Electron transport layer(ETL)is pivotal to charge carrier transport for PSCs to reach the Shockley-Queisser limit.This study provides a fundamental understanding of heterojunction electron transport layers(ETLs)at the...Electron transport layer(ETL)is pivotal to charge carrier transport for PSCs to reach the Shockley-Queisser limit.This study provides a fundamental understanding of heterojunction electron transport layers(ETLs)at the atomic level for stable and efficient perovskite solar cells(PSCs).The bilayer structure of an ETL composed of SnO_(2) on TiO_(2) was examined,revealing a critical factor limiting its potential to obtain efficient performance.Alteration of oxygen vacancies in the TiO_(2) underlayer via an annealing process is found to induce manipulated band offsets at the interface between the TiO_(2) and SnO_(2) layers.In-depth electronic investigations of the bilayer structure elucidate the importance of the electronic properties at the interface between the TiO_(2) and SnO_(2) layers.The apparent correlation in hysteresis phenomena,including current density-voltage(J-V)curves,appears as a function of the type of band alignment.Density functional theory calculations reveal the intimate relationship between oxygen vacancies,deep trap states,and charge transport efficiency at the interface between the TiO_(2) and SnO_(2) layers.The formation of cascade band alignment via control over the TiO_(2) underlayer enhances device performance and suppresses hysteresis.Optimal performance exhibits a power conversion efficiency(PCE)of 23.45%with an open-circuit voltage(V_(oc))of 1.184 V,showing better device stability under maximum power point tracking compared with a staggered bilayer under one-sun continuous illumination.展开更多
The effects of uniaxial tensile strain on the structural and electronic properties of positively charged oxygen vacancy defects in amorphous silica(a-SiO2)are systematically investigated using ab-initio calculation ba...The effects of uniaxial tensile strain on the structural and electronic properties of positively charged oxygen vacancy defects in amorphous silica(a-SiO2)are systematically investigated using ab-initio calculation based on density functional theory.Four types of positively charged oxygen vacancy defects,namely the dimer,unpuckered,and puckered four-fold(4×),and puckered five-fold(5×)configurations have been investigated.It is shown by the calculations that applying uniaxial tensile strain can lead to irreversible transitions of defect structures,which can be identified from the fluctuations of the curves of relative total energy versus strain.Driven by strain,a positively charged dimer configuration may relax into a puckered 5×configuration,and an unpuckered configuration may relax into either a puckered 4×configuration or a forward-oriented configuration.Accordingly,the Fermi contacts of the defects remarkably increase and the defect levels shift under strain.The Fermi contacts of the puckered configurations also increase under strain to the values close to that of Eα′center in a-SiO2.In addition,it is shown by the calculations that the relaxation channels of the puckered configurations after electron recombination are sensitive to strain,that is,those configurations are more likely to relax into a two-fold coordinated Si structure or to hold a puckered structure under strain,both of which may raise up the thermodynamic charge-state transition levels of the defects into Si band gap.As strain induces more puckered configurations with the transition levels in Si band gap,it may facilitate directly the development of oxide charge accumulation and indirectly that of interface charge accumulation by promoting proton generation under ionization radiation.This work sheds a light on understanding the strain effect on ionization damage at an atomic scale.展开更多
Although sodium ion capacitors(SICs)are considered as one of the most promising electrochemical energy storage devices(organic electrolyte batteries,aqueous batteries and supercapacitor,etc.)due to the combined merits...Although sodium ion capacitors(SICs)are considered as one of the most promising electrochemical energy storage devices(organic electrolyte batteries,aqueous batteries and supercapacitor,etc.)due to the combined merits of battery and capacitor,the slow reaction kinetics and low specific capacity of anode materials are the main challenges.Point defects including vacancies and heteroatoms doping have been widely used to improve the kinetics behavior and capacity of anode materials.However,the interaction between vacancies and heteroatoms doping have been seldomly investigated.In this study,a hybrid point defects(HPD)engineering has been proposed to synthesize TiO_(2) with both oxygen vacancies(OVs)and P-dopants(TiO_(2)/C-HPD).In comparison with sole OVs or P-doping treatments,the synergistic effects of HPD on its electrical conductivity and sodium storage performance have been clarified through the density func-tional theory calculation and sodium storage characterization.As expected,the kinetics and electronic conductivity of TiO_(2)/C-HPD3 are significantly improved,resulting in excellent rate performance and outstanding cycle stability.Moreover,the SICs assembled from TiO_(2)/C-HPD3 anode and nitrogen-doped porous carbon cathode show outstanding power/energy density,ultra-long life with good capacity retention.This work provides a novel point defect engineering perspective for the development of high-performance SICs electrode materials.展开更多
