Owing to their high luminous efficiency and tunable emission in both red light and far-red light regions,Mn^(4+)ion-activated phosphors have appealed significant interest in photoelectric and energy conversion devices...Owing to their high luminous efficiency and tunable emission in both red light and far-red light regions,Mn^(4+)ion-activated phosphors have appealed significant interest in photoelectric and energy conversion devices such as white light emitting diode(W-LED),plant cultivation LED,and temperature thermometer.Up to now,Mn^(4+)has been widely introduced into the lattices of various inorganic hosts for brightly redemitting phosphors.However,how to correlate the structure-activity relationship between host framework,luminescence property,and photoelectric device is urgently demanded.In this review,we thoroughly summarize the recent advances of Mn^(4+)doped phosphors.Meanwhile,several strategies like co-doping and defect passivation for improving Mn^(4+)emission are also discussed.Most importantly,the relationship between the protocols for tailoring the structures of Mn^(4+)doped phosphors,increased luminescence performance,and the targeted devices with efficient photoelectric and energy conversion efficiency is deeply correlated.Finally,the challenges and perspectives of Mn^(4+)doped phosphors for practical applications are anticipated.We cordially anticipate that this review can deliver a deep comprehension of not only Mn^(4+)luminescence mechanism but also the crystal structure tailoring strategy of phosphors,so as to spur innovative thoughts in designing advanced phosphors and deepening the applications.展开更多
In this study,a single-doped phosphors yttrium aluminum garnet(Y_(3)Al_(5)O_(12),YAG):Ce^(3+),single-doped YAG:Sc^(3+),and double-doped phosphors YAG:Ce^(3+),Sc^(3+) were prepared by spark plasma sintering(SPS)(lower ...In this study,a single-doped phosphors yttrium aluminum garnet(Y_(3)Al_(5)O_(12),YAG):Ce^(3+),single-doped YAG:Sc^(3+),and double-doped phosphors YAG:Ce^(3+),Sc^(3+) were prepared by spark plasma sintering(SPS)(lower than 1 200℃).The characteristics of synthesized phosphors were determined using scanning electron microscopy(SEM),X-ray diffraction(XRD),and fluorescence spectroscopy.During SPS,the lattice structure of YAG was maintained by the added Ce^(3+) and Sc^(3+).The emission wavelength of YAG:Ce^(3+) prepared from SPS(425-700 nm) was wider compared to that of YAG:Ce^(3+) prepared from high-temperature solid-state reaction(HSSR)(500-700 nm).The incorporation of low-dose Sc^(3+) in YAG:Ce^(3+) moved the emission peak towards the short wavelength.展开更多
For the purpose of development of highly energy-efficient light sources,one needs to design highly efficient green,red and yellow phosphors,which are able to absorb excitation energy and generate emissions.In this con...For the purpose of development of highly energy-efficient light sources,one needs to design highly efficient green,red and yellow phosphors,which are able to absorb excitation energy and generate emissions.In this contribution,we present our results on producing some efficient phosphors with improved luminescence properties.Using double activation,energy could be transferred from one luminescent activator to the other one,resulting in more efficient or brighter device operation.Co-activators could be added to a host material to change the color of the emitted light.The incorporation of Eu3+ or Tb3+ ions into the CaWO4 crystal lattice modified the luminescence spectrum due to the formation of the emission centers that generated the specific red and green light.Very efficient new red phosphors based on YNbO4 and doped by Eu3+,Ga3+,Al3+ allowed recommending these materials as good candidates for different applications including LED and X-ray intensifying screens.For double activated TAG with Ce3+ and Eu3+ and for different mole ratios of Ce/Eu,the color temperature changed from 5500 K(0.331,0.322) up to 4200 K(0.370,0.381) and the light became "warmer".Application of TAG:Ce,Eu in the light emitting device showed better chromaticity coordinates of luminescence and color rendering index of LEDs.展开更多
Photo-stimulated luminescence(PSL) is the process in which trapped charges are released by photons and produce luminescence through recombination. The variegated optical characteristics of photostimulated phosphors(PS...Photo-stimulated luminescence(PSL) is the process in which trapped charges are released by photons and produce luminescence through recombination. The variegated optical characteristics of photostimulated phosphors(PSPs) have drawn increasing attention and a large body of work encompassing mechanism and application of PSPs has been addressed. The optical data storage capacity resulting from abundant defect states enables PSPs to be applied to information storage. Moreover, PSPs provide potential application for anti-counterfeiting, as color changes due to the tunneling process. Recently, near infrared(NIR) light PSPs have been developed, exhibiting enormous potential for in vivo bio-imaging, as the stable and high noise-signal ratio characteristic of PSL. In this review, we devote to introducing the development and process of PSPs, and the challenge and future advance have also been demonstrated.展开更多
