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
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
Two-dimensional(2D)perovskites solar cells(PSCs)have attracted considerable attention owing to their excellent stability against humidity;however,some imperfectness of 2D perovskites,such as poor crystallinity,disorde...Two-dimensional(2D)perovskites solar cells(PSCs)have attracted considerable attention owing to their excellent stability against humidity;however,some imperfectness of 2D perovskites,such as poor crystallinity,disordered orientation,and inferior charge transport still limit the power conversion efficiency(PCE)of 2D PSCs.In this work,2D Ti3C2Tx MXene nanosheets with high electrical conductivity and mobility were employed as a nanosized additive to prepare 2D Ruddlesden–Popper perovskite films.The PCE of solar cells was increased from 13.69(without additive)to 15.71%after incorporating the Ti_(3)C_(2)T_(x) nanosheets with an optimized concentration.This improved performance is attributed to the enhanced crystallinity,orientation,and passivated trap states in the 3D phase that result in accelerated charge transfer process in vertical direction.More importantly,the unencapsulated cells exhibited excellent stability under ambient conditions with 55±5%relative humidity.展开更多
The actual manufacture of supercapacitors(SCs)is restricted by the inadequate energy density,and the energy density of devices can be properly promoted by assembling zinc-ion capacitors(ZICs)which used capacitive cath...The actual manufacture of supercapacitors(SCs)is restricted by the inadequate energy density,and the energy density of devices can be properly promoted by assembling zinc-ion capacitors(ZICs)which used capacitive cathode and battery-type anode.Two-dimensional(2D)MXene has brought great focuses in the electrode research on the foundation of large redox-active surface,but the specific capacitance is still affected by the tight stacking of interlaminations.Ti_(3)C_(2)T_(x)@polyaniline(PANI)heterostructures are prepared by uniformly depositing the conductive polymer PANI nanorods as the intercalation agent into the external of Ti_(3)C_(2)T_(x)nanosheets to inhibit stacking.Subsequently,by using graphene oxide(GO)-assisted low-temperature hydrothermal self-assembly manufacture,2D heterostructures are assembled into the three-dimensional(3D)porous crosslinked Ti_(3)C_(2)T_(x)@PANI-reduced graphene oxide(RGO)hydrogels.Attributed to the synergistic work of PANI nanorods,Ti_(3)C_(2)T_(X)nanosheets,and 3D crosslinking frameworks of RGO to match capacitive and battery effects,3D porous hierarchical Ti_(3)C_(2)T_(x)@PANI-RGO heterostructure hydrogels have rich ion transport channels,a large number of active sites,and excellent reaction kinetics.ZIC is assembled by using Ti_(3)C_(2)T_(x)@PANI-RGO heterostructure hydrogels as cathodes and zinc foil as anodes.In this work,Ti_(3)C_(2)T_(x)@PANI-RGO//Zn ZIC exhibits a wide working window(2.0 V),marked specific capacitance(589.89 F·g^(−1)at 0.5 A·g−1),salient energy density(327.71 Wh·kg^(−1)at 513.61 W·kg^(−1)and 192.20 Wh·kg^(−1)at 13,005.87 W·kg^(−1)),and durable cycling stability(97.87%capacitance retention after 10,000 cycles at 10 A·g^(−1)).This study emphasizes the device design of ZICs and the broad prospect of Ti_(3)C_(2)T_(x)-based hydrogels as viable cathodes for ZICs.展开更多
The Jahn-Teller distortion of C80 (D5 , C2 ) singlet was studied by ZINDO method. n ...The Jahn-Teller distortion of C80 (D5 , C2 ) singlet was studied by ZINDO method. n d v C80(D5 ) is more stable than C80(C2 ), which agrees with the experimental results. Jahn-Teller d v distortion happens in some ions for the C80 (D5d) singlet. Total energy of C80 singlet is affected by n n the increase of electric charges. Electronic spectra of C80 singlet were calculated and the reasons for n the red-shift of UV bands for some ions of C80 (D5 ) singlet compared with that of C80(D5 ) and the n d d blue-shift of UV bands for C80 (C2 ) singlet relative to that of C80(C2 ) were discussed. n v v展开更多
