Green energy generation is an indispensable task to concurrently resolve fossil fuel depletion and environmental issues to align with the global goals of achieving carbon neutrality.Photocatalysis,a process that trans...Green energy generation is an indispensable task to concurrently resolve fossil fuel depletion and environmental issues to align with the global goals of achieving carbon neutrality.Photocatalysis,a process that transforms solar energy into clean fuels through a photocatalyst,represents a felicitous direction toward sustainability.Eco-rich metal-free graphitic carbon nitride(g-C_(3)N_(4))is profiled as an attractive photocatalyst due to its fascinating properties,including excellent chemical and thermal stability,moderate band gap,visible light-active nature,and ease of fabrication.Nonetheless,the shortcomings of g-C_(3)N_(4)include fast charge recombination and limited surface-active sites,which adversely affect photocatalytic reactions.Among the modification strategies,point-to-face contact engineering of 2D g-C_(3)N_(4)with 0D nanomaterials represents an innovative and promising synergy owing to several intriguing attributes such as the high specific surface area,short effective charge-transfer pathways,and quantum confinement effects.This review introduces recent advances achieved in experimental and computational studies on the interfacial design of 0D nanostructures on 2D g-C_(3)N_(4)in the construction of point-to-face heterojunction interfaces.Notably,0D materials such as metals,metal oxides,metal sulfides,metal selenides,metal phosphides,and nonmetals on g-C_(3)N_(4)with different charge-transfer mechanisms are systematically discussed along with controllable synthesis strategies.The applications of 0D/2D g-C_(3)N_(4)-based photocatalysts are focused on solar-to-energy conversion via the hydrogen evolution reaction,the CO_(2)reduction reaction,and the N2 reduction reaction to evaluate the photocatalyst activity and elucidate reaction pathways.Finally,future perspectives for developing high-efficiency 0D/2D photocatalysts are proposed to explore potential emerging carbon nitride allotropes,large-scale production,machine learning integration,and multidisciplinary advances for technological breakthroughs.展开更多
An S-scheme heterojunction photocatalyst is capable of boosting photogenerated carrier separation and transfer,thus maintaining high photooxidation and photoredox ability.Herein,a 0D Ag_(3)PO_(4) nanoparticles(NPs)/1D...An S-scheme heterojunction photocatalyst is capable of boosting photogenerated carrier separation and transfer,thus maintaining high photooxidation and photoredox ability.Herein,a 0D Ag_(3)PO_(4) nanoparticles(NPs)/1D TiO_(2) nanofibers(NFs)S-scheme heterojunction with intimate interfacial contact was designed via the the hydro-thermal method.Benefiting from the abundant hydroxyl groups and size confinement effect of TiO_(2) NFs,the average diameter of the Ag_(3)PO_(4) nanoparticles decreased from 100 to 22 nm,which favored the construction of a 0D/1D geometry heterojunction.The multifunctional Ag_(3)PO_(4)/TiO_(2) sample exhibited excellent photocatalytic activity and stability in photocatalytic oxygen production(726μmol/g/h)and photocatalytic degradation of various organic contaminants such as rhodamine B(100%),phenol(60%)and tetracycline hydrochloride(100%).The significant improvements in the photocatalytic performance and stability can be attributed to the intimate interfacial contacts and rich active sites of 0D/1D geometry,fast charge carrier migration,and outstanding photoredox properties induced by the S-scheme charge-transfer route.This work offers a promising strategy for constructing 0D/1D S-scheme heterojunction photocatalysts for improved photocatalytic performance.展开更多
Designing and fabricating highly efficient photocatalysts for water splitting is a promising strategy to address energy and environmental issues.Cadmium sulfide(CdS)has received significant interest as a photocatalyst...Designing and fabricating highly efficient photocatalysts for water splitting is a promising strategy to address energy and environmental issues.Cadmium sulfide(CdS)has received significant interest as a photocatalyst for visible‐light‐induced hydrogen(H2)generation.However,the severe photocorrosion,high overpotential,rapid charge recombination,and sluggish surface reaction kinetics drastically hinder its practical application in water splitting.Herein,uniform zinc cadmium sulfide(Zn_(0.5)Cd_(0.5)S)nanoparticles were anchored on ultrathin Ni(OH)_(2)nanosheets via a facile solution‐phase approach to form an intimate two‐dimensional(2D)/zero‐dimensional(0D)heterojunction.Under visible light irradiation,the 