Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Comp...Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Compared to Li^(+) storage,Na^(+) storage makes higher demands on the structural optimization of perovskite bismuth ferrite(BiFeO_(3)).We propose a novel strategy of defect engineering on BiFeO_(3) through Na and V codoping for high-efficiency Na^(+) storage,to reveal the roles of oxygen vacancies and V ions played in the enhanced electrochemical energy storage performances of Na-ion capacitors.The formation of the oxygen vacancies in the Na and V codoped BiFeO_(3)(denoted as NV-BFO),is promoted by Na doping and suppressed by V doping,which can be demonstrated by XPS and EPR spectra.By the first-principles calculations,the oxygen vacancies and V ions in NV-BFO are confirmed to substantially lower the Na^(+)migration energy barriers through the space and electric field effects,to effectively promote the Na^(+) transport in the crystals.Electrochemical kinetic analysis of the NV-BFO//NV-BFO capacitors indicates the dominant capacitive-controlled capacity,which depends on fast Na^(+) deintercalation-intercalation process in the NV-BFO electrode.The NV-BFO//NV-BFO capacitors open up a new avenue for developing highperformance Na-ion capacitors.展开更多
The Sb^(3+) doping strategy has been proven to be an effective way to regulate the band gap and improve the photophysical properties of organic-inorganic hybrid metal halides(OIHMHs).However,the emission of Sb^(3+) io...The Sb^(3+) doping strategy has been proven to be an effective way to regulate the band gap and improve the photophysical properties of organic-inorganic hybrid metal halides(OIHMHs).However,the emission of Sb^(3+) ions in OIHMHs is primarily confined to the low energy region,resulting in yellow or red emissions.To date,there are few reports about green emission of Sb^(3+)-doped OIHMHs.Here,we present a novel approach for regulating the luminescence of Sb^(3+) ions in 0D C_(10)H_(2)_(2)N_(6)InCl_(7)·H_(2)O via hydrogen bond network,in which water molecules act as agents for hydrogen bonding.Sb^(3+)-doped C_(10)H_(2)2N_(6)InCl_(7)·H_(2)O shows a broadband green emission peaking at 540 nm and a high photoluminescence quantum yield(PLQY)of 80%.It is found that the intense green emission stems from the radiative recombination of the self-trapped excitons(STEs).Upon removal of water molecules with heat,C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7) generates yellow emis-sion,attributed to the breaking of the hydrogen bond network and large structural distortions of excited state.Once water molecules are adsorbed by C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7),it can subsequently emit green light.This water-induced reversible emission switching is successfully used for optical security and information encryption.Our findings expand the under-standing of how the local coordination structure influences the photophysical mechanism in Sb^(3+)-doped metal halides and provide a novel method to control the STEs emission.展开更多
A ratiometric fluorescent probe for hypoxanthine(Hx)detection was established based on the mimic enzyme and fluorescence characteristics of cobalt-doped graphite-phase carbon nitride(Co doped g-C_(3)N_(4)).In addition...A ratiometric fluorescent probe for hypoxanthine(Hx)detection was established based on the mimic enzyme and fluorescence characteristics of cobalt-doped graphite-phase carbon nitride(Co doped g-C_(3)N_(4)).In addition to emitting strong fluorescence,the peroxidase activity of Co doped g-C_(3)N_(4)can catalyze the reaction of O-phenylenediamine and H_(2)O_(2)to produce diallyl phthalate which can emit yellow fluorescence at 570 nm.Through the decomposition of Hx by xanthine oxidase,Hx can be indirectly detected by the generating hydrogen peroxide based on the measurement of fluorescent ratio I(F_(570)/F_(370)).The linear range was 1.7-272.2 mg/kg(R^(2)=0.997),and the detection limit was 1.52 mg/kg(3σ/K,n=9).The established method was applied to Hx detection in bass,grass carp,and shrimp,and the data were verified by HPLC.The result shows that the established probe is sensitive,accurate,and reliable,and can be used for Hx detection in aquatic products.展开更多
