Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has gar...Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.展开更多
Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the r...Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization.Here,we developed a solution inverse temperature crystal growth(ITCG)method to bring-up high quality Cs_(3)Cu_(2)I_(5)crystals with large size of centimeter order,in which the oleic acid(OA)is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently,as well as to decelerate the crystallization rate remarkalby.Based on these fine crystals,the vapor deposition technique is empolyed to prepare high quality Cs_(3)Cu_(2)I_(5)films for efficient X-ray imaging.Smooth surface morphology,high light yields and short decay time endow the Cs_(3)Cu_(2)I_(5)films with strong radioluminescence,high resolution(12 lp/mm),low detection limits(53 nGyair/s)and desirable stability.Subsequently,the Cs_(3)Cu_(2)I_(5)films have been applied to the practical radiography which exhibit superior X-ray imaging performance.Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.展开更多
The maximum velocity of a mobile vortex in movement is generally limited by the phenomenon of flux-flow instability(FFI),which necessitates weak vortex pinning and fast heat removal from non-equilibrium electrons.We h...The maximum velocity of a mobile vortex in movement is generally limited by the phenomenon of flux-flow instability(FFI),which necessitates weak vortex pinning and fast heat removal from non-equilibrium electrons.We here demonstrate exfoliations and nano-fabrications of Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips,which possess a rather weak pinning volume of vortices,relatively low resistivity,and large normal electron diffusion coefficient.The deduced vortex velocity in Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips can be up to 300 km/s near the superconducting transition temperature,well above the speed of sound.The observed vortex velocity is an order of magnitude faster than that of conventional superconducting systems,representing a perfect platform for exploration of ultra-fast vortex matter and a good candidate for fabrications of superconducting nanowire single photon detectors or superconducting THz modulator.展开更多
Immobilizing primary electroactive nanomaterials in porous carbon matrix is an effective approach for boosting the electrochemical performance of potassium-ion batteries (PIBs) because of the synergy among functional ...Immobilizing primary electroactive nanomaterials in porous carbon matrix is an effective approach for boosting the electrochemical performance of potassium-ion batteries (PIBs) because of the synergy among functional components. Herein, an integrated hybrid architecture composed of ultrathin Cu_(3)P nanoparticles (~20 nm) confined in porous carbon nanosheets (Cu_(3)P⊂NPCSs) as a new anode material for PIBs is synthesized through a rational self-designed self-templating strategy. Benefiting from the unique structural advantages including more active heterointerfacial sites, intimate and stable electrical contact, effectively relieved volume change, and rapid K^(+) ion migration, the Cu_(3)P⊂NPCSs indicate excellent potassium-storage performance involving high reversible capacity, exceptional rate capability, and cycling stability. Moreover, the strong adsorption of K^(+) ions and fast potassium-ion reaction kinetics in Cu_(3)P⊂NPCSs is verified by the theoretical calculation investigation. Noted, the intercalation mechanism of Cu_(3)P to store potassium ions is, for the first time, clearly confirmed during the electrochemical process by a series of advanced characterization techniques.展开更多
Transitional metal phosphides(TMPs)anode materials usually have large volume change and weak diffusion kinetics,leading to poor cycle stability.Combining TMPs with conductive carbon matrix has been widely used to boos...Transitional metal phosphides(TMPs)anode materials usually have large volume change and weak diffusion kinetics,leading to poor cycle stability.Combining TMPs with conductive carbon matrix has been widely used to boost sodium storage.However,it still needs to make efforts in the rational and facile design of nano/micro-structural TMPs/carbon hybrid anode material.Herein,a MOFs-derived strategy is developed to synthesize porous yolk–shell Mo P/Cu_(3)P@carbon microcages(Mo P/Cu_(3)P@C)through in situ and confined phosphidation reaction as a high-performance sodium-ion batteries anode.This yolk–shell structure can offer adequate internal space to buffer the large volume expansion,shorten diffusion distance,and create more active sites of Na+.Especially,the Cu nanoparticles generated from Cu_(3)P have remarkable electronic conductivity of 5.73107S m-1(the second most conductive metal)to benefit transporting electrons.And the introduction of Mo(Mo P has high theoretical capacity of 633 mA h g^(-1))can enhance the reversible capacity of the whole anode material.Therefore,these porous yolk–shell Mo P/Cu_(3)P@carbon microcages possess excellent reversible capacity of 307.8 mA h g^(-1)at 1.0 A g^(-1)and extraordinary cycle stability of 132.1 m A h g^(-1)at 5.0 A g^(-1)even after 6000 cycles.展开更多