7%Ni(OH)_(2)/Zn_(0.5)Cd_(0.5)S composite exhibited the highest H2 production rate of 6.87 mmol·h^(–1)·g^(–1)with an apparent quantum yield of 16.8%at 420 nm,which is almost 43 times higher than that of pristine Zn_(0.5)Cd_(0.5)S and considerably higher than that of the Pt/Zn_(0.5)Cd_(0.5)S photocatalyst.The high photoactivity of the 2D/0D Ni(OH)_(2)/Zn_(0.5)Cd_(0.5)S heterojunction can be ascribed to its unique and robust structure,wherein the ultrathin Ni(OH)_(2)nanosheets not only provide an excellent platform for the incorporation of Zn_(0.5)Cd_(0.5)S nanoparticles but also serve as an effective cocatalyst to promote photoinduced electron transfer and offer more active sites for photocatalytic H_(2) generation.This work paves the way toward the development of versatile,low‐cost,and highly efficient 2D/0D heterojunction photocatalysts for solar energy conversion.展开更多
The design and construction of heterojunction photocatalysts,which possess a staggered energy band structure and appropriate interfacial contact,is an effective way to achieve outstanding photocatalytic performance.In...The design and construction of heterojunction photocatalysts,which possess a staggered energy band structure and appropriate interfacial contact,is an effective way to achieve outstanding photocatalytic performance.In this study,2D/2D BiOBr/g‐C_(3)N_(4)heterojunctions were successfully obtained by a convenient in situ self‐assembly route.Under simulated sunlight irradiation,99%of RhB(10 mg·L–1,100 mL)was efficiently degraded by 1.5‐BiOBr/g‐C_(3)N_(4)within 30 min,which is better than the performance of both BiOBr and g‐C_(3)N_(4),and it has superior stability.In addition,the composite also exhibits enhanced photocatalytic activity for H2 production.The enhanced activity can be attributed to the intimate interface contact,the larger surface area,and the highly efficient separation of photoinduced electron–hole pairs.Based on the experimental results,a novel S‐scheme model was proposed to illuminate the transfer process of charge carriers.This study presents a simple way to develop novel step‐scheme photocatalysts for environmental and related applications.展开更多
TiO_(2)is a promising photocatalyst with limited use in practical applications owing to its wide bandgap,narrow light response range,and rapid recombination of photoexcited carriers.To address these limitations,a nove...TiO_(2)is a promising photocatalyst with limited use in practical applications owing to its wide bandgap,narrow light response range,and rapid recombination of photoexcited carriers.To address these limitations,a novel 1D/2D TiO_(2)/ZnIn_(2)S_(4)heterostructure was designed according to the principles of the S-scheme heterojunction.The TiO_(2)/ZnIn_(2)S_(4)(TZISx)hybrids prepared via a hydrothermal method afforded significant improvement in photocatalytic hydrogen evolution(PHE)in comparison to pristine TiO_(2)and ZnIn_(2)S_(4).In particular,the optimal TZIS2 sample(mass ratio of ZnIn_(2)S_(4)to TiO_(2)was 0.4)exhibited the highest PHE activity(6.03 mmol/h/g),which was approximately 3.7 and 2.0 times higher than those of pristine TiO_(2)and ZnIn_(2)S_(4),respectively.This improvement in the PHE of the TZIS2 sample could be attributed to the formation of an intimate heterojunction interface,high-efficiency separation of charge carriers,abundant reactive sites,and enhanced light absorption capacity.Notably,theoretical and experimental results demonstrated that the S-scheme mechanism of interfacial electron transfer in the TZISx composites facilitated the transfer and separation of photoexcited charge carriers,resulting in more isolated photoexcited electrons for the PHE reaction.展开更多
The rapid recombination of photo-generated electron-hole pairs,insufficient active sites,and strong photocorrosion have considerably restricted the practical application of Cd S in photocatalytic fields.Herein,we desi...The rapid recombination of photo-generated electron-hole pairs,insufficient active sites,and strong photocorrosion have considerably restricted the practical application of Cd S in photocatalytic fields.Herein,we designed and constructed a 2D/2D/2D layered heterojunction photocatalyst with cascaded 2D coupling interfaces.Experiments using electron spin resonance spectroscopy,ultraviolet photoelectron spectroscopy,and in-situ irradiation X-ray photoelectron spectroscopy were conducted to confirm the 2D layered CdS/WO_(3) step-scheme(S-scheme)heterojunctions and CdS/MX ohmic junctions.Impressively,it was found that the strong interfacial electric fields in the S-scheme heterojunction photocatalysts could effectively promote spatially directional charge separation and transport between CdS and