The safe operating voltage and low volume variation of Li_(3)VO_(4)(LVO)make it an ideal anode material for lithium(Li)-ion batteries.However,the insufficient understanding of the inner storage mechanism hinders the d...The safe operating voltage and low volume variation of Li_(3)VO_(4)(LVO)make it an ideal anode material for lithium(Li)-ion batteries.However,the insufficient understanding of the inner storage mechanism hinders the design of LVO-based electrodes.Herein,we investigate,for the first time,the Li-ion storage activity in LVO via Cl doping.Moreover,N-doped C coating was simultaneously achieved in the Cl doping process,resulting in synergistically improved reaction kinetics.As a result,the as-prepared Cl-doped Li_(3)VO_(4) coated with N-doped C(Cl-LVO@NC)electrodes deliver a discharge capacity of 884.1 mAh/g after 200 cycles at 0.2 A/g,which is the highest among all of the LVO-based electrodes.The Cl-LVO@NC electrodes also exhibit high-capacity retention of 331.1 mAh/g at 8.0 A/g and full capacity recovery after 5 periods of rate testing over 400 cycles.After 5000 cycles at 4.0 A/g,the discharge capacity can be maintained at 423.2 mAh/g,which is superior to most LVO-based electrodes.The Li-ion storage activity in LVO via Cl doping and significant improvement in the high-rate Li-ion storage reported in this work can be used as references for the design of advanced LVO-based electrodes for high-power applications.展开更多
Sn doping is an effective way to improve the response rate of Ga_(2)O_(3) film based solar-blind detectors. In this paper,Sn-doped Ga_(2)O_(3) films were prepared on a sapphire substrate by radio frequency magnetron s...Sn doping is an effective way to improve the response rate of Ga_(2)O_(3) film based solar-blind detectors. In this paper,Sn-doped Ga_(2)O_(3) films were prepared on a sapphire substrate by radio frequency magnetron sputtering. The films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and ultraviolet visible spectroscopy, and the effect of annealing atmosphere on the properties of films was studied. The Ga_(2)O_(3) films changed from amorphous to β-Ga_(2)O_(3) after annealing at 900 °C. The films were composed of micro crystalline particles with a diameter of about 5–20 nm.The β-Ga_(2)O_(3) had high transmittance for wavelengths above 300 nm, and obvious absorption for solar-blind signals at 200–280 nm.The metal semiconductor metal type solar-blind detectors were prepared. The detector based on Sn-doped β-Ga_(2)O_(3) thin film annealed in N_2 has the best response performance to 254 nm light. The photo-current is 10 μA at 20 V, the dark-current is 5.76 pA,the photo dark current ratio is 1.7 × 10~6, the response rate is 12.47 A/W, the external quantum efficiency is 6.09 × 10~3%, the specific detection rate is 2.61 × 10~(12) Jones, the response time and recovery time are 378 and 90 ms, respectively.展开更多
Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_...Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_(2)O_(4) coating and Mg,Fe co-doping were constructed simultaneously by Mg,Fe surface treatment to suppress lattice oxygen evolution and P2-O2 phase transformation of P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)at deep charging.Through ex-situ X-ray diffraction(XRD)tests,we found that the Mg,Fe bulk co-doping could reduce the repulsion between transition metals and Na+/vacancies ordering,thus inhibiting the P2-O2 phase transition and significantly reducing the irreversible volume change of the material.Meanwhile,the internal electric field formed by the dielectric polarization of Mg Fe_(2)O_(4) effectively inhibits the outward migration of oxidized O^(a-)(a<2),thereby suppressing the lattice oxygen evolution at deep charging,confirmed by in situ Raman and ex situ XPS techniques.P2-Na NM@MF-3 shows enhanced high-voltage cycling performance with capacity retentions of 84.8% and 81.3%at 0.1 and 1 C after cycles.This work sheds light on regulating the surface chemistry for Na-layered oxide materials to enhance the high-voltage performance of Na-ion batteries.展开更多
The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of...The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.展开更多
LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible cap...LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible capacity limits its replacement for LiCoO_(2) in high-end digital field.Herein,three-in-one modification,Na-doping and Al_(2)O_(3)@Li_(3)BO_(3) dual-coating simultaneously,is explored for single-crystalline LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(N-NCM@AB),which exhibits excellent high-voltage performance.N-NCM@AB displays a discharge-specific capacity of 201.8 mAh g^(−1) at 0.2 C with a high upper voltage of 4.6 V and maintains 158.9 mAh g^(−1) discharge capacity at 1 C over 200 cycles with the corresponding capacity retention of 87.8%.Remarkably,the N-NCM@AB||graphite pouch-type full cell retains 81.2% of its initial capacity with high working voltage of 4.4 V over 1600 cycles.More importantly,the fundamental understandings of three-in-one modification on surface morphology,crystal structure,and phase transformation of N-NCM@AB are clearly revealed.The Na+doped into the Li–O slab can enhance the bond energy,stabilize the crystal structure,and facilitate Li+transport.Additionally,the interior surface layer of Li^(+)-ions conductor Li_(3)BO_(3) relieves the charge transfer resistance with surface coating,whereas the outer surface Al_(2)O_(3) coating layer is beneficial for reducing the active materials loss and alleviating the electrode/electrolyte parasite reaction.This three-in-one strategy provides a reference for the further research on the performance attenuation mechanism of NCM,paving a new avenue to boost the high-voltage performance of NCM cathode in Li-ion batteries.展开更多
基金financial supports from National Natural Science Foundation of China(22005174 and 52271133)。
文摘Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Compared to Li^(+) storage,Na^(+) storage makes higher demands on the structural optimization of perovskite bismuth ferrite(BiFeO_(3)).We propose a novel strategy of defect engineering on BiFeO_(3) through Na and V codoping for high-efficiency Na^(+) storage,to reveal the roles of oxygen vacancies and V ions played in the enhanced electrochemical energy storage performances of Na-ion capacitors.The formation of the oxygen vacancies in the Na and V codoped BiFeO_(3)(denoted as NV-BFO),is promoted by Na doping and suppressed by V doping,which can be demonstrated by XPS and EPR spectra.By the first-principles calculations,the oxygen vacancies and V ions in NV-BFO are confirmed to substantially lower the Na^(+)migration energy barriers through the space and electric field effects,to effectively promote the Na^(+) transport in the crystals.Electrochemical kinetic analysis of the NV-BFO//NV-BFO capacitors indicates the dominant capacitive-controlled capacity,which depends on fast Na^(+) deintercalation-intercalation process in the NV-BFO electrode.The NV-BFO//NV-BFO capacitors open up a new avenue for developing highperformance Na-ion capacitors.
基金National Natural Science Foundation of China(11974063)Graduate research innovation project,School of Optoelectronic Engineering,Chongqing University(GDYKC2023002)+1 种基金Fundamental Research Funds for the Central Universities(2022CDJQY-010)The authors extend their appreciation to the Deputyship for Research and Innovation,Ministry of Education in Saudi Arabia for funding this research work through the project no.(IFKSUOR3-073-9).
文摘The Sb^(3+) doping strategy has been proven to be an effective way to regulate the band gap and improve the photophysical properties of organic-inorganic hybrid metal halides(OIHMHs).However,the emission of Sb^(3+) ions in OIHMHs is primarily confined to the low energy region,resulting in yellow or red emissions.To date,there are few reports about green emission of Sb^(3+)-doped OIHMHs.Here,we present a novel approach for regulating the luminescence of Sb^(3+) ions in 0D C_(10)H_(2)_(2)N_(6)InCl_(7)·H_(2)O via hydrogen bond network,in which water molecules act as agents for hydrogen bonding.Sb^(3+)-doped C_(10)H_(2)2N_(6)InCl_(7)·H_(2)O shows a broadband green emission peaking at 540 nm and a high photoluminescence quantum yield(PLQY)of 80%.It is found that the intense green emission stems from the radiative recombination of the self-trapped excitons(STEs).Upon removal of water molecules with heat,C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7) generates yellow emis-sion,attributed to the breaking of the hydrogen bond network and large structural distortions of excited state.Once water molecules are adsorbed by C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7),it can subsequently emit green light.This water-induced reversible emission switching is successfully used for optical security and information encryption.Our findings expand the under-standing of how the local coordination structure influences the photophysical mechanism in Sb^(3+)-doped metal halides and provide a novel method to control the STEs emission.
