The development of high-performance non-precious metal-based robust bifunctional electrocatalyst for both hydrogen evolution reaction(HER) and oxygen evolution reactions(OER) in alkaline media is essential for the ele...The development of high-performance non-precious metal-based robust bifunctional electrocatalyst for both hydrogen evolution reaction(HER) and oxygen evolution reactions(OER) in alkaline media is essential for the electrochemical overall water splitting technologies. Herein, we demonstrate that the HER/OER performance of Co Se_(2)can be significantly enhanced by tuning the 3d-orbital electron filling degree through Mo doping. Both density functional theory(DFT) calculations and experimental results imply that the doping of Mo with higher proportion of the unoccupied d-orbital(P_(un)) could not only serve as the active center for water adsorption to enhance the water molecule activation, but also modulate the electronic structures of Co metal center leading to the optimized adsorption strength of*H. As expected, the obtained Mo-Co Se_(2)exhibits a remarkable bifunctional performance with overpotential of only 85 m V for HER and 245 m V for OER to achieve the current density of 10 m A/cm^(2)in alkaline media.This work will provide a valuable insight to design highly efficient bifunctional electrocatalyst towards HER and OER.展开更多
Organic cathodes for alkali-metal-ion batteries attract great attentions in recent years,but the ion storage sites are limited to some finite functional groups.This is because an organic cathode must have proper lowes...Organic cathodes for alkali-metal-ion batteries attract great attentions in recent years,but the ion storage sites are limited to some finite functional groups.This is because an organic cathode must have proper lowest unoccupied molecular orbitals(LUMO) to accept electrons at high potential.Herein,a novel type of organophosphate-based cathode has successfully been explored by tuning the LUMO energy level of organophosphates through metal ions with an inert electron pair.For the first time,the P=O of phytate(PA),N,N,N’,N’-ethylenediaminetetrakis(methylene phytate)(EDTMP),and diethylenetriaminepentakis(methyl phytate)(DTPMP) is activated by lead/bismuth(with 6s2electron pair) to storage Li/Na/K ions reversibly.Typically,density functional theory calculations indicate that the LUMO energy of Bi-PA is greatly reduced from-0.99(PA) to-4.61 eV,which shows the first discharge capacity of 173,182 and 206mAh·g-1and the reversibly capacity of 102,102 and 101mAh·g-1with the discharge platform of 2.4,2.1 and 2.4 V for Li/Na/K-ion battery cathodes,respectively.Similarly,with proper LUMO energy level,Pb-PA(-4.63 eV),Pb-EDTMP(-3.71 eV),and Pb-DTPMP(-4.45 eV) all exhibit admirable performance.This unique strategy of organic materials to alkali-metal-ion battery cathodes offers a new avenue for future energy storage systems.展开更多
Significant interest has been focused on graphene materials for their unique properties as Hydrogen storage materials. The development of their abilities by modifying their configuration with doped or decorated transi...Significant interest has been focused on graphene materials for their unique properties as Hydrogen storage materials. The development of their abilities by modifying their configuration with doped or decorated transition metals </span><span style="font-family:Verdana;">was also of great interest. In this work</span><span style="font-family:Verdana;">,</span><span style="font-family:Verdana;"> using the DFT/B3LYP/6-31G/LanL2DZ</span><span style="font-family:Verdana;"> level of theory, graphene sheet (GS) as one of the materials of interest was doped with two transition metals, Osmium (Os) and Tungsten (W). Two active sites on the GS were tested (C4 and C16) resulted into adsorbed systems, H2@C4-GS and H2@C16-GS. C16 position showed the largest adsorption energy compared to that at C4. Therefore, C4 was replaced by the two metals and two adsorbed systems were formed</span><span style="font-family:Verdana;">: </span><span style="font-family:Verdana;">H</span><sub><span style="font-family:Verdana;vertical-align:sub;">2</span></sub><span style="font-family:Verdana;">@Os-GS and H2@W-GS. The binding energy of H</span><sub><span style="font-family:Verdana;vertical-align:sub;">2</span></sub><span style="font-family:Verdana;">@Os-GS was found to be greater than that of H2@W-GS.展开更多