Lithium-sulfur batteries(LSBs)can work at high temperatures,but they suffer from poor cycle life stability due to the“shuttle effect”of polysulfides.In this study,pollen-derived porous carbon/cuprous phosphide(PC/Cu...Lithium-sulfur batteries(LSBs)can work at high temperatures,but they suffer from poor cycle life stability due to the“shuttle effect”of polysulfides.In this study,pollen-derived porous carbon/cuprous phosphide(PC/Cu_(3)P)hybrids were rationally synthesized using a one-step carbonization method using pollen as the source material,acting as the sulfur host for LSBs.In the hybrid,polar Cu_(3)P can markedly inhibit the“shuttle effect”by regulating the adsorption ability toward polysulfides,as confirmed by theoretical calculations and experimental tests.As an example,the camellia pollen porous carbon(CPC)/Cu_(3)P/S electrode shows a high capacity of 1205.6 mAh g^(−1) at 0.1 C,an ultralow capacity decay rate of 0.038%per cycle after 1000 cycles at 1 C,and a rather high initial Coulombic efficiency of 98.5%.The CPC/Cu_(3)P LSBs can work well at high temperatures,having a high capacity of 545.9 mAh g^(−1) at 1 C even at 150℃.The strategy of the PC/Cu_(3)P hybrid proposed in this study is expected to be an ideal cathode for ultrastable high-temperature LSBs.We believe that this strategy is universal and worthy of in-depth development for the next generation energy storage devices.展开更多
Developing suitable anode materials for potassium-ion batteries(PIBs)remains a great challenge owing to the limited theoretical capacity of active materials and large radius of K+ion(1.38?).To solve these obstacles,by...Developing suitable anode materials for potassium-ion batteries(PIBs)remains a great challenge owing to the limited theoretical capacity of active materials and large radius of K+ion(1.38?).To solve these obstacles,by integrating the principles of multielectron transfer and rational porous crystal framework,we creatively propose the monoclinic Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O(CVO)as a novel anode for PIBs.Furthermore,inspired by the metastable nature of CVO under high temperature/pressure,we skillfully design a facile hydrothermal recrystallization strategy without the phase change and surfactants addition.Thus,for the first time,the porous composite of Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O nanobelts covered in situ by reduced graphene oxide(CVO NBs/r GO)was assembled,greatly improving the deficiencies of CVO.When used as a novel anode for PIBs,CVO NBs/r GO delivers large specific capacity(up to 551.4 m Ah g^(-1)at 50 m A g^(-1)),high-rate capability(215.3 m Ah g^(-1)at 2.5 A g^(-1))and super durability(203.6 m Ah g^(-1)at 500 m A g^(-1)even after 1000 cycles).The outstanding performance can be ascribed to the synergistic merits of desirable structural features of monoclinic CVO nanobelts and the highly conductive graphene 3D network,thus promoting the composite material stability and electrical/ionic conductivity.This work reveals a novel metal vanadate-based anode material for PIBs,would further motivate the subsequent batteries research on M_(3)(OH)_(2)V_(2)O_(7)-n H_(2)O(M;Co,Ni,Cu,Zn),and ultimately expands valuable fundamental understanding on designing other high-performance electrode materials,including the combined strategies of multielectron transfer with rational porous crystal framework,and the composite fabrication of 1D electrode nanostructure with conductive carbon matrix.展开更多
基金supported by the National Key R&D Program of China(No.2021YFB2800700)National Natural Science Foundation of China(Nos.12274210,62227820,and 12174183)+1 种基金Partial support is from NSF of Jiangsu Province(No.BK20220006)the Fundamental Research Funds for the Central Universities and Jiangsu Key Laboratory of Advanced Techniques for Manipulating Electromagnetic Waves。
文摘Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.
