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
Rational engineering of semiconductor photocatalysts for efficient hydrogen production is of great significance but still challenging,primarily due to the limitations in charge transfer kinetics.Herein,a fascinating p...Rational engineering of semiconductor photocatalysts for efficient hydrogen production is of great significance but still challenging,primarily due to the limitations in charge transfer kinetics.Herein,a fascinating plasmonic tandem heterojunction with the hc-CdS/Mo_(2)C@C heterostructure is aimfully prepared for effectively promoting the charge separation kinetics of the CdS photocatalyst via the synergistic strategy of phase junction,Schottky junction,and photothermal effect.The difference in atomic configuration between cubic-CdS (c-CdS) and hexagonal-CdS (h-CdS) leads to effective charge separation through a typical Ⅱ charge transfer mechanism,and plasmonic Schottky junction further extracts the electrons in the hc-CdS phase junction to realize gradient charge transfer.Besides,the photothermal effect of Mo_(2)C@C helps to expand the light absorption,accelerate charge transfer kinetics,and reduce the hydrogen evolution energy barrier.The carbon layer provides a fast channel for charge transfer and protects the photocatalyst from photocorrosion.As a result,the optimized hc-CMC photocatalyst exhibits a significantly high photocatalytic H_(2)production activity of 28.63 mmol/g/h and apparent quantum efficiency of 61.8%,surpassing most of the reported photocatalysts.This study provides a feasible strategy to enhance the charge transfer kinetics and photocatalytic activity of CdS by constructing plasmonic tandem heterogeneous junctions.展开更多
Rare earth metal ferrites-based heterojunctions have garnered significant attention in recent years due to their exceptional photocatalytic properties and potential applications in water treatment and energy conversio...Rare earth metal ferrites-based heterojunctions have garnered significant attention in recent years due to their exceptional photocatalytic properties and potential applications in water treatment and energy conversion.The incorporation of rare earth metal ferrites into heterojunction photocatalytic systems enhances light absorption,charge separation and photocatalytic efficiency.This review comprehensively discusses some common types of rare earth metal ferrites such as LaFeO_(3),GdFeO_(3),SmFeO_(3),PrFeO_(3)and CeFeO_(3)and their properties as photocatalysts.The photocatalytic pollutants removal and energy conversion mechanisms are discussed in detail and various types of heterojunctions reported in literature based on rare earth metal ferrites and their synthetic routes are also explored.The recent key findings and advances in the heterojunctions based on these rare earth metal ferrites for the pollutants removal and energy conversion applications are summarized.Despite notable progress in enhancing photocatalytic efficiency and stability,several challenges remain.Current research highlights improvements in material synthesis and performance,but issues such as high production costs,scalable synthesis and limited long-term stability persist.Future directions should focus on exploring uncharted applications,novel material combinations and enhancing the practical implementation of these heterojunctions to fully exploit their potential in environmental and energy technologies.展开更多
There is limited research reported on the multiple loss mechanism of electromagnetic waves(EMW)and the development of interface models.Dielectric loss and magnetic loss,as the two primary attenuation mechanisms in EMW...There is limited research reported on the multiple loss mechanism of electromagnetic waves(EMW)and the development of interface models.Dielectric loss and magnetic loss,as the two primary attenuation mechanisms in EMW absorbers,still pose challenges,especially in elucidating the correlation between composition,morphology,interface,and performance.Here,we construct 3D hierarchical porous conducting network structures and Schottky heterojunctions(MoNi_(4)@NC-NiFe_(2)O_(4)@NC)with a high density of defects,using trimetallic NiMoFe-MOFs.Synergistic enhancement of the dielectric and magnetic losses is realized through manipulation of the defects,interfaces,phase engineering,and magnetic resonance.In particular,the even dispersion of magnetic MoNi_(4) and NiFe_(2)O_(4)nanoparticles(NPs)within the carbon matrix triggers the creation of multiple heterogeneous interfaces.These inseparable interfaces,along with oxygen vacancies,play a role in enhancing dielectric polarization,while the closely spaced interactions among magnetic units contribute to magnetic loss.After optimizing the interfacial structure,NiFe_(2)O_(4)/MoNi_(4)-NC exhibits remarkable EMW absorption properties.A reflection loss(RL)value of-67.91 dB can be achieved at an ultra-thin thickness of 1.95 mm,and the effective absorption bandwidth(EAB,RL≤-10 dB)is as high as 5.76 GHz.Furthermore,we conducted radar scattering cross-section(RCS)simulations using computer simulation technology(CST)software,which revealed that NiFe_(2)O_(4)/MoNi_(4)-NC exhibits an RCS reduction value of 39.1 dB m^(2).Hence,this work provides comprehensive guidance for the construction of Schottky heterojunctions for lightweight EMW absorbers from a mechanistic point of view.展开更多
Efficient photocatalytic water splitting can be significantly enhanced through the careful design of S-scheme heterostructures,which play a pivotal role in optimizing performance.Herein,we report the construction of Z...Efficient photocatalytic water splitting can be significantly enhanced through the careful design of S-scheme heterostructures,which play a pivotal role in optimizing performance.Herein,we report the construction of ZnIn_(2)S_(4)/CdS S-scheme heterojunctions under ambient conditions,based on a sonochemical strategy.This structure is facilitated by the well-matched interface between the(007)plane of layered ZnIn_(2)S_(4)and the(101)plane of CdS,leading to a threshold optical response of 2.12 eV,which optimally aligns with visible light absorption.As a proof of concept,the resulting ZnIn_(2)S_(4)/CdS catalysts demonstrate a remarkable improvement in photocatalytic H_(2) evolution,achieving a rate of 5678.2μmol h^(-1)g^(-1)under visible light irradiation(λ>400 nm).This rate is approximately 10 times higher than that of pristine ZnIn_(2)S_(4)nanosheets(NSs)and about 4.6 times higher than that of CdS nanoparticles(NPs),surpassing the performance of most ZnIn_(2)S_(4)-based photocatalysts reported to date.Moreover,they deliver a robust photocatalytic performance during long-term operation of up to 60 h,showing their potential for use in practical applications.Based on the theoretical calculation and experimental results,it is verified that the movements of electrons and holes in the opposite direction could be induced by the disparity in the work function and the internal electric field within the interfaces,thus facilitating the construction of S-scheme heterojunctions,which fundamentally suppresses carrier recombination while minimizing photocorrosion of ZnIn_(2)S_(4)toward enhanced photocatalytic behaviors.展开更多