As a substitute for synthetic ammonia under mild condition, electrocatalytic nitrogen reduction reaction(NRR) provides a hopeful approach for the development of ammonia. Nevertheless, the current development of NRR el...As a substitute for synthetic ammonia under mild condition, electrocatalytic nitrogen reduction reaction(NRR) provides a hopeful approach for the development of ammonia. Nevertheless, the current development of NRR electrocatalysts is far from enough and a systematic research is needed to gain a better improvement. This article presents that 2 D C_(3)N_(4)-NV with a large specific surface area and abundant nitrogen vacancies is prepared by a simple and feasible method, and used as a metal-free catalyst for electrocatalytic NRR. Experiment result and density functional theory(DFT) calculation reveal that nitrogen vacancies in 2 D C_(3)N_(4)-NV can act as an efficient active site for catalytic NRR, which is conducive to capturing and activating N_(2), lowering Gibbs free energy(DG) in reaction and inhibiting hydrogen evolution reaction(HER) at the same time. In addition, the larger specific surface area also makes more active site exposed, which is good for the contact between the electrolyte and the active site, thus enhancing its NRR activity. The electrocatalyst shows an excellent catalytic activity for NRR in 0.1 M HCl, including Faradaic efficiency of 10.96%, NH_(3) yields of 17.85 lg h^(-1) mg_(cat)^(-1)., and good stability(over 20 h).展开更多
Over the past few decades,the design and development of carbon materials have occurred at a rapid pace.In particular,these porous graphene-like carbon nitride materials have received considerable attention due to thei...Over the past few decades,the design and development of carbon materials have occurred at a rapid pace.In particular,these porous graphene-like carbon nitride materials have received considerable attention due to their superior structures and performances in the energy transformation field.In this review,nitrogenated holey two-dimensional graphene and polymeric carbon nitride will be discussed in depth.The structural properties,synthetic methods,and applications including electrocatalytic reactions,such as hydrogen evolution reaction,oxygen reduction reaction,oxygen evolution reaction,and nitrogen reduction reaction,will be presented in detail.Finally,we will present the outlooks on the current obstacles to the development of carbon nitride materials.This comprehensive understanding will help guide and motivate researchers to develop and modify carbon nitride materials with better properties in the future.展开更多
The separation efficiency of electrons and holes and the enhancement of the surface reductive reaction in the metal sulfide semiconductor photocatalysts are important factors in boosting photocatalytic H_(2)evolution ...The separation efficiency of electrons and holes and the enhancement of the surface reductive reaction in the metal sulfide semiconductor photocatalysts are important factors in boosting photocatalytic H_(2)evolution from water.The control of both interface morphology and the charge-carrier utilization of metal sulfide-based photocatalysts can effectively improve the separation efficiency of electrons and holes and increase the surface reaction active sites,which are considered to be effective methods to improve the photocatalytic activity of semiconductors.Here,the Ti_(3)C_(2)(Mxene)modified all-sulfide 2D/2D Sscheme heterojunction Ti_(3)C_(2)/Zn In_(2)S_(4)(ZIS)/CdS composite material was firstly synthesized by a two-step solvothermal method.The formation of all-sulfide S-scheme heterojunction improves the efficiency of electron-hole separation.The intimate 2D/2D van der Waals structure provides a strong interaction force and a large contact area to enhance charge transfer.The addition of 2D Ti_(3)C_(2)forms the accumulation layer,reducing the recombination of electrons and holes.Under the synergistic promotion,the highest hydrogen production of the prepared Ti_(3)C_(2)/ZIS/CdS composite photocatalyst could reach 8.93 mmol/h/g.This work not only enriches the photocatalytic systems through integrating the ohmic junction and the 2D/2D all-sulfide S-scheme heterojunction,but also provides a satisfactory design strategy for engineering interfacial morphology and charge-carrier utilization.展开更多
Catalysis has been regarded as an effective strategy to mitigate sluggish reaction kinetics and serious shuttle effect of Li-S batteries.Herein,a spherical structure consists of ultrathin layered Ti_(3)C_(2)T_(x)-TiN ...Catalysis has been regarded as an effective strategy to mitigate sluggish reaction kinetics and serious shuttle effect of Li-S batteries.Herein,a spherical structure consists of ultrathin layered Ti_(3)C_(2)T_(x)-TiN heterostructures(MX-TiN)through in-situ nitridation method is reported.Through controllable nitridation,highly conductive TiN layer grew on the surface and close coupled with interior MXene to form unique 2D heterostructures.The ultrathin heterostructure with only several nanometers in thickness enables outstanding ability to shorten electrons diffusion distance during electrochemical reactions and enlarge active surface with abundant adsorptive and catalytic sites.Moreover,the(001)surface of TiN is dominated by metallic Ti-3d states,which ensures fast transmitting electrons from high conductive MX-TiN matrix and thus guarantees efficient catalytic performance.Calculations and experiments demonstrate that polysulfides are strongly immobilized on MX-TiN,meanwhile the bidirectional reaction kinetics are catalytically enhanced by reducing the conversion barrier between liquid LiPSs and solid Li_(2)S_(2)/Li_(2)S.As a result,the S/MX-TiN cathode achieves excellent long-term cyclability with extremely low-capacity fading rate of 0.022%over 1000 cycles and remarkable areal capacity of 8.27 mAh cm^(−2) at high sulfur loading and lean electrolytes.展开更多
