Understanding and predicting droplet breakup is essential in droplet-based microfluidic systems,as it enables precise control over droplet manipulation for various applications.In this study,droplet breakup behavior i...Understanding and predicting droplet breakup is essential in droplet-based microfluidic systems,as it enables precise control over droplet manipulation for various applications.In this study,droplet breakup behavior in a T-junction microchannel is investigated under the influence of microchannel geometry using three-dimensional numerical simulations.A theoretical model is developed based on the balance between surface tension and viscous drag forces acting on the droplet,incorporating the effects of geometric parameters on droplet length.This model predicts the critical Capillary number required for breakup to occur.The theoretical predictions are validated using both previous research data and the present numerical simulations.The results show that the model accurately predicts the transition between breakup and non-breakup regimes.Specifically,an increase in sidearm length ratio inhibits droplet breakup and leads to an asymmetric breakup regime.Furthermore,increasing the outlet-to-inlet width ratio also reduces the likelihood of droplet breakup.These findings provide a predictive framework for understanding and controlling droplet dynamics in microfluidic T-junctions,with potential applications in lab-on-a-chip technologies.展开更多
A theoretical prediction on forming limit diagram（FLD） of AZ31 magnesium alloy sheet was developed at warm temperatures based on the M-K theory. Two different yield criteria of von Mises and Hill＇48 were applied in...A theoretical prediction on forming limit diagram（FLD） of AZ31 magnesium alloy sheet was developed at warm temperatures based on the M-K theory. Two different yield criteria of von Mises and Hill＇48 were applied in this model. Mechanical properties of AZ31 magnesium alloy used in the prediction were obtained by uniaxial tensile tests and the Fields-Backofen equation was incorporated in the analysis. In addition, experimental FLDs of AZ31 were acquired by conducting rigid die swell test at different temperatures to verify the prediction. It is demonstrated from a comparison between the predicted and the experimental FLDs at 473 K and 523 K that the predicted results are influenced by the type of yield criterion used in the calculation, especially at lower temperatures. Furthermore, a better agreement between the predicted results and experimental data for AZ31 magnesium alloy sheet at warm temperatures was obtained when Hill＇48 yield criterion was applied.展开更多
In the present study,the modified Sverjensky-Molling equation,derived from a linear-free energy relationship,is used to predict the Gibbs free energies of formation of crystalline phases ofα-MOOH （with a goethite st...In the present study,the modified Sverjensky-Molling equation,derived from a linear-free energy relationship,is used to predict the Gibbs free energies of formation of crystalline phases ofα-MOOH （with a goethite structure）andα-M_2O_3（with a hematite structure）from the known thermodynamic properties of the corresponding aqueous trivalent cations（M^（3＋））.The modified equation is expressed asΔG_（f,M_VX）~0=a_（M_VX）ΔG_（0,M^（3＋））^（0）＋b_（M_VX）＋β_（M_VXγM^（3＋））,where the coefficients a_（M_VX）,b_（M_VX）,andβ_（M_VX） characterize a particular structural family of M_VX（M is a trivalent cation[M^（3＋）]and X represents the remainder of the composition of solid）;γ^（3＋）is the ionic radius of trivalent cations（M^（3＋））;ΔG_（f,M_VX）~0 is the standard Gibbs free energy of formation of M_vX;andΔG_（n,M^（3＋））~0 is the non-solvation energy of trivalent cations（M^（3＋））.By fitting the equation to the known experimental thermodynamic data,the coefficients for the goethite family（α-MOOH）are a_（M_VX）=0.8838,b_（M_VX）=-424.4431（kcal/mol）,andβ_（M_VX）=115（kcal/ mol.（？））,while the coefficients for the hematite family（α-M_2O_3）are a_（M_VX）=1.7468,b_（M_VX）=-814.9573（kcal/ mol）,andβ_（M_VX）=278（kcal/mol.（？））.The constrained relationship can be used to predict the standard Gibbs free energies of formation of crystalline phases and fictive phases（i.e.phases that are thermodynamically unstable and do not occur at standard conditions）within the isostructural families of goethite（α-MOOH）and hematite（α-M_2O_3）if the standard Gibbs free energies of formation of the trivalent cations are known.展开更多
In this work,the photovoltaic properties of BFBPD-PC61 BM system as a promising high-performance organic solar cell（OSC） were theoretically investigated by means of quantum chemistry and molecular dynamics calculati...In this work,the photovoltaic properties of BFBPD-PC61 BM system as a promising high-performance organic solar cell（OSC） were theoretically investigated by means of quantum chemistry and molecular dynamics calculations coupled with the incoherent charge-hopping model.Moreover,the hole carrier mobility of BFBPD thin-film was also estimated with the aid of an amorphous cell including 100 BFBPD molecules.Results revealed that the BFBPD-PC61 BM system possesses a middle-sized open-circuit voltage of 0.70 V,large short-circuit current density of 17.26 mA ·cm^-2,high fill factor of 0.846,and power conversion efficiency of 10%.With the Marcus model,in the BFBPD-PC61 BM interface,the exciton-dissociation rate,kdis,was predicted to be 2.684×10^13 s^-1,which is as 3-5 orders of magnitude large as the decay（radiative and non-radiative） one（10-8-10^10s^-1）,indicating a high exciton-dissociation efficiency of 100% in the BFBPD-PC61 BM interface.Furthermore,by the molecular dynamics simulation,the hole mobility of BFBPD thin-film was predicted to be as high as 1.265 × 10^-2 cm-2·V^-1·s^-1,which can be attributed to its dense packing in solid state.展开更多
Four isomers of the three-dimensionally connected bare boron cationic cluster B were investigated by using ab initio molecular orbital theory at the HF/6-31G level. The results show that the D5h symmetric isomer of B ...Four isomers of the three-dimensionally connected bare boron cationic cluster B were investigated by using ab initio molecular orbital theory at the HF/6-31G level. The results show that the D5h symmetric isomer of B is a possible isomer candidate of its stable geometries with closed structure.展开更多
