Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)na...Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)nanoflakes for hydrogen evolution reaction(HER).The doping of MoS_(2)with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics,which significantly enhances its electrical conductivity and structural stability,which are verified by various characterization tools,including X‐ray photoelectron spectroscopy,high‐resolution transmission electron microscopy,X‐ray absorption near‐edge spectroscopy,and extended X‐ray absorption fine structure.Moreover,the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites,which remarkably enhance its HER activity.The optimized P‐BMS electrocatalysts exhibit low overpotentials(60 and 72 mV at 10 mA cm^(−2))in H_(2)SO_(4)(0.5 M)and KOH(1.0 M),respectively.The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques.This study has shown that phase engineering is a promising strategy for enhancing the H*adsorption of metal sulfides.展开更多
As a promising anode material for magnesium ion rechargeable batteries,magnesium metavanadate(MgV_(2)O_(6))has attracted considerable research interest in recent years.A MgV_(2)O_(6)sample was synthesized via a facile...As a promising anode material for magnesium ion rechargeable batteries,magnesium metavanadate(MgV_(2)O_(6))has attracted considerable research interest in recent years.A MgV_(2)O_(6)sample was synthesized via a facile solid-state reaction by multistep-firing stoichiometric mixtures of MgO and V2O5 powder under an air atmosphere.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)occurred at 841 K and the enthalpy change was 4.37±0.04 kJ/mol.The endothermic effect at 1014 K and the enthalpy change was 26.54±0.26 kJ/mol,which is related to the incongruent melting ofβ-MgV_(2)O_(6).In situ XRD was performed to investigate phase transition of the as-prepared MgV_(2)O_(6)at high temperatures.The cell parameters obtained by Rietveld refinement indicated that it crystallizes in a monoclinic system with the C2/m space group,and the lattice parameters of a=9.280 A°,b=3.501 A°,c=6.731 A°,β=111.76°.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)was further studied by thermal kinetics,indicating that this process is controlled first by a fibril-like mechanism and then by a spherulitic-type mechanism with an increasing heating rate.Additionally,the enthalpy change of MgV_(2)O_(6)at high temperatures was measured utilizing the drop calorimetry,heat capacity was calculated and given as:Cp=208.3+0.03583T-4809000T^(−2)(298-923 K)(J mol^(−1)K^(−1)),the high-temperature heat capacity can be used to calculate Gibbs free energy of MgV_(2)O_(6)at high temperatures.展开更多
Quasi-2D perovskites have attracted tremendous interest for application as lightemission layers in light-emitting diodes(LEDs).However,the heterogeneous n phase and non-uniform distribution still severely limit the fu...Quasi-2D perovskites have attracted tremendous interest for application as lightemission layers in light-emitting diodes(LEDs).However,the heterogeneous n phase and non-uniform distribution still severely limit the further development of quasi-2D perovskite LEDs(Pero-LEDs).Meanwhile,the increased defect density caused by the reduced dimension and grain size induces non-radiative recombination and further deteriorates the device performance.Here,we found that a series of molecules containing phosphoryl chloride functional groups have noticeable enhancement effects on the device performance of quasi-2D Pero-LEDs.Then,we studied the modification mechanism by focusing on the bis(2-oxo-3-oxazolidinyl)phosphinic chloride(BOPCl).It is concluded that the BOPCl can not only regulate the phase distribution by decreasing the crystallization rate but also remain in the grain boundaries and passivate the defects.As a result,the corresponding quasi-2D Pero-LEDs obtained a maximum external quantum efficiency(EQE_(max))of 20.82%and an average EQE(EQE_(ave))of around 20%on the optimal 50 devices,proving excellent reproducibility.Our work provides a new selection of molecular types for regulating the crystallization and passivating the defects of quasi-2D perovskite films.展开更多
