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
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
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
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
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
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
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
Coatings of marine equipment inevitably suffer from physical or chemical damage in service,together with biofouling from microbial attachment,leading to a shorter service life of them.Herein,a multi-functional corrosi...Coatings of marine equipment inevitably suffer from physical or chemical damage in service,together with biofouling from microbial attachment,leading to a shorter service life of them.Herein,a multi-functional corrosion-resistant coating with efficient photothermal self-healing and anti-biofouling per-formance was designed by using CuO/g-C_(3)N_(4)(CuO/CN)S-scheme heterojunction filler in combination with polydimethylsiloxane(PDMS)as the coating matrix for achieving the effective protection of Q235 steel.The results of the electrochemical impedance spectroscopy(EIS)experiments indicate that the CuO/CN/PDMS composite coatings possessed excellent corrosion resistance,in which the impedance ra-dius of optimal CuO/CN-1/PDMS composite coating could still remain 3.49×10^(9)Ωcm^(2)after 60 d of immersion in seawater under sunlight irradiation.Meanwhile,the as-prepared CuO/CN/PDMS compos-ite coating not only can be rapidly heated up under the Xenon lamp illumination to achieve complete self-repair of scratches within 45 min,but also exhibited excellent antimicrobial effects in the antifouling experiments.This study opens a new avenue for the development of g-C_(3)N_(4)-based multifunctional coat-ings and provides guidance for the development of the next generation of intelligent protective coatings.展开更多
Composite solid electrolytes(CSEs)are considered among the most promising candidates for solid-state batteries.However,their practical application is hindered by low ionic conductivity and a limited lithium-ion transf...Composite solid electrolytes(CSEs)are considered among the most promising candidates for solid-state batteries.However,their practical application is hindered by low ionic conductivity and a limited lithium-ion transference number,primarily owing to the insufficient mobility of Li+.In this work,we design a heterojunc-tion nanoparticle composed of bimetallic zeolitic imidazolate frameworks(ZIFs)coupled with amorphous tita-nium oxide(TiO_(2)@Zn/Co–ZIF)as a filler to fabricate a composite solid-state electrolyte(PVZT).The amor-phous TiO_(2) coating facilitates salt dissociation through Lewis acid–base interactions with the anions of the lithium salt.Meanwhile,the Zn/Co–ZIF framework not only provides additional selective pathways for Li+transport but also effectively restricts anion migration through its confined pore size.The synergistic effect results in a high room-temperature ionic conductivity(8.8×10^(-4) S·cm^(-1))and a lithium-ion transference number of 0.47 for PVZT.A symmetrical cell using PVZT demonstrates stable Li+deposition/stripping for over 1100 h at a current density of 0.1 mA·cm^(-2).Additionally,a LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li full cell using PVZT retains 75.0%of its capacity after 1200 cycles at a 2 C rate.This work offers valuable insights into the design of func-tional fillers for CSEs with highly efficient ion transport.展开更多
S-scheme heterojunctions have gained widespread application in photocatalytic reactions due to their dis-tinctive carrier transport mechanism and remarkable redox capabilities.However,a significant challenge persists ...S-scheme heterojunctions have gained widespread application in photocatalytic reactions due to their dis-tinctive carrier transport mechanism and remarkable redox capabilities.However,a significant challenge persists in extending carrier lifetimes while simultaneously enhancing light absorption,both of which are essential for optimizing photocatalytic activity.Herein,we report the solvothermal synthesis of ul-trathin CdS nanosheets grown in situ on two-dimensional(2D)Ni-MOF to construct 2D/2D S-scheme heterojunctions.Comprehensive characterizations reveal that the incorporation of Ni-MOF(metal-organic framework)with ligand-to-metal charge transfer(LMCT)states not only broadens optical absorption but also significantly prolongs carrier lifetimes.This synergistic enhancement,coupled with the S-scheme charge transport mechanism,enables the composite to function as a bifunctional catalyst for photocat-alytic hydrogen production and simultaneous benzylamine coupling.The optimal system demonstrates an impressive hydrogen evolution rate of 8.5 mmol g^(-1) h^(-1) and an N-benzylidenebenzylamine yield of 4.6 mmol g^(-1) h^(-1) without requiring a cocatalyst.This work underscores the potential of integrating MOFs with LMCT states into S-scheme heterojunctions to enhance interfacial charge transfer,offering valuable insights for the design of S-scheme heterojunctions for artificial photosynthesis and related fields.展开更多