WO_(3) nanosheets.In addition,2D Ti_(3)C_(2) MXene nanosheets with a smaller work function and excellent metal conductivity when used as a co-catalyst could build ohmic junctions with Cd S nanosheets,thus providing a greater number of electron transfer pathways and hydrogen evolution sites.Results showed that the highest visible-light hydrogen evolution rate of the optimized MX-Cd S/WO_(3) layered multi-heterostructures could reach as high as 27.5 mmol/g/h,which was 11.0 times higher than that of pure CdS nanosheets.Notably,the apparent quantum efficiency reached 12.0% at 450 nm.It is hoped that this study offers a reliable approach for developing multifunctional photocatalysts by integrating S-scheme and ohmic-junction built-in electric fields and rationally designing a 2D/2D interface for efficient light-to-hydrogen fuel production.展开更多
Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high...Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic performance.Herein,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction efficiency.Charge transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area interface.Work function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance spectroscopy.Moreover,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform spectra.Density functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and CO.Introducing Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 eV.This study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.展开更多
Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination ra...Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate.Herein,a novel metal-free 2D/2D van der Waals heterojunction,composed of a two-dimensional(2D)COF with ketoenamine linkage(TpPa-1-COF)and 2D defective hexagonal boron nitride(h-BN),is successfully constructed through in situ solvothermal method.Benefitting from the presence of VDW heterojunction,larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN,which make contributions to promoting charge car-riers separation.The introduced defects can also endow the h-BN with porous structure,thus providing more reactive sites.Moreover,the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN,which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF,and suppress electron backflow,corroborated by experimental and density functional theory calculations results.Accordingly,the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays out-standing solar energy catalytic activity for water splitting without co-catalysts,and the H_(2) evolution rate can reach up to 3.15 mmol g^(−1) h^(−1),which is about 67 times greater than that of pristine TpPa-1-COF,also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date.In particular,it is the first work for constructing COFs-based heterojunctions with the help of h-BN,which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H_(2) evolution.展开更多
In this work,a set of novel Cu2ZnSnS4/Bi2WO6(CZTS/BWO)two-dimensional(2 D)/two-dimensional(2 D)type-Ⅱheterojunctions with different CZTS weight ratios(1%,2%,and 5%)were successfully synthesized via a brief secondary ...In this work,a set of novel Cu2ZnSnS4/Bi2WO6(CZTS/BWO)two-dimensional(2 D)/two-dimensional(2 D)type-Ⅱheterojunctions with different CZTS weight ratios(1%,2%,and 5%)were successfully synthesized via a brief secondary solvothermal process.The successful formation of the heterojunctions was affirmed by characterization methods such as X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy.The photocatalytic activity results showed that the prepared CZTS/BWO heterojunctions had excellent photocatalytic behaviors for organic degradation,especially when the mass fraction of CZTS with respect to BWO in the composite was 2%.Moreover,the addition of hydrogen peroxide(H2O2)could further improve the dye and antibiotic degradation efficiencies.The reinforced photocatalytic and photo-Fenton degradation performance were primarily attributable to the introduction of BWO,which afforded increased active sites,expanded the solar spectral response range,and accelerated the cycle of Cu(Ⅱ)/Cu(Ⅰ);after four cycling times,its catalytic activity did not decrease significantly.In addition,reasonable hypotheses of the photocatalytic and photo-Fenton catalytic mechanisms were formulated.This study is expected to provide a visual approach for designing a novel photo-Fenton catalyst to jointly utilize the photocatalytic and Fenton activities,which can be better applied to the purification of residual organics in wastewater.展开更多