基金supported by the National Natural Science Foundation of China(21804050)the National Key R and D Program of China(2018YFD0901003)+2 种基金the Science and Technology Planning Project of Xiamen,China(3502Z20183031)the Fujian Provincial Fund Project(2018J01432)the Xiamen Science and Technology Planning Project,China(3502Z20183031)。
文摘A ratiometric fluorescent probe for hypoxanthine(Hx)detection was established based on the mimic enzyme and fluorescence characteristics of cobalt-doped graphite-phase carbon nitride(Co doped g-C_(3)N_(4)).In addition to emitting strong fluorescence,the peroxidase activity of Co doped g-C_(3)N_(4)can catalyze the reaction of O-phenylenediamine and H_(2)O_(2)to produce diallyl phthalate which can emit yellow fluorescence at 570 nm.Through the decomposition of Hx by xanthine oxidase,Hx can be indirectly detected by the generating hydrogen peroxide based on the measurement of fluorescent ratio I(F_(570)/F_(370)).The linear range was 1.7-272.2 mg/kg(R^(2)=0.997),and the detection limit was 1.52 mg/kg(3σ/K,n=9).The established method was applied to Hx detection in bass,grass carp,and shrimp,and the data were verified by HPLC.The result shows that the established probe is sensitive,accurate,and reliable,and can be used for Hx detection in aquatic products.
基金supported by the National Natural Science Foundation of China(No.52101262)Distinguished Youth Foundation of Hubei Province(2019CFA084)+1 种基金Educational offi ce of Hubei Province(Q20201201)the 111 project(D20015).
文摘The safe operating voltage and low volume variation of Li_(3)VO_(4)(LVO)make it an ideal anode material for lithium(Li)-ion batteries.However,the insufficient understanding of the inner storage mechanism hinders the design of LVO-based electrodes.Herein,we investigate,for the first time,the Li-ion storage activity in LVO via Cl doping.Moreover,N-doped C coating was simultaneously achieved in the Cl doping process,resulting in synergistically improved reaction kinetics.As a result,the as-prepared Cl-doped Li_(3)VO_(4) coated with N-doped C(Cl-LVO@NC)electrodes deliver a discharge capacity of 884.1 mAh/g after 200 cycles at 0.2 A/g,which is the highest among all of the LVO-based electrodes.The Cl-LVO@NC electrodes also exhibit high-capacity retention of 331.1 mAh/g at 8.0 A/g and full capacity recovery after 5 periods of rate testing over 400 cycles.After 5000 cycles at 4.0 A/g,the discharge capacity can be maintained at 423.2 mAh/g,which is superior to most LVO-based electrodes.The Li-ion storage activity in LVO via Cl doping and significant improvement in the high-rate Li-ion storage reported in this work can be used as references for the design of advanced LVO-based electrodes for high-power applications.
基金supported by the National Natural Science Foundation of China (Grant No. 62204203)the Shaanxi Natural Science Basic Research Program (Grant No. 2022JQ-701)。
文摘Sn doping is an effective way to improve the response rate of Ga_(2)O_(3) film based solar-blind detectors. In this paper,Sn-doped Ga_(2)O_(3) films were prepared on a sapphire substrate by radio frequency magnetron sputtering. The films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and ultraviolet visible spectroscopy, and the effect of annealing atmosphere on the properties of films was studied. The Ga_(2)O_(3) films changed from amorphous to β-Ga_(2)O_(3) after annealing at 900 °C. The films were composed of micro crystalline particles with a diameter of about 5–20 nm.The β-Ga_(2)O_(3) had high transmittance for wavelengths above 300 nm, and obvious absorption for solar-blind signals at 200–280 nm.The metal semiconductor metal type solar-blind detectors were prepared. The detector based on Sn-doped β-Ga_(2)O_(3) thin film annealed in N_2 has the best response performance to 254 nm light. The photo-current is 10 μA at 20 V, the dark-current is 5.76 pA,the photo dark current ratio is 1.7 × 10~6, the response rate is 12.47 A/W, the external quantum efficiency is 6.09 × 10~3%, the specific detection rate is 2.61 × 10~(12) Jones, the response time and recovery time are 378 and 90 ms, respectively.