The distribution patterns of mangrove Bruguiera gymnorrhiza population s in southern China are analyzed using the box-counting method of fractal theory. The patterns of B. gymnorrhiza populations could be thought of a...The distribution patterns of mangrove Bruguiera gymnorrhiza population s in southern China are analyzed using the box-counting method of fractal theory. The patterns of B. gymnorrhiza populations could be thought of as fractals as they exhibit self-similarity within the range of scale considered. Their fractal dimensions are not integer but fractional, ranging from 1.04 to 1.51. The unoccupied dimensions change from 0.49 to 0.96. The combined conditions of population density, pattern type and aggregation intensity together influence the values of fractal dimensions of patterns. The box counting is a useful and efficient method to investigate the complexity of patterns. Fractal dimension may be a most desirable and appropriate index for quantifying the horizontal spatial microstructure and fractal behaviors of patterns over a certain range of scales.展开更多
Lithium-sulfur batteries(LSBs)offer high energy density and eco-friendly sulfur cathodes,but commercialization is hindered by slow sulfur redox kinetics and the“shuttle effect”,which limit capacity and cycle life.Th...Lithium-sulfur batteries(LSBs)offer high energy density and eco-friendly sulfur cathodes,but commercialization is hindered by slow sulfur redox kinetics and the“shuttle effect”,which limit capacity and cycle life.This study used inverse photoemission spectroscopy and ultraviolet photoelectron spectroscopy(IPES/UPS)to investigate the S redox mechanism.The BNOC matrix,with fully occupied electron states near the Fermi level,enhances conductivity and oxygen covalency by downshifting the lowest unoccupied molecular orbital(LUMO)to hybridize with the highest occupied molecular orbital(HOMO).This matrix traps lithium polysulfides(LiPSs),where loosely bound oxygen atoms facilitate S redox,particularly the key Li_(2)S↔LiPSs conversion.Additionally,the strong covalent B-N bonds,synergizing with the hollow BNOC cages,confine S redox reactions within structurally stable nanoscale spaces,effectively mitigating the shuttle effect.As a result,the LSB in our study delivers extended 1300 cycles at 4 C,maintaining 337.8 mAh·g^(-1)specific capacity.It also possesses a high areal capacity of 7.76 mAh·cm^(-2)at a high sulfur loading of 5.6 mg·cm^(-2),and is capable of powering a pouch-type LSB at a current density of 8 mAh·cm^(-2)for over 15 cycles.This study lays a foundation for the rational design and performance enhancement of future LSB.展开更多
The issue of unoccupied or abandoned homesteads(courtyards)in China emerges given the increasing aging population,rapid urbanization and massive rural-urban migration.From the aspect of rural vitalization,land-use pla...The issue of unoccupied or abandoned homesteads(courtyards)in China emerges given the increasing aging population,rapid urbanization and massive rural-urban migration.From the aspect of rural vitalization,land-use planning,and policy making,determining the number of unoccupied courtyards is important.Field and questionnaire-based surveys were currently the main approaches,but these traditional methods were often expensive and laborious.A new workflow is explored using deep learning and machine learning algorithms on unmanned aerial vehicle(UAV)images.Initially,features of the built environment were extracted using deep learning to evaluate the courtyard management,including extracting complete or collapsed farmhouses by Alexnet,detecting solar water heaters by YOLOv5s,calculating green looking ratio(GLR)by FCN.Their precisions exceeded 98%.Then,seven machine learning algorithms(Adaboost,binomial logistic regression,neural network,random forest,support vector machine,decision trees,and XGBoost algorithms)were applied to identify the rural courtyards’utilization status.The Adaboost algorithm showed the best performance with the comprehensive consideration of most metrics(Accuracy:0.933,Precision:0.932,Recall:0.984,F1-score:0.957).Results showed that identifying the courtyards’utilization statuses based on the courtyard built environment is feasible.It is transferable and cost-effective for large-scale village surveys,and may contribute to the intensive and sustainable approach to rural land use.展开更多