Fenton method combined with light to accelerate the production of free radicals from H2O2 can achieve more efficient pollutant degradation.In this paper,a novel BiOI/FeWO4 S-scheme heterojunction photocatalyst was obt...Fenton method combined with light to accelerate the production of free radicals from H2O2 can achieve more efficient pollutant degradation.In this paper,a novel BiOI/FeWO4 S-scheme heterojunction photocatalyst was obtained by in situ synthesis,which can activate H2O2 and degrade the organic pollutant OFC(ofloxacin)under visible light.The S-scheme charge transfer mechanism was confirmed by XPS spectroscopy,in situ KPFM and theoretical calculation.The photogenerated electrons were transferred from FeWO4 to BiOI driven by the built-in electric field and band bending,which inhibited carrier recombination and facilitated the activation of H2O2.The BiFe-5/Vis/H2O2 system degraded OFC up to 96.4%in 60 min.This study provides new systematic insights into the activation of H2O2 by S-scheme heterojunctions,which is of great significance for the treatment of antibiotic wastewater.展开更多
We have developed a novel S-scheme heterojunction photocatalyst for the photocatalytic production of hydrogen peroxide(H_(2)O_(2))via a two-electron(2e^(-))oxygen reduction reaction.This S-scheme heterojunction Tph-Dh...We have developed a novel S-scheme heterojunction photocatalyst for the photocatalytic production of hydrogen peroxide(H_(2)O_(2))via a two-electron(2e^(-))oxygen reduction reaction.This S-scheme heterojunction Tph-Dha-COF@Nb_(2)C was fabricated via the in-situ solvothermal growth of Tph-Dha-COF nanostructures on amino-functionalized Nb_(2)C MXene nanoflakes(Nb_(2)C-NH_(2)).The integration of Nb_(2)C significantly extended the visible light absorption of Tph-Dha-COF into the near-infrared region for photocatalytic H_(2)O_(2) production.The Tph-Dha-COF@Nb_(2)C composite demonstrated efficient charge separation,rapid electron transfer,and enhanced oxygen adsorption.Consequently,the Tph-Dha-COF@Nb_(2)C heterojunction exhibited a high H_(2)O_(2) production rate of 1833μmol g^(-1) h^(-1) without sacrificial agents.In-situ Fourier transformed infrared spectroscopy and density functional theory calculations revealed the photocatalytic H_(2)O_(2) production mechanism.The generated H_(2)O_(2) demonstrated enhanced antibacterial activity.This work presents the first application of Nb_(2)C in the photocatalytic synthesis of H_(2)O_(2) and provides a novel strategy for constructing COF-based heterojunctions for photocatalytic H_(2)O_(2) generation and wastewater treatment.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
Photo-assisted Li–O_(2)batteries present a promising avenue for reducing overpotential and enhancing the capacity of next-generation energy storage devices.In this study,we introduce a novel photo-assisted Li–O_(2)s...Photo-assisted Li–O_(2)batteries present a promising avenue for reducing overpotential and enhancing the capacity of next-generation energy storage devices.In this study,we introduce a novel photo-assisted Li–O_(2)system featuring a Z-scheme In_(2)S_(3)/MnO_(2)/BiOCl heterojunction as a photocathode.This innovative design significantly boosts visible light absorption and facilitates the spatial separation of photogenerated electron-hole pairs.The Z-scheme charge transfer pathway establishes efficient channels for enhancing electron transfer and charge separation,thereby fostering high photocatalytic efficiency.During illumination,photo-generated electrons traverse within the band structure,participating in the Oxygen Reduction Reaction(ORR)during discharging,while photo-induced holes in the valence band facilitate the oxidation reaction of discharge products during the charging process.Under illumination,the surface electrons of In_(2)S_(3)/MnO_(2)/BiOCl modify the morphology of the discharge product(Li_(2)O_(2)),leading to accelerated decomposition kinetics of Li_(2)O_(2)during charging.Remarkably,the In_(2)S_(3)/MnO_(2)/BiOCl photoelectrode exhibits a high specific capacity of 19330 mAh/g under illumination,surpassing performance in the dark by a significant margin.This results in an ultranarrow discharge/charge overpotential of 0.19/0.16 V,coupled with excellent cyclic stability and a long cycle life of 1500 h at 200 mA/g.Further surface tests on the photoelectrode demonstrate that light energy application promotes the decomposition of Li_(2)O_(2),corroborated by density function theory(DFT)theoretical calculations.This study of Z-scheme heterostructured photocathodes sheds light on the mechanism of photo-generated charge carriers in Li–O_(2)batteries,providing valuable insights into their functionality and potential for future battery technologies.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.
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 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.
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(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.