Lithium-sulfur(Li-S) batteries are one of the most promising rechargeable storage devices due to the high theoretical energy density.However,the low areal sulfur loading impedes their commercial development.Herein,a 3...Lithium-sulfur(Li-S) batteries are one of the most promising rechargeable storage devices due to the high theoretical energy density.However,the low areal sulfur loading impedes their commercial development.Herein,a 3 D free-standing sulfur cathode scaffold is rationally designed and fabricated by coaxially coating polar Ti_3 C_2 T_x flakes on sulfur-impregnated carbon cloth(Ti_3 C_2 T_x@S/CC) to achieve high loading and high energy density Li-S batteries,in which,the flexible CC substrate with highly porous structure can accommodate large amounts of sulfur and ensure fast electron transfer,while the outer-coated Ti_3 C_2 T_x can serve as a polar and conductive protective layer to further promote the conductivity of the whole electrode,achieve physical blocking and chemical anchoring of lithium-polysulfides as well as catalyze their conversion.Due to these advantages,at a sulfur loading of 4 mg cm^(-2),Li-S cells with Ti_3 C_2 T_x@S/CC cathodes can deliver outstanding cycling stability(746.1 mAh g^(-1) after 200 cycles at1 C),superb rate performance(866.8 mAh g^(-1) up to 2 C) and a high specific energy density(564.2 Wh kg^(-1) after 100 cycles at 0.5 C).More significantly,they also show the commercial potential that can compete with current lithium-ion batteries due to the high areal capacity of 6.7 mAh cm^(-2) at the increased loading of 8 mg cm^(-2).展开更多
As a two-dimensional carbon based semiconductor,C_(3)N acts as a promising material in many application areas.However,the basic physical properties such as Raman spectrum properties of C_(3)N is still not clear.In thi...As a two-dimensional carbon based semiconductor,C_(3)N acts as a promising material in many application areas.However,the basic physical properties such as Raman spectrum properties of C_(3)N is still not clear.In this paper,we clarify the Raman spectrum properties of multilayer C_(3)N.Moreover,the stacking driven Raman spectra change of multilayer C_(3)N is also discussed.展开更多
As a class of metal-free two-dimensional(2D)semiconductor materials,polymeric carbon nitrides have attracted wide attention recently due to its facile regulation of the molecular and electronic structures,availability...As a class of metal-free two-dimensional(2D)semiconductor materials,polymeric carbon nitrides have attracted wide attention recently due to its facile regulation of the molecular and electronic structures,availability in abundance and high stability.According to the different ratios of C and N atoms in the fra mework,a series of C_(x)N_(y)materials have been successfully synthesized by virtue of various precursors,which further triggers extensive investigations of broad applications ranging from sustainable photocatalytic reactions and highly sensitive optoelectronic biosensing.In view of topological structures on their electronic structures and material properties,the as-reported C_(x)N_(y)could be generally classified into two main categories with three-or six-bond-extending frameworks.Owing to the effective n→π*transition in most C_(x)N_(y)materials,the relative energy level of the lone-pair electrons on N atoms is high,which thus endows the mate rials with the capability of visible light absorption.Meanwhile,the different repeating units,bridging groups and defect sites of these two kinds of C_(x)N_(y)allow them to effectively drive a diverse of promising applications that require specific electronic,inte rfacial and geometric properties.This review paper aims to summarize the recent progress in topological structure design and the relevant electronic band structures and striking properties of C_(x)N_(y)materials,In the final part,we also discuss the existing challenges of C_(x)N_(y)and outlook the prospect possibilities.展开更多