Imide-based conjugated molecules have emerged as a highly promising class of building blocks for constructing n-type semiconducting materials with lowlying lowest unoccupied molecular orbitals and exceptional stabilit...Imide-based conjugated molecules have emerged as a highly promising class of building blocks for constructing n-type semiconducting materials with lowlying lowest unoccupied molecular orbitals and exceptional stability.Although imides,such as naphthalene diimides,perylene diimides and their lateral fused analogs,have been synthesized extensively,the design and synthesis of largerπ-extended molecules incorporating more than two imide groups are desirable but still very challenging.Herein,we report the synthesis of an unprecedented electron-deficient bisanthene tetraimide(ATI)containing a bisantheneconjugated core and four five-membered imide groups,which was successfully achieved via a combined approach of solution and on-surface synthesis.The chemical structures,electronic states,formation mechanism and aromaticity of ATI were systematically investigated by scanning tunneling microscopy,noncontact atomic force microscopy,scanning tunneling spectroscopy,and density functional theory calculations.展开更多
High-order nonlinear multiphoton absorption is usually inefficient,but can be enhanced by designing resonant excitations between occupied and unoccupied energy levels.We conducted angle-resolved multi-photon photoemis...High-order nonlinear multiphoton absorption is usually inefficient,but can be enhanced by designing resonant excitations between occupied and unoccupied energy levels.We conducted angle-resolved multi-photon photoemission(mPPE)studies on the SnSe_(2)(001)surfaces excited by ultrashort laser pulses.By tuning photon energy and light polarization,we demonstrate the presence of a resonant four-photon photoemission(4PPE)process involving the occupied valence band(VB),the unoccupied second conduction band(CB2)and the unoccupied image-potential state(IPs)of SnSe_(2).In this 4PPE process,VB electrons of SnSe_(2) are resonantly excited into CB2 by adsorbing two photons,followed by the adsorption of another photon to populate the n=1 IPs before being emitted out to the vacuum by adsorbing one more photon.This results in a double-resonant 4PPE process,which exhibits approximately a 40 times enhancement in photoemission yields compared to cases where one of the resonant pathways,CB2→IPs,is inhibited by involving a virtual state instead of the IPs in the 4PPE.The double-resonant 4PPE process efficiently excite the bulk VB electrons outside the vacuum,like taking advantage of resonant“ladders”through two real empty electronic states of SnSe_(2).Our results highlight the important applications of mPPE in probing the band-structure,particularly the unoccupied states,of recently emerging main group dichalcogenide semiconductors.Furthermore,the discovered resonant mPPE process contributes to the exploration of their promising optoelectronic applications.展开更多
In organic solar cells(OSCs),it is an effective way to improve the power conversion efficiency(PCE)by adding a vip component with appropriate absorption and energy levels in the host system.Herein,a new nonfullerene...In organic solar cells(OSCs),it is an effective way to improve the power conversion efficiency(PCE)by adding a vip component with appropriate absorption and energy levels in the host system.Herein,a new nonfullerene acceptor(NFA)named TBF-2Cl was developed by the strategy of expanding theπconjugated core of 2,2’-(((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b’]dithiophene-2,7-diyl)bis(methaneylylidene))bis(5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(IDT-4Cl)with two benzene rings.With increase of benzene units,TBF-2Cl exhibits higher lowest unoccupied molecular orbital(LUMO)level of-3.75 eV than that of one benzene unit based NFA IDT-4Cl and fluorene core based NFA F-2Cl,which facilitates enhancing the open-circuit voltage(V_(oc))of ternary devices.Moreover,TBF-2Cl film shows a medium optical bandgap with the absorption range from 500-800 nm,being well complementary with the wide bandgap polymer donor D18 and narrow bandgap NFA CH-6F.Accordingly,a remarkable PCE of 18.92%with a high short-circuit current density(J_(sc))of 27.40 mA·cm^(-2),a fill factor(FF)of 0.749,especially an outstanding V_(oc) of 0.922 V was achieved for the optimal ternary device based on D18:TBF-2Cl:CH-6F,surpassing the binary counterpart(17.08%).The findings provide insight into the development of new vip acceptors for obtaining more efficient OSCs.展开更多