In this work,BiOCl/OVs-BiPO_(4)heterojunction photocatalysts were successfully in-situ prepared by treating of BiPO_(4)with dilute hydrochloric acid(HCl)under hydrothermal condition.Systematically characterization res...In this work,BiOCl/OVs-BiPO_(4)heterojunction photocatalysts were successfully in-situ prepared by treating of BiPO_(4)with dilute hydrochloric acid(HCl)under hydrothermal condition.Systematically characterization results confirm that BiOCl/BiPO_(4)heterojunctions have been successfully in-situ constructed and oxygen vacancies(OVs)are significantly increased.The OVs on the surface of the BiOCl/OVS-BiPO_(4)heterojunctions photocatalyst and the interface electric field at the interface of the heterojunctions effectively accelerate the separation and migration of photogenerated carriers,and the surface OVs provide more sites for adsorption and reaction.Consequently,BiOCl/OVs-BiPO_(4)heterojunction photocatalysts have higher separation rate of photoexcited e-/h+pairs and exhibit ascendant photocatalytic degradation activity.Electron paramagnetic resonance(EPR)technology and free radical capture experiments give strong evidence that·O2-exists in the reaction system and is the leading species during the degradation process.The experimental results reveal that the degradation efficiency of rhodamine B(RhB)over BiPO_(4)treated with 3 ml of 0.1%dilute hydrochloric acid(3HCl-BPO)is 2.42 times of that over the reference BiPO_(4).After ultraviolet(UV)light illumination for 20 min,the destruction degree of RhB on the 3HCl-BPO sample reaches 99%.Moreover,the degradation rate of tetracycline(TC)is also obviously improved over 3HCl-BPO compared with that on the reference BiPO_(4)after 40 min exposure to ultraviolet light.The excellent stability of the sample was demonstrated by five cycles.A reasonable enhancement mechanism for BiOCl/OVs-BiPO_(4)heterojunctions was proposed to elucidate the boosted photocatalytic performance.This work offers a facile and reliable reference to design high performance BiPO_(4)-based photocatalysts for environment purification.展开更多
Low-concentration acetone detection is of great importance for acetone sensor in the fields of environmental protection and noninvasive diagnosis.In this work,mesoporous Fe_(2)O_(3)/Cr_(2)O_(3)n-p heterojunctions were...Low-concentration acetone detection is of great importance for acetone sensor in the fields of environmental protection and noninvasive diagnosis.In this work,mesoporous Fe_(2)O_(3)/Cr_(2)O_(3)n-p heterojunctions were constructed for efficient improvement of low-concentration acetone gas sensing.The gas-sensing results indicated that the mesoporous Fe_(2)O_(3)/Cr_(2)O_(3)composites with a significantly large specific surface area exhibited significantlyenhanced acetone gas-sensitive performance compared to pure Fe_(2)O_(3).The Fe_(2)O_(3)/Cr_(2)O_(3)composites demonstrated a high response,good selectivity and excellent stability over200 days to 10 ppm acetone at 220℃.And the theoretical detection limit was calculated to reach 0.285 ppm acetone.A feasible acetone sensing mechanism was proposed through electronic band structure and density functional theory.The improved low-concentration acetone sensing performance was due to the formed mesoporous Fe_(2)O_(3)/Cr_(2)O_(3)n-p heterojunctions with a large specific surface area.The Fe_(2)O_(3)/Cr_(2)O_(3)composites showed excellent acetone gas-sensitive performance,which could be a promising candidate for developing low-concentration acetone sensing devices at low working temperatures.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
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
BiVO_(4)porous spheres modified by ZnO were designed and synthesized using a facile two-step method.The resulting ZnO/BiVO_(4)composite catalysts have shown remarkable efficiency as piezoelectric catalysts for degradi...BiVO_(4)porous spheres modified by ZnO were designed and synthesized using a facile two-step method.The resulting ZnO/BiVO_(4)composite catalysts have shown remarkable efficiency as piezoelectric catalysts for degrading Rhodamine B(RhB)unde mechanical vibrations,they exhibit superior activity compared to pure ZnO.The 40wt%ZnO/BiVO_(4)heterojunction composite displayed the highest activity,along with good stability and recyclability.The enhanced piezoelectric catalytic activity can be attributed to the form ation of an I-scheme heterojunction structure,which can effectively inhibit the electron-hole recombination.Furthermore,hole(h+)and superoxide radical(·O_(2)^(-))are proved to be the primary active species.Therefore,ZnO/BiVO_(4)stands as an efficient and stable piezoelectric catalyst with broad potential application in the field of environmental water pollution treatment.展开更多
The rapid development of rare earth metal elements in the field of photocatalysis is due to their excellent optical and physicochemical properties.Benefiting from the unique external electronic structure of 4f_15d_16S...The rapid development of rare earth metal elements in the field of photocatalysis is due to their excellent optical and physicochemical properties.Benefiting from the unique external electronic structure of 4f_15d_16S_2,superior electronegativity of the 4f orbitals,and strong oxygen storage-release ability in Ce^(4+)/Ce^(3+)reversible pairs,cerium dioxide(CeO_(2))has attracted increasing interest from scientists.Nevertheless,the fast recombination of photoinduced electron-hole pairs and wide energy band gap of bare CeO_(2)significantly limit its practical applications.To overcome the above drawbacks,the construction of heterojunctions has been developed to broaden the absorption spectrum and accelerate the charge transfer.This review presents a mini-review of the synthesis of CeO_(2)-based heterojunctions including typeⅡ,Z-scheme,and S-scheme photocatalysts,as well as the corresponding applications in photocatalytic bactericidal and antitumor therapy.Finally,the latest advancements and potential perspectives on their future development are also discussed.展开更多
The rising global energy demand and climate crisis have intensified the need for sustainable technologies to mitigate carbon emissions while enabling renewable energy conversion.Photocatalysis,particularly using solar...The rising global energy demand and climate crisis have intensified the need for sustainable technologies to mitigate carbon emissions while enabling renewable energy conversion.Photocatalysis,particularly using solar energy,has emerged as a promising green solution for hydrogen production and CO_(2)reduction.Among various semiconductor photocatalysts,cerium oxide(CeO_(2))has garnered considerable interest due to its favourable properties,including strong redox capability,high oxy-gen storage capacity,chemical stability,and earth abundance.However,intrinsic drawbacks such as a wide band gap,limited visible-light absorption,and rapid charge recombination restrict its standalone performance.This review comprehensively examines recent advancements in CeO_(2)-based photocatalysts,focusing on structural modifications and the formation of heterojunctions,including S-scheme,Type II,and Z-scheme architectures,that enhance charge separation and retain redox potential.Fabrication strategies are broadly classifi ed into bottom-up and top-down methodologies,with particular emphasis on techniques such as sol-gel,hydrothermal,and co-precipitation methods,which are comprehensively discussed for their effectiveness in optimizing morphology and surface activity.Furthermore,the integration of CeO_(2)with advanced materials(e.g.g-C_(3)N_(4),Ti_(3)C_(2),Metal-organic frameworks(MOFs))and defect engineering approaches is highlighted for improving photocatalytic efficiency under solar irradiation.Promising applications in photocatalytic reduction of CO_(2)to value-added chemicals and solar-driven catalytic hydrogen evolution are explored.The review also outlines current challenges,such as poor selectivity,low photostability,and scalability,and provides future perspectives on rational design,real-world testing,and eco-friendly fabrication routes to accelerate the deployment of CeO_(2)-based photocatalytic systems.展开更多