FeOx electrocatalysts for the oxygen reduction reaction were prepared via one-step synthesis using electron impact with cold plasma as the electron source.Given the low operation temperature,FeOx by plasma technology ...FeOx electrocatalysts for the oxygen reduction reaction were prepared via one-step synthesis using electron impact with cold plasma as the electron source.Given the low operation temperature,FeOx by plasma technology showed a smaller particle size than that prepared via conventional calcination.Notably,electron impact produced more oxygen vacancies and a larger surface area on FeOx,which increased active sites and electronic conductivity,than plasma.Electrochemical investigations indicated that FeOx prepared by plasma exhibited remarkable oxygen reduction reaction activity toward the four-electron electrochemical reduction of oxygen.The results demonstrated that this facile fabrication method is a promising route for developing cost-eff ective and high-performance catalysts to be used in electrochemical applications.展开更多
Oxygen vacancies(OVs) play a critical role in the physical properties and applications of titanium dioxide nanostructures, which are widely used in electrochemistry and photo catalysis nowadays. In this work, OVs were...Oxygen vacancies(OVs) play a critical role in the physical properties and applications of titanium dioxide nanostructures, which are widely used in electrochemistry and photo catalysis nowadays. In this work, OVs were artificially introduced in the surface of a pure TiO_2 single crystal by pulsed laser irradiation. Raman spectra showed that the intensity of E_g mode was enhanced. Theoretical calculations disclose that this was caused by the strong coupling effect between the phonon vibration and plasmon induced by the OVs-related surface deformation, and good agreement was achieved between the experiments and theory.展开更多
The relationship between temperature and oxygen vacancy concentration is deduced in this paper. Based on the data of thermal weight-loss experiment, the formation enthalpies of congruent and several doped LN crystals ...The relationship between temperature and oxygen vacancy concentration is deduced in this paper. Based on the data of thermal weight-loss experiment, the formation enthalpies of congruent and several doped LN crystals have been calculated. It was found that the formation enthalpy of oxygen vacancies can be decreased evidently by doping valence-changeable ions. The experimental results were discussed and a new reduction process of the photorefractive LN crystal at a relatively low temperature was proposed, and the reduced crystals showed a good effect in practical use.展开更多
The low-valence cations Na^(+)and Sr^(2+)were selected as the co-dopants to increase the vacancies concentration in the Y_(2.982)Ce_(0.018)Al_(2)Ga_(3)O_(12)phosphor.The successful incorporation of Na^(+)and Sr^(2+)wa...The low-valence cations Na^(+)and Sr^(2+)were selected as the co-dopants to increase the vacancies concentration in the Y_(2.982)Ce_(0.018)Al_(2)Ga_(3)O_(12)phosphor.The successful incorporation of Na^(+)and Sr^(2+)was confirmed by the X-Ray Difiraction(XRD)results.All the samples show 5d-4f green persistent luminescence of Ce^(3+)after 450 nm excitation.The decay curves demonstrate that the persistent luminescence is efiectively enhanced with Na+and Sr2+doping.The thermoluminescence glow curves also show not only does the trap concentration increase,but also the distribution of trap depths is broadened.In addition,the air-and H_(2)/Ar-annealing treatments were conducted on every as-made sample.The experimental results prove that the increased traps after the Na^(+)/Sr^(2+)doping are mainly attributed to the oxygen vacancies,and the traps have a continuous and broad distribution of trap depths.We hope this work could give new inspiration for designing a high-performance persistent phosphor.展开更多
