Manganese-based materials are influenced by the Jahn-Teller effect,causing the spontaneous dismutation of Mn^(3+)(2Mn^(3+)→Mn^(2+)+Mn^(4+))and the dissolution of Mn^(2+),which often results in diminished activity.Thi...Manganese-based materials are influenced by the Jahn-Teller effect,causing the spontaneous dismutation of Mn^(3+)(2Mn^(3+)→Mn^(2+)+Mn^(4+))and the dissolution of Mn^(2+),which often results in diminished activity.This study uniquely employs a W doping strategy to suppress this effect.Externally,a simple template-free method was initially used to prepare cobalt-and manganese-based precursors,followed by a W doping process during the synthesis of transition bimetallic phosphides.Ultimately,W-doped bimetallic phosphides(W-CoMnP)were obtained.The W-CoMnP material demonstrates excellent HER and OER performance with low overpotentials of 95 mV(η_(₁₀)HER)and 225 mV(η_(₅₀)OER),and can achieve overall water splitting at a voltage of 1.52 V while maintaining stable cycling for 24 h.To enable commercial application,W-CoMnP was incorporated into an anion exchange membrane(AEM)electrolysis water device,demonstrating continuous and stable hydrogen production under ambient temperature conditions.This study offers a promising strategy for the future development of catalysts for AEM electrolysis water devices.展开更多
Rechargeable magnesium batteries(RMBs)hold promise for offering higher volumetric energy density and safety features,attracting increasing research interest as the next post lithium-ion batteries.Developing high perfo...Rechargeable magnesium batteries(RMBs)hold promise for offering higher volumetric energy density and safety features,attracting increasing research interest as the next post lithium-ion batteries.Developing high performance cathode material by inducing multi-electron reaction process as well as maintaining structural stability is the key to the development and application of RMBs.Herein,multielectron reaction occurred in VS_(4)by simple W doping strategy.W doping induces valence of partial V as V^(2+)and V^(3+)in VS_(4)structure,and then stimulates electrochemical reaction involving multi-electrons in 0.5%W-V-S.The flower-like microsphere morphology as well as rich S vacancies is also modulated by W doping to neutralize structure change in such multi-electron reaction process.The fabricated 0.5%W-V-S delivers higher specific capacity(149.3 m A h g^(-1)at 50 m A g^(-1),which is 1.6 times higher than that of VS_(4)),superior rate capability(76 mA h g^(-1)at 1000 mA g^(-1)),and stable cycling performance(1500cycles with capacity retention ratio of 93.8%).Besides that,pesudocapaticance-like contribution analysis as well as galvanostatic intermittent titration technique(GITT)further confirms the enhanced Mg^(2+)storage kinetics during such multi-electron involved electrochemical reaction process.Such discovery provides new insights into the designing of multi-electron reaction process in cathode as well as neutralizing structural change during such reaction for realizing superior electrochemical performance in energy storage devices.展开更多
Face-centered cubic (f.c.c.) high entropy alloys (HEAs) are attracting more and more attention owing to their excellent strength and ductility synergy, irradiation resistance, etc. However, the yield strength of f.c.c...Face-centered cubic (f.c.c.) high entropy alloys (HEAs) are attracting more and more attention owing to their excellent strength and ductility synergy, irradiation resistance, etc. However, the yield strength of f.c.c. HEAs is generally low, significantly limiting their practical applications. Recently, the alloying of W has been evidenced to be able to remarkably improve the mechanical properties of f.c.c. HEAs and is becoming a hot topic in the community of HEAs. To date, when W is introduced, multiple strengthening mechanisms, including solid-solution strengthening, precipitation strengthening (μphase,σphase, and b.c.c. phase), and grain-refinement strengthening, have been discovered to be activated or enhanced. Apart from mechanical properties, the addition of W improves corrosion resistance as W helps to form a dense WO_(3) film on the alloy surface. Until now, despite the extensive studies in the literature, there is no available review paper focusing on the W doping of the f.c.c. HEAs. In that context, the effects of W doping on f.c.c. HEAs were reviewed in this work from three aspects, i.e., microstructure,mechanical property, and corrosion resistance. We expect this work can advance the application of the W alloying strategy in the f.c.c. HEAs.展开更多
