agricultural greenhouses and insulation roofing,which shows that the surface texturization strategy can provide promising application prospects for ST-OPVs in economically sustainable agricultural development.展开更多
To address the urgent need for water environment purification and clean water production,this study proposes a strategy to construct a hydrophobic S-scheme heterojunction KTaO_(3)/BiOI.This strategy extends the light ...To address the urgent need for water environment purification and clean water production,this study proposes a strategy to construct a hydrophobic S-scheme heterojunction KTaO_(3)/BiOI.This strategy extends the light response range of KTaO_(3)from the ultraviolet(UV)region to the visible light region and achieves efficient carrier separation capability,thereby enabling selective degradation of water-soluble components in sewage.After 5 cycles of indoor photodegradation,the degradation efficiency of Rhodamine B(Rh B)reached 91.84%,while 2 cycles of outdoor photodegradation achieved an efficiency of 97.11%.Additionally,the degradation efficiency for methylene blue(MB)attained 98.26%.Meanwhile,the constructed superhydrophobic canvas exhibits excellent selective adsorption performance for water-insoluble floating pollutants such as cyclohexane.Based on the construction of a superhydrophobic interface and an S-scheme heterojunction,simultaneous oil-water separation and photocatalytic degradation are realized.Through Kelvin probe force microscopy(KPFM)and theoretical calculation analyses,the S-scheme charge transfer mechanism between KTaO_(3)and BiOI is systematically confirmed.This work shows broad application prospects in the treatment of oil-containing wastewater.展开更多
Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt ...Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min^(-1),which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e^(-))accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O_(2)^(·-),^(·)OH,and SO_(4)^(·-)) and non-radicals(such as ^(1)O_(2),h^(+),and e^(-)) were both presented in the Vis-CoOOH@COFs/PMS system,with O_(2)^(-) playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.展开更多
Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systemat...Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.展开更多
As the chemical industry expands,the use of benzene,toluene,and xylene(collectively known as BTX)in industrial production has increased greatly.Meanwhile,the toxic nature and potential health hazards of BTX gases cann...As the chemical industry expands,the use of benzene,toluene,and xylene(collectively known as BTX)in industrial production has increased greatly.Meanwhile,the toxic nature and potential health hazards of BTX gases cannot be ignored due to low-concentration leaks underline the critical need for rapid and real-time monitoring of these gases.Chemiresistive metal oxide semiconductor(MOS)-based gas sensors,which are extensively used for gas detection in both industrial settings and everyday life,emerge as one of the optimal solutions for trace BTX detection.These sensors are highly valued for their high sensitivity and low detection limits.Nevertheless,the improvement of selectivity towards specific BTX gases to achieve efficient and precise detection still remains challenging.This review summarizes the chemiresistive MOS-based gas sensors designed for BTX detection,categorizing them based on the components of sensing materials-basically into three groups:single-component,single heterojunction,and multiple heterojunctions gas sensing materials.Further,the review proposes the future application prospects of chemiresistive MOS-based BTX gas sensors,with specific emphasis on their significance in promoting industrial safety and environmental monitoring.展开更多
With the rapid advancement of optoelectronic technology,high-performance photodetectors are increasingly in demand in fields such as environmental monitoring,optical communication,and defense systems,where ultraviolet...With the rapid advancement of optoelectronic technology,high-performance photodetectors are increasingly in demand in fields such as environmental monitoring,optical communication,and defense systems,where ultraviolet detection is critical.However,conventional semiconductor materials suffer from limited UV-visible detection capabilities owing to their narrow bandgaps and high dark currents.To address these challenges,wide-bandgap semiconductors have emerged as promising alternatives.Here,we fabricated a horizontally structured n–n heterojunction photodetector by growingβ-Ga_(2)O_(3) on Si–GaN via plasma-enhanced chemical vapor deposition.The device exhibits a self-powered photocurrent of 3.5 nA at zero bias,enabled by the photovoltaic effect of the space charge region.Under 254-nm and 365-nm illumination,it exhibits rectification behavior,achieving a responsivity of 0.475 m A/W(0 V,220??W/cm~2 at 254 nm)and 257.6 mA/W(-5 V),respectively.Notably,the photodetector demonstrates a high photocurrent-to-dark current ratio of 10~5 under-5-V bias,highlighting its potential for self-powered and high-performance UV detection applications.展开更多
Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen ba...Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen batteries(LOBs)due to their poor OER performance,resulting from poor electrical conductivity and overly strong intermediate adsorption.In this work,fancy double heterojunctions on 1T/2H-MoS_(2)@Co_(3)S_(4)(1T/2H-MCS)were constructed derived from the charge donation from Co to Mo ions,thus inducing the phase transformation of Mo S_(2)from 2H to 1T.The unique features of these double heterojunctions endow the1T/2H-MCS with complementary catalysis during charging and discharging processes.It is worth noting that 1T-Mo S2@Co3S4could provide fast Co-S-Mo electron transport channels to promote ORR/OER kinetics,and 2H-MoS_(2)@Co_(3)S_(4)contributed to enabling moderate egorbital occupancy when adsorbed with oxygen-containing intermediates.On the basis,the Li_(2)O_(2)nucleation route was changed to solution and surface dual pathways,improving reversible deposition and decomposition kinetics.As a result,1T/2H-MCS cathodes exhibit an improved electrocatalytic performance compared with those of Co_(3)S_(4)and Mo S2cathodes.This innovative heterostructure design provides a reliable strategy to construct efficient transition metal sulfide catalysts by improving electrical conductivity and modulating adsorption toward oxygenated intermediates for LOBs.展开更多