Improving the complete ethanol electrooxidation on Pd-based catalysts in alkaline media has drawn widely attention due to the high mass energy density.However,the weak adsorption energy of CH_(3)CO^(*) on Pd restricts...Improving the complete ethanol electrooxidation on Pd-based catalysts in alkaline media has drawn widely attention due to the high mass energy density.However,the weak adsorption energy of CH_(3)CO^(*) on Pd restricts the C–C bond cleavage.Inspired by the molecular orbital theory,we proposed the d-state-editing strategy to construct more unoccupied d-states of Pd for the enhanced interaction with CH_(3)CO^(*) to break C–C bonds.As expected,the reduced number of e_g electrons and more unoccupied d-states of Pd successfully formed on as-prepared porous Rh Au–Pd Cu nanosheets(PNSs).Theoretical calculations show that the optimized d-states of Rh Au–Pd Cu PNS can effectively improve the adsorption of CH_(3)CO^(*) and drastically reduce the energy barrier of C–C bond cleavage,thus boosting the complete oxidation of ethanol.The charge ratio of C_1 pathway on Rh Au–Pd Cu PNSs is 51.5%,more than 2 times higher than that of Pd NSs.Our finding provides an innovative perspective for the design of highly-efficient noble-based electrocatalysts.展开更多
The high unoccupied d band energy of Ni_(3)N basically results in weak orbital coupling with water molecule,consequently leading to slow water dissociation kinetics.Herein,we demonstrate Cr doping can downshift the un...The high unoccupied d band energy of Ni_(3)N basically results in weak orbital coupling with water molecule,consequently leading to slow water dissociation kinetics.Herein,we demonstrate Cr doping can downshift the unoccupied d orbitals and strengthen the interfacial orbital coupling to boost the water dissociation kinetics.The prepared Cr-Ni_(3)N/Ni displays an impressive overpotential of 37 mV at 10 mA·cmgeo-2,close to the benchmark Pt/C in 1.0 M KOH solution.Refined structural analysis reveals the Cr dopant exists as the Cr-N_(6)states and the average d band energy of Ni_(3)N is also lowered.Density functional theory calculation further confirms the downshifted d band energy can strengthen the orbital coupling between the unpaired electrons in O 2p and the unoccupied state of Ni 3d,which thus facilitates the water adsorption and dissociation.The work provides a new concept to achieve on-demand functions for hydrogen evolution catalysis and beyond,by regulating the interfacial orbital coupling.展开更多
To increase the current density of the hole only device, 1, 4, 5, 8, 9, 11-hexaazatriphenylene-hexacarbonitrile (HAT-CN) material has been inserted in the device at the indium tin oxide (ITO)/organic interface. Since ...To increase the current density of the hole only device, 1, 4, 5, 8, 9, 11-hexaazatriphenylene-hexacarbonitrile (HAT-CN) material has been inserted in the device at the indium tin oxide (ITO)/organic interface. Since HATCN molecule can withdraw electrons, it can alter electronic properties of the electrodes and hence inserted between the organic/metal interfaces. This paper deals with the optimization of the thickness of organic-metal layers to enhance the efficiency. Also, efforts have been made to increase the current density and reduce the operating voltage of the device. The material 2, 7-bis [N, N-bis (4- methoxy-phenyl) amino]-9, 9-spirobifluorene (Meo-Spiro-TPD) is used to simulate the hole only device because it is a thermally stable hole transport material. Simulated results shows that better current density values can be achieved compared to fabricated one by optimizing the organic metal layer thickness. The best optimized layer thickness of 22 nm for Alq3, 25 nm for *CBP doped with Ir(ppy)3, 9 nm for Meo-Spiro TPD and 4 nm for HAT-CN which results in current density of 0.12 A/cm2 with a reduction in operating voltage by approximately 2 V.展开更多