The construction of S‐scheme heterojunction photocatalysts has been regarded as an effective avenue to facilitate the conversion of solar energy to fuel.However,there are still considerable challenges with regard to ...The construction of S‐scheme heterojunction photocatalysts has been regarded as an effective avenue to facilitate the conversion of solar energy to fuel.However,there are still considerable challenges with regard to efficient charge transfer,the abundance of catalytic sites,and extended light absorption.Herein,an S‐scheme heterojunction of 2D/2D zinc porphyrin‐based metal‐organic frameworks/BiVO_(4)nanosheets(Zn‐MOF/BVON)was fabricated for efficient photocatalytic CO_(2)conversion.The optimal one shows a 22‐fold photoactivity enhancement when compared to the previously reported BiVO4 nanoflake(ca.15 nm),and even exhibits~2‐time improvement than the traditional g‐C3N4/BiVO4 heterojunction.The excellent photoactivities are ascribed to the strengthened S‐scheme charge transfer and separation,promoted CO_(2)activation by the well‐dispersed metal nodes Zn_(2)(COO)_(4)in the Zn‐MOF,and extended visible light response range based on the results of the electrochemical reduction,electron paramagnetic resonance,and in‐situ diffuse reflectance infrared Fourier transform spectroscopy.The dimension‐matched Zn‐MOF/BVON S‐scheme heterojunction endowed with highly efficient charge separation and abundant catalytic active sites contributed to the superior CO2 conversion.This study offers a facile strategy for constructing S‐scheme heterojunctions involving porphyrin‐based MOFs for solar fuel production.展开更多
The fabrication of S-scheme heterojunctions with fast charge transfer and good interface contacts,such as intermolecularπ–πinteractions,is a promising approach to improve photocatalytic performance.A unique two-dim...The fabrication of S-scheme heterojunctions with fast charge transfer and good interface contacts,such as intermolecularπ–πinteractions,is a promising approach to improve photocatalytic performance.A unique two-dimensional/two-dimensional(2D/2D)S-scheme heterojunction containing TpPa-1-COF/g-C_(3)N_(4) nanosheets(denoted as TPCNNS)was developed.The established maximum interfacial interaction between TpPa-1-COF NS and g-C_(3)N_(4) NS may result in aπ–πconjugated heterointerface.Furthermore,the difference in the work functions of TpPa-1-COF and g-C_(3)N_(4) results in a large Fermi level gap,leading to upward/downward band edge bending.The spontaneous interfacial charge transfer from g-C_(3)N_(4) to TpPa-1-COF at theπ–πconjugated interface area results in the presence of a built-in electric field,according to the charge density difference analysis based on density functional theory calculations.Such an enhanced built-in electric field can efficiently drive directional charge migration via the S-scheme mechanism,which enhances charge separation and utilization.Thus,an approximately 2.8 and 5.6 times increase in the photocatalytic hydrogen evolution rate was recorded in TPCNNS-2(1153μmol g^(-1) h^(-1))compared to pristine TpPa-1-COF and g-C_(3)N_(4) NS,respectively,under visible light irradiation.Overall,this work opens new avenues in the fabrication of 2D/2Dπ–πconjugated S-scheme heterojunction photocatalysts with highly efficient hydrogen evolution performance.展开更多
Fabrication of large-area atomically thin transition metal dichalcogenides is of critical importance for the preparation of new heterojunction-based devices.In this paper, we report the fabrication and optical investi...Fabrication of large-area atomically thin transition metal dichalcogenides is of critical importance for the preparation of new heterojunction-based devices.In this paper, we report the fabrication and optical investigation of large-scale chemical vapor deposition(CVD)-grown monolayer MoS2 and exfoliated few-layer GaS heterojunctions.As revealed by photoluminescence(PL) characterization, the as-fabricated heterojunctions demonstrated edge interaction between the two layers.The heterojunction was sensitive to annealing and showed increased interaction upon annealing at 300℃ under vacuum conditions, which led to changes in both the emission peak position and intensity resulting from the strong coupling interaction between the two layers.Low-temperature PL measurements further confirmed the strong coupling interaction.In addition, defect-related GaS luminescence was observed in our few-layer GaS, and the PL mapping provided evidence of edge interaction coupling between the two layers.These findings are interesting and provide the basis for creating new material systems with rich functionalities and novel physical effects.展开更多