基金supported by the National Natural Science Foundation of China(Nos.22006057 and 21906072)the China Postdoctoral Science Foundation(No.2023M743178)+2 种基金the Jiangsu Province Industry-University-Research Cooperation Project(No.BY20231482)the Open Fund of the Key Laboratory of Solar Cell electrode Materials in China Petroleum,Chemical Industry(No.2024A093)the Key Laboratory of Functional Inorganic Mate-rial Chemistry(Heilongjiang University),Ministry of Education and Postgraduate Research&Practice Innovation Program of Jiangsu Province(China)(No.SJCX24_2481).
文摘Coatings of marine equipment inevitably suffer from physical or chemical damage in service,together with biofouling from microbial attachment,leading to a shorter service life of them.Herein,a multi-functional corrosion-resistant coating with efficient photothermal self-healing and anti-biofouling per-formance was designed by using CuO/g-C_(3)N_(4)(CuO/CN)S-scheme heterojunction filler in combination with polydimethylsiloxane(PDMS)as the coating matrix for achieving the effective protection of Q235 steel.The results of the electrochemical impedance spectroscopy(EIS)experiments indicate that the CuO/CN/PDMS composite coatings possessed excellent corrosion resistance,in which the impedance ra-dius of optimal CuO/CN-1/PDMS composite coating could still remain 3.49×10^(9)Ωcm^(2)after 60 d of immersion in seawater under sunlight irradiation.Meanwhile,the as-prepared CuO/CN/PDMS compos-ite coating not only can be rapidly heated up under the Xenon lamp illumination to achieve complete self-repair of scratches within 45 min,but also exhibited excellent antimicrobial effects in the antifouling experiments.This study opens a new avenue for the development of g-C_(3)N_(4)-based multifunctional coat-ings and provides guidance for the development of the next generation of intelligent protective coatings.
基金supported by National Science Fund for Distinguished Young Scholars(Grant No.52325206)National Key Research and Development Program of China(Grant No.2021YFF0500600)+3 种基金National Natural Science Foundation of China(Grant Nos.U2001220 and 52203298)Shenzhen Technical Plan Project(Grant Nos.RCJC20200714114436091,JCYJ20220530143012027,JCYJ20220818101003008,and JCYJ20220818101003007)Tsinghua Shenzhen International Graduate School-Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(Grant No.SZPR2023006)Shenzhen Science and Technology Program(Grant No.WDZC20231126160733001).
文摘Composite solid electrolytes(CSEs)are considered among the most promising candidates for solid-state batteries.However,their practical application is hindered by low ionic conductivity and a limited lithium-ion transference number,primarily owing to the insufficient mobility of Li+.In this work,we design a heterojunc-tion nanoparticle composed of bimetallic zeolitic imidazolate frameworks(ZIFs)coupled with amorphous tita-nium oxide(TiO_(2)@Zn/Co–ZIF)as a filler to fabricate a composite solid-state electrolyte(PVZT).The amor-phous TiO_(2) coating facilitates salt dissociation through Lewis acid–base interactions with the anions of the lithium salt.Meanwhile,the Zn/Co–ZIF framework not only provides additional selective pathways for Li+transport but also effectively restricts anion migration through its confined pore size.The synergistic effect results in a high room-temperature ionic conductivity(8.8×10^(-4) S·cm^(-1))and a lithium-ion transference number of 0.47 for PVZT.A symmetrical cell using PVZT demonstrates stable Li+deposition/stripping for over 1100 h at a current density of 0.1 mA·cm^(-2).Additionally,a LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li full cell using PVZT retains 75.0%of its capacity after 1200 cycles at a 2 C rate.This work offers valuable insights into the design of func-tional fillers for CSEs with highly efficient ion transport.
基金financially supported by the National Key Re-search and Development Program of China(Nos.2022YFB3803600 and 2022YFE0115900)the National Natural Science Foundation of China(Nos.U24A2071,22278324,22238009,22361142704,22202187,and U23A20102)+1 种基金the National Science Foundation of Hubei Province of China(No.2022CFA001)Key R&D Program Projects in Hubei Province(No.2023BAB113).
文摘S-scheme heterojunctions have gained widespread application in photocatalytic reactions due to their dis-tinctive carrier transport mechanism and remarkable redox capabilities.However,a significant challenge persists in extending carrier lifetimes while simultaneously enhancing light absorption,both of which are essential for optimizing photocatalytic activity.Herein,we report the solvothermal synthesis of ul-trathin CdS nanosheets grown in situ on two-dimensional(2D)Ni-MOF to construct 2D/2D S-scheme heterojunctions.Comprehensive characterizations reveal that the incorporation of Ni-MOF(metal-organic framework)with ligand-to-metal charge transfer(LMCT)states not only broadens optical absorption but also significantly prolongs carrier lifetimes.This synergistic enhancement,coupled with the S-scheme charge transport mechanism,enables the composite to function as a bifunctional catalyst for photocat-alytic hydrogen production and simultaneous benzylamine coupling.The optimal system demonstrates an impressive hydrogen evolution rate of 8.5 mmol g^(-1) h^(-1) and an N-benzylidenebenzylamine yield of 4.6 mmol g^(-1) h^(-1) without requiring a cocatalyst.This work underscores the potential of integrating MOFs with LMCT states into S-scheme heterojunctions to enhance interfacial charge transfer,offering valuable insights for the design of S-scheme heterojunctions for artificial photosynthesis and related fields.