The pursuit of advanced sodium-ion batteries(SIBs)has been intensified due to the escalating demand for sustainable energy storage solutions.A W-doped P2-type layered cathode material,Na_(0.67)Ni_(0.246)W_(0.004)Mn_(0...The pursuit of advanced sodium-ion batteries(SIBs)has been intensified due to the escalating demand for sustainable energy storage solutions.A W-doped P2-type layered cathode material,Na_(0.67)Ni_(0.246)W_(0.004)Mn_(0.75)O_(2)(NNWMO),has been developed to address the limitations of traditional cathode materials.Compared to the pristine Na_(0.67)Ni_(0.25)Mn_(0.75)O_(2)(NNMO),NNWMO exhibits improved reversible capacity,excellent cycle performance,and remarkable rate performance.It can deliver an increased discharge capacity of 142.20 mAh/g at 0.1 C,with an admirable capacity retention of 80.5% after 100 cycles at high voltage.In situ XRD results demonstrate that the rivet effect related to the strong W—O bonds inhibits irreversible phase transition and enhances structural reversibility during charge/discharge processes.High-resolution scanning transmission electron microscopy and X-ray diffraction results confirm successful lattice doping of W^(6+)and increased layer spacing,contributing to favorable sodium ion diffusion kinetics.Density-functional theory(DFT)calculation results further reveal that the smoother Na+ion diffusion dynamics is attributed to the reduced migration energy barrier of Na^(+)with the insertion of W^(6+).This study provides valuable insights into the design of high-performance cathode materials for next-generation SIBs,showcasing the potential for more efficient,stable,and enduring energy storage solutions.展开更多
The forming process of the bodil y fault in doped W wire was observed by SEM and TEM. The forming kinetics was de scibed by the perturbing theory. The interaction among the bodily fault and the dislocation or the grai...The forming process of the bodil y fault in doped W wire was observed by SEM and TEM. The forming kinetics was de scibed by the perturbing theory. The interaction among the bodily fault and the dislocation or the grain boundary was also observed. The strengthen effect cause d by the interaction is counted initially by each submitted probable models. The results show that the strengthening mechanism at middle and high temperature is different.展开更多
Cu/W multilayer nanofilms are prepared in pure Ar and He/At mixing atmosphere by the rf magnetron sputtering method. The cross-sectional morphology and the defect distribution of the Cu/W multilayer nanofilms are char...Cu/W multilayer nanofilms are prepared in pure Ar and He/At mixing atmosphere by the rf magnetron sputtering method. The cross-sectional morphology and the defect distribution of the Cu/W multilayer nanofilms are characterized by scanning electron microscopy and Doppler broadening positron annihilation spectroscopy. The results show that plenty of point defects can be produced by introducing He during the growth of the multilayer nanofilms. With the increasing natural storage time, He located in the near surface of the Cu//W multilayer nanofilm at room temperature could be released gradually and induce the segregation of He-related defects due to the diffusion of He and defects. However, more He in the deep region spread along the interface of the Cu/W multilayer nanofilm. Meanwhile, the layer interfaces can still maintain their stability.展开更多
Electrooxidation of the biomass derivative 5-hydroxymethylfurfural (HMF) is a highly promising approach for attaining versatile value-added chemicals (e.g.,2,5-furandicarboxylic acid,FDCA).Ni-based sulfides are promis...Electrooxidation of the biomass derivative 5-hydroxymethylfurfural (HMF) is a highly promising approach for attaining versatile value-added chemicals (e.g.,2,5-furandicarboxylic acid,FDCA).Ni-based sulfides are promising electrocatalysts for HMF electrooxidation reaction (HMFOR).However,the HMFOR activity of Ni-based catalysts is far from satisfactory due to the unfavorable adsorption of HMF and OH^(*).Herein,we propose controlled W doping to effectively modify the electronic configuration of nanostructured Ni_(3)S_(2) to manipulate adsorption of HMF and OH^(*),for efficiently converting HMF into FDCA.Experimental and theoretical calculations indicate the incorporation of high-valence W results in the upshift of d-band center of Ni_(3)S_(2),which facilitates the adsorption and dissociation of water to produce more OH^(*).Meanwhile,the high-valence W has strong electron-withdrawing ability and attracts electrons from Ni,leading to the elevated Ni valence,which is beneficial to optimizing the adsorption energy of HMF.Both concurrently contribute to the superb HMFOR performance.As a result,W_(20)-Ni_(3)S_(2)@NF with optimal W dopant exhibits a low driving potential (1.34 V vs.RHE at 10 mA cm^(-2)),accompanying with the 100% HMF conversion,99.2%FDCA selectivity,and 97.3%Faraday efficiency.This work provides a design principle for HMFOR electrocatalysts by modulating the adsorption behaviors of HMF and OH^(*)via rational electronic structure engineering.展开更多