CaCl_(2)·6H_(2)O/expanded vermiculite shape stabilized phase change materials(CEV)was prepared by atmospheric impregnation method.Using gold mine tailings as aggregate of cemented paste backfill(CPB)material,the ...CaCl_(2)·6H_(2)O/expanded vermiculite shape stabilized phase change materials(CEV)was prepared by atmospheric impregnation method.Using gold mine tailings as aggregate of cemented paste backfill(CPB)material,the CPB with CEV added was prepared,and the specific heat capacity,thermal conductivity,and uniaxial compressive strength(UCS)of CPB with different cement-tailing ratios and CEV addition ratios were tested,the influence of the above variables on the thermal and mechanical properties of CPB was analyzed.The results show that the maximum encapsulation capacity of expanded vermiculite for CaCl_(2)·6H_(2)O is about 60%,and the melting and solidification enthalpies of CEV can reach 98.87 J/g and 97.56 J/g,respectively.For the CPB without CEV,the specific heat capacity,thermal conductivity,and UCS decrease with the decrease of cement-tailing ratio.For the CPB with CEV added,with the increase of CEV addition ratio,the specific heat capacity increases significantly,and the sensible heat storage capacity and latent heat storage capacity can be increased by at least 10.74%and 218.97%respectively after adding 12%CEV.However,the addition of CEV leads to the increase of pores,and the thermal conductivity and UCS both decrease with the increase of CEV addition.When cement-tailing ratio is 1:8 and 6%,9%,and 12%of CEV are added,the 28-days UCS of CPB is less than 1 MPa.Considering the heat storage capacity and cost price of backfill,the recommended proportion scheme of CPB material presents cement-tailing ratio of 1:6 and 12%CEV,and the most recommended heat storage/release temperature cycle range of CPB with added CEV is from 20 to 40℃.This work can provide theoretical basis for the utilization of heat storage backfill in green mines.展开更多
The two-dimensional(2D)material-based thermal switch is attracting attention due to its novel applications,such as energy conversion and thermal management,in nanoscale devices.In this paper,we observed that the rever...The two-dimensional(2D)material-based thermal switch is attracting attention due to its novel applications,such as energy conversion and thermal management,in nanoscale devices.In this paper,we observed that the reversible 2H–1T′phase transition in MoTe_(2)is associated with about a fourfold/tenfold change in thermal conductivity along the X/Y direction by using first-principles calculations.This phenomenon can be profoundly understood by comparing the Mo–Te bonding strength between the two phases.The 2H-MoTe_(2)has one stronger bonding type,while 1T′-MoTe_(2)has three weaker types of bonds,suggesting bonding inhomogeneity in 1T′-MoTe_(2).Meanwhile,the bonding inhomogeneity can induce more scattering of vibration modes.The weaker bonding indicates a softer structure,resulting in lower phonon group velocity,a shorter phonon relaxation lifetime and larger Gr¨uneisen constants.The impact caused by the 2H to 1T′phase transition in MoTe_(2)hinders the propagation of phonons,thereby reducing thermal conductivity.Our study describes the possibility for the provision of the MoTe_(2)-based controllable and reversible thermal switch device.展开更多
We report systematic studies on superconducting properties of the Laves phase superconductor ZrIr_(2).It crystallizes in a C15-type(cubic MgCu_(2)-type,space group Fd3m)structure in which the Ir atoms form a kagome la...We report systematic studies on superconducting properties of the Laves phase superconductor ZrIr_(2).It crystallizes in a C15-type(cubic MgCu_(2)-type,space group Fd3m)structure in which the Ir atoms form a kagome lattice,with cell parameters a=b=c=7.3596(1)?.Resistivity and magnetic susceptibility measurements indicate that ZrIr_(2) is a type-Ⅱsuperconductor with a transition temperature of 4.0 K.The estimated lower and upper critical fields are 12.8 mT and 4.78 T,respectively.Heat capacity measurements confirm the bulk superconductivity in ZrIr_(2).ZrIr_(2) is found to possibly host strong-coupled s-wave superconductivity with the normalized specific heat change△C_(e)/γT_(c)~1.86 and the coupling strength△_(0)/k_BT_(c)~1.92.First-principles calculations suggest that ZrIr_(2) has three-dimensional Fermi surfaces with simple topologies,and the states at Fermi level mainly originate from the Ir-5d and Zr-4d orbitals.Similar to SrIr_(2) and ThIr_(2),spin–orbit coupling has dramatic influences on the band structure in ZrIr_(2).展开更多
Dining lampblack as a source of atmospheric pollution,urban residents had to spend a lot of economic costs all year round to solve its impact.However,traditional treatment methods often carry the risk of secondary pol...Dining lampblack as a source of atmospheric pollution,urban residents had to spend a lot of economic costs all year round to solve its impact.However,traditional treatment methods often carry the risk of secondary pollution.The use of phase change absorption solvent(PCAS)controlled by CO_(2)can effectively absorb the oily components in dining lampblack,and smoothly avoid the generation of secondary pollutants and squandering of resources.The reversibility of PCASs under CO_(2)control was explained by pH changes and