Chlorinated antibiotics pose great challenges in efficient removal,while for the first time,this work greatly enhanced their electrocatalytic dechlorination performance by construction of non-noble metal Co_(3)O_(4)/g...Chlorinated antibiotics pose great challenges in efficient removal,while for the first time,this work greatly enhanced their electrocatalytic dechlorination performance by construction of non-noble metal Co_(3)O_(4)/g-C_(3)N_(4) heterojunctions to improve process cost-effectiveness.The Co_(3)O_(4)/g-C_(3)N_(4) heterojunction demonstrated an effective removal of 93.6%thiamphenicol(TAP)within 45 min,with the rate constant(0.0584 min^(-1))that was 2.4 and 2.8 times that of Co_(3)O_(4) and g-C_(3)N_(4) alone,respectively.The formation of heterojunctions facilitated electron transfer,enriched the electron density on Co_(3)O_(4),and enhanced the adsorption of pollutants as well as the desorption of degradation intermediates.The enhanced production of atomic hydrogen(H*)of Co_(3)O_(4)/g-C_(3)N_(4),which increased by 13.6-28.2 times,contributed more to pollutant removal(64.0%),much higher than that of Co_(3)O_(4)(37.3%)and g-C_(3)N_(4)(6.1%).The energy barrier for H_(2) formation on Co_(3)O_(4)/g-C_(3)N_(4)(0.75 eV)was higher than that on Co_(3)O_(4)(-1.84 eV),supporting that it could stabilize H*and inhibit the formation of H_(2).The Co_(3)O_(4)/g-C_(3)N_(4) heterojunction exhibited stable performance with less impact by pH and co-existing ions,and posed effectiveness for the dechlorination of typical chlorinated antibiotics.This study offers an efficient and sustainable strategy for constructing heterojunctions to enhance the performance of non-noble metal catalysts in electrocatalytic dechlorination.展开更多
Recent advances in van der Waals(vdW) ferroelectrics have sparked the development of related heterostructures with non-volatile and field-tunable functionalities. In vdW ferroelectric heterojunctions, the interfacial ...Recent advances in van der Waals(vdW) ferroelectrics have sparked the development of related heterostructures with non-volatile and field-tunable functionalities. In vdW ferroelectric heterojunctions, the interfacial electrical characteristics play a crucial role in determining their performance and functionality. In this study,we explore the interfacial polarization coupling in two-dimensional(2D) ferroelectric heterojunctions by fabricating a graphene/h-BN/CuInP_(2)S_(6)/α-In_(2)Se_(3)/Au ferroelectric field-effect transistor. By varying the gate electric field, the CuInP_(2)S_(6)/α-In_(2)Se_(3) heterojunction displays distinct interfacial polarization coupling states, resulting in significantly different electrical transport behaviors. Under strong gate electric fields, the migration of Cu ions further enhances the interfacial polarization effect, enabling continuous tuning of both the polarization state and carrier concentration in α-In_(2)Se_(3). Our findings offer valuable insights for the development of novel multifunctional devices based on 2D ferroelectric materials.展开更多
The design of customized crystal plane heterojunction can effectively leverage the optimal anisotropic interaction of crystal plane,thereby enhancing photocatalytic activity.In this study,Co_(3)O_(4) exposed(111),(110...The design of customized crystal plane heterojunction can effectively leverage the optimal anisotropic interaction of crystal plane,thereby enhancing photocatalytic activity.In this study,Co_(3)O_(4) exposed(111),(110),and(100)crystal planes(designated as HCO,NCO,and CCO,respectively)were synthesized and successfully coupled with Cd_(0.5)Zn_(0.5)S(CZS).Among these composites,the HCO/CZS exhibited best hydrogen evolution activity.In conjunction with DFT calculations and femtosecond transient absorption spectroscopy,it has been found that:the crystal plane interaction between HCO and CZS enabled the composite catalyst to exhibit optimal anisotropy in crystal plane carrier transport,crystal plane active sites,and crystal plane electronic structure.This interaction induces a redistribution of electrons at their contact interface,thereby establishing a built-in electric field that facilitates the formation of ohmic heterojunction between HCO and CZS.The synergistic effect of the ohmic heterojunction and crystal plane anisotropy not only decreases the Gibbs free energy of hydrogen adsorption but also facilitates the efficient spatial separation and rapid transfer of electron-hole pairs.This study offers valuable insights into the customization of crystal plane heterojunctions,aiming to maximize anisotropic interactions between crystal planes in order to enhance photocatalytic hydrogen evolution.展开更多
The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS...The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In_(2)O_(3)is successfully achieved using an electrostatic self-assembly method.Under visible light irradiation,all CdS-In_(2)O_(3)composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs.Notably,the photocatalytic H_(2)evolution rate of the optimal CdS-7%In_(2)O_(3)composite is determined to be 2258.59μmol g^(−1)h^(−1),approximately 12.3 times higher than that of pure CdS.The cyclic test indicates that the CdS-In_(2)O_(3)composite maintains considerable activity even after 5 cycles,indicating its excellent stability.In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In_(2)O_(3)composites adheres to a typical S-scheme heterojunction mechanism.Additionally,a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In_(2)O_(3)and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs,thus achieving enhanced photocatalytic performance.This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H_(2)production and offers novel insights into the construction of effective composite photocatalysts.展开更多