Covalent organic frameworks(COFs)are newly developed crystalline substances that are garnering growing interest because of their ultrahigh porosity,crystalline nature,and easy-modified architecture,showing promise in ...Covalent organic frameworks(COFs)are newly developed crystalline substances that are garnering growing interest because of their ultrahigh porosity,crystalline nature,and easy-modified architecture,showing promise in the field of photocatalysis.However,it is difficult for pure COFs materials to achieve excellent photocatalytic hydrogen production due to their severe carrier recombination problems.To mitigate this crucial issue,establishing heterojunction is deemed an effective approach.Nonetheless,many of the metal-containing materials that have been used to construct heterojunctions with COFs own a number of drawbacks,including small specific surface area and rare active sites(for inorganic semiconductor materials),wider bandgaps and higher preparation costs(for MOFs).Therefore,it is necessary to choose metal-free materials that are easy to prepare.Red phosphorus(RP),as a semiconductor material without metal components,with suitable bandgap,moderate redox potential,relatively minimal toxicity,is affordable and readily available.Herein,a range of RP/TpPa-1-COF(RP/TP1C)composites have been successfully prepared through solvothermal method.The two-dimensional structure of the two materials causes strong interactions between the materials,and the construction of heterojunctions effectively inhibits the recombination of photogenic charge carriers.As a consequence,the 9%RP/TP1C composite,with the optimal photocatalytic ability,achieves a photocatalytic H2 evolution rate of 6.93 mmol g^(-1) h^(-1),demonstrating a 10.19-fold increase compared to that of bare RP and a 4.08-fold improvement over that of pure TP1C.This article offers a novel and innovative method for the advancement of efficient COF-based photocatalysts.展开更多
Developing heterojunction photocatalyst with well-matched interfaces andmultiple charge transfer paths is vital to boost carrier separation efficiency for photocatalytic antibiotics removal,but still remains a great c...Developing heterojunction photocatalyst with well-matched interfaces andmultiple charge transfer paths is vital to boost carrier separation efficiency for photocatalytic antibiotics removal,but still remains a great challenge.In present work,a new strategy of chloride anion intercalation in Bi_(2)O_(3)via one-pot hydrothermal process is proposed.The as-prepared Ta-BiOCl/Bi_(24)O_(31)Cl_(10)(TBB)heterojunctions are featured with Ta-Bi_(24)O_(31)Cl_(10)and Ta-BiOCl lined shoulder-by-shouleder via semi-coherent interfaces.In this TBB heterojunctions,the well-matched semi-coherent interfaces and shoulder-by-shoulder structures provide fast electron transfer andmultiple transfer paths,respectively,leading to enhanced visible light response and improved photogenerated charge separation.Meanwhile,a type-II heterojunction for photocharge separation has been obtained,in which photogenerated electrons are drove from the CB(conduction band)of Ta-Bi_(24)O_(31)Cl_(10)to the both of bilateral empty CB of Ta-BiOCl and gathered on the CB of Ta-BiOCl,while the photogenerated holes are left on the VB(valence band)of Ta-Bi_(24)O_(31)Cl_(10),effectively hindering the recombination of photogenerated electron-hole pairs.Furthermore,the separated electrons can effectively activate dissolved oxygen for the generation of reactive oxygen species(·O_(2)^(−)).Such TBB heterojunctions exhibit remarkably superior photocatalytic degradation activity for tetracycline hydrochloride(TCH)solution to Bi_(2)O_(3),Ta-BiOCl and Ta-Bi_(24)O_(31)Cl_(10).This work not only proposes a Ta-BiOCl/Bi_(24)O_(31)Cl_(10)shoulder-by-shoulder micro-ribbon architectures with semi-coherent interfaces and successive type-Ⅱheterojunction for highly efficient photocatalytic activity,but offers a new insight into the design of highly efficient heterojunction through phasestructure synergistic transformation strategy.展开更多
The advanced oxidation process presents a perfect solution for eliminating organic pollutants in water resources,and the local microenvironment and surface state of metal reactive sites are crucial for the selective a...The advanced oxidation process presents a perfect solution for eliminating organic pollutants in water resources,and the local microenvironment and surface state of metal reactive sites are crucial for the selective activation of peroxomonosulfate(PMS),which possibly determines the degradation pathways of organic contaminants.In this study,by virtue of the precursor alternation,we constructed the state-switched dual metal species with the porous carbon fibers through the electrospinning strategy.Impressively,the optimal catalyst,featuring the electron-deficient cobalt surface oxidative state and most abundant oxygen vacancies(Ov)with MnO_(2)within porous carbon fibers,provides abundant mesoporosity,facilitating the diffusion and accommodation of big carbamazepine molecules during the reaction process.Benefiting from the tandem configuration of carbon fiber-encapsulated nanocrystalline species,a p-n heterojunction configuration evidenced by Mott-Schottky analysis induced local built-in electric field(BIEF)between electron-deficient cobalt and Ov-rich MnO_(2)within carbon matrix-mediated interfacial interactions,which optimizes the adsorption and activation of PMS and intermediates,increases the concentration of reactive radicals around the active site,and significantly enhances the degradation performance.As a result,the optimal catalyst could achieve 100%degradation of 20 ppm carbamazepine(CBZ)within only 4 min with a rate constant of 1.099 min^(-1),showcasing a low activation energy(50 kJ mol^(-1)),obviously outperforming the other counterparts.We further demonstrated the generation pathways of active species by activation of PMS mainly including sulfate radical(·SO_(4)^(-)),hydroxyl radical(·OH),superoxide radicals(·O_(2)^(-)),and singlet oxygen(^(1)O_(2)),unveiling their contribution to CBZ degradation.The degradation route of CBZ and toxicity analysis of various intermediates were further evaluated.By anchoring the optimal catalyst onto polyester fiber sponge,the photothermal conversion synergistic monolith floatable catalyst and its easy recovery can be achieved,showing good reproducibility and generalizability in the practical application.展开更多