In this study,we developed a facile one-step hydrothermal process that allows to synthesize high-purity V0_(2)(M/R)nanoparticles with various morphologies such as nanorods,nanogranules,nanoblocks,and nanospheres.W dop...In this study,we developed a facile one-step hydrothermal process that allows to synthesize high-purity V0_(2)(M/R)nanoparticles with various morphologies such as nanorods,nanogranules,nanoblocks,and nanospheres.W dopants are successfully implanted in V02(M/R)unit cells with high doping efficiency,which allows to regulate the size,morphology,and phase of obtained nanoparticles.The underlying regulation mechanism is presented in detail to reveal how hydrothermal products vary with W doping contents,which provides a synthetic strategy for the preparation of shape-controlling V02(M/R)nanoparticles with high purity to satisfy different specific demands for corresponding applications in the field of thermochromic smart windows.展开更多
文摘Manganese-based materials are influenced by the Jahn-Teller effect,causing the spontaneous dismutation of Mn^(3+)(2Mn^(3+)→Mn^(2+)+Mn^(4+))and the dissolution of Mn^(2+),which often results in diminished activity.This study uniquely employs a W doping strategy to suppress this effect.Externally,a simple template-free method was initially used to prepare cobalt-and manganese-based precursors,followed by a W doping process during the synthesis of transition bimetallic phosphides.Ultimately,W-doped bimetallic phosphides(W-CoMnP)were obtained.The W-CoMnP material demonstrates excellent HER and OER performance with low overpotentials of 95 mV(η_(₁₀)HER)and 225 mV(η_(₅₀)OER),and can achieve overall water splitting at a voltage of 1.52 V while maintaining stable cycling for 24 h.To enable commercial application,W-CoMnP was incorporated into an anion exchange membrane(AEM)electrolysis water device,demonstrating continuous and stable hydrogen production under ambient temperature conditions.This study offers a promising strategy for the future development of catalysts for AEM electrolysis water devices.
基金supported by the National Natural Science Foundation of China under Grant No.52072196,52002200,52102106,52202262,22379081,and 22379080Major Basic Research Program of the Natural Science Foundation of Shandong Province under Grant No.ZR2020ZD09+1 种基金the Natural Science Foundation of Shandong Province under Grant No.ZR2020QE063,ZR202108180009,ZR2023QE059the Postdoctoral Program in Qingdao under No.QDBSH20220202019。
文摘Rechargeable magnesium batteries(RMBs)hold promise for offering higher volumetric energy density and safety features,attracting increasing research interest as the next post lithium-ion batteries.Developing high performance cathode material by inducing multi-electron reaction process as well as maintaining structural stability is the key to the development and application of RMBs.Herein,multielectron reaction occurred in VS_(4)by simple W doping strategy.W doping induces valence of partial V as V^(2+)and V^(3+)in VS_(4)structure,and then stimulates electrochemical reaction involving multi-electrons in 0.5%W-V-S.The flower-like microsphere morphology as well as rich S vacancies is also modulated by W doping to neutralize structure change in such multi-electron reaction process.The fabricated 0.5%W-V-S delivers higher specific capacity(149.3 m A h g^(-1)at 50 m A g^(-1),which is 1.6 times higher than that of VS_(4)),superior rate capability(76 mA h g^(-1)at 1000 mA g^(-1)),and stable cycling performance(1500cycles with capacity retention ratio of 93.8%).Besides that,pesudocapaticance-like contribution analysis as well as galvanostatic intermittent titration technique(GITT)further confirms the enhanced Mg^(2+)storage kinetics during such multi-electron involved electrochemical reaction process.Such discovery provides new insights into the designing of multi-electron reaction process in cathode as well as neutralizing structural change during such reaction for realizing superior electrochemical performance in energy storage devices.