基金supported by the National Key Research and Development Program of China(2020YFD1100501)Thanks zkec(www.zjkec.cc)for XRD.
文摘Fenton method combined with light to accelerate the production of free radicals from H2O2 can achieve more efficient pollutant degradation.In this paper,a novel BiOI/FeWO4 S-scheme heterojunction photocatalyst was obtained by in situ synthesis,which can activate H2O2 and degrade the organic pollutant OFC(ofloxacin)under visible light.The S-scheme charge transfer mechanism was confirmed by XPS spectroscopy,in situ KPFM and theoretical calculation.The photogenerated electrons were transferred from FeWO4 to BiOI driven by the built-in electric field and band bending,which inhibited carrier recombination and facilitated the activation of H2O2.The BiFe-5/Vis/H2O2 system degraded OFC up to 96.4%in 60 min.This study provides new systematic insights into the activation of H2O2 by S-scheme heterojunctions,which is of great significance for the treatment of antibiotic wastewater.
文摘We have developed a novel S-scheme heterojunction photocatalyst for the photocatalytic production of hydrogen peroxide(H_(2)O_(2))via a two-electron(2e^(-))oxygen reduction reaction.This S-scheme heterojunction Tph-Dha-COF@Nb_(2)C was fabricated via the in-situ solvothermal growth of Tph-Dha-COF nanostructures on amino-functionalized Nb_(2)C MXene nanoflakes(Nb_(2)C-NH_(2)).The integration of Nb_(2)C significantly extended the visible light absorption of Tph-Dha-COF into the near-infrared region for photocatalytic H_(2)O_(2) production.The Tph-Dha-COF@Nb_(2)C composite demonstrated efficient charge separation,rapid electron transfer,and enhanced oxygen adsorption.Consequently,the Tph-Dha-COF@Nb_(2)C heterojunction exhibited a high H_(2)O_(2) production rate of 1833μmol g^(-1) h^(-1) without sacrificial agents.In-situ Fourier transformed infrared spectroscopy and density functional theory calculations revealed the photocatalytic H_(2)O_(2) production mechanism.The generated H_(2)O_(2) demonstrated enhanced antibacterial activity.This work presents the first application of Nb_(2)C in the photocatalytic synthesis of H_(2)O_(2) and provides a novel strategy for constructing COF-based heterojunctions for photocatalytic H_(2)O_(2) generation and wastewater treatment.
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funded by the Natural Science Project of the Zhengzhou Science and Technology Bureau(No.22ZZRDZX04).
文摘Photo-assisted Li–O_(2)batteries present a promising avenue for reducing overpotential and enhancing the capacity of next-generation energy storage devices.In this study,we introduce a novel photo-assisted Li–O_(2)system featuring a Z-scheme In_(2)S_(3)/MnO_(2)/BiOCl heterojunction as a photocathode.This innovative design significantly boosts visible light absorption and facilitates the spatial separation of photogenerated electron-hole pairs.The Z-scheme charge transfer pathway establishes efficient channels for enhancing electron transfer and charge separation,thereby fostering high photocatalytic efficiency.During illumination,photo-generated electrons traverse within the band structure,participating in the Oxygen Reduction Reaction(ORR)during discharging,while photo-induced holes in the valence band facilitate the oxidation reaction of discharge products during the charging process.Under illumination,the surface electrons of In_(2)S_(3)/MnO_(2)/BiOCl modify the morphology of the discharge product(Li_(2)O_(2)),leading to accelerated decomposition kinetics of Li_(2)O_(2)during charging.Remarkably,the In_(2)S_(3)/MnO_(2)/BiOCl photoelectrode exhibits a high specific capacity of 19330 mAh/g under illumination,surpassing performance in the dark by a significant margin.This results in an ultranarrow discharge/charge overpotential of 0.19/0.16 V,coupled with excellent cyclic stability and a long cycle life of 1500 h at 200 mA/g.Further surface tests on the photoelectrode demonstrate that light energy application promotes the decomposition of Li_(2)O_(2),corroborated by density function theory(DFT)theoretical calculations.This study of Z-scheme heterostructured photocathodes sheds light on the mechanism of photo-generated charge carriers in Li–O_(2)batteries,providing valuable insights into their functionality and potential for future battery technologies.