基金the financially support of the National Natural Science Foundation of China(12164051)the Joint Foundation of Provincial Science and Technology Department-Double First-class Construction of Yunnan University(2019FY003016)+4 种基金the Young Top Talent Project of Yunnan Province(YNWR-QNBJ-2018-229)the financially support by Yunnan Major Scientific and Technological Projects(202202AG050016)Advanced Analysis and Measurement Center of Yunnan University for the sample characterization service and the Postgraduate Research and Innovation Foundation of Yunnan University(2021Y036)the financially support of the National Natural Science Foundation of China(62064013)the Application Basic Research Project of Yunnan Province[2019FB130]。
文摘Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization.Here,we developed a solution inverse temperature crystal growth(ITCG)method to bring-up high quality Cs_(3)Cu_(2)I_(5)crystals with large size of centimeter order,in which the oleic acid(OA)is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently,as well as to decelerate the crystallization rate remarkalby.Based on these fine crystals,the vapor deposition technique is empolyed to prepare high quality Cs_(3)Cu_(2)I_(5)films for efficient X-ray imaging.Smooth surface morphology,high light yields and short decay time endow the Cs_(3)Cu_(2)I_(5)films with strong radioluminescence,high resolution(12 lp/mm),low detection limits(53 nGyair/s)and desirable stability.Subsequently,the Cs_(3)Cu_(2)I_(5)films have been applied to the practical radiography which exhibit superior X-ray imaging performance.Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.
基金supporting high quality of post growth treatment Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ)single crystalssupported by the National Key Research and Development Program of China(Grant No.2017YFA0304000)+4 种基金the National Natural Science Foundation of China(Grant Nos.61971408 and 61827823)Shanghai Municipal Science and Technology Major Project(Grant No.2019SHZDZX01)Shanghai Rising-Star Program(Grant No.20QA1410900)the Youth Innovation Promotion Association of Chinese Academy of Sciences(Grant Nos.2020241 and 2021230)the Natural Science Foundation of Shanghai(Grant No.19ZR1467400)。
文摘The maximum velocity of a mobile vortex in movement is generally limited by the phenomenon of flux-flow instability(FFI),which necessitates weak vortex pinning and fast heat removal from non-equilibrium electrons.We here demonstrate exfoliations and nano-fabrications of Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips,which possess a rather weak pinning volume of vortices,relatively low resistivity,and large normal electron diffusion coefficient.The deduced vortex velocity in Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips can be up to 300 km/s near the superconducting transition temperature,well above the speed of sound.The observed vortex velocity is an order of magnitude faster than that of conventional superconducting systems,representing a perfect platform for exploration of ultra-fast vortex matter and a good candidate for fabrications of superconducting nanowire single photon detectors or superconducting THz modulator.
基金the financial supports provided by the National Natural Science Foundation of China(Nos.21971145,21871164)the Taishan Scholar Project Foundation of Shandong Province(No.ts20190908)+1 种基金the Natural Science Foundation of Shandong Province(No.ZR2019MB024)the Young Scholars Program of Shandong University(No.2017WLJH15)。
文摘Immobilizing primary electroactive nanomaterials in porous carbon matrix is an effective approach for boosting the electrochemical performance of potassium-ion batteries (PIBs) because of the synergy among functional components. Herein, an integrated hybrid architecture composed of ultrathin Cu_(3)P nanoparticles (~20 nm) confined in porous carbon nanosheets (Cu_(3)P⊂NPCSs) as a new anode material for PIBs is synthesized through a rational self-designed self-templating strategy. Benefiting from the unique structural advantages including more active heterointerfacial sites, intimate and stable electrical contact, effectively relieved volume change, and rapid K^(+) ion migration, the Cu_(3)P⊂NPCSs indicate excellent potassium-storage performance involving high reversible capacity, exceptional rate capability, and cycling stability. Moreover, the strong adsorption of K^(+) ions and fast potassium-ion reaction kinetics in Cu_(3)P⊂NPCSs is verified by the theoretical calculation investigation. Noted, the intercalation mechanism of Cu_(3)P to store potassium ions is, for the first time, clearly confirmed during the electrochemical process by a series of advanced characterization techniques.
