MnO_(x)-CeO_(2)catalysts for the low-temperature selective catalytic reduction(SCR)of NO remain vulnerable to water and sulfur poisoning,limting their practical applications.Herein,we report a hydrophobic-modified MnO...MnO_(x)-CeO_(2)catalysts for the low-temperature selective catalytic reduction(SCR)of NO remain vulnerable to water and sulfur poisoning,limting their practical applications.Herein,we report a hydrophobic-modified MnO_(x)-CeO_(2)catalyst that achieves enhanced NO conversion rate and stability under harsh conditions.The catalyst was synthesized by decorating MnOx crystals with amorphous CeO_(2),followed by loading hydrophobic silica on the external surfaces.The hydrophobic silica allowed the adsorption of NH_(3)and NO and diffusion of H,suppressed the adsorption of H_(2)O,and prevented SO_(2)interaction with the Mn active sites,achieving selective molecular discrimination at the catalyst surface.At 120℃,under H_(2)O and SO_(2)exposure,the optimal hydrophobic catalyst maintains 82%NO conversion rate compared with 69%for the unmodified catalyst.The average adsorption energies of NH_(3),H_(2)O,and SO_(2)decreased by 0.05,0.43,and 0.52 eV,respectively.The NO reduction pathway follows the Eley-Rideal mechanism,NH_(3)^(*)+*→NH_(2)^(*)+H^(*)followed by NH_(2)^(*)+NO^(*)→N_(2)^(*)+H_(2)O^(*),with NH_(3)dehydrogenation being the rate determining step.Hydrophobic modification increased the activation energy for H atom transfer,leading to a minor decrease in the NO conversion rate at 120℃.This work demonstrates a viable strategy for developing robust NH_(3)-S CR catalysts capable of efficient operation in water-and sulfur-rich environments.展开更多
The NASICON-structured Na_(2)VTi(PO_(4))_(3)(NVTPO)has attracted significant attention due to its exceptional structural stability and rapid Na~+mobility.However,the development of this material has been hindered by p...The NASICON-structured Na_(2)VTi(PO_(4))_(3)(NVTPO)has attracted significant attention due to its exceptional structural stability and rapid Na~+mobility.However,the development of this material has been hindered by poor electronic conductivity and inadequate low-temperature performance.Herein,a feasible strategy of lattice regulation integrated with surface modification for NVTPO by nitrogen(N)deep doping is proposed.Systematic characterizations and theoretical calculations confirm that N is doped into both the inner crystal structure of NVTPO and the outer carbon layer.The blueshift of the P—O bonds and charge redistribution induced by the V/Ti—N bonds strengthen the local environment and narrow the bandgap,thereby enabling reversible structural evolution and improving electronic conductivity.As expected,the optimized NVTPO/N@CN material achieves an ultra-high capacity of 188.48 mA h g^(-1)at 10 mA g^(-1)and a long-term lifespan of 2000 cycles at 1 A g^(-1).More importantly,it exhibits competitive low-temperature performance(92.15%retention after 1000 cycles at 300 mA g^(-1)and-15℃)due to reduced charge transfer impedance and activation energy.This deep doping strategy modification is expected to broaden the applications of NASICON-type cathodes.展开更多
Structural modification of three dimensional(3D)materials for the application of dielectric loss-based microwave absorbing materials(MAMs)usually relies on intricate synthesis process and can pose challenges in terms ...Structural modification of three dimensional(3D)materials for the application of dielectric loss-based microwave absorbing materials(MAMs)usually relies on intricate synthesis process and can pose challenges in terms of scalability and mass production for practical application.In this work,we reported a successful attempt in modifying the 3D structure of mesoporous lanthanum oxide(La_(2)O_(3))for effective broadband MAMs candidate via simple co-precipitation process.The inclusion of cetyltrimethylammonium bromide(CTAB)and hydrothermal aging treatment result in a