Defect engineering has been used to develop low-cost and effective catalysts to boost oxygen reduction reactions.However,the development of catalysts that use metal cation vacancies as the active sites for oxygen redu...Defect engineering has been used to develop low-cost and effective catalysts to boost oxygen reduction reactions.However,the development of catalysts that use metal cation vacancies as the active sites for oxygen reduction reaction is lacking.In this study,ZnS nanoparticles on N-doped carbon serve as an oxygen reduction reaction catalyst.These catalysts were prepared via a one-step method at 900℃.Amazingly,the high-resolution transmission electron microscope image revealed obvious defects in the ZnS nanoparticles.These facilitated the catalyst synthesis,and the product displayed good electrocatalytic performance for the oxygen reduction reaction in an alkaline medium,including a lower onset potential,lower mid-wave potential,four electron transfer process,and better durability compared with 20 wt%Pt/C.More importantly,the density functional theory results indicated that using the Zn vacancies in the prepared catalyst as active sites required a lower reaction energy to produce OOH*from*OO toward oxygen reduction reaction.Therefore,the proposed catalyst with Zn vacancies can be used as a potential electrocatalyst and may be substitutes for Pt-based catalysts in fuel cells,given the novel catalyst’s resulting performance.展开更多
This paper investigates the excited states of Si 3 O molecule by using the single-excitation configuration interaction and density functional theory.It finds that the visible light absorption spectrum of Si 3 O molecu...This paper investigates the excited states of Si 3 O molecule by using the single-excitation configuration interaction and density functional theory.It finds that the visible light absorption spectrum of Si 3 O molecule comprises the yellow and the purple light without external electric field,however all the visible light is included except the green light under the action of external electric field.Oxygen-deficient defects,which also can be found in Si 3 O molecule,have been used to explain the luminescence from silicon-based materials but the microstructures of the materials are still uncertain.Our results accord with the experimental values perfectly,this fact suggests that the structure of Si 3 O molecule is expected to be one of the main basic structures of the materials,so the oxygen-deficient defect structural model for Si 3 O molecule also has been provided to research the structures of materials.展开更多
The rational design of oxygen vacancies and electronic microstructures of electrode materials for energy storage devices still remains a challenge. Herein, we synthesize nickel cobalt-based oxides nanoflower arrays as...The rational design of oxygen vacancies and electronic microstructures of electrode materials for energy storage devices still remains a challenge. Herein, we synthesize nickel cobalt-based oxides nanoflower arrays assembled with nanowires grown on Ni foam via the hydrothermal process followed annealing process in air and argon atmospheres respectively. It is found that the annealing atmosphere has a vital influence on the oxygen vacancies and electronic microstructures of resulting NiCo_(2)O_(4) (NCO-Air) and CoNiO_(2) (NCO-Ar) products, which NCO-Ar has more oxygen vacancies and larger specific surface area of 163.48 m^(2)/g. The density functional theory calculation reveals that more oxygen vacancies can provide more electrons to adsorb –OH free anions resulting in superior electrochemical energy storage performance. Therefore, the assembled asymmetric supercapacitor of NCO-Ar//active carbon delivers an excellent energy density of 112.52 Wh/kg at a power density of 558.73 W/kg and the fabricated NCO-Ar//Zn battery presents the specific capacity of 180.20 mAh/g and energy density of 308.14 Wh/kg. The experimental measurement and theoretical calculation not only provide a facile strategy to construct flower-like mesoporous architectures with massive oxygen vacancies, but also demonstrate that NCO-Ar is an ideal electrode material for the next generation of energy storage devices.展开更多
In this study, we investigate the photoluminescence(PL) properties of γ and θ-alumina nanoparticles synthesized by the chemical wet method followed by annealing. The obtained experimental results indicate the presen...In this study, we investigate the photoluminescence(PL) properties of γ and θ-alumina nanoparticles synthesized by the chemical wet method followed by annealing. The obtained experimental results indicate the presence of some favorable near ultraviolet(NUV)-orange luminescent centers for usage in various luminescence applications, such as oxygen vacancies(F, F^+_2, F^(2+)_2, and F_2centers), OH related defects, cation interstitial centers, and some new luminescence bands attributed to trapped-hole centers or donor–acceptor centers. The energy states of each defect are discussed in detail. The defects mentioned could alter the electronic structure by producing some energy states in the band gap that result in the optical absorption in the middle ultraviolet(MUV) region. Spectra show that photoionazation of F and F_2 centers plays a crucial role in providing either free electrons for the conduction band, or the photoconversions of aggregated oxygen vacancies into each other, or mobile electrons for electrons-holes recombination process by the Shockley–Read–Hall(SRH)mechanism.展开更多