Eu^2＋-doped Ba3Si6012N2 green phosphors were prepared by microwave assisted sintering method at 1275℃ for 4 h, while the counterparts using conventional solid-state reaction method were synthesized at temperature hi...Eu^2＋-doped Ba3Si6012N2 green phosphors were prepared by microwave assisted sintering method at 1275℃ for 4 h, while the counterparts using conventional solid-state reaction method were synthesized at temperature higher than 1300℃ and for to 10 h. Microwave assisted sintering could reduce the activation energy and enhance the diffu- sion rate, thus greatly improved the sintering. Moreover, the influence of Si3N4 content on phase formation, morphol- ogy, absorption, and quantum efficiency, and photoluminescence properties of phosphors were studied. As a result, the Ba3Si6OI2N2：Eu^2＋ samples sintered by microwave assisted sintering method have a higher phase purity and photo- luminescence intensity under ultraviolet excitation as compared with samples sintered in the conventional tube furnace The proposed method is a potential preparation method for the oxynitride phosphors with strong photoluminescence and high phase purity.展开更多
The remarkable narrow-band emission of trivalent lanthanide-doped phosphors excited by the vacuum ultraviolet(VUV)radiation lines of Xe atoms/Xe_(2) molecules at 147/172 nm are extensively investigated in the developm...The remarkable narrow-band emission of trivalent lanthanide-doped phosphors excited by the vacuum ultraviolet(VUV)radiation lines of Xe atoms/Xe_(2) molecules at 147/172 nm are extensively investigated in the development of plasma display panels and Hg-free fluorescent lamps,which are frequently used in our daily lives.Numerous solid materials,particularly Tb^(3+)-doped oxides,such as silicates,phosphates and borates,are efficient green/blue sources with color-tunable properties.The excitation wavelength and rare earth concentration are usually varied to optimize efficiency and the luminescent properties.However,some underlying mechanisms for the shift in the emission colors remain unclear.The present study shows that a UV/VUV switch systematically controls the change in the phosphor(Ba_(3)Si_(6)O_(12)N_(2):Tb)photoluminescence from green to blue,resulting in a green emission when the system is excited with UV radiation.However,a blue color is observed when the radiation wavelength shifts to the VUV region.Thus,a configurational coordinate model is proposed for the color-reversal effect.In this model,the dominant radiative decay results in a green emission under low-energy UV excitation from the ^(5)D_(4) state of the f–f inner-shell transition in the Tb system.However,under high-energy VUV excitation,the state switches into the ^(5)D_(3) state,which exhibits a blue emission.This mechanism is expected to be generally applicable to Tb-doped phosphors and useful in adjusting the optical properties against well-known cross-relaxation processes by varying the ratio of the green/blue contributions.展开更多
Nitrogen-rich Eu2+-doped Ca-α-SiAlON phosphors(Cam/2-xSi12-m-nAlm+nOnN16-n:xEu) were synthesized by a freeze-drying assisted combustion synthesis(CS) route. Fast-synthesized products with high purity and uniform part...Nitrogen-rich Eu2+-doped Ca-α-SiAlON phosphors(Cam/2-xSi12-m-nAlm+nOnN16-n:xEu) were synthesized by a freeze-drying assisted combustion synthesis(CS) route. Fast-synthesized products with high purity and uniform particle morphology were confirmed by X-ray diffraction(XRD) and scanning electron microscopy(SEM). The analysis of lattice parameters by comparison with empirical equations showed that the as-prepared phosphors had low oxygen content. A series of samples were prepared according to the stoichiometry of Cam/2-0.08Si12-mAlmN16:0.08 Eu for further research. The influences of m value on the luminescence properties were investigated in detail. As m increased, a redshift phenomenon was observed in both the excitation and emission spectra. First-principle electronic structure calculations showed that the 3d energy level of Ca played an important role in the occurrence of the redshift phenomenon.展开更多
With the development circular economy, the use of agricultural waste to prepare biomass materials to remove pollutants has become a research hotspot. In this study, sunflower straw activated carbon (SSAC) was prepared...With the development circular economy, the use of agricultural waste to prepare biomass materials to remove pollutants has become a research hotspot. In this study, sunflower straw activated carbon (SSAC) was prepared by the one-step activation method, with sunflower straw (SS) used as the raw material and H3PO4 used as the activator. Four types of SSAC were prepared with impregnation ratios (weight of SS to weight of H3PO4) of 1:1, 1:2, 1:3, and 1:5, corresponding to SSAC1, SSAC2, SSAC3, and SSAC4, respectively. The adsorption process of acid fuchsin (AF) in water using the four types of SSAC was studied. The results showed that the impregnation ratio significantly affected the structure of the materials. The increase in the impregnation ratio increased the specific surface area and pore volume of SSAC