significant transformation of La_(2)O_(3)particles from their original polygonal form to a 3D coral-like and nano needle-like structure.The utilization of CTAB and hydrothermal aging results in the increase of surface area and a two-fold increase in pore volume of the resulting La_(2)O_(3).Due to its unique 3D structure,the 3D coral-like and nano needle-like La_(2)O_(3)materials possess a broadband electromagnetic(EM)wave absorption characteristic with the effective absorption bandwidth(EAB)covering the C-band frequency range.Specifically,in the La_(2)O_(3)C-H sample(with CTAB-with hydrothermal),it exhibits strong EM wave absorption with a reflection loss(RL)value of-33.07 dB which equals to 99.95%EM wave absorption at a thickness of only 1.50 mm.The detailed analysis of EM wave absorption properties reveals that the improvement of La_(2)O_(3)materials to attenuate EM wave energy arises from the dielectric loss phenomenon,the enhanced interfacial polarization,multiple reflections mechanism,and conduction loss mechanism induced by the 3D structural formation of the La_(2)O_(3)structure.This work proposes a novel and efficient approach in synthesizing and modifying 3D materials for effective broadband EM wave absorption.展开更多
Ischemic stroke(IS)presents a major threat to human life and health due to its high disability and mortality rates.3-n-Butylphthalide(NBP),derived from celery seeds of the Apiaceae family native to the Mediterranean r...Ischemic stroke(IS)presents a major threat to human life and health due to its high disability and mortality rates.3-n-Butylphthalide(NBP),derived from celery seeds of the Apiaceae family native to the Mediterranean region,was first introduced in China for acute IS treatment in 2004.NBP demonstrates multiple therapeutic actions,including reconstruction of microcirculation in the cerebral ischemia area,inhibition of platelet aggregation,reduction of cerebral infarction volume,maintenance of blood-brain barrier(BBB)integrity,and enhancement of cerebral blood perfusion.However,its overall efficacy remains moderate,limited by poor water solubility and low bioavailability,which constrains its clinical application.To address these limitations,researchers have actively pursued the development of NBP derivatives and analogs,achieving notable progress.These efforts,including substituent introduction,ring opening derivatization,esterification,and atom substitution,have generated diverse NBP derivatives.Several of these derivatives have advanced to clinical studies.Specifically,potassium 2-(1-hydroxypentyl)-benzoate(PHPB),brozopentyl sodium(BZP),and XY-03-EA(ZONK1103)have reached phase II clinical trials,while(S)-2-(1-acetoxypentyl)benzoic acid L-arginine salt(AAPB)has received clinical trial approval for 2024.This review examines the structural modification and optimization of NBP over the past two decades from a medicinal chemistry perspective,aiming to facilitate the development of superior derivatives and advance cerebral ischemia treatment.展开更多
Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.L...Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.Li^(+)/Li)constrains their use in ultrahighvoltage systems(e.g.,4.8 V).In this work,ferroelectric Ba TiO_(3)(BTO)nanoparticles with optimized thickness of~50-100 nm were successfully coated onto Li_(2.5)Y_(0.5)Zr_(0.5)Cl_(6)(LYZC@5BTO)electrolytes using a time-efficient ball-milling process.The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity,which remained at 1.06 m S cm^(-1)for LYZC@5BTO.Furthermore,this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes,suppresses parasitic interfacial reactions with single-crystal NCM811(SCNCM811),and inhibits the irreversible phase transition of SCNCM811.Consequently,the cycling stability of LYZC under high-voltage conditions(4.8 V vs.Li+/Li)is significantly improved.Specifically,ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 m Ah g^(-1)over 200 cycles at 1 C,way outperforming cell using pristine LYZC that only shows a capacity of 55.4 m Ah g^(-1).Furthermore,time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially,rising to 26% after 200 cycles in pristine LYZC.In contrast,LYZC@5BTO limited this increase to only 14%,confirming the effectiveness of BTO in stabilizing the interfacial chemistry.This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.展开更多