Nitrogen-doped carbon materials with vacancies/defects have been developed as highly efficient ORR electrocatalysts but with poor activity for OER,which limits their application in rechargeable metal-air batteries.Fil...Nitrogen-doped carbon materials with vacancies/defects have been developed as highly efficient ORR electrocatalysts but with poor activity for OER,which limits their application in rechargeable metal-air batteries.Filling the vacancies/defects with heteroatoms is expected to be an effective strategy to obtain surprising catalytic activities and improve their stability especially under the strongly oxidizing conditions during the OER process.Herein,we successfully transformed the defect-rich 3 D carbon nanosheets(DCN)into a bifunctional ORR/OER electrocatalyst(DCN-M)by utilizing the in-situ generated vacancies to capture metal cations via a modified salt-sealed strategy.By varying the metal(Fe,Ni)content,the captured metal cations in DCN-M existed in different chemical states,i.e.,metal atoms were stabilized by CàN bonds at low metal contents,while at high metal contents,bimetal particles were covered by graphene layers,taking responsibility for catalyzing the ORR and OER,respectively.In addition,the in-situ formed graphene layers with an interconnected structure facilitate the electron transport during the reactions.The Janus-feature of DCN-M in structures ensures superior bifunctional activity and good stability towards ORR/OER for the rechargeable Zn-air battery.This work provides an effective strategy to design multifunctional electrocatalysts by heteroatom filling into vacancies of carbon materials.展开更多
Our calculations demonstrate that the concentration of neutral oxygen vacancies can affect the geometrical structrue,electronic structure, and optical properties of α-quartz. Moreover, the distribution of the neutral...Our calculations demonstrate that the concentration of neutral oxygen vacancies can affect the geometrical structrue,electronic structure, and optical properties of α-quartz. Moreover, the distribution of the neutral oxygen divacancy can also exert some influence on the properties of α-quartz. The dissimilarity and similarities are presented in the corresponding density of state(DOS) and absorption spectrum. In addition, when a higher defect concentration is involved in α-quartz,the influence of E1 center on the geometry of α-quartz becomes more significant. However, the introduction of an E1 center barely results in any improvement compared with the influence produced by the corresponding neutral defect.展开更多
Defective layered Mn-based materials were synthesized by Li/Na ion exchange to improve their electrochemical activity and Coulombic efficiency.The annealing temperature of the Na precursors was important to control th...Defective layered Mn-based materials were synthesized by Li/Na ion exchange to improve their electrochemical activity and Coulombic efficiency.The annealing temperature of the Na precursors was important to control the P3-P2 phase transition,which directly affected the structure and electrochemical characteristics of the final products obtained by ion exchange.The O3-Li_(0.78)[Li_(0.25)Fe_(0.075)Mn_(0.675)]O_(δ) cathode made from a P3-type precursor calcined at 700℃ was analyzed using X-ray photoelectron spectrometry and electron paramagnetic resonance.The results showed that the presence of abundant trivalent manganese and defects resulted in a discharge capacity of 230 mAh/g with an initial Coulombic efficiency of about 109%.Afterward,galvanostatic intermittent titration was performed to examine the Li^(+) ion diffusion coefficients,which affected the reversible capacity.First principles calculations suggested that the charge redistribution induced by oxygen vacancies(OV_(s))greatly affected the local Mn coordination environment and enhanced the structural activity.Moreover,the Li-deficient cathode was a perfect match for the pre-lithiation anode,providing a novel approach to improve the initial Coulombic efficiency and activity of Mn-based materials in the commercial application.展开更多
基金supported by the New&Renewable Energy Core Technology Program of the Korea Institute of Energy Technology Evaluation and Planning(KETEP)granted financial resource from the Ministry of Trade,Industry&Energy(MOTIE),Republic of Korea(No.20213091010020)National Research Foundation of Korea(NRF)grant funded by the Korea Government(MSIT)(2020R1A2C1101085)+2 种基金the Korea Institute of Planning and Evaluation for Technology in Food,Agriculture and Forestry(IPET)and Korea Smart Farm R&D Foundation(KosFarm)through Smart Farm Innovation Technology Development Programfunded by the Ministry of Agriculture,Food and Rural Affairs(MAFRA)the Ministry of Science and ICT(MSIT),Rural Development Administration(RDA)(421036-03).