and improved the adsorption capacity of AF. However, an impregnation ratio that was too large led to a decrease in specific surface area. SSAC3, with an impregnation ratio of 1:3, had the largest specific surface area (1 794.01 m2/g), and SSAC4, with an impregnation ratio of 1:5, exhibited the smallest microporosity (0.052 7 cm3/g) and the largest pore volume (2.549 cm3/g). The adsorption kinetics of AF using the four types of SSAC agreed with the quasi-second-order adsorption kinetic model. The Langmuir isotherm model was suitable to describe SSAC3 and SSAC4, and the Freundlich isotherm model was appropriate to describe SSAC1 and SSAC2. The result of thermodynamics showed that the adsorption process was spontaneous and endothermic. At 303 K, SSAC4 showed a removal rate of 97.73% for 200-mg/L AF with a maximum adsorption capacity of 2 763.36 mg/g, the highest among the four types of SSAC. This study showed that SAAC prepared by the H3PO4-based one-step activation method is a green and efficient carbon material and has significant application potential for the treatment of dye-containing wastewater.展开更多
Using a simple combustion process, rare earth doped novel compounds like fluorides LiBF4 and Li3BF6 can be prepared. Combustion synthesis furnishes a quick method for preparation of these phosphors. The prepared phosp...Using a simple combustion process, rare earth doped novel compounds like fluorides LiBF4 and Li3BF6 can be prepared. Combustion synthesis furnishes a quick method for preparation of these phosphors. The prepared phosphors were characterized by the photoluminescence (PL) techniques. It is suggested that borofluoride based materials can be developed as low-cost phosphors. Formation of single phase compounds was confirmed by XRD. It is observed that prepared phosphors exhibited intense and characteristic Ce3+ and Eu2+ photoluminescence emission in blue visible region. This article summarizes fundamentals and possible applications of optically useful inorganic fluoride materials, with visible photoluminescence of Ce3+ and Eu2+ doped ions.展开更多
Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to i...Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to its low solubility in aqueous electrolytes.Herein,we propose phosphorus-activated Cu electrocatalysts to generate electron-deficient Cu sites on the catalyst surface to promote the adsorption of N_(2) molecules.The eNRR system is further modified using a gas diffusion electrode(GDE) coated with polytetrafluoroethylene(PTFE) to form an effective three-phase boundary of liquid water-gas N_(2)-solid catalyst to facilitate easy access of N_(2) to the catalytic sites.As a result,the new catalyst in the flow-type cell records a Faradaic efficiency of 13.15% and an NH_(3) production rate of 7.69 μg h^(-1) cm^(-2) at-0.2 V_(RHE),which represent 3.56 and 59.2 times increases from those obtained with a pristine Cu electrode in a typical electrolytic cell.This work represents a successful demonstration of dual modification strategies;catalyst modification and N_(2) supplying system engineering,and the results would provide a useful platform for further developments of electrocatalysts and reaction systems.展开更多
基金financially supported by the National Natural Science Foundation of China(52072101,51972088,U20A20122 and U1663225)the Program for Changjiang Scholars and Innovative Research Team in University(IRT_15R52)of the Chinese Ministry of Education+2 种基金the Program of Introducing Talents of Discipline to Universities-Plan 111(Grant No.B20002)from the Ministry of Science and Technology and the Ministry of Education of ChinaHubei Provincial Department of Education for the“Chutian Scholar”programsupported by the European Commission Interreg V FranceWallonie-Vlaanderen project“Depollut Air”。
文摘Owing to their high luminous efficiency and tunable emission in both red light and far-red light regions,Mn^(4+)ion-activated phosphors have appealed significant interest in photoelectric and energy conversion devices such as white light emitting diode(W-LED),plant cultivation LED,and temperature thermometer.Up to now,Mn^(4+)has been widely introduced into the lattices of various inorganic hosts for brightly redemitting phosphors.However,how to correlate the structure-activity relationship between host framework,luminescence property,and photoelectric device is urgently demanded.In this review,we thoroughly summarize the recent advances of Mn^(4+)doped phosphors.Meanwhile,several strategies like co-doping and defect passivation for improving Mn^(4+)emission are also discussed.Most importantly,the relationship between the protocols for tailoring the structures of Mn^(4+)doped phosphors,increased luminescence performance,and the targeted devices with efficient photoelectric and energy conversion efficiency is deeply correlated.Finally,the challenges and perspectives of Mn^(4+)doped phosphors for practical applications are anticipated.We cordially anticipate that this review can deliver a deep comprehension of not only Mn^(4+)luminescence mechanism but also the crystal structure tailoring strategy of phosphors,so as to spur innovative thoughts in designing advanced phosphors and deepening the applications.