基金supported by the National Natural Science Foundation of China(no.21646012)China Postdoctoral Science Foundation(no.2016M600253,2017T100246)+1 种基金the State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(no.2019DX13)the Fundamental Research Funds for the Central Universities(Grant No.HIT.NSRIF.201836)
文摘Transitional metal phosphides(TMPs)anode materials usually have large volume change and weak diffusion kinetics,leading to poor cycle stability.Combining TMPs with conductive carbon matrix has been widely used to boost sodium storage.However,it still needs to make efforts in the rational and facile design of nano/micro-structural TMPs/carbon hybrid anode material.Herein,a MOFs-derived strategy is developed to synthesize porous yolk–shell Mo P/Cu_(3)P@carbon microcages(Mo P/Cu_(3)P@C)through in situ and confined phosphidation reaction as a high-performance sodium-ion batteries anode.This yolk–shell structure can offer adequate internal space to buffer the large volume expansion,shorten diffusion distance,and create more active sites of Na+.Especially,the Cu nanoparticles generated from Cu_(3)P have remarkable electronic conductivity of 5.73107S m-1(the second most conductive metal)to benefit transporting electrons.And the introduction of Mo(Mo P has high theoretical capacity of 633 mA h g^(-1))can enhance the reversible capacity of the whole anode material.Therefore,these porous yolk–shell Mo P/Cu_(3)P@carbon microcages possess excellent reversible capacity of 307.8 mA h g^(-1)at 1.0 A g^(-1)and extraordinary cycle stability of 132.1 m A h g^(-1)at 5.0 A g^(-1)even after 6000 cycles.
基金supported by the Innovation Platform of Energy Storage Engineering and New Material in Zhejiang University(No.K19-534202-002)the National Natural Science Foundation of China(No.21978261)the Zhejiang Provincial Key Research and Development Program of China(No.2021C01030).
文摘Lithium-sulfur batteries(LSBs)can work at high temperatures,but they suffer from poor cycle life stability due to the“shuttle effect”of polysulfides.In this study,pollen-derived porous carbon/cuprous phosphide(PC/Cu_(3)P)hybrids were rationally synthesized using a one-step carbonization method using pollen as the source material,acting as the sulfur host for LSBs.In the hybrid,polar Cu_(3)P can markedly inhibit the“shuttle effect”by regulating the adsorption ability toward polysulfides,as confirmed by theoretical calculations and experimental tests.As an example,the camellia pollen porous carbon(CPC)/Cu_(3)P/S electrode shows a high capacity of 1205.6 mAh g^(−1) at 0.1 C,an ultralow capacity decay rate of 0.038%per cycle after 1000 cycles at 1 C,and a rather high initial Coulombic efficiency of 98.5%.The CPC/Cu_(3)P LSBs can work well at high temperatures,having a high capacity of 545.9 mAh g^(−1) at 1 C even at 150℃.The strategy of the PC/Cu_(3)P hybrid proposed in this study is expected to be an ideal cathode for ultrastable high-temperature LSBs.We believe that this strategy is universal and worthy of in-depth development for the next generation energy storage devices.
基金supported by the National Natural Science Foundation of China(52072118,51772089)the Youth 1000 Talent Program of China+3 种基金the Research and Development Plan of Key Areas in Hunan Province(2019GK2235)the Key Research and Development Program of Ningxia(2020BDE03007)the China Postdoctoral Science Foundation(2019M653649)the Guangdong Basic and Applied Basic Research Fund(2019A1515110518,2019A1515111188,2020B0909030004)。
文摘Developing suitable anode materials for potassium-ion batteries(PIBs)remains a great challenge owing to the limited theoretical capacity of active materials and large radius of K+ion(1.38?).To solve these obstacles,by integrating the principles of multielectron transfer and rational porous crystal framework,we creatively propose the monoclinic Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O(CVO)as a novel anode for PIBs.Furthermore,inspired by the metastable nature of CVO under high temperature/pressure,we skillfully design a facile hydrothermal recrystallization strategy without the phase change and surfactants addition.Thus,for the first time,the porous composite of Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O nanobelts covered in situ by reduced graphene oxide(CVO NBs/r GO)was assembled,greatly improving the deficiencies of CVO.When used as a novel anode for PIBs,CVO NBs/r GO delivers large specific capacity(up to 551.4 m Ah g^(-1)at 50 m A g^(-1)),high-rate capability(215.3 m Ah g^(-1)at 2.5 A g^(-1))and super durability(203.6 m Ah g^(-1)at 500 m A g^(-1)even after 1000 cycles).The outstanding performance can be ascribed to the synergistic merits of desirable structural features of monoclinic CVO nanobelts and the highly conductive graphene 3D network,thus promoting the composite material stability and electrical/ionic conductivity.This work reveals a novel metal vanadate-based anode material for PIBs,would further motivate the subsequent batteries research on M_(3)(OH)_(2)V_(2)O_(7)-n H_(2)O(M;Co,Ni,Cu,Zn),and ultimately expands valuable fundamental understanding on designing other high-performance electrode materials,including the combined strategies of multielectron transfer with rational porous crystal framework,and the composite fabrication of 1D electrode nanostructure with conductive carbon matrix.