Photothermal catalysis utilizing the full solar spectrum to convert CO_(2)and H2O into valuable products holds promise for sustainable energy solutions.However,a major challenge remains in enhancing the photothermal c...Photothermal catalysis utilizing the full solar spectrum to convert CO_(2)and H2O into valuable products holds promise for sustainable energy solutions.However,a major challenge remains in enhancing the photothermal conversion efficiency and carrier mobility of semiconductors like Bi_(2)MoO_(6),which restricts their catalytic performance.Here,we developed a facile strategy to synthesize vertically grown Bi_(2)MoO_(6)(BMO)nanosheets that mimic a bionic butterfly wing scale structure on a biomass-derived carbon framework(BCF).BCF/BMO exhibits high catalytic activity,achieving a CO yield of 165μmol/(g·h),which is an increase of eight times compared to pristine BMO.The wing scale structured BCF/BMO minimizes sunlight reflection and increases the photothermal conversion temperature.BCF consists of crystalline carbon(sp^(2)-C region)dispersed within amorphous carbon(sp^(3)-C hybridized regions),where the crystalline carbon forms“nano-islands”.The N-C-O-Bi covalent bonds at the S-scheme heterojunction interface of BCF/BMO function as electron bridges,connecting the sp^(2)-C nano-islands and enhancing the multilevel built-in electric field and directional trans-interface transport of carriers.As evidenced by DFT calculation,the rich pyridinic-N on the carbon nano-island can establish strong electron coupling with CO_(2),thereby accelerating the cleavage of*COOH and facilitating the formation of CO.Biomass waste-derived carbon nano-islands represent advanced amorphous/crystalline phase materials and offer a simple and low-cost strategy to facilitate carrier migration.This study provides deep insights into carrier migration in photocatalysis and offers guidance for designing efficient heterojunctions inspired by biological systems.展开更多
In order to investigate the effect of different doping types on the band alignment of heterojunctions,we prepared PtSe_(2)/n-GaN,PtSe_(2)/p-GaN,and PtSe_(2)/u-GaN heterojunctions by wet transfer technique.The valence ...In order to investigate the effect of different doping types on the band alignment of heterojunctions,we prepared PtSe_(2)/n-GaN,PtSe_(2)/p-GaN,and PtSe_(2)/u-GaN heterojunctions by wet transfer technique.The valence band offsets(VBO)of the three heterojunctions were measured by x-ray photoelectron spectroscopy(XPS),while the PtSe_(2)/n-GaN is 3.70±0.15 eV,PtSe_(2)/p-GaN is 0.264±0.15 eV,and PtSe_(2)/u-GaN is 3.02±0.15 eV.The conduction band offset(CBO)of the three heterojunctions was calculated from the material bandgap and VBO,while the PtSe_(2)/n-GaN is 0.61±0.15 eV,PtSe_(2)/p-GaN is 2.83±0.15 eV,and PtSe_(2)/u-GaN is 0.07±0.15 eV.This signifies that both PtSe_(2)/u-GaN and PtSe_(2)/p-GaN exhibit type-Ⅰband alignment,but the PtSe_(2)/n-GaN heterojunction has type-Ⅲband alignment.This signifies that the band engineering of PtSe_(2)/GaN heterojunction can be achieved by manipulating the concentration and type of doping,which is significantly relevant for the advancement of related devices through the realization of band alignment and the modulation of the material properties of the PtSe_(2)/GaN heterojunction.展开更多
Efficient interfacial charge transfer and robust interfacial interactions are crucial for achieving the superior spatial separation of carriers and developing efficient heterojunction photocatalysts.Herein,BiOBr/AgBr ...Efficient interfacial charge transfer and robust interfacial interactions are crucial for achieving the superior spatial separation of carriers and developing efficient heterojunction photocatalysts.Herein,BiOBr/AgBr S-scheme heterojunctions are synthesized via the co-sharing of Br atoms using an ion-exchange approach,which involves the in-situ growth of AgBr nanoparticles on the surfaces of BiOBr nanosheets.It is revealed that successful construction of a high-quality interface with strong interactions via Br atom bridge between BiOBr and AgBr,which provided a rapid migration channel for charge carriers.In addition,in-situ XPS,Kelvin probe force microscopy,and electron spin resonance evaluations confirmed the establishment of an S-scheme charge-transfer pathway in this tightly contacted heterojunction,which could efficiently prevent the recombination of photogenerated carriers while retaining carriers with a high redox capacity.Finally,the photocatalytic test confirmed that the BiOBr/AgBr heterojunction showed excellent photocatalytic performance and wide applicability thanks to the construction of high quality heterojunction.Overall,this work highlights the importance of rational designing of heterogeneous interfaces at the atomic level in photocatalysis,and contributes to rationally design BiOBr-based S-scheme heterojunctions photocatalytic materials with high quality atomic cosharing interfaces.展开更多
It is a challenging task to efficiently convert deleterious hydrogen sulfide(H_(2)S)into less harmful products such as SO_(4)^(2-)species.In an effort to address such issue,a step-scheme(S-scheme)heterojunction photoc...It is a challenging task to efficiently convert deleterious hydrogen sulfide(H_(2)S)into less harmful products such as SO_(4)^(2-)species.In an effort to address such issue,a step-scheme(S-scheme)heterojunction photocatalyst has been built by concatenating TiO_(2)(P25)and ultrathin Bi_(4)O_(5)Br_(2)into TiO_(2)/Bi_(4)O_(5)Br_(2)(namely,x-TB-y:x and y denote the molar ratio of TiO_(2):Bi_(4)O_(5)Br_(2)and pH value for solution-based synthesis,respectively)via in-situ hydrothermal method.The S-scheme charge transfer pathway in TB is confirmed by electron spin resonance and band structure analysis while experimental data and density functional theory calculations suggest the formation of an internal electric field to facilitate the separation and transfer of photoinduced charge carriers.Accordingly,the optimized heterojunction photocatalyst,i.e.,5-TB-9,showcases significantly high(>99%)removal efficiency against 10 ppm H_(2)S in a 17 L chamber within 12 minutes(removal kinetic rate r:0.7 mmol·h^(-1)·g^(-1),specific clean air delivery rate SCADR:5554 L·h^(-1)·g^(-1),quantum yield QY:3.24 E-3 molecules·photon^(-1),and space-time yield STY:3.24 E-3 molecules·photon^(-1)·mg^(-1)).Combined analysis of in-situ diffuse reflectance infrared Fourier transform adsorption spectra and gas chromatography-mass spectrometry allows to evaluate the mechanisms leading to the complete degradation of H_(2)S(i.e.,into SO_(4)^(2-)without forming any intermediate species).This work demonstrates the promising remediation potential of an S-scheme TiO_(2)/Bi_(4)O_(5)Br_(2)photocatalyst against hazardous H_(2)S gas for sustainable environmental remediation.展开更多
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.