In the quest for effective solutions to address Environ.Pollut.and meet the escalating energy demands,heterojunction photocatalysts have emerged as a captivating and versatile technology.These photocatalysts have garn...In the quest for effective solutions to address Environ.Pollut.and meet the escalating energy demands,heterojunction photocatalysts have emerged as a captivating and versatile technology.These photocatalysts have garnered significant interest due to their wideranging applications,including wastewater treatment,air purification,CO_(2) capture,and hydrogen generation via water splitting.This technique harnesses the power of semiconductors,which are activated under light illumination,providing the necessary energy for catalytic reactions.With visible light constituting a substantial portion(46%)of the solar spectrum,the development of visible-light-driven semiconductors has become imperative.Heterojunction photocatalysts offer a promising strategy to overcome the limitations associated with activating semiconductors under visible light.In this comprehensive review,we present the recent advancements in the field of photocatalytic degradation of contaminants across diverse media,as well as the remarkable progress made in renewable energy production.Moreover,we delve into the crucial role played by various operating parameters in influencing the photocatalytic performance of heterojunction systems.Finally,we address emerging challenges and propose novel perspectives to provide valuable insights for future advancements in this dynamic research domain.By unraveling the potential of heterojunction photocatalysts,this reviewcontributes to the broader understanding of their applications and paves the way for exciting avenues of exploration and innovation.展开更多
Inefficient photo-carrier separation and sluggish photoreaction dynamics appreciably undermine the photocatalytic decontamination efficacy of photocatalysts.Herein,an S-scheme Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)heterojunc...Inefficient photo-carrier separation and sluggish photoreaction dynamics appreciably undermine the photocatalytic decontamination efficacy of photocatalysts.Herein,an S-scheme Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)heterojunction with interfacial Mo-S chemical bond is designed as an efficient photocatalyst.In this integrated photosystem,Bi2MoO6 and Mn_(0.5)Cd_(0.5)S function as oxidation and reduction centers of Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)microspheres,respectively.Importantly,the unique charge transfer mechanism in the chemically bonded S-scheme heterojunction with Mo-S bond as atom-scale charge transport highway effectively inhibits the photocorrosion of Mn_(0.5)Cd_(0.5)S and the recombination of photo-generated electron-hole pairs,endowing Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)photocatalyst with excellent photocatalytic decontamination performance and stability.Besides,integration of Mn_(0.5)Cd_(0.5)S nanocrystals into Bi2MoO6 improves hydrophilicity,conducive to the photoreactions.Strikingly,compared with Mn_(0.5)Cd_(0.5)S and Bi2MoO6,the Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)unveils much augmented photoactivity in tetracycline eradication,among which Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)-2 possesses the highest activity with the rate constant up to 0.0323 min-1,prominently outperforming other counterparts.This research offers a chemical bonding engineering combining with S-scheme heterojunction strategy for constructing extraordinary photocatalysts for environmental purification.展开更多
It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for elec...It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for electrocatalytic HMF oxidative reaction(e-HMFOR)have been facing low Faradaic efficiency(FE)and high water splitting voltage.Herein,we propose a strategy of the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction by constructing a Co-Ni paired site,where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site,thus giving the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction superior electrocata lytic performances for e-HMFOR and water splitting.By optimizing conditions,the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction has high conversion of 99.7%,high selectivity of 99.9%,and high FE of 98.4%at 1.3 V,as well as low cell voltage of 1.31 V at 10 mA cm^(-2)in 1 M KOH+0.1 M HMF.This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H_(2)in an economical manner.展开更多
The goal of photocatalytic CO_(2)reduction is to obtain a single energy-bearing product with high efficiency and stability.Consequently,constructing highly selective photocatalysts with enhanced surface and optoelectr...The goal of photocatalytic CO_(2)reduction is to obtain a single energy-bearing product with high efficiency and stability.Consequently,constructing highly selective photocatalysts with enhanced surface and optoelectronic properties is crucial for achieving this objective.Here,we have developed a simple one-pot vulcanization method to synthesize a MIL-68(In)-derived Cd In_(2)S_(4)/In_(2)S_(3)heterojunction that exhibited stable and high selectivity.Multiple characterizations of the Cd In_(2)S_(4)/In_(2)S_(3)heterojunction revealed a hierarchical tubular structure with numerous surface reactive sites,a high visible-light utilization rate(λ<600 nm),efficient charge separation,and a prolonged charge-carrier lifetime.Moreover,an S-scheme charge transfer mechanism,based on the interleaved band between the two components,improved the reduction capability of the electrons.Benefiting from the compositional and structural synergy,the yield CO by Cd In_(2)S_(4)/In_(2)S_(3)-250(CI-250)reached 135.62μmol·g^(-1)·h^(-1),which was 49.32 times and 32.88 times higher than that of In_(2)S_(3)and Cd In_(2)S_(4),respectively.The Cd In_(2)S_(4)/In_(2)S_(3)heterojunction exhibited a quantum efficiency of 4.23%with a CO selectivity of 71%.Four cycle tests confirmed the good stability and recyclability of the CI-250.This work provides a new approach for designing and preparing high-performance hollow MOFsbased photocatalysts for scalable and sustainable CO_(2)reduction.展开更多