文摘Electron transport layer(ETL)is pivotal to charge carrier transport for PSCs to reach the Shockley-Queisser limit.This study provides a fundamental understanding of heterojunction electron transport layers(ETLs)at the atomic level for stable and efficient perovskite solar cells(PSCs).The bilayer structure of an ETL composed of SnO_(2) on TiO_(2) was examined,revealing a critical factor limiting its potential to obtain efficient performance.Alteration of oxygen vacancies in the TiO_(2) underlayer via an annealing process is found to induce manipulated band offsets at the interface between the TiO_(2) and SnO_(2) layers.In-depth electronic investigations of the bilayer structure elucidate the importance of the electronic properties at the interface between the TiO_(2) and SnO_(2) layers.The apparent correlation in hysteresis phenomena,including current density-voltage(J-V)curves,appears as a function of the type of band alignment.Density functional theory calculations reveal the intimate relationship between oxygen vacancies,deep trap states,and charge transport efficiency at the interface between the TiO_(2) and SnO_(2) layers.The formation of cascade band alignment via control over the TiO_(2) underlayer enhances device performance and suppresses hysteresis.Optimal performance exhibits a power conversion efficiency(PCE)of 23.45%with an open-circuit voltage(V_(oc))of 1.184 V,showing better device stability under maximum power point tracking compared with a staggered bilayer under one-sun continuous illumination.
基金Project supported by the Science Challenge Project,China(Grant No.TZ2016003-1-105)the CAEP Microsystem and THz Science and Technology Foundation(Grant No.CAT201501)。
文摘The effects of uniaxial tensile strain on the structural and electronic properties of positively charged oxygen vacancy defects in amorphous silica(a-SiO2)are systematically investigated using ab-initio calculation based on density functional theory.Four types of positively charged oxygen vacancy defects,namely the dimer,unpuckered,and puckered four-fold(4×),and puckered five-fold(5×)configurations have been investigated.It is shown by the calculations that applying uniaxial tensile strain can lead to irreversible transitions of defect structures,which can be identified from the fluctuations of the curves of relative total energy versus strain.Driven by strain,a positively charged dimer configuration may relax into a puckered 5×configuration,and an unpuckered configuration may relax into either a puckered 4×configuration or a forward-oriented configuration.Accordingly,the Fermi contacts of the defects remarkably increase and the defect levels shift under strain.The Fermi contacts of the puckered configurations also increase under strain to the values close to that of Eα′center in a-SiO2.In addition,it is shown by the calculations that the relaxation channels of the puckered configurations after electron recombination are sensitive to strain,that is,those configurations are more likely to relax into a two-fold coordinated Si structure or to hold a puckered structure under strain,both of which may raise up the thermodynamic charge-state transition levels of the defects into Si band gap.As strain induces more puckered configurations with the transition levels in Si band gap,it may facilitate directly the development of oxide charge accumulation and indirectly that of interface charge accumulation by promoting proton generation under ionization radiation.This work sheds a light on understanding the strain effect on ionization damage at an atomic scale.