基金supported by the Special Project for the Central Government to Guide Local Technological Development (GUIKE ZY20198008)the Guangxi Technology Base and talent Subject (GUIKE AD20238012,AD20297086)+5 种基金the Natural Science Foundation of Guangxi Province (2021GXNSFDA075012)the National Natural Science Foundation of China (51902108,52104298,22169004)the National Natural Science Foundation of China (U20A20249)the Regional Innovation and Development Joint Fundthe Guangxi Innovation Driven Development Subject (GUIKE AA19182020,19254004)the Special Fund for Guangxi Distinguished Expert。
文摘Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_(2)O_(4) coating and Mg,Fe co-doping were constructed simultaneously by Mg,Fe surface treatment to suppress lattice oxygen evolution and P2-O2 phase transformation of P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)at deep charging.Through ex-situ X-ray diffraction(XRD)tests,we found that the Mg,Fe bulk co-doping could reduce the repulsion between transition metals and Na+/vacancies ordering,thus inhibiting the P2-O2 phase transition and significantly reducing the irreversible volume change of the material.Meanwhile,the internal electric field formed by the dielectric polarization of Mg Fe_(2)O_(4) effectively inhibits the outward migration of oxidized O^(a-)(a<2),thereby suppressing the lattice oxygen evolution at deep charging,confirmed by in situ Raman and ex situ XPS techniques.P2-Na NM@MF-3 shows enhanced high-voltage cycling performance with capacity retentions of 84.8% and 81.3%at 0.1 and 1 C after cycles.This work sheds light on regulating the surface chemistry for Na-layered oxide materials to enhance the high-voltage performance of Na-ion batteries.
基金the National Natural Science Foundation of China (92034301,22078063 and 22022804)Major Program of Qingyuan Innovation Laboratory (00121003)the Natural Science Foundation of Fujian Province (2020H6007)。
文摘The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.
基金We gratefully acknowledge the financial support from the National Natural Science Foundation of China(52070194,51902347,51908555,and 51822812)Natural Science Foundation of Hunan Province(2020JJ5741)the Graduate Innovation Project of Central South University(2020zzts093).
文摘LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible capacity limits its replacement for LiCoO_(2) in high-end digital field.Herein,three-in-one modification,Na-doping and Al_(2)O_(3)@Li_(3)BO_(3) dual-coating simultaneously,is explored for single-crystalline LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(N-NCM@AB),which exhibits excellent high-voltage performance.N-NCM@AB displays a discharge-specific capacity of 201.8 mAh g^(−1) at 0.2 C with a high upper voltage of 4.6 V and maintains 158.9 mAh g^(−1) discharge capacity at 1 C over 200 cycles with the corresponding capacity retention of 87.8%.Remarkably,the N-NCM@AB||graphite pouch-type full cell retains 81.2% of its initial capacity with high working voltage of 4.4 V over 1600 cycles.More importantly,the fundamental understandings of three-in-one modification on surface morphology,crystal structure,and phase transformation of N-NCM@AB are clearly revealed.The Na+doped into the Li–O slab can enhance the bond energy,stabilize the crystal structure,and facilitate Li+transport.Additionally,the interior surface layer of Li^(+)-ions conductor Li_(3)BO_(3) relieves the charge transfer resistance with surface coating,whereas the outer surface Al_(2)O_(3) coating layer is beneficial for reducing the active materials loss and alleviating the electrode/electrolyte parasite reaction.This three-in-one strategy provides a reference for the further research on the performance attenuation mechanism of NCM,paving a new avenue to boost the high-voltage performance of NCM cathode in Li-ion batteries.