基金National Natural Science Foundation of China (Nos. 22371165, 22209098 and 21971143)111 Project (D20015)Opening Found of Hubei Three Gorges Laboratory (SC232001, SK213002)。
文摘Rational engineering of semiconductor photocatalysts for efficient hydrogen production is of great significance but still challenging,primarily due to the limitations in charge transfer kinetics.Herein,a fascinating plasmonic tandem heterojunction with the hc-CdS/Mo_(2)C@C heterostructure is aimfully prepared for effectively promoting the charge separation kinetics of the CdS photocatalyst via the synergistic strategy of phase junction,Schottky junction,and photothermal effect.The difference in atomic configuration between cubic-CdS (c-CdS) and hexagonal-CdS (h-CdS) leads to effective charge separation through a typical Ⅱ charge transfer mechanism,and plasmonic Schottky junction further extracts the electrons in the hc-CdS phase junction to realize gradient charge transfer.Besides,the photothermal effect of Mo_(2)C@C helps to expand the light absorption,accelerate charge transfer kinetics,and reduce the hydrogen evolution energy barrier.The carbon layer provides a fast channel for charge transfer and protects the photocatalyst from photocorrosion.As a result,the optimized hc-CMC photocatalyst exhibits a significantly high photocatalytic H_(2)production activity of 28.63 mmol/g/h and apparent quantum efficiency of 61.8%,surpassing most of the reported photocatalysts.This study provides a feasible strategy to enhance the charge transfer kinetics and photocatalytic activity of CdS by constructing plasmonic tandem heterogeneous junctions.
文摘Rare earth metal ferrites-based heterojunctions have garnered significant attention in recent years due to their exceptional photocatalytic properties and potential applications in water treatment and energy conversion.The incorporation of rare earth metal ferrites into heterojunction photocatalytic systems enhances light absorption,charge separation and photocatalytic efficiency.This review comprehensively discusses some common types of rare earth metal ferrites such as LaFeO_(3),GdFeO_(3),SmFeO_(3),PrFeO_(3)and CeFeO_(3)and their properties as photocatalysts.The photocatalytic pollutants removal and energy conversion mechanisms are discussed in detail and various types of heterojunctions reported in literature based on rare earth metal ferrites and their synthetic routes are also explored.The recent key findings and advances in the heterojunctions based on these rare earth metal ferrites for the pollutants removal and energy conversion applications are summarized.Despite notable progress in enhancing photocatalytic efficiency and stability,several challenges remain.Current research highlights improvements in material synthesis and performance,but issues such as high production costs,scalable synthesis and limited long-term stability persist.Future directions should focus on exploring uncharted applications,novel material combinations and enhancing the practical implementation of these heterojunctions to fully exploit their potential in environmental and energy technologies.
基金supported by the National Natural Science Foundation of China(No.22269010)the Jiangxi Provincial Natural Science Foundation(No.20224BAB214021).
文摘There is limited research reported on the multiple loss mechanism of electromagnetic waves(EMW)and the development of interface models.Dielectric loss and magnetic loss,as the two primary attenuation mechanisms in EMW absorbers,still pose challenges,especially in elucidating the correlation between composition,morphology,interface,and performance.Here,we construct 3D hierarchical porous conducting network structures and Schottky heterojunctions(MoNi_(4)@NC-NiFe_(2)O_(4)@NC)with a high density of defects,using trimetallic NiMoFe-MOFs.Synergistic enhancement of the dielectric and magnetic losses is realized through manipulation of the defects,interfaces,phase engineering,and magnetic resonance.In particular,the even dispersion of magnetic MoNi_(4) and NiFe_(2)O_(4)nanoparticles(NPs)within the carbon matrix triggers the creation of multiple heterogeneous interfaces.These inseparable interfaces,along with oxygen vacancies,play a role in enhancing dielectric polarization,while the closely spaced interactions among magnetic units contribute to magnetic loss.After optimizing the interfacial structure,NiFe_(2)O_(4)/MoNi_(4)-NC exhibits remarkable EMW absorption properties.A reflection loss(RL)value of-67.91 dB can be achieved at an ultra-thin thickness of 1.95 mm,and the effective absorption bandwidth(EAB,RL≤-10 dB)is as high as 5.76 GHz.Furthermore,we conducted radar scattering cross-section(RCS)simulations using computer simulation technology(CST)software,which revealed that NiFe_(2)O_(4)/MoNi_(4)-NC exhibits an RCS reduction value of 39.1 dB m^(2).Hence,this work provides comprehensive guidance for the construction of Schottky heterojunctions for lightweight EMW absorbers from a mechanistic point of view.
基金supported by the National Natural Science Foundation of China(NSFC,Grant No.52372063,62204246 and 52401244)the Young Elite Scientists Sponsorship Program by CAST(Grant No.2023QNRC001)+1 种基金the Postdoctoral Fellowship Program of CPSF(Grant No.GZC20233001,GZC20233006)the China Postdoctoral Science Foundation(Grant No.2024M753526)。
文摘Efficient photocatalytic water splitting can be significantly enhanced through the careful design of S-scheme heterostructures,which play a pivotal role in optimizing performance.Herein,we report the construction of ZnIn_(2)S_(4)/CdS S-scheme heterojunctions under ambient conditions,based on a sonochemical strategy.This structure is facilitated by the well-matched interface between the(007)plane of layered ZnIn_(2)S_(4)and the(101)plane of CdS,leading to a threshold optical response of 2.12 eV,which optimally aligns with visible light absorption.As a proof of concept,the resulting ZnIn_(2)S_(4)/CdS catalysts demonstrate a remarkable improvement in photocatalytic H_(2) evolution,achieving a rate of 5678.2μmol h^(-1)g^(-1)under visible light irradiation(λ>400 nm).This rate is approximately 10 times higher than that of pristine ZnIn_(2)S_(4)nanosheets(NSs)and about 4.6 times higher than that of CdS nanoparticles(NPs),surpassing the performance of most ZnIn_(2)S_(4)-based photocatalysts reported to date.Moreover,they deliver a robust photocatalytic performance during long-term operation of up to 60 h,showing their potential for use in practical applications.Based on the theoretical calculation and experimental results,it is verified that the movements of electrons and holes in the opposite direction could be induced by the disparity in the work function and the internal electric field within the interfaces,thus facilitating the construction of S-scheme heterojunctions,which fundamentally suppresses carrier recombination while minimizing photocorrosion of ZnIn_(2)S_(4)toward enhanced photocatalytic behaviors.
基金supported by Sichuan University of Science and Engineering(No.2021RC26)Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province(No.CSPC202105).