基金Funded by the Primary Research and Development Plan of Jiangsu Province(No.BE2016175)。
文摘In this study,a single-doped phosphors yttrium aluminum garnet(Y_(3)Al_(5)O_(12),YAG):Ce^(3+),single-doped YAG:Sc^(3+),and double-doped phosphors YAG:Ce^(3+),Sc^(3+) were prepared by spark plasma sintering(SPS)(lower than 1 200℃).The characteristics of synthesized phosphors were determined using scanning electron microscopy(SEM),X-ray diffraction(XRD),and fluorescence spectroscopy.During SPS,the lattice structure of YAG was maintained by the added Ce^(3+) and Sc^(3+).The emission wavelength of YAG:Ce^(3+) prepared from SPS(425-700 nm) was wider compared to that of YAG:Ce^(3+) prepared from high-temperature solid-state reaction(HSSR)(500-700 nm).The incorporation of low-dose Sc^(3+) in YAG:Ce^(3+) moved the emission peak towards the short wavelength.
基金Project supported by the Korea Science and Engineering Foundation (KOSEF) through NRL (M10400000045-04J0000-04510)NCRC (R15-2008-006-00000-0)+1 种基金the Basic Research Program (R01-2005-000-10530-0)Ministry of Education,Science and Technology in Korea
文摘For the purpose of development of highly energy-efficient light sources,one needs to design highly efficient green,red and yellow phosphors,which are able to absorb excitation energy and generate emissions.In this contribution,we present our results on producing some efficient phosphors with improved luminescence properties.Using double activation,energy could be transferred from one luminescent activator to the other one,resulting in more efficient or brighter device operation.Co-activators could be added to a host material to change the color of the emitted light.The incorporation of Eu3+ or Tb3+ ions into the CaWO4 crystal lattice modified the luminescence spectrum due to the formation of the emission centers that generated the specific red and green light.Very efficient new red phosphors based on YNbO4 and doped by Eu3+,Ga3+,Al3+ allowed recommending these materials as good candidates for different applications including LED and X-ray intensifying screens.For double activated TAG with Ce3+ and Eu3+ and for different mole ratios of Ce/Eu,the color temperature changed from 5500 K(0.331,0.322) up to 4200 K(0.370,0.381) and the light became "warmer".Application of TAG:Ce,Eu in the light emitting device showed better chromaticity coordinates of luminescence and color rendering index of LEDs.
基金Project supported by the National Natural Science Foundation of China(61565009,11664022,11804038)the Foundation of Natural Science of Yunnan Province(2016FB088)+3 种基金the Reserve Talents Project of Yunnan Province(2017HB011)the Young Talents Support Program of Faculty of Materials Science and Engineering,Kunming University of Science and Technology(14078342)Chongqing Natural Science Foundation(cstc2017jcyjAX0418,cstc2018jcyjAX0569)Foundation of Chongqing University of Arts and Sciences(R2016DQ10)
文摘Photo-stimulated luminescence(PSL) is the process in which trapped charges are released by photons and produce luminescence through recombination. The variegated optical characteristics of photostimulated phosphors(PSPs) have drawn increasing attention and a large body of work encompassing mechanism and application of PSPs has been addressed. The optical data storage capacity resulting from abundant defect states enables PSPs to be applied to information storage. Moreover, PSPs provide potential application for anti-counterfeiting, as color changes due to the tunneling process. Recently, near infrared(NIR) light PSPs have been developed, exhibiting enormous potential for in vivo bio-imaging, as the stable and high noise-signal ratio characteristic of PSL. In this review, we devote to introducing the development and process of PSPs, and the challenge and future advance have also been demonstrated.