In photocatalysis field,S-scheme heterojunctions show unique advantages and prospects.However,the carrier shielding effect of heterojunctions limits the separation and migration of interfacial charges.In this study,a ...In photocatalysis field,S-scheme heterojunctions show unique advantages and prospects.However,the carrier shielding effect of heterojunctions limits the separation and migration of interfacial charges.In this study,a strategy of“dynamic cascade electric fields to deplete unilaterally accumulated charges”was innovatively proposed to overcome this drawback.By modulating g-C_(3)N_(4)(CN)and Bi_(2)WO_(6)(BWO)using the polarized electric field(PEF)of spontaneously polarized ceramic(SPC),a BWO/SPC-CN composite with cascade internal electric field(IEF)and PEF was successfully constructed for efficient piezophotocatalytic degradation of recalcitrant pollutants.BWO/SPC-CN contributed to 96.8% degradation of carbamazepine,significantly surpassing BWO/CN(70.5%).BWO/SPC-CN performed excellent capacity of harvesting piezoelectric energy due to its unique three-dimensional porous nano-network structure.The PEF of SPC modulated the electronic band structure and thus strengthened the IEF of BWO/SPC-CN,providing a persistent driving force for interfacial charge migration.Moreover,SPC with a strong PEF unilaterally consumed the charges accumulated on CN under periodic piezoelectricity,weakening the shielding electric field to inhibit the recombination of electron-hole pairs.As a consequence,the dynamic cascade PEF-IEF ultimately broke the carrier shielding effect in heterojunction photocatalysis and enhanced interfacial electron transfer.This work provides reliable methods to enhance the interfacial charge transfer in heterojunction and new insights into piezo-photocatalytic mechanism.展开更多
文摘The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor featuring a broad spectral absorption range,is successfully employed as the electron acceptor to combine with CdS for constructing a S-scheme heterojunction.The optimized photocatalyst(CdSCuO2∶1)delivers an exceptional hydrogen evolution rate of 18.89 mmol/(g·h),4.15-fold higher compared with bare CdS.X-ray photoelectron spectroscopy(XPS)and ultraviolet-visible diffuse reflection absorption spectroscopy(UV-vis DRS)confirmed the S-scheme band structure of the composites.Moreover,the surface photovoltage(SPV)and electron paramagnetic resonance(EPR)indicated that the photogenerated electrons and photogenerated holes of CdS-CuO2∶1 were respectively transferred to the conduction band(CB)of CdS with a higher reduction potential and the valence band(VB)of CuO with a higher oxidation potential under illumination,as expected for the S-scheme mechanism.Density-functional-theory calculations of the electron density difference(EDD)disclose an interfacial electric field oriented from CdS to CuO.This built-in field suppresses charge recombination and accelerates carrier migration,rationalizing the markedly enhanced PHE activity.This study offers a novel strategy for designing S-scheme heterojunctions with high light harvesting and charge utilization toward sustainable solar-tohydrogen conversion.
基金the financial support from the National Natural Science Foundation of China (22109127)the Chinese Postdoctoral Science Foundation (2021M702666)+2 种基金the Research Fund of the State Key Laboratory of Solidification Processing (NPU),China (Grant No.2023-TS-02)The financial support from the Youth Project of"Shaanxi High-level Talents Introduction Plan"the Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) are also sincerely appreciated
文摘Photo-assisted lithium–sulfur batteries(PALSBs)offer an eco-friendly solution to address the issue of sluggish reaction kinetics of conventional LSBs.However,designing an efficient photoelectrode for practical implementation remains a significant challenge.Herein,we construct a free-standing polymer–inorganic hybrid photoelectrode with a direct Z-scheme heterostructure to develop high-efficiency PALSBs.Specifically,polypyrrole(PPy)is in situ vapor-phase polymerized on the surface of N-doped TiO_(2) nanorods supported on carbon cloth(N-TiO_(2)/CC),thereby forming a well-defined p–n heterojunction.This architecture efficiently facilitates the carrier separation of photo-generated electron–hole pairs and significantly enhances carrier transport by creating a built-in electric field.Thus,the PPy@N-TiO_(2)/CC can simultaneously act as a photocatalyst and an electrocatalyst to accelerate the reduction and evolution of sulfur,enabling ultrafast sulfur redox dynamics,as convincingly validated by both theoretical simulations and experimental results.Consequently,the PPy@N-TiO_(2)/CC PALSB achieves a high discharge capacity of 1653 mAh g^(−1),reaching 98.7%of the theoretical value.Furthermore,5 h of photo-charging without external voltage enables the PALSB to deliver a discharge capacity of 333 mAh g^(−1),achieving dual-mode energy harvesting capabilities.This work successfully integrates solar energy conversion and storage within a rechargeable battery system,providing a promising strategy for sustainable energy storage technologies.
基金financially supported the National Key R&D Program of China (No.2022YFA1502902)the National Natural Science Foundation of China (NSFC,Nos.22475152 and U21A20286)the 111 Project of China (No.D17003)。
文摘Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchange strategy for the in-situ growth of BiVO_(4) on an InVO_(4) substrate to generate a Z-scheme heterojunction of InVO_(4)/BiVO_(4) .This in-situ partial transformation approach endows the InVO_(4)/BiVO_(4) heterojunction with a tightly connected interface,resulting in a significant improvement in charge separation efficiency between InVO_(4) and BiVO_(4).Moreover,the construction of the heterojunction reduces the formation energy barrier of the ^(*)COOH intermediate during the photoreduction of CO_(2) and increases the desorption energy barrier of the ^(*)CO intermediate,facilitating the deep reduction of ^(*)CO.Consequently,the InVO_(4)/BiVO_(4) heterojunction is capable of photocatalytic CO_(2) reduction to CH_(3)OH with high efficiency and selectivity.Under conditions where water serves as the electron source and a light intensity of 100 m W/cm^(2),the yield of CH_(3)OH reaches 130.5 μmol g^(-1)h^(-1) with a selectivity of 92 %,outperforming photocatalysts reported under similar conditions.