Two-/three-dimensional(2D/3D)heterojunction-based photodetectors have attracted much attention due to their highly efficient photoelectric conversion driven by the built-in electric field for high-speed photoresponse....Two-/three-dimensional(2D/3D)heterojunction-based photodetectors have attracted much attention due to their highly efficient photoelectric conversion driven by the built-in electric field for high-speed photoresponse.However,a large dark current induced by unexpected surface states at the interface between 2D materials and 3D bulks is widely observed in such structures,greatly degrading their optoelectronic performance.Herein,a heterojunction of proton acid HCl treated MXene(H-MXene)/TiO_(2)/Si via integrating surface and interface engineering is fabricated,which exhibits decreased dark current and improved environmental stability.A feasible strategy to optimize the interface properties between MXene and Si is proposed by an in-situ oxidation process of MXene into TiO_(2),resulting in a suppressed dark current as well as high specific detectivity.Benefitting from the enhanced light absorption of MXene on the bulk Si substrate,the photoresponse of as-fabricated devices in the near-infrared region is also elevated.Moreover,the treatment of proton acid HCl on the surface of MXene brings better conductivity and environmental stability due to the decreased layer spacing of MXene,which is further confirmed by both experimental and theoretical methods.This work opens a unique way to comprehensively boost the optoelectronic performance of MXene-based photodetectors.展开更多
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.
基金the National Natural Science Foundation of China(No.11974129 to X.-F.W.)“the Fundamental Research Funds for the Central Universities,Jilin University.”。
文摘Two-dimensional(2D)perovskites solar cells(PSCs)have attracted considerable attention owing to their excellent stability against humidity;however,some imperfectness of 2D perovskites,such as poor crystallinity,disordered orientation,and inferior charge transport still limit the power conversion efficiency(PCE)of 2D PSCs.In this work,2D Ti3C2Tx MXene nanosheets with high electrical conductivity and mobility were employed as a nanosized additive to prepare 2D Ruddlesden–Popper perovskite films.The PCE of solar cells was increased from 13.69(without additive)to 15.71%after incorporating the Ti_(3)C_(2)T_(x) nanosheets with an optimized concentration.This improved performance is attributed to the enhanced crystallinity,orientation,and passivated trap states in the 3D phase that result in accelerated charge transfer process in vertical direction.More importantly,the unencapsulated cells exhibited excellent stability under ambient conditions with 55±5%relative humidity.
基金the National Key Research and Development Program of China(No.2022YFC2105900)the National Natural Science Foundation of China(No.52073022).
文摘The actual manufacture of supercapacitors(SCs)is restricted by the inadequate energy density,and the energy density of devices can be properly promoted by assembling zinc-ion capacitors(ZICs)which used capacitive cathode and battery-type anode.Two-dimensional(2D)MXene has brought great focuses in the electrode research on the foundation of large redox-active surface,but the specific capacitance is still affected by the tight stacking of interlaminations.Ti_(3)C_(2)T_(x)@polyaniline(PANI)heterostructures are prepared by uniformly depositing the conductive polymer PANI nanorods as the intercalation agent into the external of Ti_(3)C_(2)T_(x)nanosheets to inhibit stacking.Subsequently,by using graphene oxide(GO)-assisted low-temperature hydrothermal self-assembly manufacture,2D heterostructures are assembled into the three-dimensional(3D)porous crosslinked Ti_(3)C_(2)T_(x)@PANI-reduced graphene oxide(RGO)hydrogels.Attributed to the synergistic work of PANI nanorods,Ti_(3)C_(2)T_(X)nanosheets,and 3D crosslinking frameworks of RGO to match capacitive and battery effects,3D porous hierarchical Ti_(3)C_(2)T_(x)@PANI-RGO heterostructure hydrogels have rich ion transport channels,a large number of active sites,and excellent reaction kinetics.ZIC is assembled by using Ti_(3)C_(2)T_(x)@PANI-RGO heterostructure hydrogels as cathodes and zinc foil as anodes.In this work,Ti_(3)C_(2)T_(x)@PANI-RGO//Zn ZIC exhibits a wide working window(2.0 V),marked specific capacitance(589.89 F·g^(−1)at 0.5 A·g−1),salient energy density(327.71 Wh·kg^(−1)at 513.61 W·kg^(−1)and 192.20 Wh·kg^(−1)at 13,005.87 W·kg^(−1)),and durable cycling stability(97.87%capacitance retention after 10,000 cycles at 10 A·g^(−1)).This study emphasizes the device design of ZICs and the broad prospect of Ti_(3)C_(2)T_(x)-based hydrogels as viable cathodes for ZICs.