基金the financial supports from the MOST (2019YFE0191500)the Natural Science Foundation of Jiangsu Province of China (BK20211172)the Fundamental Research Funds for the Central Universities
文摘Although sodium ion capacitors(SICs)are considered as one of the most promising electrochemical energy storage devices(organic electrolyte batteries,aqueous batteries and supercapacitor,etc.)due to the combined merits of battery and capacitor,the slow reaction kinetics and low specific capacity of anode materials are the main challenges.Point defects including vacancies and heteroatoms doping have been widely used to improve the kinetics behavior and capacity of anode materials.However,the interaction between vacancies and heteroatoms doping have been seldomly investigated.In this study,a hybrid point defects(HPD)engineering has been proposed to synthesize TiO_(2) with both oxygen vacancies(OVs)and P-dopants(TiO_(2)/C-HPD).In comparison with sole OVs or P-doping treatments,the synergistic effects of HPD on its electrical conductivity and sodium storage performance have been clarified through the density func-tional theory calculation and sodium storage characterization.As expected,the kinetics and electronic conductivity of TiO_(2)/C-HPD3 are significantly improved,resulting in excellent rate performance and outstanding cycle stability.Moreover,the SICs assembled from TiO_(2)/C-HPD3 anode and nitrogen-doped porous carbon cathode show outstanding power/energy density,ultra-long life with good capacity retention.This work provides a novel point defect engineering perspective for the development of high-performance SICs electrode materials.
基金by the National Key Research and Development Program of China(No.2016YFF0102503)National Natural Science Foundation of China(No.21878214)State Key Laboratory of Efficient Utilization for Low Grade Phosphate Rock and Its Associated Resources(No.WFKF2019-03).
文摘FeOx electrocatalysts for the oxygen reduction reaction were prepared via one-step synthesis using electron impact with cold plasma as the electron source.Given the low operation temperature,FeOx by plasma technology showed a smaller particle size than that prepared via conventional calcination.Notably,electron impact produced more oxygen vacancies and a larger surface area on FeOx,which increased active sites and electronic conductivity,than plasma.Electrochemical investigations indicated that FeOx prepared by plasma exhibited remarkable oxygen reduction reaction activity toward the four-electron electrochemical reduction of oxygen.The results demonstrated that this facile fabrication method is a promising route for developing cost-eff ective and high-performance catalysts to be used in electrochemical applications.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.61574080,11404162,61505085,and 61264008)the Natural Science Foundation of Jiangsu Province,China(Grant No.BK20130549)
文摘Oxygen vacancies(OVs) play a critical role in the physical properties and applications of titanium dioxide nanostructures, which are widely used in electrochemistry and photo catalysis nowadays. In this work, OVs were artificially introduced in the surface of a pure TiO_2 single crystal by pulsed laser irradiation. Raman spectra showed that the intensity of E_g mode was enhanced. Theoretical calculations disclose that this was caused by the strong coupling effect between the phonon vibration and plasmon induced by the OVs-related surface deformation, and good agreement was achieved between the experiments and theory.
文摘The relationship between temperature and oxygen vacancy concentration is deduced in this paper. Based on the data of thermal weight-loss experiment, the formation enthalpies of congruent and several doped LN crystals have been calculated. It was found that the formation enthalpy of oxygen vacancies can be decreased evidently by doping valence-changeable ions. The experimental results were discussed and a new reduction process of the photorefractive LN crystal at a relatively low temperature was proposed, and the reduced crystals showed a good effect in practical use.
文摘The low-valence cations Na^(+)and Sr^(2+)were selected as the co-dopants to increase the vacancies concentration in the Y_(2.982)Ce_(0.018)Al_(2)Ga_(3)O_(12)phosphor.The successful incorporation of Na^(+)and Sr^(2+)was confirmed by the X-Ray Difiraction(XRD)results.All the samples show 5d-4f green persistent luminescence of Ce^(3+)after 450 nm excitation.The decay curves demonstrate that the persistent luminescence is efiectively enhanced with Na+and Sr2+doping.The thermoluminescence glow curves also show not only does the trap concentration increase,but also the distribution of trap depths is broadened.In addition,the air-and H_(2)/Ar-annealing treatments were conducted on every as-made sample.The experimental results prove that the increased traps after the Na^(+)/Sr^(2+)doping are mainly attributed to the oxygen vacancies,and the traps have a continuous and broad distribution of trap depths.We hope this work could give new inspiration for designing a high-performance persistent phosphor.