基金supported by the National Natural Science Foundation of China (Grant No.52470078)the Natural Science Foundation of Jiangxi Province (Grant No.20252BAC250042)the Key Laboratory of Jiangxi Province for Persistent Pollutants Prevention Control and Resource Reuse (Grant No.2023SSY02061)。
文摘The rapid recombination of photogenerated charge carriers and the poor stability of metal sulfides remain bottlenecks limiting their practical applications. In this study, sulfur vacancies were introduced into an S-scheme AgIn_(5)S_(8)/Bi_(2)S_(3) heterojunction via an in situ hydrothermal method. The sulfur vacancies induced charge density redistribution within the heterojunction and generated efficient active sites for electrons, thereby creating a localized electron-rich environment. The synergistic effects of the sulfur vacancies, internal electric field, and defect energy levels accelerated the separation and transfer of photogenerated charge carriers via the S-scheme pathway, thereby enhancing the visible-light photocatalytic performance, by achieving a Cr(Ⅵ) reduction efficiency of 99.6%. More importantly, the long-term stability and excellent anti-interference capability of the S-scheme AgIn_(5)S_(8)/Bi_(2)S_(3) heterojunction demonstrate its practical application potential, achieving 98.9% Cr(Ⅵ) removal from real electroplating wastewater and meeting discharge standards. This work provides a theoretical basis for constructing highly-catalytic S-scheme heterojunctions and serves as a promising solution for Cr(VI)-containing electroplating wastewater treatment.
基金the support from the National Natural Science Foundation of China(52333006)the support from the National Natural Science Foundation of China(52303232)+1 种基金the Natural Science Foundation of Jiangxi Province(20242BAB20184)the support from National Natural Science Foundation of China(52373186)。
文摘Semi-transparent organic photovoltaics(ST-OPVs)have great potential for photovoltaic building integration and agricultural greenhouse energy.However,the mutually constraining relationship between average visible transmittance(AVT)and power conversion efficiency(PCE)remains a key issue of STOPVs.Herein,we innovatively applied a surface texturization strategy by integrating with a pseudo-planar heterojunction(PPHJ)structure to fabricate ST-OPVs,which possess outstanding photoelectric conversion and light management capability.The textured active layer performs significantly improved light capture capability and reduced optical loss due to that the micro-patterned arrays can deflect incident light multiple times.Moreover,the surface texturization strategy can enhance the crystallinity of the active layer and precisely control donor/acceptor inter-penetration,which magnifies exciton dissociation interface and forms ordered carrier dynamics.Consequently,the textured opaque device via blade-coating performs a record PCE of 19.17%(certified 19.02%)and the semi-transparent device achieves one of the highest light utilization efficiency(LUE)of 5.54%with prominent PCE(14.40%)and AVT(38.43%).Most importantly,the excellent thermal insulation performance and color rendering index of ST-OPVs are fitting for the agricultural greenhouses and insulation roofing,which shows that the surface texturization strategy can provide promising application prospects for ST-OPVs in economically sustainable agricultural development.
基金supported by the National Natural Science Foundation of China(Grant No.52305196)the Natural Science Foundation of Shandong Province(Grant Nos.ZR2022ME073,ZR2023MB090)the Guangyue Young Scholar Innovation Team of Liaocheng University(Grant No.LCUGYTD2023-02)。
文摘To address the urgent need for water environment purification and clean water production,this study proposes a strategy to construct a hydrophobic S-scheme heterojunction KTaO_(3)/BiOI.This strategy extends the light response range of KTaO_(3)from the ultraviolet(UV)region to the visible light region and achieves efficient carrier separation capability,thereby enabling selective degradation of water-soluble components in sewage.After 5 cycles of indoor photodegradation,the degradation efficiency of Rhodamine B(Rh B)reached 91.84%,while 2 cycles of outdoor photodegradation achieved an efficiency of 97.11%.Additionally,the degradation efficiency for methylene blue(MB)attained 98.26%.Meanwhile,the constructed superhydrophobic canvas exhibits excellent selective adsorption performance for water-insoluble floating pollutants such as cyclohexane.Based on the construction of a superhydrophobic interface and an S-scheme heterojunction,simultaneous oil-water separation and photocatalytic degradation are realized.Through Kelvin probe force microscopy(KPFM)and theoretical calculation analyses,the S-scheme charge transfer mechanism between KTaO_(3)and BiOI is systematically confirmed.This work shows broad application prospects in the treatment of oil-containing wastewater.
文摘Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min^(-1),which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e^(-))accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O_(2)^(·-),^(·)OH,and SO_(4)^(·-)) and non-radicals(such as ^(1)O_(2),h^(+),and e^(-)) were both presented in the Vis-CoOOH@COFs/PMS system,with O_(2)^(-) playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
基金support of the National Natural Science Foundation of China(22075131 and 22078265)the Shaanxi Fundamental Science Research Project for Mathematics and Physics under Grants(No.22JSZ005)the State-Key Laboratory of Multiphase Complex Systems(No.MPCS-2021-A).
文摘Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.
基金supported by the National Natural Science Foundation of China(Nos.62104045,52101213)Jiangsu Provincial Department of Science and Technology of China(No.BE2022426).