文摘In this work,BiOCl/OVs-BiPO_(4)heterojunction photocatalysts were successfully in-situ prepared by treating of BiPO_(4)with dilute hydrochloric acid(HCl)under hydrothermal condition.Systematically characterization results confirm that BiOCl/BiPO_(4)heterojunctions have been successfully in-situ constructed and oxygen vacancies(OVs)are significantly increased.The OVs on the surface of the BiOCl/OVS-BiPO_(4)heterojunctions photocatalyst and the interface electric field at the interface of the heterojunctions effectively accelerate the separation and migration of photogenerated carriers,and the surface OVs provide more sites for adsorption and reaction.Consequently,BiOCl/OVs-BiPO_(4)heterojunction photocatalysts have higher separation rate of photoexcited e-/h+pairs and exhibit ascendant photocatalytic degradation activity.Electron paramagnetic resonance(EPR)technology and free radical capture experiments give strong evidence that·O2-exists in the reaction system and is the leading species during the degradation process.The experimental results reveal that the degradation efficiency of rhodamine B(RhB)over BiPO_(4)treated with 3 ml of 0.1%dilute hydrochloric acid(3HCl-BPO)is 2.42 times of that over the reference BiPO_(4).After ultraviolet(UV)light illumination for 20 min,the destruction degree of RhB on the 3HCl-BPO sample reaches 99%.Moreover,the degradation rate of tetracycline(TC)is also obviously improved over 3HCl-BPO compared with that on the reference BiPO_(4)after 40 min exposure to ultraviolet light.The excellent stability of the sample was demonstrated by five cycles.A reasonable enhancement mechanism for BiOCl/OVs-BiPO_(4)heterojunctions was proposed to elucidate the boosted photocatalytic performance.This work offers a facile and reliable reference to design high performance BiPO_(4)-based photocatalysts for environment purification.
基金financially supported by the National Natural Science Foundation of China(Nos.62374154 and12374128)the National Key R&D Program of China(Nos.2022YFB3903200 and 2022YFB3903203)
文摘Low-concentration acetone detection is of great importance for acetone sensor in the fields of environmental protection and noninvasive diagnosis.In this work,mesoporous Fe_(2)O_(3)/Cr_(2)O_(3)n-p heterojunctions were constructed for efficient improvement of low-concentration acetone gas sensing.The gas-sensing results indicated that the mesoporous Fe_(2)O_(3)/Cr_(2)O_(3)composites with a significantly large specific surface area exhibited significantlyenhanced acetone gas-sensitive performance compared to pure Fe_(2)O_(3).The Fe_(2)O_(3)/Cr_(2)O_(3)composites demonstrated a high response,good selectivity and excellent stability over200 days to 10 ppm acetone at 220℃.And the theoretical detection limit was calculated to reach 0.285 ppm acetone.A feasible acetone sensing mechanism was proposed through electronic band structure and density functional theory.The improved low-concentration acetone sensing performance was due to the formed mesoporous Fe_(2)O_(3)/Cr_(2)O_(3)n-p heterojunctions with a large specific surface area.The Fe_(2)O_(3)/Cr_(2)O_(3)composites showed excellent acetone gas-sensitive performance,which could be a promising candidate for developing low-concentration acetone sensing devices at low working temperatures.
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.
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.
基金financially supported by the National Natural Science Foundation of China(No.22272151)Public Welfare Technology Application Research Project of Jinhua City,China(No.2023-4-022)。
文摘BiVO_(4)porous spheres modified by ZnO were designed and synthesized using a facile two-step method.The resulting ZnO/BiVO_(4)composite catalysts have shown remarkable efficiency as piezoelectric catalysts for degrading Rhodamine B(RhB)unde mechanical vibrations,they exhibit superior activity compared to pure ZnO.The 40wt%ZnO/BiVO_(4)heterojunction composite displayed the highest activity,along with good stability and recyclability.The enhanced piezoelectric catalytic activity can be attributed to the form ation of an I-scheme heterojunction structure,which can effectively inhibit the electron-hole recombination.Furthermore,hole(h+)and superoxide radical(·O_(2)^(-))are proved to be the primary active species.Therefore,ZnO/BiVO_(4)stands as an efficient and stable piezoelectric catalyst with broad potential application in the field of environmental water pollution treatment.
基金Project supported by the National Key Research and Development Program of China(2022YFB3504100,2021YFB3500600)Chunhui Project Foundation of the Education Department of China(202200554)。
文摘The rapid development of rare earth metal elements in the field of photocatalysis is due to their excellent optical and physicochemical properties.Benefiting from the unique external electronic structure of 4f_15d_16S_2,superior electronegativity of the 4f orbitals,and strong oxygen storage-release ability in Ce^(4+)/Ce^(3+)reversible pairs,cerium dioxide(CeO_(2))has attracted increasing interest from scientists.Nevertheless,the fast recombination of photoinduced electron-hole pairs and wide energy band gap of bare CeO_(2)significantly limit its practical applications.To overcome the above drawbacks,the construction of heterojunctions has been developed to broaden the absorption spectrum and accelerate the charge transfer.This review presents a mini-review of the synthesis of CeO_(2)-based heterojunctions including typeⅡ,Z-scheme,and S-scheme photocatalysts,as well as the corresponding applications in photocatalytic bactericidal and antitumor therapy.Finally,the latest advancements and potential perspectives on their future development are also discussed.
文摘The rising global energy demand and climate crisis have intensified the need for sustainable technologies to mitigate carbon emissions while enabling renewable energy conversion.Photocatalysis,particularly using solar energy,has emerged as a promising green solution for hydrogen production and CO_(2)reduction.Among various semiconductor photocatalysts,cerium oxide(CeO_(2))has garnered considerable interest due to its favourable properties,including strong redox capability,high oxy-gen storage capacity,chemical stability,and earth abundance.However,intrinsic drawbacks such as a wide band gap,limited visible-light absorption,and rapid charge recombination restrict its standalone performance.This review comprehensively examines recent advancements in CeO_(2)-based photocatalysts,focusing on structural modifications and the formation of heterojunctions,including S-scheme,Type II,and Z-scheme architectures,that enhance charge separation and retain redox potential.Fabrication strategies are broadly classifi ed into bottom-up and top-down methodologies,with particular emphasis on techniques such as sol-gel,hydrothermal,and co-precipitation methods,which are comprehensively discussed for their effectiveness in optimizing morphology and surface activity.Furthermore,the integration of CeO_(2)with advanced materials(e.g.g-C_(3)N_(4),Ti_(3)C_(2),Metal-organic frameworks(MOFs))and defect engineering approaches is highlighted for improving photocatalytic efficiency under solar irradiation.Promising applications in photocatalytic reduction of CO_(2)to value-added chemicals and solar-driven catalytic hydrogen evolution are explored.The review also outlines current challenges,such as poor selectivity,low photostability,and scalability,and provides future perspectives on rational design,real-world testing,and eco-friendly fabrication routes to accelerate the deployment of CeO_(2)-based photocatalytic systems.