基金financially sponsored by the National Natural Science Foundation of China(No.52204414)the National Energy-Saving and Low-Carbon Materials Production and Application Demonstration Platform Program,China(No.TC220H06N)+1 种基金the National Key R&D Program of China(No.2021YFC1910504)the Fundamental Research Funds for the Central Universities,China(No.FRFTP-20-097A1Z)。
文摘MnO_(x)-CeO_(2)catalysts for the low-temperature selective catalytic reduction(SCR)of NO remain vulnerable to water and sulfur poisoning,limting their practical applications.Herein,we report a hydrophobic-modified MnO_(x)-CeO_(2)catalyst that achieves enhanced NO conversion rate and stability under harsh conditions.The catalyst was synthesized by decorating MnOx crystals with amorphous CeO_(2),followed by loading hydrophobic silica on the external surfaces.The hydrophobic silica allowed the adsorption of NH_(3)and NO and diffusion of H,suppressed the adsorption of H_(2)O,and prevented SO_(2)interaction with the Mn active sites,achieving selective molecular discrimination at the catalyst surface.At 120℃,under H_(2)O and SO_(2)exposure,the optimal hydrophobic catalyst maintains 82%NO conversion rate compared with 69%for the unmodified catalyst.The average adsorption energies of NH_(3),H_(2)O,and SO_(2)decreased by 0.05,0.43,and 0.52 eV,respectively.The NO reduction pathway follows the Eley-Rideal mechanism,NH_(3)^(*)+*→NH_(2)^(*)+H^(*)followed by NH_(2)^(*)+NO^(*)→N_(2)^(*)+H_(2)O^(*),with NH_(3)dehydrogenation being the rate determining step.Hydrophobic modification increased the activation energy for H atom transfer,leading to a minor decrease in the NO conversion rate at 120℃.This work demonstrates a viable strategy for developing robust NH_(3)-S CR catalysts capable of efficient operation in water-and sulfur-rich environments.
基金supported by the National Natural Science Foundation of China(22272205 and 22178094)the Hunan Provincial Nature Science Foundation of China(2022JJ30685,2023JJ20059 and 2024JJ5292)+2 种基金the Hunan Provincial Science and Technology Plan Projects of China(2022RC3050 and 2017TP1001)the financial support from the Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Provincesupport from the Young Elite Scientists Sponsorship Program by CAST(YESS20220432)。
文摘The NASICON-structured Na_(2)VTi(PO_(4))_(3)(NVTPO)has attracted significant attention due to its exceptional structural stability and rapid Na~+mobility.However,the development of this material has been hindered by poor electronic conductivity and inadequate low-temperature performance.Herein,a feasible strategy of lattice regulation integrated with surface modification for NVTPO by nitrogen(N)deep doping is proposed.Systematic characterizations and theoretical calculations confirm that N is doped into both the inner crystal structure of NVTPO and the outer carbon layer.The blueshift of the P—O bonds and charge redistribution induced by the V/Ti—N bonds strengthen the local environment and narrow the bandgap,thereby enabling reversible structural evolution and improving electronic conductivity.As expected,the optimized NVTPO/N@CN material achieves an ultra-high capacity of 188.48 mA h g^(-1)at 10 mA g^(-1)and a long-term lifespan of 2000 cycles at 1 A g^(-1).More importantly,it exhibits competitive low-temperature performance(92.15%retention after 1000 cycles at 300 mA g^(-1)and-15℃)due to reduced charge transfer impedance and activation energy.This deep doping strategy modification is expected to broaden the applications of NASICON-type cathodes.