macroscopic visualizations.The absorption effects of favorable absorbents and PCASs on dining lampblack were compared and analyzed.The fatty acid(FA)in the oil absorption mixture was desorbed by interacting with D230.The results of GC/MS analysis on the oil components separated by desorption showed that the desorption of PCASs was effective for these refractory oil components.FAs can be enriched and applied to the subsequent dining lampblack treatment link to realize the waste recycling.In addition,the absorption and desorption of oily components by PCASs were combined with the CO_(2)-controlled phase transformation of PCASs itself to achieve the absorption circulation of treating dining lampblack by using PCASs.展开更多
CO_(2)dissolution into an aqueous phase and water evaporation into a gaseous phase takes place during CO_(2)injection into an oil reservoir.This study aims to evaluate the phase behaviors of the oil-gas-water system i...CO_(2)dissolution into an aqueous phase and water evaporation into a gaseous phase takes place during CO_(2)injection into an oil reservoir.This study aims to evaluate the phase behaviors of the oil-gas-water system in the displacement of crude oil by CO_(2).The composition of the JL oilfield in the northeast of China is taken as an example.The flash calculation of the oil-gas-water system was performed,based on the method presented by Li and Nghiem.The research results show that CO_(2)dissolution in the aqueous phase declines as the NaCl concentration in formation water rises.CO_(2)injection is beneficial for the evaporation of formation water.The NaCl concentration in formation water has little effect on water evaporation and dissolved-gas escape.When the injection-gas mole fraction of CO_(2)is 0.5,CO_(2)injection can reverse the phase behavior of the petroleum mixture and the oil-gas system is converted to a pure gas-condensate system.For CO_(2)injection,water vapor has little effect on the miscibility of multiple contacts,but can reduce the miscibility of the first contact.展开更多
基金National Natural Science Foundation of China,Grant/Award Number:NSFC‐U1904215National Research Foundation of Korea,Grant/Award Number:2021R1A2C2012127。
文摘Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)nanoflakes for hydrogen evolution reaction(HER).The doping of MoS_(2)with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics,which significantly enhances its electrical conductivity and structural stability,which are verified by various characterization tools,including X‐ray photoelectron spectroscopy,high‐resolution transmission electron microscopy,X‐ray absorption near‐edge spectroscopy,and extended X‐ray absorption fine structure.Moreover,the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites,which remarkably enhance its HER activity.The optimized P‐BMS electrocatalysts exhibit low overpotentials(60 and 72 mV at 10 mA cm^(−2))in H_(2)SO_(4)(0.5 M)and KOH(1.0 M),respectively.The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques.This study has shown that phase engineering is a promising strategy for enhancing the H*adsorption of metal sulfides.
基金supported by the National Key R&D Program of China(2018YFC1900500)the Graduate Scientific Research and Innovation Foundation of Chongqing,China(Grant No.CYB20002).
文摘As a promising anode material for magnesium ion rechargeable batteries,magnesium metavanadate(MgV_(2)O_(6))has attracted considerable research interest in recent years.A MgV_(2)O_(6)sample was synthesized via a facile solid-state reaction by multistep-firing stoichiometric mixtures of MgO and V2O5 powder under an air atmosphere.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)occurred at 841 K and the enthalpy change was 4.37±0.04 kJ/mol.The endothermic effect at 1014 K and the enthalpy change was 26.54±0.26 kJ/mol,which is related to the incongruent melting ofβ-MgV_(2)O_(6).In situ XRD was performed to investigate phase transition of the as-prepared MgV_(2)O_(6)at high temperatures.The cell parameters obtained by Rietveld refinement indicated that it crystallizes in a monoclinic system with the C2/m space group,and the lattice parameters of a=9.280 A°,b=3.501 A°,c=6.731 A°,β=111.76°.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)was further studied by thermal kinetics,indicating that this process is controlled first by a fibril-like mechanism and then by a spherulitic-type mechanism with an increasing heating rate.Additionally,the enthalpy change of MgV_(2)O_(6)at high temperatures was measured utilizing the drop calorimetry,heat capacity was calculated and given as:Cp=208.3+0.03583T-4809000T^(−2)(298-923 K)(J mol^(−1)K^(−1)),the high-temperature heat capacity can be used to calculate Gibbs free energy of MgV_(2)O_(6)at high temperatures.