基金financially supported by the National Natural Science Foundation of China (No. 21972107)Natural Science Foundation of Jiangsu Province (No. BK20191186)Natural Science Foundation of Hubei Province (No. 2020CFA095)。
文摘The development of high-performance non-precious metal-based robust bifunctional electrocatalyst for both hydrogen evolution reaction(HER) and oxygen evolution reactions(OER) in alkaline media is essential for the electrochemical overall water splitting technologies. Herein, we demonstrate that the HER/OER performance of Co Se_(2)can be significantly enhanced by tuning the 3d-orbital electron filling degree through Mo doping. Both density functional theory(DFT) calculations and experimental results imply that the doping of Mo with higher proportion of the unoccupied d-orbital(P_(un)) could not only serve as the active center for water adsorption to enhance the water molecule activation, but also modulate the electronic structures of Co metal center leading to the optimized adsorption strength of*H. As expected, the obtained Mo-Co Se_(2)exhibits a remarkable bifunctional performance with overpotential of only 85 m V for HER and 245 m V for OER to achieve the current density of 10 m A/cm^(2)in alkaline media.This work will provide a valuable insight to design highly efficient bifunctional electrocatalyst towards HER and OER.
基金financially supported by the Science and Technology Commission of Shanghai Municipality (No. 22ZR1471300)the National Science Foundation of China (Nos. 21871008,51922103 and 21801247)+1 种基金the Key Research Program of Chinese Academy of Sciences (No.QYZDJ-SSW-JSC013)China Postdoctoral Science Foundation (Nos.2020M671242 and 2021T140688)。
文摘Organic cathodes for alkali-metal-ion batteries attract great attentions in recent years,but the ion storage sites are limited to some finite functional groups.This is because an organic cathode must have proper lowest unoccupied molecular orbitals(LUMO) to accept electrons at high potential.Herein,a novel type of organophosphate-based cathode has successfully been explored by tuning the LUMO energy level of organophosphates through metal ions with an inert electron pair.For the first time,the P=O of phytate(PA),N,N,N’,N’-ethylenediaminetetrakis(methylene phytate)(EDTMP),and diethylenetriaminepentakis(methyl phytate)(DTPMP) is activated by lead/bismuth(with 6s2electron pair) to storage Li/Na/K ions reversibly.Typically,density functional theory calculations indicate that the LUMO energy of Bi-PA is greatly reduced from-0.99(PA) to-4.61 eV,which shows the first discharge capacity of 173,182 and 206mAh·g-1and the reversibly capacity of 102,102 and 101mAh·g-1with the discharge platform of 2.4,2.1 and 2.4 V for Li/Na/K-ion battery cathodes,respectively.Similarly,with proper LUMO energy level,Pb-PA(-4.63 eV),Pb-EDTMP(-3.71 eV),and Pb-DTPMP(-4.45 eV) all exhibit admirable performance.This unique strategy of organic materials to alkali-metal-ion battery cathodes offers a new avenue for future energy storage systems.
文摘Significant interest has been focused on graphene materials for their unique properties as Hydrogen storage materials. The development of their abilities by modifying their configuration with doped or decorated transition metals </span><span style="font-family:Verdana;">was also of great interest. In this work</span><span style="font-family:Verdana;">,</span><span style="font-family:Verdana;"> using the DFT/B3LYP/6-31G/LanL2DZ</span><span style="font-family:Verdana;"> level of theory, graphene sheet (GS) as one of the materials of interest was doped with two transition metals, Osmium (Os) and Tungsten (W). Two active sites on the GS were tested (C4 and C16) resulted into adsorbed systems, H2@C4-GS and H2@C16-GS. C16 position showed the largest adsorption energy compared to that at C4. Therefore, C4 was replaced by the two metals and two adsorbed systems were formed</span><span style="font-family:Verdana;">: </span><span style="font-family:Verdana;">H</span><sub><span style="font-family:Verdana;vertical-align:sub;">2</span></sub><span style="font-family:Verdana;">@Os-GS and H2@W-GS. The binding energy of H</span><sub><span style="font-family:Verdana;vertical-align:sub;">2</span></sub><span style="font-family:Verdana;">@Os-GS was found to be greater than that of H2@W-GS.