文摘As the chemical industry expands,the use of benzene,toluene,and xylene(collectively known as BTX)in industrial production has increased greatly.Meanwhile,the toxic nature and potential health hazards of BTX gases cannot be ignored due to low-concentration leaks underline the critical need for rapid and real-time monitoring of these gases.Chemiresistive metal oxide semiconductor(MOS)-based gas sensors,which are extensively used for gas detection in both industrial settings and everyday life,emerge as one of the optimal solutions for trace BTX detection.These sensors are highly valued for their high sensitivity and low detection limits.Nevertheless,the improvement of selectivity towards specific BTX gases to achieve efficient and precise detection still remains challenging.This review summarizes the chemiresistive MOS-based gas sensors designed for BTX detection,categorizing them based on the components of sensing materials-basically into three groups:single-component,single heterojunction,and multiple heterojunctions gas sensing materials.Further,the review proposes the future application prospects of chemiresistive MOS-based BTX gas sensors,with specific emphasis on their significance in promoting industrial safety and environmental monitoring.
基金Project supported by the Joints Fund of the National Natural Science Foundation of China(Grant No.U23A20349)the Young Scientists Fund of the National Natural Science Foundation of China(Grant Nos.62204126,62305171,62304113)。
文摘With the rapid advancement of optoelectronic technology,high-performance photodetectors are increasingly in demand in fields such as environmental monitoring,optical communication,and defense systems,where ultraviolet detection is critical.However,conventional semiconductor materials suffer from limited UV-visible detection capabilities owing to their narrow bandgaps and high dark currents.To address these challenges,wide-bandgap semiconductors have emerged as promising alternatives.Here,we fabricated a horizontally structured n–n heterojunction photodetector by growingβ-Ga_(2)O_(3) on Si–GaN via plasma-enhanced chemical vapor deposition.The device exhibits a self-powered photocurrent of 3.5 nA at zero bias,enabled by the photovoltaic effect of the space charge region.Under 254-nm and 365-nm illumination,it exhibits rectification behavior,achieving a responsivity of 0.475 m A/W(0 V,220??W/cm~2 at 254 nm)and 257.6 mA/W(-5 V),respectively.Notably,the photodetector demonstrates a high photocurrent-to-dark current ratio of 10~5 under-5-V bias,highlighting its potential for self-powered and high-performance UV detection applications.
基金financially supported by the National Natural Science Foundation of China(U21A20311,U24A2040,52171141,52272117)the Natural Science Foundation of Shandong Province(ZR2022JQ19)+3 种基金the Key Technology Research Project of Shandong Province(2023CXGC010202)the Taishan Industrial Experts Program(TSCX202306142)the Core Facility Sharing Platform of Shandong Universitythe Foundation of Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University。
文摘Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen batteries(LOBs)due to their poor OER performance,resulting from poor electrical conductivity and overly strong intermediate adsorption.In this work,fancy double heterojunctions on 1T/2H-MoS_(2)@Co_(3)S_(4)(1T/2H-MCS)were constructed derived from the charge donation from Co to Mo ions,thus inducing the phase transformation of Mo S_(2)from 2H to 1T.The unique features of these double heterojunctions endow the1T/2H-MCS with complementary catalysis during charging and discharging processes.It is worth noting that 1T-Mo S2@Co3S4could provide fast Co-S-Mo electron transport channels to promote ORR/OER kinetics,and 2H-MoS_(2)@Co_(3)S_(4)contributed to enabling moderate egorbital occupancy when adsorbed with oxygen-containing intermediates.On the basis,the Li_(2)O_(2)nucleation route was changed to solution and surface dual pathways,improving reversible deposition and decomposition kinetics.As a result,1T/2H-MCS cathodes exhibit an improved electrocatalytic performance compared with those of Co_(3)S_(4)and Mo S2cathodes.This innovative heterostructure design provides a reliable strategy to construct efficient transition metal sulfide catalysts by improving electrical conductivity and modulating adsorption toward oxygenated intermediates for LOBs.
基金supported by Natural Science Foundation of China(Nos.U23B20165 and 52170085)National Key R&D Program International Cooperation Project(No.2023YFE0108100)+1 种基金Key Project of Natural Science Foundation of Tianjin(No.21JCZDJC00320)Fundamental Research Funds for the Central Universities,Nankai University.
文摘Chlorinated antibiotics pose great challenges in efficient removal,while for the first time,this work greatly enhanced their electrocatalytic dechlorination performance by construction of non-noble metal Co_(3)O_(4)/g-C_(3)N_(4) heterojunctions to improve process cost-effectiveness.The Co_(3)O_(4)/g-C_(3)N_(4) heterojunction demonstrated an effective removal of 93.6%thiamphenicol(TAP)within 45 min,with the rate constant(0.0584 min^(-1))that was 2.4 and 2.8 times that of Co_(3)O_(4) and g-C_(3)N_(4) alone,respectively.The formation of heterojunctions facilitated electron transfer,enriched the electron density on Co_(3)O_(4),and enhanced the adsorption of pollutants as well as the desorption of degradation intermediates.The enhanced production of atomic hydrogen(H*)of Co_(3)O_(4)/g-C_(3)N_(4),which increased by 13.6-28.2 times,contributed more to pollutant removal(64.0%),much higher than that of Co_(3)O_(4)(37.3%)and g-C_(3)N_(4)(6.1%).The energy barrier for H_(2) formation on Co_(3)O_(4)/g-C_(3)N_(4)(0.75 eV)was higher than that on Co_(3)O_(4)(-1.84 eV),supporting that it could stabilize H*and inhibit the formation of H_(2).The Co_(3)O_(4)/g-C_(3)N_(4) heterojunction exhibited stable performance with less impact by pH and co-existing ions,and posed effectiveness for the dechlorination of typical chlorinated antibiotics.This study offers an efficient and sustainable strategy for constructing heterojunctions to enhance the performance of non-noble metal catalysts in electrocatalytic dechlorination.