基金supported by the National Natural Science Foundation of China(U21A2078)Natural Science Foundation of Fujian Province(2020J06021,2019J01057,and 2020J01064)Scientific Research Funds of Huaqiao University.
文摘Quasi-2D perovskites have attracted tremendous interest for application as lightemission layers in light-emitting diodes(LEDs).However,the heterogeneous n phase and non-uniform distribution still severely limit the further development of quasi-2D perovskite LEDs(Pero-LEDs).Meanwhile,the increased defect density caused by the reduced dimension and grain size induces non-radiative recombination and further deteriorates the device performance.Here,we found that a series of molecules containing phosphoryl chloride functional groups have noticeable enhancement effects on the device performance of quasi-2D Pero-LEDs.Then,we studied the modification mechanism by focusing on the bis(2-oxo-3-oxazolidinyl)phosphinic chloride(BOPCl).It is concluded that the BOPCl can not only regulate the phase distribution by decreasing the crystallization rate but also remain in the grain boundaries and passivate the defects.As a result,the corresponding quasi-2D Pero-LEDs obtained a maximum external quantum efficiency(EQE_(max))of 20.82%and an average EQE(EQE_(ave))of around 20%on the optimal 50 devices,proving excellent reproducibility.Our work provides a new selection of molecular types for regulating the crystallization and passivating the defects of quasi-2D perovskite films.
基金supported by the National Natural Science Foundation of China(Nos.51974225,51874229,51674188,51904224,51904225)the Shaanxi Innovative Talents Cultivate Program-New-star Plan of Science and Technology,China(No.2018KJXX-083)+2 种基金the Natural Science Basic Research Plan of Shaanxi Province of China(Nos.2018JM 5161,2018JQ5183,2019JM-074)the Scientific Research Program funded by the Shaanxi Provincial Education Department,China(No.19JK0543)the Outstanding Youth Science Fund of Xi’an University of Science and Technology,China(No.2018YQ2-01)。
文摘CaCl_(2)·6H_(2)O/expanded vermiculite shape stabilized phase change materials(CEV)was prepared by atmospheric impregnation method.Using gold mine tailings as aggregate of cemented paste backfill(CPB)material,the CPB with CEV added was prepared,and the specific heat capacity,thermal conductivity,and uniaxial compressive strength(UCS)of CPB with different cement-tailing ratios and CEV addition ratios were tested,the influence of the above variables on the thermal and mechanical properties of CPB was analyzed.The results show that the maximum encapsulation capacity of expanded vermiculite for CaCl_(2)·6H_(2)O is about 60%,and the melting and solidification enthalpies of CEV can reach 98.87 J/g and 97.56 J/g,respectively.For the CPB without CEV,the specific heat capacity,thermal conductivity,and UCS decrease with the decrease of cement-tailing ratio.For the CPB with CEV added,with the increase of CEV addition ratio,the specific heat capacity increases significantly,and the sensible heat storage capacity and latent heat storage capacity can be increased by at least 10.74%and 218.97%respectively after adding 12%CEV.However,the addition of CEV leads to the increase of pores,and the thermal conductivity and UCS both decrease with the increase of CEV addition.When cement-tailing ratio is 1:8 and 6%,9%,and 12%of CEV are added,the 28-days UCS of CPB is less than 1 MPa.Considering the heat storage capacity and cost price of backfill,the recommended proportion scheme of CPB material presents cement-tailing ratio of 1:6 and 12%CEV,and the most recommended heat storage/release temperature cycle range of CPB with added CEV is from 20 to 40℃.This work can provide theoretical basis for the utilization of heat storage backfill in green mines.
基金the China Scholarship Council(Grant No.202107000030)RIE2020 Advanced Manufacturing and Engineering(AME)Programmatic(Grant No.A1898b0043)A*STAR Aerospace Programme(Grant No.M2115a0092)。
文摘The two-dimensional(2D)material-based thermal switch is attracting attention due to its novel applications,such as energy conversion and thermal management,in nanoscale devices.In this paper,we observed that the reversible 2H–1T′phase transition in MoTe_(2)is associated with about a fourfold/tenfold change in thermal conductivity along the X/Y direction by using first-principles calculations.This phenomenon can be profoundly understood by comparing the Mo–Te bonding strength between the two phases.The 2H-MoTe_(2)has one stronger bonding type,while 1T′-MoTe_(2)has three weaker types of bonds,suggesting bonding inhomogeneity in 1T′-MoTe_(2).Meanwhile,the bonding inhomogeneity can induce more scattering of vibration modes.The weaker bonding indicates a softer structure,resulting in lower phonon group velocity,a shorter phonon relaxation lifetime and larger Gr¨uneisen constants.The impact caused by the 2H to 1T′phase transition in MoTe_(2)hinders the propagation of phonons,thereby reducing thermal conductivity.Our study describes the possibility for the provision of the MoTe_(2)-based controllable and reversible thermal switch device.