文摘The Jahn-Teller distortion of C80 (D5 , C2 ) singlet was studied by ZINDO method. n d v C80(D5 ) is more stable than C80(C2 ), which agrees with the experimental results. Jahn-Teller d v distortion happens in some ions for the C80 (D5d) singlet. Total energy of C80 singlet is affected by n n the increase of electric charges. Electronic spectra of C80 singlet were calculated and the reasons for n the red-shift of UV bands for some ions of C80 (D5 ) singlet compared with that of C80(D5 ) and the n d d blue-shift of UV bands for C80 (C2 ) singlet relative to that of C80(C2 ) were discussed. n v v
基金funded by the National Natural Science Foundation of China (21802058 and 21872066)the Fundamental Research Funds for the Central Universities (China, lzujbky-2020-42)the Natural Science Foundation of Gansu Province (20JR5RA225)。
文摘As a substitute for synthetic ammonia under mild condition, electrocatalytic nitrogen reduction reaction(NRR) provides a hopeful approach for the development of ammonia. Nevertheless, the current development of NRR electrocatalysts is far from enough and a systematic research is needed to gain a better improvement. This article presents that 2 D C_(3)N_(4)-NV with a large specific surface area and abundant nitrogen vacancies is prepared by a simple and feasible method, and used as a metal-free catalyst for electrocatalytic NRR. Experiment result and density functional theory(DFT) calculation reveal that nitrogen vacancies in 2 D C_(3)N_(4)-NV can act as an efficient active site for catalytic NRR, which is conducive to capturing and activating N_(2), lowering Gibbs free energy(DG) in reaction and inhibiting hydrogen evolution reaction(HER) at the same time. In addition, the larger specific surface area also makes more active site exposed, which is good for the contact between the electrolyte and the active site, thus enhancing its NRR activity. The electrocatalyst shows an excellent catalytic activity for NRR in 0.1 M HCl, including Faradaic efficiency of 10.96%, NH_(3) yields of 17.85 lg h^(-1) mg_(cat)^(-1)., and good stability(over 20 h).
基金The authors acknowledge the financial support from the National Natural Science Foundation of China(22001228)the“Double-First Class”University Construction Project(C176220100022 and C176220100042)+2 种基金the Major Science and Technology Project of Precious Metal Materials Genetic Engineering in Yunnan Province(2019ZE001-1 and 202002AB080001)the International Joint Research Center for Advanced Energy Materials of Yunnan Province(202003AE140001)Guangzhi Hu is grateful to the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University(2019FY003025).
文摘Over the past few decades,the design and development of carbon materials have occurred at a rapid pace.In particular,these porous graphene-like carbon nitride materials have received considerable attention due to their superior structures and performances in the energy transformation field.In this review,nitrogenated holey two-dimensional graphene and polymeric carbon nitride will be discussed in depth.The structural properties,synthetic methods,and applications including electrocatalytic reactions,such as hydrogen evolution reaction,oxygen reduction reaction,oxygen evolution reaction,and nitrogen reduction reaction,will be presented in detail.Finally,we will present the outlooks on the current obstacles to the development of carbon nitride materials.This comprehensive understanding will help guide and motivate researchers to develop and modify carbon nitride materials with better properties in the future.