The electronic properties and transport properties of MoTe2/SnS2 heterostructure Tunneling FETs are investigated by the density functional theory coupled with non-equilibrium Green’s function method.Two dimensional(2...The electronic properties and transport properties of MoTe2/SnS2 heterostructure Tunneling FETs are investigated by the density functional theory coupled with non-equilibrium Green’s function method.Two dimensional(2D)monolayer MoTe2 and SnS2 are combined to a vertical van der Waals heterojunction.A small staggered band gap is formed in the overlap region,while larger gaps remain in the underlap source and drain regions of monolayer MoTe2 and SnS2 respectively.Such a type-II heterojunction is favorable for tunneling FET.Furthermore,we suggest short stack length and large gate-to-drain overlap to enhance the on-state current suppress the leakage current respectively.The numerical results show that at a low drain to source voltage Vds=0.05V,On/Off current ratio can reach 108 and the On-state currents is over 20μA/μm for ntype devices.Our results present that van der Waals heterostructure TFETs can be potential candidate as next generation ultra-steep subthreshold and low-power electronic applications.展开更多
基金Ministry of Higher Education,Malaysia,Grant/Award Number:FRGS/1/2020/TK0/XMU/02/1Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2021A1515111019+1 种基金Hengyuan International Sdn.Bhd.,Grant/Award Number:EENG/0003Xiamen University Malaysia,Grant/Award Numbers:IENG/0038,ICOE/0001,XMUMRF/2019-C3/IENG/0013,XMUMRF/2021-C8/IENG/0041。
文摘Green energy generation is an indispensable task to concurrently resolve fossil fuel depletion and environmental issues to align with the global goals of achieving carbon neutrality.Photocatalysis,a process that transforms solar energy into clean fuels through a photocatalyst,represents a felicitous direction toward sustainability.Eco-rich metal-free graphitic carbon nitride(g-C_(3)N_(4))is profiled as an attractive photocatalyst due to its fascinating properties,including excellent chemical and thermal stability,moderate band gap,visible light-active nature,and ease of fabrication.Nonetheless,the shortcomings of g-C_(3)N_(4)include fast charge recombination and limited surface-active sites,which adversely affect photocatalytic reactions.Among the modification strategies,point-to-face contact engineering of 2D g-C_(3)N_(4)with 0D nanomaterials represents an innovative and promising synergy owing to several intriguing attributes such as the high specific surface area,short effective charge-transfer pathways,and quantum confinement effects.This review introduces recent advances achieved in experimental and computational studies on the interfacial design of 0D nanostructures on 2D g-C_(3)N_(4)in the construction of point-to-face heterojunction interfaces.Notably,0D materials such as metals,metal oxides,metal sulfides,metal selenides,metal phosphides,and nonmetals on g-C_(3)N_(4)with different charge-transfer mechanisms are systematically discussed along with controllable synthesis strategies.The applications of 0D/2D g-C_(3)N_(4)-based photocatalysts are focused on solar-to-energy conversion via the hydrogen evolution reaction,the CO_(2)reduction reaction,and the N2 reduction reaction to evaluate the photocatalyst activity and elucidate reaction pathways.Finally,future perspectives for developing high-efficiency 0D/2D photocatalysts are proposed to explore potential emerging carbon nitride allotropes,large-scale production,machine learning integration,and multidisciplinary advances for technological breakthroughs.
文摘An S-scheme heterojunction photocatalyst is capable of boosting photogenerated carrier separation and transfer,thus maintaining high photooxidation and photoredox ability.Herein,a 0D Ag_(3)PO_(4) nanoparticles(NPs)/1D TiO_(2) nanofibers(NFs)S-scheme heterojunction with intimate interfacial contact was designed via the the hydro-thermal method.Benefiting from the abundant hydroxyl groups and size confinement effect of TiO_(2) NFs,the average diameter of the Ag_(3)PO_(4) nanoparticles decreased from 100 to 22 nm,which favored the construction of a 0D/1D geometry heterojunction.The multifunctional Ag_(3)PO_(4)/TiO_(2) sample exhibited excellent photocatalytic activity and stability in photocatalytic oxygen production(726μmol/g/h)and photocatalytic degradation of various organic contaminants such as rhodamine B(100%),phenol(60%)and tetracycline hydrochloride(100%).The significant improvements in the photocatalytic performance and stability can be attributed to the intimate interfacial contacts and rich active sites of 0D/1D geometry,fast charge carrier migration,and outstanding photoredox properties induced by the S-scheme charge-transfer route.This work offers a promising strategy for constructing 0D/1D S-scheme heterojunction photocatalysts for improved photocatalytic performance.