基金The paper is supported by grants from the NSFC (No. 39825106 and 39860023).
文摘The distribution patterns of mangrove Bruguiera gymnorrhiza population s in southern China are analyzed using the box-counting method of fractal theory. The patterns of B. gymnorrhiza populations could be thought of as fractals as they exhibit self-similarity within the range of scale considered. Their fractal dimensions are not integer but fractional, ranging from 1.04 to 1.51. The unoccupied dimensions change from 0.49 to 0.96. The combined conditions of population density, pattern type and aggregation intensity together influence the values of fractal dimensions of patterns. The box counting is a useful and efficient method to investigate the complexity of patterns. Fractal dimension may be a most desirable and appropriate index for quantifying the horizontal spatial microstructure and fractal behaviors of patterns over a certain range of scales.
基金supported by the Basic Research Support Program for Outstanding Young Teachers in Provincial Undergraduate Colleges and Universities in Heilongjiang Province(No.YQJH2023159)the Heilongjiang Province College Students Innovation and Entrepreneurship Training Program(No.HSDSSCX2022-149).
文摘Lithium-sulfur batteries(LSBs)offer high energy density and eco-friendly sulfur cathodes,but commercialization is hindered by slow sulfur redox kinetics and the“shuttle effect”,which limit capacity and cycle life.This study used inverse photoemission spectroscopy and ultraviolet photoelectron spectroscopy(IPES/UPS)to investigate the S redox mechanism.The BNOC matrix,with fully occupied electron states near the Fermi level,enhances conductivity and oxygen covalency by downshifting the lowest unoccupied molecular orbital(LUMO)to hybridize with the highest occupied molecular orbital(HOMO).This matrix traps lithium polysulfides(LiPSs),where loosely bound oxygen atoms facilitate S redox,particularly the key Li_(2)S↔LiPSs conversion.Additionally,the strong covalent B-N bonds,synergizing with the hollow BNOC cages,confine S redox reactions within structurally stable nanoscale spaces,effectively mitigating the shuttle effect.As a result,the LSB in our study delivers extended 1300 cycles at 4 C,maintaining 337.8 mAh·g^(-1)specific capacity.It also possesses a high areal capacity of 7.76 mAh·cm^(-2)at a high sulfur loading of 5.6 mg·cm^(-2),and is capable of powering a pouch-type LSB at a current density of 8 mAh·cm^(-2)for over 15 cycles.This study lays a foundation for the rational design and performance enhancement of future LSB.
基金the project“National Key Research and Development Program of China,No.2018YFD1100803”.
文摘The issue of unoccupied or abandoned homesteads(courtyards)in China emerges given the increasing aging population,rapid urbanization and massive rural-urban migration.From the aspect of rural vitalization,land-use planning,and policy making,determining the number of unoccupied courtyards is important.Field and questionnaire-based surveys were currently the main approaches,but these traditional methods were often expensive and laborious.A new workflow is explored using deep learning and machine learning algorithms on unmanned aerial vehicle(UAV)images.Initially,features of the built environment were extracted using deep learning to evaluate the courtyard management,including extracting complete or collapsed farmhouses by Alexnet,detecting solar water heaters by YOLOv5s,calculating green looking ratio(GLR)by FCN.Their precisions exceeded 98%.Then,seven machine learning algorithms(Adaboost,binomial logistic regression,neural network,random forest,support vector machine,decision trees,and XGBoost algorithms)were applied to identify the rural courtyards’utilization status.The Adaboost algorithm showed the best performance with the comprehensive consideration of most metrics(Accuracy:0.933,Precision:0.932,Recall:0.984,F1-score:0.957).Results showed that identifying the courtyards’utilization statuses based on the courtyard built environment is feasible.It is transferable and cost-effective for large-scale village surveys,and may contribute to the intensive and sustainable approach to rural land use.