基金financially supported by the National Key R&D Program of China (No.2021YFA1200203)the National Natural Science Foundation of China (Nos.51922026 and 51975111)+1 种基金the Fundamental Research Funds for the Central Universities (No.N2202015,N2002005,and N2105001)the 111 Project of China (No.BP0719037 and B20029)。
文摘Face-centered cubic (f.c.c.) high entropy alloys (HEAs) are attracting more and more attention owing to their excellent strength and ductility synergy, irradiation resistance, etc. However, the yield strength of f.c.c. HEAs is generally low, significantly limiting their practical applications. Recently, the alloying of W has been evidenced to be able to remarkably improve the mechanical properties of f.c.c. HEAs and is becoming a hot topic in the community of HEAs. To date, when W is introduced, multiple strengthening mechanisms, including solid-solution strengthening, precipitation strengthening (μphase,σphase, and b.c.c. phase), and grain-refinement strengthening, have been discovered to be activated or enhanced. Apart from mechanical properties, the addition of W improves corrosion resistance as W helps to form a dense WO_(3) film on the alloy surface. Until now, despite the extensive studies in the literature, there is no available review paper focusing on the W doping of the f.c.c. HEAs. In that context, the effects of W doping on f.c.c. HEAs were reviewed in this work from three aspects, i.e., microstructure,mechanical property, and corrosion resistance. We expect this work can advance the application of the W alloying strategy in the f.c.c. HEAs.
基金supported by the Talent Recruitment Program of Sichuan University of Science and Engineering(2023RC06)the Innovation Center for Chenguang High-Performance Fluorine Material(SCFY2207)+3 种基金the Key Laboratories of Fine Chemicals and Surfactants in Sichuan Provincial Universities(2022JXY04)College Students Innovation and Entrepreneurship Training Program(S20221062208,S202010622054)the Scientific Research and Innovation Team Program of Sichuan University of Science and Engineering(SUSE652B008)the Central Government Guide Local Science and Technology Development Fund(24ZYTXJS0055).
文摘The pursuit of advanced sodium-ion batteries(SIBs)has been intensified due to the escalating demand for sustainable energy storage solutions.A W-doped P2-type layered cathode material,Na_(0.67)Ni_(0.246)W_(0.004)Mn_(0.75)O_(2)(NNWMO),has been developed to address the limitations of traditional cathode materials.Compared to the pristine Na_(0.67)Ni_(0.25)Mn_(0.75)O_(2)(NNMO),NNWMO exhibits improved reversible capacity,excellent cycle performance,and remarkable rate performance.It can deliver an increased discharge capacity of 142.20 mAh/g at 0.1 C,with an admirable capacity retention of 80.5% after 100 cycles at high voltage.In situ XRD results demonstrate that the rivet effect related to the strong W—O bonds inhibits irreversible phase transition and enhances structural reversibility during charge/discharge processes.High-resolution scanning transmission electron microscopy and X-ray diffraction results confirm successful lattice doping of W^(6+)and increased layer spacing,contributing to favorable sodium ion diffusion kinetics.Density-functional theory(DFT)calculation results further reveal that the smoother Na+ion diffusion dynamics is attributed to the reduced migration energy barrier of Na^(+)with the insertion of W^(6+).This study provides valuable insights into the design of high-performance cathode materials for next-generation SIBs,showcasing the potential for more efficient,stable,and enduring energy storage solutions.