文摘Designing and fabricating highly efficient photocatalysts for water splitting is a promising strategy to address energy and environmental issues.Cadmium sulfide(CdS)has received significant interest as a photocatalyst for visible‐light‐induced hydrogen(H2)generation.However,the severe photocorrosion,high overpotential,rapid charge recombination,and sluggish surface reaction kinetics drastically hinder its practical application in water splitting.Herein,uniform zinc cadmium sulfide(Zn_(0.5)Cd_(0.5)S)nanoparticles were anchored on ultrathin Ni(OH)_(2)nanosheets via a facile solution‐phase approach to form an intimate two‐dimensional(2D)/zero‐dimensional(0D)heterojunction.Under visible light irradiation,the 7%Ni(OH)_(2)/Zn_(0.5)Cd_(0.5)S composite exhibited the highest H2 production rate of 6.87 mmol·h^(–1)·g^(–1)with an apparent quantum yield of 16.8%at 420 nm,which is almost 43 times higher than that of pristine Zn_(0.5)Cd_(0.5)S and considerably higher than that of the Pt/Zn_(0.5)Cd_(0.5)S photocatalyst.The high photoactivity of the 2D/0D Ni(OH)_(2)/Zn_(0.5)Cd_(0.5)S heterojunction can be ascribed to its unique and robust structure,wherein the ultrathin Ni(OH)_(2)nanosheets not only provide an excellent platform for the incorporation of Zn_(0.5)Cd_(0.5)S nanoparticles but also serve as an effective cocatalyst to promote photoinduced electron transfer and offer more active sites for photocatalytic H_(2) generation.This work paves the way toward the development of versatile,low‐cost,and highly efficient 2D/0D heterojunction photocatalysts for solar energy conversion.
文摘The design and construction of heterojunction photocatalysts,which possess a staggered energy band structure and appropriate interfacial contact,is an effective way to achieve outstanding photocatalytic performance.In this study,2D/2D BiOBr/g‐C_(3)N_(4)heterojunctions were successfully obtained by a convenient in situ self‐assembly route.Under simulated sunlight irradiation,99%of RhB(10 mg·L–1,100 mL)was efficiently degraded by 1.5‐BiOBr/g‐C_(3)N_(4)within 30 min,which is better than the performance of both BiOBr and g‐C_(3)N_(4),and it has superior stability.In addition,the composite also exhibits enhanced photocatalytic activity for H2 production.The enhanced activity can be attributed to the intimate interface contact,the larger surface area,and the highly efficient separation of photoinduced electron–hole pairs.Based on the experimental results,a novel S‐scheme model was proposed to illuminate the transfer process of charge carriers.This study presents a simple way to develop novel step‐scheme photocatalysts for environmental and related applications.
文摘TiO_(2)is a promising photocatalyst with limited use in practical applications owing to its wide bandgap,narrow light response range,and rapid recombination of photoexcited carriers.To address these limitations,a novel 1D/2D TiO_(2)/ZnIn_(2)S_(4)heterostructure was designed according to the principles of the S-scheme heterojunction.The TiO_(2)/ZnIn_(2)S_(4)(TZISx)hybrids prepared via a hydrothermal method afforded significant improvement in photocatalytic hydrogen evolution(PHE)in comparison to pristine TiO_(2)and ZnIn_(2)S_(4).In particular,the optimal TZIS2 sample(mass ratio of ZnIn_(2)S_(4)to TiO_(2)was 0.4)exhibited the highest PHE activity(6.03 mmol/h/g),which was approximately 3.7 and 2.0 times higher than those of pristine TiO_(2)and ZnIn_(2)S_(4),respectively.This improvement in the PHE of the TZIS2 sample could be attributed to the formation of an intimate heterojunction interface,high-efficiency separation of charge carriers,abundant reactive sites,and enhanced light absorption capacity.Notably,theoretical and experimental results demonstrated that the S-scheme mechanism of interfacial electron transfer in the TZISx composites facilitated the transfer and separation of photoexcited charge carriers,resulting in more isolated photoexcited electrons for the PHE reaction.
文摘The rapid recombination of photo-generated electron-hole pairs,insufficient active sites,and strong photocorrosion have considerably restricted the practical application of Cd S in photocatalytic fields.Herein,we designed and constructed a 2D/2D/2D layered heterojunction photocatalyst with cascaded 2D coupling interfaces.Experiments using electron spin resonance spectroscopy,ultraviolet photoelectron spectroscopy,and in-situ irradiation X-ray photoelectron spectroscopy were conducted to confirm the 2D layered CdS/WO_(3) step-scheme(S-scheme)heterojunctions and CdS/MX ohmic junctions.Impressively,it was found that the strong interfacial electric fields in the S-scheme heterojunction photocatalysts could effectively promote spatially directional charge separation and transport between CdS and WO_(3) nanosheets.In addition,2D Ti_(3)C_(2) MXene nanosheets with a smaller work function and excellent metal conductivity when used as a co-catalyst could build ohmic junctions with Cd S nanosheets,thus providing a greater number of electron transfer pathways and hydrogen evolution sites.Results showed that the highest visible-light hydrogen evolution rate of the optimized MX-Cd S/WO_(3) layered multi-heterostructures could reach as high as 27.5 mmol/g/h,which was 11.0 times higher than that of pure CdS nanosheets.Notably,the apparent quantum efficiency reached 12.0% at 450 nm.It is hoped that this study offers a reliable approach for developing multifunctional photocatalysts by integrating S-scheme and ohmic-junction built-in electric fields and rationally designing a 2D/2D interface for efficient light-to-hydrogen fuel production.