基金support from the National Natural Science Foundation of China(grant nos.22161132026,21790053,51821002,and 21602225)the Suzhou Key Laboratory of Surface and Interface Intelligent Matter(grant no.SZS2022011)+2 种基金the Collaborative Innovation Center of Suzhou Nano Science and Technologythe Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the 111 project.
文摘Imide-based conjugated molecules have emerged as a highly promising class of building blocks for constructing n-type semiconducting materials with lowlying lowest unoccupied molecular orbitals and exceptional stability.Although imides,such as naphthalene diimides,perylene diimides and their lateral fused analogs,have been synthesized extensively,the design and synthesis of largerπ-extended molecules incorporating more than two imide groups are desirable but still very challenging.Herein,we report the synthesis of an unprecedented electron-deficient bisanthene tetraimide(ATI)containing a bisantheneconjugated core and four five-membered imide groups,which was successfully achieved via a combined approach of solution and on-surface synthesis.The chemical structures,electronic states,formation mechanism and aromaticity of ATI were systematically investigated by scanning tunneling microscopy,noncontact atomic force microscopy,scanning tunneling spectroscopy,and density functional theory calculations.
基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XD30000000)the National Key R&D Program of China(Grant Nos.2018YFA0305802 and 2017YFA0303500)the National Natural Science Foundation of China(Grant No.11774267).Calculations were performed at the supercomputing center of WHU of China.
文摘High-order nonlinear multiphoton absorption is usually inefficient,but can be enhanced by designing resonant excitations between occupied and unoccupied energy levels.We conducted angle-resolved multi-photon photoemission(mPPE)studies on the SnSe_(2)(001)surfaces excited by ultrashort laser pulses.By tuning photon energy and light polarization,we demonstrate the presence of a resonant four-photon photoemission(4PPE)process involving the occupied valence band(VB),the unoccupied second conduction band(CB2)and the unoccupied image-potential state(IPs)of SnSe_(2).In this 4PPE process,VB electrons of SnSe_(2) are resonantly excited into CB2 by adsorbing two photons,followed by the adsorption of another photon to populate the n=1 IPs before being emitted out to the vacuum by adsorbing one more photon.This results in a double-resonant 4PPE process,which exhibits approximately a 40 times enhancement in photoemission yields compared to cases where one of the resonant pathways,CB2→IPs,is inhibited by involving a virtual state instead of the IPs in the 4PPE.The double-resonant 4PPE process efficiently excite the bulk VB electrons outside the vacuum,like taking advantage of resonant“ladders”through two real empty electronic states of SnSe_(2).Our results highlight the important applications of mPPE in probing the band-structure,particularly the unoccupied states,of recently emerging main group dichalcogenide semiconductors.Furthermore,the discovered resonant mPPE process contributes to the exploration of their promising optoelectronic applications.
基金supported by the National Natural Science Foundation of China(No.52173010)Jining University(Nos.2022HHKJ11,2019BSZX01).
文摘In organic solar cells(OSCs),it is an effective way to improve the power conversion efficiency(PCE)by adding a vip component with appropriate absorption and energy levels in the host system.Herein,a new nonfullerene acceptor(NFA)named TBF-2Cl was developed by the strategy of expanding theπconjugated core of 2,2’-(((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b’]dithiophene-2,7-diyl)bis(methaneylylidene))bis(5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(IDT-4Cl)with two benzene rings.With increase of benzene units,TBF-2Cl exhibits higher lowest unoccupied molecular orbital(LUMO)level of-3.75 eV than that of one benzene unit based NFA IDT-4Cl and fluorene core based NFA F-2Cl,which facilitates enhancing the open-circuit voltage(V_(oc))of ternary devices.Moreover,TBF-2Cl film shows a medium optical bandgap with the absorption range from 500-800 nm,being well complementary with the wide bandgap polymer donor D18 and narrow bandgap NFA CH-6F.Accordingly,a remarkable PCE of 18.92%with a high short-circuit current density(J_(sc))of 27.40 mA·cm^(-2),a fill factor(FF)of 0.749,especially an outstanding V_(oc) of 0.922 V was achieved for the optimal ternary device based on D18:TBF-2Cl:CH-6F,surpassing the binary counterpart(17.08%).The findings provide insight into the development of new vip acceptors for obtaining more efficient OSCs.