基金financially supported by the National Natural Science Foundation of China(Nos.21975084 and 51672089)the Ding Ying Talent Project of South China Agricultural University for their support。
文摘The separation efficiency of electrons and holes and the enhancement of the surface reductive reaction in the metal sulfide semiconductor photocatalysts are important factors in boosting photocatalytic H_(2)evolution from water.The control of both interface morphology and the charge-carrier utilization of metal sulfide-based photocatalysts can effectively improve the separation efficiency of electrons and holes and increase the surface reaction active sites,which are considered to be effective methods to improve the photocatalytic activity of semiconductors.Here,the Ti_(3)C_(2)(Mxene)modified all-sulfide 2D/2D Sscheme heterojunction Ti_(3)C_(2)/Zn In_(2)S_(4)(ZIS)/CdS composite material was firstly synthesized by a two-step solvothermal method.The formation of all-sulfide S-scheme heterojunction improves the efficiency of electron-hole separation.The intimate 2D/2D van der Waals structure provides a strong interaction force and a large contact area to enhance charge transfer.The addition of 2D Ti_(3)C_(2)forms the accumulation layer,reducing the recombination of electrons and holes.Under the synergistic promotion,the highest hydrogen production of the prepared Ti_(3)C_(2)/ZIS/CdS composite photocatalyst could reach 8.93 mmol/h/g.This work not only enriches the photocatalytic systems through integrating the ohmic junction and the 2D/2D all-sulfide S-scheme heterojunction,but also provides a satisfactory design strategy for engineering interfacial morphology and charge-carrier utilization.
基金supported by the National Natural Science Foundation of China (Grant Nos.52225204, 11974074, and 11804048)the Innovation Program of Shanghai Municipal Education Commission (2021-01-07-00-03-E00109)+3 种基金the Fundamental Research Funds for the Central Universities (2232022G-07 and 2232021D-28)Graduate Student Innovation Fund of Donghua University (CUSF-DH-D-2022007)the Program Innovative Research Team in University (IRT_16R13)the International Joint Laboratory for Advanced fiber and Low- dimension Materials (18520750400).
文摘Catalysis has been regarded as an effective strategy to mitigate sluggish reaction kinetics and serious shuttle effect of Li-S batteries.Herein,a spherical structure consists of ultrathin layered Ti_(3)C_(2)T_(x)-TiN heterostructures(MX-TiN)through in-situ nitridation method is reported.Through controllable nitridation,highly conductive TiN layer grew on the surface and close coupled with interior MXene to form unique 2D heterostructures.The ultrathin heterostructure with only several nanometers in thickness enables outstanding ability to shorten electrons diffusion distance during electrochemical reactions and enlarge active surface with abundant adsorptive and catalytic sites.Moreover,the(001)surface of TiN is dominated by metallic Ti-3d states,which ensures fast transmitting electrons from high conductive MX-TiN matrix and thus guarantees efficient catalytic performance.Calculations and experiments demonstrate that polysulfides are strongly immobilized on MX-TiN,meanwhile the bidirectional reaction kinetics are catalytically enhanced by reducing the conversion barrier between liquid LiPSs and solid Li_(2)S_(2)/Li_(2)S.As a result,the S/MX-TiN cathode achieves excellent long-term cyclability with extremely low-capacity fading rate of 0.022%over 1000 cycles and remarkable areal capacity of 8.27 mAh cm^(−2) at high sulfur loading and lean electrolytes.
基金supported by the National Natural Science Foundation of China (51772069)。
文摘Lithium-sulfur(Li-S) batteries are one of the most promising rechargeable storage devices due to the high theoretical energy density.However,the low areal sulfur loading impedes their commercial development.Herein,a 3 D free-standing sulfur cathode scaffold is rationally designed and fabricated by coaxially coating polar Ti_3 C_2 T_x flakes on sulfur-impregnated carbon cloth(Ti_3 C_2 T_x@S/CC) to achieve high loading and high energy density Li-S batteries,in which,the flexible CC substrate with highly porous structure can accommodate large amounts of sulfur and ensure fast electron transfer,while the outer-coated Ti_3 C_2 T_x can serve as a polar and conductive protective layer to further promote the conductivity of the whole electrode,achieve physical blocking and chemical anchoring of lithium-polysulfides as well as catalyze their conversion.Due to these advantages,at a sulfur loading of 4 mg cm^(-2),Li-S cells with Ti_3 C_2 T_x@S/CC cathodes can deliver outstanding cycling stability(746.1 mAh g^(-1) after 200 cycles at1 C),superb rate performance(866.8 mAh g^(-1) up to 2 C) and a high specific energy density(564.2 Wh kg^(-1) after 100 cycles at 0.5 C).More significantly,they also show the commercial potential that can compete with current lithium-ion batteries due to the high areal capacity of 6.7 mAh cm^(-2) at the increased loading of 8 mg cm^(-2).