基金Project supported by the National Key Research and Development of China (Grant Nos.2018YFA0704200 and 2021YFA1401800)the National Natural Science Foundation of China (Grant Nos.12074414 and 11774402)the Strategic Priority Research Program of Chinese Academy of Sciences (Grant No.XDB25000000)。
文摘We report systematic studies on superconducting properties of the Laves phase superconductor ZrIr_(2).It crystallizes in a C15-type(cubic MgCu_(2)-type,space group Fd3m)structure in which the Ir atoms form a kagome lattice,with cell parameters a=b=c=7.3596(1)?.Resistivity and magnetic susceptibility measurements indicate that ZrIr_(2) is a type-Ⅱsuperconductor with a transition temperature of 4.0 K.The estimated lower and upper critical fields are 12.8 mT and 4.78 T,respectively.Heat capacity measurements confirm the bulk superconductivity in ZrIr_(2).ZrIr_(2) is found to possibly host strong-coupled s-wave superconductivity with the normalized specific heat change△C_(e)/γT_(c)~1.86 and the coupling strength△_(0)/k_BT_(c)~1.92.First-principles calculations suggest that ZrIr_(2) has three-dimensional Fermi surfaces with simple topologies,and the states at Fermi level mainly originate from the Ir-5d and Zr-4d orbitals.Similar to SrIr_(2) and ThIr_(2),spin–orbit coupling has dramatic influences on the band structure in ZrIr_(2).
基金supported by the Chengdu Science and Technology Project of the Chengdu Bureau of Science and Technology(2021-YF05-00194-SN)the Foundation of Department of Science and Technology of Sichuan Province(2022NSFSC0203)。
文摘Dining lampblack as a source of atmospheric pollution,urban residents had to spend a lot of economic costs all year round to solve its impact.However,traditional treatment methods often carry the risk of secondary pollution.The use of phase change absorption solvent(PCAS)controlled by CO_(2)can effectively absorb the oily components in dining lampblack,and smoothly avoid the generation of secondary pollutants and squandering of resources.The reversibility of PCASs under CO_(2)control was explained by pH changes and macroscopic visualizations.The absorption effects of favorable absorbents and PCASs on dining lampblack were compared and analyzed.The fatty acid(FA)in the oil absorption mixture was desorbed by interacting with D230.The results of GC/MS analysis on the oil components separated by desorption showed that the desorption of PCASs was effective for these refractory oil components.FAs can be enriched and applied to the subsequent dining lampblack treatment link to realize the waste recycling.In addition,the absorption and desorption of oily components by PCASs were combined with the CO_(2)-controlled phase transformation of PCASs itself to achieve the absorption circulation of treating dining lampblack by using PCASs.
基金The National Major Science and Technology Projects of China(2017ZX05030)supported this work。
文摘CO_(2)dissolution into an aqueous phase and water evaporation into a gaseous phase takes place during CO_(2)injection into an oil reservoir.This study aims to evaluate the phase behaviors of the oil-gas-water system in the displacement of crude oil by CO_(2).The composition of the JL oilfield in the northeast of China is taken as an example.The flash calculation of the oil-gas-water system was performed,based on the method presented by Li and Nghiem.The research results show that CO_(2)dissolution in the aqueous phase declines as the NaCl concentration in formation water rises.CO_(2)injection is beneficial for the evaporation of formation water.The NaCl concentration in formation water has little effect on water evaporation and dissolved-gas escape.When the injection-gas mole fraction of CO_(2)is 0.5,CO_(2)injection can reverse the phase behavior of the petroleum mixture and the oil-gas system is converted to a pure gas-condensate system.For CO_(2)injection,water vapor has little effect on the miscibility of multiple contacts,but can reduce the miscibility of the first contact.