基金supported by the National Natural Science Foundation of China(Nos.52071171,52202248,22101105)Liaoning Province Centrally Guided Local Science and Technology Development Fund Program(2024JH6/100700010,2024JH6/100700011)+8 种基金Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(2024-35)Open Research Fund of Guangdong Advanced Carbon Materials Co.,Ltd.(Kargen-2024B1001),and Key Research Project of Department of Education of Liaoning Province(LJKZZ20220015)T.M.acknowledged the Australian Research Council(ARC)through Future Fellowship(FT210100298)Discovery Project(DP220100603)Linkage Project(LP210200504,LP220100088,LP230200897)Industrial Transformation Research Hub(IH240100009)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077)the Australian Renewable Energy Agency(ARENA)as part of ARENA's Transformative Research Accelerating Commercialisation Program(TM021)European Commission's Australia-Spain Network for Innovation and Research Excellence(AuSpire)。
文摘Covalent organic frameworks(COFs)are newly developed crystalline substances that are garnering growing interest because of their ultrahigh porosity,crystalline nature,and easy-modified architecture,showing promise in the field of photocatalysis.However,it is difficult for pure COFs materials to achieve excellent photocatalytic hydrogen production due to their severe carrier recombination problems.To mitigate this crucial issue,establishing heterojunction is deemed an effective approach.Nonetheless,many of the metal-containing materials that have been used to construct heterojunctions with COFs own a number of drawbacks,including small specific surface area and rare active sites(for inorganic semiconductor materials),wider bandgaps and higher preparation costs(for MOFs).Therefore,it is necessary to choose metal-free materials that are easy to prepare.Red phosphorus(RP),as a semiconductor material without metal components,with suitable bandgap,moderate redox potential,relatively minimal toxicity,is affordable and readily available.Herein,a range of RP/TpPa-1-COF(RP/TP1C)composites have been successfully prepared through solvothermal method.The two-dimensional structure of the two materials causes strong interactions between the materials,and the construction of heterojunctions effectively inhibits the recombination of photogenic charge carriers.As a consequence,the 9%RP/TP1C composite,with the optimal photocatalytic ability,achieves a photocatalytic H2 evolution rate of 6.93 mmol g^(-1) h^(-1),demonstrating a 10.19-fold increase compared to that of bare RP and a 4.08-fold improvement over that of pure TP1C.This article offers a novel and innovative method for the advancement of efficient COF-based photocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.22208262,52271228,52202298,52201279,51834009,and 51801151)the Natural Science Foundation of Shaanxi Province(Nos.2021JQ-468,2020JZ-47)+3 种基金the Natural Science Foundation of Shaanxi Provincial Department of Education(No.21JP086)the Postdoctoral Research Foundation of China(Nos.2020M683528 and 2018M633643XB)the Young Talent Fund of Association for Science and Technology in Shaanxi,China(No.20230625)the Hundred Talent Program of Shaanxi Province.
文摘Developing heterojunction photocatalyst with well-matched interfaces andmultiple charge transfer paths is vital to boost carrier separation efficiency for photocatalytic antibiotics removal,but still remains a great challenge.In present work,a new strategy of chloride anion intercalation in Bi_(2)O_(3)via one-pot hydrothermal process is proposed.The as-prepared Ta-BiOCl/Bi_(24)O_(31)Cl_(10)(TBB)heterojunctions are featured with Ta-Bi_(24)O_(31)Cl_(10)and Ta-BiOCl lined shoulder-by-shouleder via semi-coherent interfaces.In this TBB heterojunctions,the well-matched semi-coherent interfaces and shoulder-by-shoulder structures provide fast electron transfer andmultiple transfer paths,respectively,leading to enhanced visible light response and improved photogenerated charge separation.Meanwhile,a type-II heterojunction for photocharge separation has been obtained,in which photogenerated electrons are drove from the CB(conduction band)of Ta-Bi_(24)O_(31)Cl_(10)to the both of bilateral empty CB of Ta-BiOCl and gathered on the CB of Ta-BiOCl,while the photogenerated holes are left on the VB(valence band)of Ta-Bi_(24)O_(31)Cl_(10),effectively hindering the recombination of photogenerated electron-hole pairs.Furthermore,the separated electrons can effectively activate dissolved oxygen for the generation of reactive oxygen species(·O_(2)^(−)).Such TBB heterojunctions exhibit remarkably superior photocatalytic degradation activity for tetracycline hydrochloride(TCH)solution to Bi_(2)O_(3),Ta-BiOCl and Ta-Bi_(24)O_(31)Cl_(10).This work not only proposes a Ta-BiOCl/Bi_(24)O_(31)Cl_(10)shoulder-by-shoulder micro-ribbon architectures with semi-coherent interfaces and successive type-Ⅱheterojunction for highly efficient photocatalytic activity,but offers a new insight into the design of highly efficient heterojunction through phasestructure synergistic transformation strategy.
基金financially supported by the National Natural Science Foundation of China(No.21908085)the Natural Science Foundation of Jiangsu province(No.BK20241950)+3 种基金China Postdoctoral Science Foundation(No.2023M731422)the Open Project of State Key Laboratory of Materials Chemical Engineering(No.SKL-MCE-23B)Hubei Key Laboratory of Processing and Application of Catalytic materials(No.202441204)the Science and Technology Plan School-Enterprise Cooperation Industry-University-Research Forward-looking Project of Zhangjiagang(No.ZKYY2341)
文摘The advanced oxidation process presents a perfect solution for eliminating organic pollutants in water resources,and the local microenvironment and surface state of metal reactive sites are crucial for the selective activation of peroxomonosulfate(PMS),which possibly determines the degradation pathways of organic contaminants.In this study,by virtue of the precursor alternation,we constructed the state-switched dual metal species with the porous carbon fibers through the electrospinning strategy.Impressively,the optimal catalyst,featuring the electron-deficient cobalt surface oxidative state and most abundant oxygen vacancies(Ov)with MnO_(2)within porous carbon fibers,provides abundant mesoporosity,facilitating the diffusion and accommodation of big carbamazepine molecules during the reaction process.Benefiting from the tandem configuration of carbon fiber-encapsulated nanocrystalline species,a p-n heterojunction configuration evidenced by Mott-Schottky analysis induced local built-in electric field(BIEF)between electron-deficient cobalt and Ov-rich MnO_(2)within carbon matrix-mediated interfacial interactions,which optimizes the adsorption and activation of PMS and intermediates,increases the concentration of reactive radicals around the active site,and significantly enhances the degradation performance.As a result,the optimal catalyst could achieve 100%degradation of 20 ppm carbamazepine(CBZ)within only 4 min with a rate constant of 1.099 min^(-1),showcasing a low activation energy(50 kJ mol^(-1)),obviously outperforming the other counterparts.We further demonstrated the generation pathways of active species by activation of PMS mainly including sulfate radical(·SO_(4)^(-)),hydroxyl radical(·OH),superoxide radicals(·O_(2)^(-)),and singlet oxygen(^(1)O_(2)),unveiling their contribution to CBZ degradation.The degradation route of CBZ and toxicity analysis of various intermediates were further evaluated.By anchoring the optimal catalyst onto polyester fiber sponge,the photothermal conversion synergistic monolith floatable catalyst and its easy recovery can be achieved,showing good reproducibility and generalizability in the practical application.