基金financially supported by the National Natural Science Foundation of China (22209039)Top-notch Personnel Fund of Henan Agricultural University (30500682)。
文摘Improving the complete ethanol electrooxidation on Pd-based catalysts in alkaline media has drawn widely attention due to the high mass energy density.However,the weak adsorption energy of CH_(3)CO^(*) on Pd restricts the C–C bond cleavage.Inspired by the molecular orbital theory,we proposed the d-state-editing strategy to construct more unoccupied d-states of Pd for the enhanced interaction with CH_(3)CO^(*) to break C–C bonds.As expected,the reduced number of e_g electrons and more unoccupied d-states of Pd successfully formed on as-prepared porous Rh Au–Pd Cu nanosheets(PNSs).Theoretical calculations show that the optimized d-states of Rh Au–Pd Cu PNS can effectively improve the adsorption of CH_(3)CO^(*) and drastically reduce the energy barrier of C–C bond cleavage,thus boosting the complete oxidation of ethanol.The charge ratio of C_1 pathway on Rh Au–Pd Cu PNSs is 51.5%,more than 2 times higher than that of Pd NSs.Our finding provides an innovative perspective for the design of highly-efficient noble-based electrocatalysts.
基金The work was supported by the National Natural Science Foundation of China(Nos.21771169 and 11722543)the National Key Research and Development Program of China(No.2017YFA0206703)+1 种基金Anhui Provincial Natural Science Foundation(No.BJ2060190077)Collaborative Innovation Program of Hefei Science Center,CAS,and the Fundamental Research Funds for the Central Universities(Nos.WK2060190074,WK2060190081,WK2310000066,and WK2060000015).
文摘The high unoccupied d band energy of Ni_(3)N basically results in weak orbital coupling with water molecule,consequently leading to slow water dissociation kinetics.Herein,we demonstrate Cr doping can downshift the unoccupied d orbitals and strengthen the interfacial orbital coupling to boost the water dissociation kinetics.The prepared Cr-Ni_(3)N/Ni displays an impressive overpotential of 37 mV at 10 mA·cmgeo-2,close to the benchmark Pt/C in 1.0 M KOH solution.Refined structural analysis reveals the Cr dopant exists as the Cr-N_(6)states and the average d band energy of Ni_(3)N is also lowered.Density functional theory calculation further confirms the downshifted d band energy can strengthen the orbital coupling between the unpaired electrons in O 2p and the unoccupied state of Ni 3d,which thus facilitates the water adsorption and dissociation.The work provides a new concept to achieve on-demand functions for hydrogen evolution catalysis and beyond,by regulating the interfacial orbital coupling.
文摘To increase the current density of the hole only device, 1, 4, 5, 8, 9, 11-hexaazatriphenylene-hexacarbonitrile (HAT-CN) material has been inserted in the device at the indium tin oxide (ITO)/organic interface. Since HATCN molecule can withdraw electrons, it can alter electronic properties of the electrodes and hence inserted between the organic/metal interfaces. This paper deals with the optimization of the thickness of organic-metal layers to enhance the efficiency. Also, efforts have been made to increase the current density and reduce the operating voltage of the device. The material 2, 7-bis [N, N-bis (4- methoxy-phenyl) amino]-9, 9-spirobifluorene (Meo-Spiro-TPD) is used to simulate the hole only device because it is a thermally stable hole transport material. Simulated results shows that better current density values can be achieved compared to fabricated one by optimizing the organic metal layer thickness. The best optimized layer thickness of 22 nm for Alq3, 25 nm for *CBP doped with Ir(ppy)3, 9 nm for Meo-Spiro TPD and 4 nm for HAT-CN which results in current density of 0.12 A/cm2 with a reduction in operating voltage by approximately 2 V.