基金supported by the Chinese Academy of Sciences Project for Young Scientists in Basic Research(Grant No.YSBR-049)the Innovation Program for Quantum Science and Technology(Grant No.2021ZD0302800)the Fundamental Research Funds for the Central Universities(Grant No.WK3510000013)。
文摘Recent advances in van der Waals(vdW) ferroelectrics have sparked the development of related heterostructures with non-volatile and field-tunable functionalities. In vdW ferroelectric heterojunctions, the interfacial electrical characteristics play a crucial role in determining their performance and functionality. In this study,we explore the interfacial polarization coupling in two-dimensional(2D) ferroelectric heterojunctions by fabricating a graphene/h-BN/CuInP_(2)S_(6)/α-In_(2)Se_(3)/Au ferroelectric field-effect transistor. By varying the gate electric field, the CuInP_(2)S_(6)/α-In_(2)Se_(3) heterojunction displays distinct interfacial polarization coupling states, resulting in significantly different electrical transport behaviors. Under strong gate electric fields, the migration of Cu ions further enhances the interfacial polarization effect, enabling continuous tuning of both the polarization state and carrier concentration in α-In_(2)Se_(3). Our findings offer valuable insights for the development of novel multifunctional devices based on 2D ferroelectric materials.
文摘The design of customized crystal plane heterojunction can effectively leverage the optimal anisotropic interaction of crystal plane,thereby enhancing photocatalytic activity.In this study,Co_(3)O_(4) exposed(111),(110),and(100)crystal planes(designated as HCO,NCO,and CCO,respectively)were synthesized and successfully coupled with Cd_(0.5)Zn_(0.5)S(CZS).Among these composites,the HCO/CZS exhibited best hydrogen evolution activity.In conjunction with DFT calculations and femtosecond transient absorption spectroscopy,it has been found that:the crystal plane interaction between HCO and CZS enabled the composite catalyst to exhibit optimal anisotropy in crystal plane carrier transport,crystal plane active sites,and crystal plane electronic structure.This interaction induces a redistribution of electrons at their contact interface,thereby establishing a built-in electric field that facilitates the formation of ohmic heterojunction between HCO and CZS.The synergistic effect of the ohmic heterojunction and crystal plane anisotropy not only decreases the Gibbs free energy of hydrogen adsorption but also facilitates the efficient spatial separation and rapid transfer of electron-hole pairs.This study offers valuable insights into the customization of crystal plane heterojunctions,aiming to maximize anisotropic interactions between crystal planes in order to enhance photocatalytic hydrogen evolution.
文摘The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In_(2)O_(3)is successfully achieved using an electrostatic self-assembly method.Under visible light irradiation,all CdS-In_(2)O_(3)composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs.Notably,the photocatalytic H_(2)evolution rate of the optimal CdS-7%In_(2)O_(3)composite is determined to be 2258.59μmol g^(−1)h^(−1),approximately 12.3 times higher than that of pure CdS.The cyclic test indicates that the CdS-In_(2)O_(3)composite maintains considerable activity even after 5 cycles,indicating its excellent stability.In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In_(2)O_(3)composites adheres to a typical S-scheme heterojunction mechanism.Additionally,a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In_(2)O_(3)and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs,thus achieving enhanced photocatalytic performance.This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H_(2)production and offers novel insights into the construction of effective composite photocatalysts.
基金supported by the National Natural Science Foundation of China (Nos.52072152 and 51802126)Jiangsu University Jinshan Professor Fund,Jiangsu Specially-Appointed Professor Fund,the Open Fund from Guangxi Key Laboratory of Electrochemical Energy Materials,Zhenjiang“Jinshan Talents”Project 2021,China PostDoctoral Science Foundation (No.2022M721372)+1 种基金the“Doctor of Entrepreneurship and Innovation”in Jiangsu Province (No.JSSCBS20221197)the Postgraduate Research&Practice Innovation Program of Jiangsu Province (No.KYCX22_3645).
文摘In the quest for effective solutions to address Environ.Pollut.and meet the escalating energy demands,heterojunction photocatalysts have emerged as a captivating and versatile technology.These photocatalysts have garnered significant interest due to their wideranging applications,including wastewater treatment,air purification,CO_(2) capture,and hydrogen generation via water splitting.This technique harnesses the power of semiconductors,which are activated under light illumination,providing the necessary energy for catalytic reactions.With visible light constituting a substantial portion(46%)of the solar spectrum,the development of visible-light-driven semiconductors has become imperative.Heterojunction photocatalysts offer a promising strategy to overcome the limitations associated with activating semiconductors under visible light.In this comprehensive review,we present the recent advancements in the field of photocatalytic degradation of contaminants across diverse media,as well as the remarkable progress made in renewable energy production.Moreover,we delve into the crucial role played by various operating parameters in influencing the photocatalytic performance of heterojunction systems.Finally,we address emerging challenges and propose novel perspectives to provide valuable insights for future advancements in this dynamic research domain.By unraveling the potential of heterojunction photocatalysts,this reviewcontributes to the broader understanding of their applications and paves the way for exciting avenues of exploration and innovation.