基金supported by the National Natural Science Foundation of China(52276099,52406219)Graduate Research and Innovation Foundation of Chongqing,China(CYB23034)+2 种基金China Scholarship Council(202406050113)the Australian Research Council(DE230100327)DCCEEW International Clean Innovation Researcher Networks Grant(ICIRN000011)。
文摘Photothermal catalysis utilizing the full solar spectrum to convert CO_(2)and H2O into valuable products holds promise for sustainable energy solutions.However,a major challenge remains in enhancing the photothermal conversion efficiency and carrier mobility of semiconductors like Bi_(2)MoO_(6),which restricts their catalytic performance.Here,we developed a facile strategy to synthesize vertically grown Bi_(2)MoO_(6)(BMO)nanosheets that mimic a bionic butterfly wing scale structure on a biomass-derived carbon framework(BCF).BCF/BMO exhibits high catalytic activity,achieving a CO yield of 165μmol/(g·h),which is an increase of eight times compared to pristine BMO.The wing scale structured BCF/BMO minimizes sunlight reflection and increases the photothermal conversion temperature.BCF consists of crystalline carbon(sp^(2)-C region)dispersed within amorphous carbon(sp^(3)-C hybridized regions),where the crystalline carbon forms“nano-islands”.The N-C-O-Bi covalent bonds at the S-scheme heterojunction interface of BCF/BMO function as electron bridges,connecting the sp^(2)-C nano-islands and enhancing the multilevel built-in electric field and directional trans-interface transport of carriers.As evidenced by DFT calculation,the rich pyridinic-N on the carbon nano-island can establish strong electron coupling with CO_(2),thereby accelerating the cleavage of*COOH and facilitating the formation of CO.Biomass waste-derived carbon nano-islands represent advanced amorphous/crystalline phase materials and offer a simple and low-cost strategy to facilitate carrier migration.This study provides deep insights into carrier migration in photocatalysis and offers guidance for designing efficient heterojunctions inspired by biological systems.
基金Project supported by the National Natural Science Foundation of China(Grant No.61874108)the Fundamental Research Funds for the Central Universities(Grant No.lzujbky-2024-04)the Gansu Provincial Scientific and Technologic Planning Program(Grant No.22ZD6GE016).
文摘In order to investigate the effect of different doping types on the band alignment of heterojunctions,we prepared PtSe_(2)/n-GaN,PtSe_(2)/p-GaN,and PtSe_(2)/u-GaN heterojunctions by wet transfer technique.The valence band offsets(VBO)of the three heterojunctions were measured by x-ray photoelectron spectroscopy(XPS),while the PtSe_(2)/n-GaN is 3.70±0.15 eV,PtSe_(2)/p-GaN is 0.264±0.15 eV,and PtSe_(2)/u-GaN is 3.02±0.15 eV.The conduction band offset(CBO)of the three heterojunctions was calculated from the material bandgap and VBO,while the PtSe_(2)/n-GaN is 0.61±0.15 eV,PtSe_(2)/p-GaN is 2.83±0.15 eV,and PtSe_(2)/u-GaN is 0.07±0.15 eV.This signifies that both PtSe_(2)/u-GaN and PtSe_(2)/p-GaN exhibit type-Ⅰband alignment,but the PtSe_(2)/n-GaN heterojunction has type-Ⅲband alignment.This signifies that the band engineering of PtSe_(2)/GaN heterojunction can be achieved by manipulating the concentration and type of doping,which is significantly relevant for the advancement of related devices through the realization of band alignment and the modulation of the material properties of the PtSe_(2)/GaN heterojunction.
基金supported by the National Natural Science Foundation of China (No. 12204207)the National Natural Science Foundation of China-Yunnan Joint Fund (No. U2102215)+1 种基金the National Natural Science Foundation of High and Foreign Experts Introduction Plan (No. G2022039008L)Yunnan XingDian Youth Talent Support Program (No. XDYC-QNRC-2022-0591)。
文摘Efficient interfacial charge transfer and robust interfacial interactions are crucial for achieving the superior spatial separation of carriers and developing efficient heterojunction photocatalysts.Herein,BiOBr/AgBr S-scheme heterojunctions are synthesized via the co-sharing of Br atoms using an ion-exchange approach,which involves the in-situ growth of AgBr nanoparticles on the surfaces of BiOBr nanosheets.It is revealed that successful construction of a high-quality interface with strong interactions via Br atom bridge between BiOBr and AgBr,which provided a rapid migration channel for charge carriers.In addition,in-situ XPS,Kelvin probe force microscopy,and electron spin resonance evaluations confirmed the establishment of an S-scheme charge-transfer pathway in this tightly contacted heterojunction,which could efficiently prevent the recombination of photogenerated carriers while retaining carriers with a high redox capacity.Finally,the photocatalytic test confirmed that the BiOBr/AgBr heterojunction showed excellent photocatalytic performance and wide applicability thanks to the construction of high quality heterojunction.Overall,this work highlights the importance of rational designing of heterogeneous interfaces at the atomic level in photocatalysis,and contributes to rationally design BiOBr-based S-scheme heterojunctions photocatalytic materials with high quality atomic cosharing interfaces.
文摘It is a challenging task to efficiently convert deleterious hydrogen sulfide(H_(2)S)into less harmful products such as SO_(4)^(2-)species.In an effort to address such issue,a step-scheme(S-scheme)heterojunction photocatalyst has been built by concatenating TiO_(2)(P25)and ultrathin Bi_(4)O_(5)Br_(2)into TiO_(2)/Bi_(4)O_(5)Br_(2)(namely,x-TB-y:x and y denote the molar ratio of TiO_(2):Bi_(4)O_(5)Br_(2)and pH value for solution-based synthesis,respectively)via in-situ hydrothermal method.The S-scheme charge transfer pathway in TB is confirmed by electron spin resonance and band structure analysis while experimental data and density functional theory calculations suggest the formation of an internal electric field to facilitate the separation and transfer of photoinduced charge carriers.Accordingly,the optimized heterojunction photocatalyst,i.e.,5-TB-9,showcases significantly high(>99%)removal efficiency against 10 ppm H_(2)S in a 17 L chamber within 12 minutes(removal kinetic rate r:0.7 mmol·h^(-1)·g^(-1),specific clean air delivery rate SCADR:5554 L·h^(-1)·g^(-1),quantum yield QY:3.24 E-3 molecules·photon^(-1),and space-time yield STY:3.24 E-3 molecules·photon^(-1)·mg^(-1)).Combined analysis of in-situ diffuse reflectance infrared Fourier transform adsorption spectra and gas chromatography-mass spectrometry allows to evaluate the mechanisms leading to the complete degradation of H_(2)S(i.e.,into SO_(4)^(2-)without forming any intermediate species).This work demonstrates the promising remediation potential of an S-scheme TiO_(2)/Bi_(4)O_(5)Br_(2)photocatalyst against hazardous H_(2)S gas for sustainable environmental remediation.