文摘Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic performance.Herein,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction efficiency.Charge transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area interface.Work function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance spectroscopy.Moreover,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform spectra.Density functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and CO.Introducing Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 eV.This study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.
基金supported by the National Natural Science Foundation of China(Nos.22101105,52071171,52202248)the Research Fund for the Doctoral Program of Liaoning Province(2021-BS-086)+6 种基金Liaoning BaiQianWan Talents Program(LNBQW2018B0048)Shenyang Science and Technology Project(21-108-9-04)Australian Research Council(ARC)through Future Fellowship(FT210100298,FT210100806)Discovery Project(DP220100603)Linkage Project(LP210100467,LP210200504,LP210200345,LP220100088)Industrial Transformation Training Centre(IC180100005)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077).
文摘Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate.Herein,a novel metal-free 2D/2D van der Waals heterojunction,composed of a two-dimensional(2D)COF with ketoenamine linkage(TpPa-1-COF)and 2D defective hexagonal boron nitride(h-BN),is successfully constructed through in situ solvothermal method.Benefitting from the presence of VDW heterojunction,larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN,which make contributions to promoting charge car-riers separation.The introduced defects can also endow the h-BN with porous structure,thus providing more reactive sites.Moreover,the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN,which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF,and suppress electron backflow,corroborated by experimental and density functional theory calculations results.Accordingly,the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays out-standing solar energy catalytic activity for water splitting without co-catalysts,and the H_(2) evolution rate can reach up to 3.15 mmol g^(−1) h^(−1),which is about 67 times greater than that of pristine TpPa-1-COF,also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date.In particular,it is the first work for constructing COFs-based heterojunctions with the help of h-BN,which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H_(2) evolution.
基金supported by the National Natural Science Foundation of China(21663030,21666039)the Open Project of State Key Laboratory of Organic-Inorganic Composites Beijing Key Laboratory,Beijing University of Chemical Technology(oic-201901009)+2 种基金the Project of Science&Technology Office of Shannxi Province(2018TSCXL-NY-02-01,2013K11-08,2013SZS20-P01)Industrial Key Project of Yan’an Science and Technology Bureau(2018KG-04)the Project of Yan’an Science Graduate Innovation Project of Yan’an University(YCX201988)~~
文摘In this work,a set of novel Cu2ZnSnS4/Bi2WO6(CZTS/BWO)two-dimensional(2 D)/two-dimensional(2 D)type-Ⅱheterojunctions with different CZTS weight ratios(1%,2%,and 5%)were successfully synthesized via a brief secondary solvothermal process.The successful formation of the heterojunctions was affirmed by characterization methods such as X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy.The photocatalytic activity results showed that the prepared CZTS/BWO heterojunctions had excellent photocatalytic behaviors for organic degradation,especially when the mass fraction of CZTS with respect to BWO in the composite was 2%.Moreover,the addition of hydrogen peroxide(H2O2)could further improve the dye and antibiotic degradation efficiencies.The reinforced photocatalytic and photo-Fenton degradation performance were primarily attributable to the introduction of BWO,which afforded increased active sites,expanded the solar spectral response range,and accelerated the cycle of Cu(Ⅱ)/Cu(Ⅰ);after four cycling times,its catalytic activity did not decrease significantly.In addition,reasonable hypotheses of the photocatalytic and photo-Fenton catalytic mechanisms were formulated.This study is expected to provide a visual approach for designing a novel photo-Fenton catalyst to jointly utilize the photocatalytic and Fenton activities,which can be better applied to the purification of residual organics in wastewater.