文摘The forming process of the bodil y fault in doped W wire was observed by SEM and TEM. The forming kinetics was de scibed by the perturbing theory. The interaction among the bodily fault and the dislocation or the grain boundary was also observed. The strengthen effect cause d by the interaction is counted initially by each submitted probable models. The results show that the strengthening mechanism at middle and high temperature is different.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11275132,51171124 and 11505121the International Science and Technology Cooperation Program of China under Grant No 2014DFR50710the Scientific and Technical Supporting Programs Funded by the Science and Technology Department of Sichuan Province under Grant No 2014GZ0004
文摘Cu/W multilayer nanofilms are prepared in pure Ar and He/At mixing atmosphere by the rf magnetron sputtering method. The cross-sectional morphology and the defect distribution of the Cu/W multilayer nanofilms are characterized by scanning electron microscopy and Doppler broadening positron annihilation spectroscopy. The results show that plenty of point defects can be produced by introducing He during the growth of the multilayer nanofilms. With the increasing natural storage time, He located in the near surface of the Cu//W multilayer nanofilm at room temperature could be released gradually and induce the segregation of He-related defects due to the diffusion of He and defects. However, more He in the deep region spread along the interface of the Cu/W multilayer nanofilm. Meanwhile, the layer interfaces can still maintain their stability.
基金supported by the National Natural Science Foundation of China (22322104, 22171074, 21901064)Heilongjiang Provincial Natural Science Foundation of China (YQ2021B009)+1 种基金the Reform and Development Fund Project of Local University supported by the Central Government (Outstanding Youth Program)the Basic Research Fund of Heilongjiang University in Heilongjiang Province (2021KYYWF-0031)。
文摘Electrooxidation of the biomass derivative 5-hydroxymethylfurfural (HMF) is a highly promising approach for attaining versatile value-added chemicals (e.g.,2,5-furandicarboxylic acid,FDCA).Ni-based sulfides are promising electrocatalysts for HMF electrooxidation reaction (HMFOR).However,the HMFOR activity of Ni-based catalysts is far from satisfactory due to the unfavorable adsorption of HMF and OH^(*).Herein,we propose controlled W doping to effectively modify the electronic configuration of nanostructured Ni_(3)S_(2) to manipulate adsorption of HMF and OH^(*),for efficiently converting HMF into FDCA.Experimental and theoretical calculations indicate the incorporation of high-valence W results in the upshift of d-band center of Ni_(3)S_(2),which facilitates the adsorption and dissociation of water to produce more OH^(*).Meanwhile,the high-valence W has strong electron-withdrawing ability and attracts electrons from Ni,leading to the elevated Ni valence,which is beneficial to optimizing the adsorption energy of HMF.Both concurrently contribute to the superb HMFOR performance.As a result,W_(20)-Ni_(3)S_(2)@NF with optimal W dopant exhibits a low driving potential (1.34 V vs.RHE at 10 mA cm^(-2)),accompanying with the 100% HMF conversion,99.2%FDCA selectivity,and 97.3%Faraday efficiency.This work provides a design principle for HMFOR electrocatalysts by modulating the adsorption behaviors of HMF and OH^(*)via rational electronic structure engineering.
文摘In this study,we developed a facile one-step hydrothermal process that allows to synthesize high-purity V0_(2)(M/R)nanoparticles with various morphologies such as nanorods,nanogranules,nanoblocks,and nanospheres.W dopants are successfully implanted in V02(M/R)unit cells with high doping efficiency,which allows to regulate the size,morphology,and phase of obtained nanoparticles.The underlying regulation mechanism is presented in detail to reveal how hydrothermal products vary with W doping contents,which provides a synthetic strategy for the preparation of shape-controlling V02(M/R)nanoparticles with high purity to satisfy different specific demands for corresponding applications in the field of thermochromic smart windows.