基金supported by the National Natural Science Foundation of China(21865025)the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT_15R46)
文摘Defect engineering has been used to develop low-cost and effective catalysts to boost oxygen reduction reactions.However,the development of catalysts that use metal cation vacancies as the active sites for oxygen reduction reaction is lacking.In this study,ZnS nanoparticles on N-doped carbon serve as an oxygen reduction reaction catalyst.These catalysts were prepared via a one-step method at 900℃.Amazingly,the high-resolution transmission electron microscope image revealed obvious defects in the ZnS nanoparticles.These facilitated the catalyst synthesis,and the product displayed good electrocatalytic performance for the oxygen reduction reaction in an alkaline medium,including a lower onset potential,lower mid-wave potential,four electron transfer process,and better durability compared with 20 wt%Pt/C.More importantly,the density functional theory results indicated that using the Zn vacancies in the prepared catalyst as active sites required a lower reaction energy to produce OOH*from*OO toward oxygen reduction reaction.Therefore,the proposed catalyst with Zn vacancies can be used as a potential electrocatalyst and may be substitutes for Pt-based catalysts in fuel cells,given the novel catalyst’s resulting performance.
基金Project supported by the Foundation for University Young Core Instructors of Henan Province,China(Grant No.2009GGJS-044)the Natural Science Foundation of the Education Bureau of Henan Province,China(Grant No.2010A140008)+1 种基金the Natural Science Foundation of Henan Province,China(Grant No.092300410249)the Natural Science Foundation of the Education Bureau of Henan Province,China(Grant No.2010A140008)
文摘This paper investigates the excited states of Si 3 O molecule by using the single-excitation configuration interaction and density functional theory.It finds that the visible light absorption spectrum of Si 3 O molecule comprises the yellow and the purple light without external electric field,however all the visible light is included except the green light under the action of external electric field.Oxygen-deficient defects,which also can be found in Si 3 O molecule,have been used to explain the luminescence from silicon-based materials but the microstructures of the materials are still uncertain.Our results accord with the experimental values perfectly,this fact suggests that the structure of Si 3 O molecule is expected to be one of the main basic structures of the materials,so the oxygen-deficient defect structural model for Si 3 O molecule also has been provided to research the structures of materials.
基金This work was supported by the Natural Science Foundation of China(51962032,61704114,and 51764049)the Youth Innovative Talents Cultivation Fund,Shihezi University(KX01480109)the Opening Project of The Research Center for Material Chemical Engineering Technology of Xinjiang Bingtuan(2017BTRC007).
文摘The rational design of oxygen vacancies and electronic microstructures of electrode materials for energy storage devices still remains a challenge. Herein, we synthesize nickel cobalt-based oxides nanoflower arrays assembled with nanowires grown on Ni foam via the hydrothermal process followed annealing process in air and argon atmospheres respectively. It is found that the annealing atmosphere has a vital influence on the oxygen vacancies and electronic microstructures of resulting NiCo_(2)O_(4) (NCO-Air) and CoNiO_(2) (NCO-Ar) products, which NCO-Ar has more oxygen vacancies and larger specific surface area of 163.48 m^(2)/g. The density functional theory calculation reveals that more oxygen vacancies can provide more electrons to adsorb –OH free anions resulting in superior electrochemical energy storage performance. Therefore, the assembled asymmetric supercapacitor of NCO-Ar//active carbon delivers an excellent energy density of 112.52 Wh/kg at a power density of 558.73 W/kg and the fabricated NCO-Ar//Zn battery presents the specific capacity of 180.20 mAh/g and energy density of 308.14 Wh/kg. The experimental measurement and theoretical calculation not only provide a facile strategy to construct flower-like mesoporous architectures with massive oxygen vacancies, but also demonstrate that NCO-Ar is an ideal electrode material for the next generation of energy storage devices.