文摘The construction of S‐scheme heterojunction photocatalysts has been regarded as an effective avenue to facilitate the conversion of solar energy to fuel.However,there are still considerable challenges with regard to efficient charge transfer,the abundance of catalytic sites,and extended light absorption.Herein,an S‐scheme heterojunction of 2D/2D zinc porphyrin‐based metal‐organic frameworks/BiVO_(4)nanosheets(Zn‐MOF/BVON)was fabricated for efficient photocatalytic CO_(2)conversion.The optimal one shows a 22‐fold photoactivity enhancement when compared to the previously reported BiVO4 nanoflake(ca.15 nm),and even exhibits~2‐time improvement than the traditional g‐C3N4/BiVO4 heterojunction.The excellent photoactivities are ascribed to the strengthened S‐scheme charge transfer and separation,promoted CO_(2)activation by the well‐dispersed metal nodes Zn_(2)(COO)_(4)in the Zn‐MOF,and extended visible light response range based on the results of the electrochemical reduction,electron paramagnetic resonance,and in‐situ diffuse reflectance infrared Fourier transform spectroscopy.The dimension‐matched Zn‐MOF/BVON S‐scheme heterojunction endowed with highly efficient charge separation and abundant catalytic active sites contributed to the superior CO2 conversion.This study offers a facile strategy for constructing S‐scheme heterojunctions involving porphyrin‐based MOFs for solar fuel production.
文摘The fabrication of S-scheme heterojunctions with fast charge transfer and good interface contacts,such as intermolecularπ–πinteractions,is a promising approach to improve photocatalytic performance.A unique two-dimensional/two-dimensional(2D/2D)S-scheme heterojunction containing TpPa-1-COF/g-C_(3)N_(4) nanosheets(denoted as TPCNNS)was developed.The established maximum interfacial interaction between TpPa-1-COF NS and g-C_(3)N_(4) NS may result in aπ–πconjugated heterointerface.Furthermore,the difference in the work functions of TpPa-1-COF and g-C_(3)N_(4) results in a large Fermi level gap,leading to upward/downward band edge bending.The spontaneous interfacial charge transfer from g-C_(3)N_(4) to TpPa-1-COF at theπ–πconjugated interface area results in the presence of a built-in electric field,according to the charge density difference analysis based on density functional theory calculations.Such an enhanced built-in electric field can efficiently drive directional charge migration via the S-scheme mechanism,which enhances charge separation and utilization.Thus,an approximately 2.8 and 5.6 times increase in the photocatalytic hydrogen evolution rate was recorded in TPCNNS-2(1153μmol g^(-1) h^(-1))compared to pristine TpPa-1-COF and g-C_(3)N_(4) NS,respectively,under visible light irradiation.Overall,this work opens new avenues in the fabrication of 2D/2Dπ–πconjugated S-scheme heterojunction photocatalysts with highly efficient hydrogen evolution performance.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11104250,61274099,and 11774313)the Science Technology Department of Zhejiang Province,China(Grant No.2012C21007)+1 种基金Zhejiang Province Innovation Team,China(Grant No.2011R50012)Zhejiang Provincial Natural Science Foundation,China(Grant No.LY17A040003)
文摘Fabrication of large-area atomically thin transition metal dichalcogenides is of critical importance for the preparation of new heterojunction-based devices.In this paper, we report the fabrication and optical investigation of large-scale chemical vapor deposition(CVD)-grown monolayer MoS2 and exfoliated few-layer GaS heterojunctions.As revealed by photoluminescence(PL) characterization, the as-fabricated heterojunctions demonstrated edge interaction between the two layers.The heterojunction was sensitive to annealing and showed increased interaction upon annealing at 300℃ under vacuum conditions, which led to changes in both the emission peak position and intensity resulting from the strong coupling interaction between the two layers.Low-temperature PL measurements further confirmed the strong coupling interaction.In addition, defect-related GaS luminescence was observed in our few-layer GaS, and the PL mapping provided evidence of edge interaction coupling between the two layers.These findings are interesting and provide the basis for creating new material systems with rich functionalities and novel physical effects.
基金the Training Program of the Major Research Plan of the National Natural Science Foundation of China(61774168,91964103)and the MOST(2016YFA0202300).
文摘The electronic properties and transport properties of MoTe2/SnS2 heterostructure Tunneling FETs are investigated by the density functional theory coupled with non-equilibrium Green’s function method.Two dimensional(2D)monolayer MoTe2 and SnS2 are combined to a vertical van der Waals heterojunction.A small staggered band gap is formed in the overlap region,while larger gaps remain in the underlap source and drain regions of monolayer MoTe2 and SnS2 respectively.Such a type-II heterojunction is favorable for tunneling FET.Furthermore,we suggest short stack length and large gate-to-drain overlap to enhance the on-state current suppress the leakage current respectively.The numerical results show that at a low drain to source voltage Vds=0.05V,On/Off current ratio can reach 108 and the On-state currents is over 20μA/μm for ntype devices.Our results present that van der Waals heterostructure TFETs can be potential candidate as next generation ultra-steep subthreshold and low-power electronic applications.