基金Project supported by National Research and Innovation Agency through Rumah Program Organisasi Riset Nanoteknologi dan Material Maj u(ORNM)2024Indonesia Ministry of Finance through the competitive research program of RISPRO Kompetisi(PRJ-68/LPDP/2023)。
文摘Structural modification of three dimensional(3D)materials for the application of dielectric loss-based microwave absorbing materials(MAMs)usually relies on intricate synthesis process and can pose challenges in terms of scalability and mass production for practical application.In this work,we reported a successful attempt in modifying the 3D structure of mesoporous lanthanum oxide(La_(2)O_(3))for effective broadband MAMs candidate via simple co-precipitation process.The inclusion of cetyltrimethylammonium bromide(CTAB)and hydrothermal aging treatment result in a significant transformation of La_(2)O_(3)particles from their original polygonal form to a 3D coral-like and nano needle-like structure.The utilization of CTAB and hydrothermal aging results in the increase of surface area and a two-fold increase in pore volume of the resulting La_(2)O_(3).Due to its unique 3D structure,the 3D coral-like and nano needle-like La_(2)O_(3)materials possess a broadband electromagnetic(EM)wave absorption characteristic with the effective absorption bandwidth(EAB)covering the C-band frequency range.Specifically,in the La_(2)O_(3)C-H sample(with CTAB-with hydrothermal),it exhibits strong EM wave absorption with a reflection loss(RL)value of-33.07 dB which equals to 99.95%EM wave absorption at a thickness of only 1.50 mm.The detailed analysis of EM wave absorption properties reveals that the improvement of La_(2)O_(3)materials to attenuate EM wave energy arises from the dielectric loss phenomenon,the enhanced interfacial polarization,multiple reflections mechanism,and conduction loss mechanism induced by the 3D structural formation of the La_(2)O_(3)structure.This work proposes a novel and efficient approach in synthesizing and modifying 3D materials for effective broadband EM wave absorption.
基金supported by the National Natural Science Foundation of China(Nos.21977058 and 82473840)the Key R&D Program of Jiangsu Province(No.BE2021677)+2 种基金China Postdoctoral Science Foundation(No.2018T110533)the Key Natural Science Foundation of Jiangsu Higher Education Institutions(No.20KJA350002)Jiangsu Province Innovation Project of Postgraduate Training(No.KYCX22_3380).
文摘Ischemic stroke(IS)presents a major threat to human life and health due to its high disability and mortality rates.3-n-Butylphthalide(NBP),derived from celery seeds of the Apiaceae family native to the Mediterranean region,was first introduced in China for acute IS treatment in 2004.NBP demonstrates multiple therapeutic actions,including reconstruction of microcirculation in the cerebral ischemia area,inhibition of platelet aggregation,reduction of cerebral infarction volume,maintenance of blood-brain barrier(BBB)integrity,and enhancement of cerebral blood perfusion.However,its overall efficacy remains moderate,limited by poor water solubility and low bioavailability,which constrains its clinical application.To address these limitations,researchers have actively pursued the development of NBP derivatives and analogs,achieving notable progress.These efforts,including substituent introduction,ring opening derivatization,esterification,and atom substitution,have generated diverse NBP derivatives.Several of these derivatives have advanced to clinical studies.Specifically,potassium 2-(1-hydroxypentyl)-benzoate(PHPB),brozopentyl sodium(BZP),and XY-03-EA(ZONK1103)have reached phase II clinical trials,while(S)-2-(1-acetoxypentyl)benzoic acid L-arginine salt(AAPB)has received clinical trial approval for 2024.This review examines the structural modification and optimization of NBP over the past two decades from a medicinal chemistry perspective,aiming to facilitate the development of superior derivatives and advance cerebral ischemia treatment.
基金financially supported by Shenzhen Science and Technology Program(JCYJ20240813142900001)Guangdong Provincial Key Laboratory of New Energy Materials Service Safety。
文摘Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.Li^(+)/Li)constrains their use in ultrahighvoltage systems(e.g.,4.8 V).In this work,ferroelectric Ba TiO_(3)(BTO)nanoparticles with optimized thickness of~50-100 nm were successfully coated onto Li_(2.5)Y_(0.5)Zr_(0.5)Cl_(6)(LYZC@5BTO)electrolytes using a time-efficient ball-milling process.The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity,which remained at 1.06 m S cm^(-1)for LYZC@5BTO.Furthermore,this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes,suppresses parasitic interfacial reactions with single-crystal NCM811(SCNCM811),and inhibits the irreversible phase transition of SCNCM811.Consequently,the cycling stability of LYZC under high-voltage conditions(4.8 V vs.Li+/Li)is significantly improved.Specifically,ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 m Ah g^(-1)over 200 cycles at 1 C,way outperforming cell using pristine LYZC that only shows a capacity of 55.4 m Ah g^(-1).Furthermore,time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially,rising to 26% after 200 cycles in pristine LYZC.In contrast,LYZC@5BTO limited this increase to only 14%,confirming the effectiveness of BTO in stabilizing the interfacial chemistry.This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.