基金Iran’s Nanotechnology initiative council for their financial support
文摘In this study, we investigate the photoluminescence(PL) properties of γ and θ-alumina nanoparticles synthesized by the chemical wet method followed by annealing. The obtained experimental results indicate the presence of some favorable near ultraviolet(NUV)-orange luminescent centers for usage in various luminescence applications, such as oxygen vacancies(F, F^+_2, F^(2+)_2, and F_2centers), OH related defects, cation interstitial centers, and some new luminescence bands attributed to trapped-hole centers or donor–acceptor centers. The energy states of each defect are discussed in detail. The defects mentioned could alter the electronic structure by producing some energy states in the band gap that result in the optical absorption in the middle ultraviolet(MUV) region. Spectra show that photoionazation of F and F_2 centers plays a crucial role in providing either free electrons for the conduction band, or the photoconversions of aggregated oxygen vacancies into each other, or mobile electrons for electrons-holes recombination process by the Shockley–Read–Hall(SRH)mechanism.
基金financially supported by the National Natural Science Foundation of China(21776146)the Key Research and Development Programme of Shandong Province(2019JZZY010905)the Taishan Scholar Program of Shandong Province(ts201712046)。
文摘Nitrogen-doped carbon materials with vacancies/defects have been developed as highly efficient ORR electrocatalysts but with poor activity for OER,which limits their application in rechargeable metal-air batteries.Filling the vacancies/defects with heteroatoms is expected to be an effective strategy to obtain surprising catalytic activities and improve their stability especially under the strongly oxidizing conditions during the OER process.Herein,we successfully transformed the defect-rich 3 D carbon nanosheets(DCN)into a bifunctional ORR/OER electrocatalyst(DCN-M)by utilizing the in-situ generated vacancies to capture metal cations via a modified salt-sealed strategy.By varying the metal(Fe,Ni)content,the captured metal cations in DCN-M existed in different chemical states,i.e.,metal atoms were stabilized by CàN bonds at low metal contents,while at high metal contents,bimetal particles were covered by graphene layers,taking responsibility for catalyzing the ORR and OER,respectively.In addition,the in-situ formed graphene layers with an interconnected structure facilitate the electron transport during the reactions.The Janus-feature of DCN-M in structures ensures superior bifunctional activity and good stability towards ORR/OER for the rechargeable Zn-air battery.This work provides an effective strategy to design multifunctional electrocatalysts by heteroatom filling into vacancies of carbon materials.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11176020 and 11374217)the Doctoral Program of Higher Education of China(Grant No.20100181110080)
文摘Our calculations demonstrate that the concentration of neutral oxygen vacancies can affect the geometrical structrue,electronic structure, and optical properties of α-quartz. Moreover, the distribution of the neutral oxygen divacancy can also exert some influence on the properties of α-quartz. The dissimilarity and similarities are presented in the corresponding density of state(DOS) and absorption spectrum. In addition, when a higher defect concentration is involved in α-quartz,the influence of E1 center on the geometry of α-quartz becomes more significant. However, the introduction of an E1 center barely results in any improvement compared with the influence produced by the corresponding neutral defect.
基金The Beijing Municipal Education Commission(KZ201910005003)supported this work。
文摘Defective layered Mn-based materials were synthesized by Li/Na ion exchange to improve their electrochemical activity and Coulombic efficiency.The annealing temperature of the Na precursors was important to control the P3-P2 phase transition,which directly affected the structure and electrochemical characteristics of the final products obtained by ion exchange.The O3-Li_(0.78)[Li_(0.25)Fe_(0.075)Mn_(0.675)]O_(δ) cathode made from a P3-type precursor calcined at 700℃ was analyzed using X-ray photoelectron spectrometry and electron paramagnetic resonance.The results showed that the presence of abundant trivalent manganese and defects resulted in a discharge capacity of 230 mAh/g with an initial Coulombic efficiency of about 109%.Afterward,galvanostatic intermittent titration was performed to examine the Li^(+) ion diffusion coefficients,which affected the reversible capacity.First principles calculations suggested that the charge redistribution induced by oxygen vacancies(OV_(s))greatly affected the local Mn coordination environment and enhanced the structural activity.Moreover,the Li-deficient cathode was a perfect match for the pre-lithiation anode,providing a novel approach to improve the initial Coulombic efficiency and activity of Mn-based materials in the commercial application.