文摘Eu^2＋-doped Ba3Si6012N2 green phosphors were prepared by microwave assisted sintering method at 1275℃ for 4 h, while the counterparts using conventional solid-state reaction method were synthesized at temperature higher than 1300℃ and for to 10 h. Microwave assisted sintering could reduce the activation energy and enhance the diffu- sion rate, thus greatly improved the sintering. Moreover, the influence of Si3N4 content on phase formation, morphol- ogy, absorption, and quantum efficiency, and photoluminescence properties of phosphors were studied. As a result, the Ba3Si6OI2N2：Eu^2＋ samples sintered by microwave assisted sintering method have a higher phase purity and photo- luminescence intensity under ultraviolet excitation as compared with samples sintered in the conventional tube furnace The proposed method is a potential preparation method for the oxynitride phosphors with strong photoluminescence and high phase purity.
基金the Science and Technology of Taiwan(Contract No.MOST 104-2113-M-002-012-MY3,MOST 104-2119-M-002-027-MY3,MOST 104-2923-M-002-007-MY3 and MOST 104-2917-I-564-060).
文摘The remarkable narrow-band emission of trivalent lanthanide-doped phosphors excited by the vacuum ultraviolet(VUV)radiation lines of Xe atoms/Xe_(2) molecules at 147/172 nm are extensively investigated in the development of plasma display panels and Hg-free fluorescent lamps,which are frequently used in our daily lives.Numerous solid materials,particularly Tb^(3+)-doped oxides,such as silicates,phosphates and borates,are efficient green/blue sources with color-tunable properties.The excitation wavelength and rare earth concentration are usually varied to optimize efficiency and the luminescent properties.However,some underlying mechanisms for the shift in the emission colors remain unclear.The present study shows that a UV/VUV switch systematically controls the change in the phosphor(Ba_(3)Si_(6)O_(12)N_(2):Tb)photoluminescence from green to blue,resulting in a green emission when the system is excited with UV radiation.However,a blue color is observed when the radiation wavelength shifts to the VUV region.Thus,a configurational coordinate model is proposed for the color-reversal effect.In this model,the dominant radiative decay results in a green emission under low-energy UV excitation from the ^(5)D_(4) state of the f–f inner-shell transition in the Tb system.However,under high-energy VUV excitation,the state switches into the ^(5)D_(3) state,which exhibits a blue emission.This mechanism is expected to be generally applicable to Tb-doped phosphors and useful in adjusting the optical properties against well-known cross-relaxation processes by varying the ratio of the green/blue contributions.
基金This work was financially supported by the Chinese Academy of Sciences(CAS)Interdisciplinary Innovation Teamthe Fundamental Research Funds for the Central Universitiesthe Research Funds of Renmin University of China(No.19XNLG13).
文摘Nitrogen-rich Eu2+-doped Ca-α-SiAlON phosphors(Cam/2-xSi12-m-nAlm+nOnN16-n:xEu) were synthesized by a freeze-drying assisted combustion synthesis(CS) route. Fast-synthesized products with high purity and uniform particle morphology were confirmed by X-ray diffraction(XRD) and scanning electron microscopy(SEM). The analysis of lattice parameters by comparison with empirical equations showed that the as-prepared phosphors had low oxygen content. A series of samples were prepared according to the stoichiometry of Cam/2-0.08Si12-mAlmN16:0.08 Eu for further research. The influences of m value on the luminescence properties were investigated in detail. As m increased, a redshift phenomenon was observed in both the excitation and emission spectra. First-principle electronic structure calculations showed that the 3d energy level of Ca played an important role in the occurrence of the redshift phenomenon.
基金supported by the National Natural Science Foundation of China(Grant No.41865010)the 2020 Leading Talents of Young Science and Technology Talents in Colleges and Universities of the Inner Mongolia Autonomous Region(Grant No.NJYT-20-A04)the Project of the 10th Group of Grassland Talents of the Inner Mongolia Autonomous Region,the 2022 Inner Mongolia Outstanding Youth Fund Project,and the Key Research and Development and Achievement Transformation Program of the Inner Mongolia Autonomous Region in 2022(Grant No.2022YFHH0035).