基金supported by The National Natural Science Foundation of China (Nos. 11804353 and 11774368)Shanghai Science and Technology Committee (No. 18511110600)
文摘As a two-dimensional carbon based semiconductor,C_(3)N acts as a promising material in many application areas.However,the basic physical properties such as Raman spectrum properties of C_(3)N is still not clear.In this paper,we clarify the Raman spectrum properties of multilayer C_(3)N.Moreover,the stacking driven Raman spectra change of multilayer C_(3)N is also discussed.
基金the National Natural Science Foundation of China(Nos.21775018,21675022)the Natural Science Foundation of Jiangsu Province(No.BK20170084)+1 种基金the Open Funds of the State Key Laboratory of Electroanalytical Chemistry(No.SKLEAC201909)the Fundamental Research Funds for the Central Universities。
文摘As a class of metal-free two-dimensional(2D)semiconductor materials,polymeric carbon nitrides have attracted wide attention recently due to its facile regulation of the molecular and electronic structures,availability in abundance and high stability.According to the different ratios of C and N atoms in the fra mework,a series of C_(x)N_(y)materials have been successfully synthesized by virtue of various precursors,which further triggers extensive investigations of broad applications ranging from sustainable photocatalytic reactions and highly sensitive optoelectronic biosensing.In view of topological structures on their electronic structures and material properties,the as-reported C_(x)N_(y)could be generally classified into two main categories with three-or six-bond-extending frameworks.Owing to the effective n→π*transition in most C_(x)N_(y)materials,the relative energy level of the lone-pair electrons on N atoms is high,which thus endows the mate rials with the capability of visible light absorption.Meanwhile,the different repeating units,bridging groups and defect sites of these two kinds of C_(x)N_(y)allow them to effectively drive a diverse of promising applications that require specific electronic,inte rfacial and geometric properties.This review paper aims to summarize the recent progress in topological structure design and the relevant electronic band structures and striking properties of C_(x)N_(y)materials,In the final part,we also discuss the existing challenges of C_(x)N_(y)and outlook the prospect possibilities.
基金H.P.W.from Tsinghua University contributed to the theoretical calculation.All the authors discussed and participated into the paper writing.The authors are grateful for the financial support from the National Natural Science Foundation of China(Nos.62104017 and 62074015)the project funded by China Postdoctoral Science Foundation under Grant 2022M720422Beijing Institute of Technology Research Fund Program for Young Scholars.
文摘Two-/three-dimensional(2D/3D)heterojunction-based photodetectors have attracted much attention due to their highly efficient photoelectric conversion driven by the built-in electric field for high-speed photoresponse.However,a large dark current induced by unexpected surface states at the interface between 2D materials and 3D bulks is widely observed in such structures,greatly degrading their optoelectronic performance.Herein,a heterojunction of proton acid HCl treated MXene(H-MXene)/TiO_(2)/Si via integrating surface and interface engineering is fabricated,which exhibits decreased dark current and improved environmental stability.A feasible strategy to optimize the interface properties between MXene and Si is proposed by an in-situ oxidation process of MXene into TiO_(2),resulting in a suppressed dark current as well as high specific detectivity.Benefitting from the enhanced light absorption of MXene on the bulk Si substrate,the photoresponse of as-fabricated devices in the near-infrared region is also elevated.Moreover,the treatment of proton acid HCl on the surface of MXene brings better conductivity and environmental stability due to the decreased layer spacing of MXene,which is further confirmed by both experimental and theoretical methods.This work opens a unique way to comprehensively boost the optoelectronic performance of MXene-based photodetectors.