文摘Inefficient photo-carrier separation and sluggish photoreaction dynamics appreciably undermine the photocatalytic decontamination efficacy of photocatalysts.Herein,an S-scheme Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)heterojunction with interfacial Mo-S chemical bond is designed as an efficient photocatalyst.In this integrated photosystem,Bi2MoO6 and Mn_(0.5)Cd_(0.5)S function as oxidation and reduction centers of Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)microspheres,respectively.Importantly,the unique charge transfer mechanism in the chemically bonded S-scheme heterojunction with Mo-S bond as atom-scale charge transport highway effectively inhibits the photocorrosion of Mn_(0.5)Cd_(0.5)S and the recombination of photo-generated electron-hole pairs,endowing Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)photocatalyst with excellent photocatalytic decontamination performance and stability.Besides,integration of Mn_(0.5)Cd_(0.5)S nanocrystals into Bi2MoO6 improves hydrophilicity,conducive to the photoreactions.Strikingly,compared with Mn_(0.5)Cd_(0.5)S and Bi2MoO6,the Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)unveils much augmented photoactivity in tetracycline eradication,among which Mn_(0.5)Cd_(0.5)S/Bi_(2)MoO_(6)-2 possesses the highest activity with the rate constant up to 0.0323 min-1,prominently outperforming other counterparts.This research offers a chemical bonding engineering combining with S-scheme heterojunction strategy for constructing extraordinary photocatalysts for environmental purification.
基金supported by the National Natural Science Foundation of China(22302019)the Changzhou Sci&Tech Program(CJ20220214).
文摘It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for electrocatalytic HMF oxidative reaction(e-HMFOR)have been facing low Faradaic efficiency(FE)and high water splitting voltage.Herein,we propose a strategy of the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction by constructing a Co-Ni paired site,where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site,thus giving the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction superior electrocata lytic performances for e-HMFOR and water splitting.By optimizing conditions,the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction has high conversion of 99.7%,high selectivity of 99.9%,and high FE of 98.4%at 1.3 V,as well as low cell voltage of 1.31 V at 10 mA cm^(-2)in 1 M KOH+0.1 M HMF.This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H_(2)in an economical manner.
基金financially supported by the Program for the Development of Science and Technology of Jilin Province(Nos.20240601047RC and YDZJ202201ZYTS629)Hainan Province Science and Technology Special Fund(No.ZDYF2022SHFZ090)+1 种基金the National Natural Science Foundation(Nos.22466017 and 22061014)the specific research fund of the Innovation Platform for Academicians of Hainan Province。
文摘The goal of photocatalytic CO_(2)reduction is to obtain a single energy-bearing product with high efficiency and stability.Consequently,constructing highly selective photocatalysts with enhanced surface and optoelectronic properties is crucial for achieving this objective.Here,we have developed a simple one-pot vulcanization method to synthesize a MIL-68(In)-derived Cd In_(2)S_(4)/In_(2)S_(3)heterojunction that exhibited stable and high selectivity.Multiple characterizations of the Cd In_(2)S_(4)/In_(2)S_(3)heterojunction revealed a hierarchical tubular structure with numerous surface reactive sites,a high visible-light utilization rate(λ<600 nm),efficient charge separation,and a prolonged charge-carrier lifetime.Moreover,an S-scheme charge transfer mechanism,based on the interleaved band between the two components,improved the reduction capability of the electrons.Benefiting from the compositional and structural synergy,the yield CO by Cd In_(2)S_(4)/In_(2)S_(3)-250(CI-250)reached 135.62μmol·g^(-1)·h^(-1),which was 49.32 times and 32.88 times higher than that of In_(2)S_(3)and Cd In_(2)S_(4),respectively.The Cd In_(2)S_(4)/In_(2)S_(3)heterojunction exhibited a quantum efficiency of 4.23%with a CO selectivity of 71%.Four cycle tests confirmed the good stability and recyclability of the CI-250.This work provides a new approach for designing and preparing high-performance hollow MOFsbased photocatalysts for scalable and sustainable CO_(2)reduction.
基金financially supported by the National Natural Science Foundation of China(No.22068007).
文摘In photocatalysis field,S-scheme heterojunctions show unique advantages and prospects.However,the carrier shielding effect of heterojunctions limits the separation and migration of interfacial charges.In this study,a strategy of“dynamic cascade electric fields to deplete unilaterally accumulated charges”was innovatively proposed to overcome this drawback.By modulating g-C_(3)N_(4)(CN)and Bi_(2)WO_(6)(BWO)using the polarized electric field(PEF)of spontaneously polarized ceramic(SPC),a BWO/SPC-CN composite with cascade internal electric field(IEF)and PEF was successfully constructed for efficient piezophotocatalytic degradation of recalcitrant pollutants.BWO/SPC-CN contributed to 96.8% degradation of carbamazepine,significantly surpassing BWO/CN(70.5%).BWO/SPC-CN performed excellent capacity of harvesting piezoelectric energy due to its unique three-dimensional porous nano-network structure.The PEF of SPC modulated the electronic band structure and thus strengthened the IEF of BWO/SPC-CN,providing a persistent driving force for interfacial charge migration.Moreover,SPC with a strong PEF unilaterally consumed the charges accumulated on CN under periodic piezoelectricity,weakening the shielding electric field to inhibit the recombination of electron-hole pairs.As a consequence,the dynamic cascade PEF-IEF ultimately broke the carrier shielding effect in heterojunction photocatalysis and enhanced interfacial electron transfer.This work provides reliable methods to enhance the interfacial charge transfer in heterojunction and new insights into piezo-photocatalytic mechanism.