文摘With the development circular economy, the use of agricultural waste to prepare biomass materials to remove pollutants has become a research hotspot. In this study, sunflower straw activated carbon (SSAC) was prepared by the one-step activation method, with sunflower straw (SS) used as the raw material and H3PO4 used as the activator. Four types of SSAC were prepared with impregnation ratios (weight of SS to weight of H3PO4) of 1:1, 1:2, 1:3, and 1:5, corresponding to SSAC1, SSAC2, SSAC3, and SSAC4, respectively. The adsorption process of acid fuchsin (AF) in water using the four types of SSAC was studied. The results showed that the impregnation ratio significantly affected the structure of the materials. The increase in the impregnation ratio increased the specific surface area and pore volume of SSAC and improved the adsorption capacity of AF. However, an impregnation ratio that was too large led to a decrease in specific surface area. SSAC3, with an impregnation ratio of 1:3, had the largest specific surface area (1 794.01 m2/g), and SSAC4, with an impregnation ratio of 1:5, exhibited the smallest microporosity (0.052 7 cm3/g) and the largest pore volume (2.549 cm3/g). The adsorption kinetics of AF using the four types of SSAC agreed with the quasi-second-order adsorption kinetic model. The Langmuir isotherm model was suitable to describe SSAC3 and SSAC4, and the Freundlich isotherm model was appropriate to describe SSAC1 and SSAC2. The result of thermodynamics showed that the adsorption process was spontaneous and endothermic. At 303 K, SSAC4 showed a removal rate of 97.73% for 200-mg/L AF with a maximum adsorption capacity of 2 763.36 mg/g, the highest among the four types of SSAC. This study showed that SAAC prepared by the H3PO4-based one-step activation method is a green and efficient carbon material and has significant application potential for the treatment of dye-containing wastewater.
文摘Using a simple combustion process, rare earth doped novel compounds like fluorides LiBF4 and Li3BF6 can be prepared. Combustion synthesis furnishes a quick method for preparation of these phosphors. The prepared phosphors were characterized by the photoluminescence (PL) techniques. It is suggested that borofluoride based materials can be developed as low-cost phosphors. Formation of single phase compounds was confirmed by XRD. It is observed that prepared phosphors exhibited intense and characteristic Ce3+ and Eu2+ photoluminescence emission in blue visible region. This article summarizes fundamentals and possible applications of optically useful inorganic fluoride materials, with visible photoluminescence of Ce3+ and Eu2+ doped ions.
基金supported by KU Leuven (GOA/13/008 and IOFKP RARE3)FWO-Flanders for a SB PhD fellowship (1S23518N)the European Research Council (ERC) under the European Union’s Horizon 2020 Research and Innovation Programme: Grant Agreement 694078-Solvometallurgy for critical metals (SOLCRIMET)
基金supported by the Climate Change Response Project (NRF-2019M1A2A2065612)the Brainlink Project (NRF2022H1D3A3A01081140)+3 种基金the NRF-2021R1A4A3027878 and the No. RS-2023-00212273 funded by the Ministry of Science and ICT of Korea via National Research Foundationresearch funds from Hanhwa Solutions Chemicals (1.220029.01)UNIST (1.190013.01)supported by the Institute for Basic Science (IBS-R019-D1)。
文摘Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to its low solubility in aqueous electrolytes.Herein,we propose phosphorus-activated Cu electrocatalysts to generate electron-deficient Cu sites on the catalyst surface to promote the adsorption of N_(2) molecules.The eNRR system is further modified using a gas diffusion electrode(GDE) coated with polytetrafluoroethylene(PTFE) to form an effective three-phase boundary of liquid water-gas N_(2)-solid catalyst to facilitate easy access of N_(2) to the catalytic sites.As a result,the new catalyst in the flow-type cell records a Faradaic efficiency of 13.15% and an NH_(3) production rate of 7.69 μg h^(-1) cm^(-2) at-0.2 V_(RHE),which represent 3.56 and 59.2 times increases from those obtained with a pristine Cu electrode in a typical electrolytic cell.This work represents a successful demonstration of dual modification strategies;catalyst modification and N_(2) supplying system engineering,and the results would provide a useful platform for further developments of electrocatalysts and reaction systems.