CONSPECTUS:Dislocation loops(DLs),characterized by closed dislocation lines,are a category of defects of vital importance in determining the mechanical properties of metals,particularly under extreme conditions,such a...CONSPECTUS:Dislocation loops(DLs),characterized by closed dislocation lines,are a category of defects of vital importance in determining the mechanical properties of metals,particularly under extreme conditions,such as irradiation,severe plastic deformation,and hydrogen embrittlement.These loops,more intricate than simple dislocations,exhibit far more intricate reaction and evolution pathways arising from the loop type transformation and the associated planar fault transition.This can significantly alter dislocation activities contributing to dislocation channels and complex dislocation networks,which are closely linked to crack initiation and propagation during fracture.Understanding the transformation of DLs is crucial for the development of materials capable of withstanding harsh environments,including those encountered in nuclear reactors,aerospace applications,and hydrogen-rich environments.This Account delves into the computational advancements in studying DL transformations in FCC,HCP,and BCC metals.Traditional simulations often struggle to capture the complexity of DL structures and interactions.To overcome these limitations,a novel computational approach has been developed,enabling precise construction and analysis of DLs.Not only does it automatically account for necessary atom addition or deletion,it is also generic and versatile,applicable for any arbitrary DL morphology with planar fault or fault combination in both pristine metal and complex alloy systems.The new construction approach of DLs provides a critical enabler for studying the transformation of DLs across different crystal structures.In high-symmetry FCC metals,these transformations involve complex unfaulting driven by Shockley and Frank loop interactions,influenced by variations in stress,temperature,and radiation.Meanwhile,HCP metals,with a lower crystal symmetry,exhibit more complex DL transformations due to high anisotropy in the slip systems,variation in Burgers vectors,and different planar faults.Unlike pristine FCC and HCP lattices,ordered intermetallic systems like L12-Ni3Al experience a disruption of translational symmetry within the lattice.The ordered nature of these alloys complicates DL interacting with line dislocation,causing asymmetrical shearing and looping mechanisms.BCC metals,in contrast,exhibit different DL evolution due to the lack of stable stacking faults,leading to stronger interactions with impurities such as carbon and hydrogen.In particular,the interaction between DLs and hydrogen in BCC metals is a critical aspect worth investigating as it can cause severe damage in BCC materials under irradiation,hydrogen embrittlement,and intense deformation.This Account highlights the complex nature of DL transformation in metals under extreme environments and recent computational advances.Differences in the evolution of DLs across crystal structures and their interactions with cracks and solute elements are critical areas for future research.Key challenges include extending DL transformation theories to ordered lattice structures,developing machine-learning-based interatomic potentials,and refining multiscale models to better capture the dynamic behavior of DLs.These efforts will help develop more accurate predictive models,leading to materials with improved resistance to deformation and fracture in harsh environments.展开更多
Designing and synthesizing high-performable electron donor materials are very important for fabricating organic solar cell devices with high power conversion efficiency （PCE）. In this work, quantum chemical and mole...Designing and synthesizing high-performable electron donor materials are very important for fabricating organic solar cell devices with high power conversion efficiency （PCE）. In this work, quantum chemical and molecular dynamics calculations coupled with the Marcus-Hush charge transfer model were used to investigate the photovoltaic properties of 4Cl-BPPQ/PC61BM. Results reveal that 4Cl-BPPQ/PCrlBM system theoretically possesses a large open-circuit voltage （1.29 V）, high fill factor （0.90）, and over 9% PCE. Moreover, calculations also reveal that the 4Cl-BPPQ/PC61BM system has a middle-sized exciton binding energy （0.492 eV）, but relatively small charge-dissociation and charge-recombination reorganization energies （0.345 eV and 0.355 eV）. Based on the 4CI-BPPQ/PC61BM complex, the charge-dissociation rate constant, kdis, is estimated to be as large as 6.575× 10^12 s^-1, while the charge-recombination one, krec, is very small （〈 1.0 s^-1） under the same condition due to the very small driving force （AGree=-1.900 eV）. In addition, by means of an amorphous cell containing one hundred 4C1-BPPQ molecules, the hole carrier mobility of 4CI-BPPQ solid is estimated as high as 3.191 × 10^-3 cm^2·V^-1·s^-1. In brief, our calculation shows that 4Cl-BPPQ/PC61BM system is a very promising organic solar cell system, and is worth of making further device research by experiments.展开更多
The Forming Limit Curve （FLC） of the third generation aluminum-lithium （Al-Li） alloy 2198-T3 is measured by conducting a hemispherical dome test with specimens of different widths. The theoretical prediction of th...The Forming Limit Curve （FLC） of the third generation aluminum-lithium （Al-Li） alloy 2198-T3 is measured by conducting a hemispherical dome test with specimens of different widths. The theoretical prediction of the FLC of 2198-T3 is based on the M-K theory utilizing respectively the von Mises, Hill＇48, Hosford and Barlat 89 yield functions, and the different predicted curves due to different yield functions are compared with the experimentally measured FLC of 2198-T3. The results show that though there are differences among the four predicted curves, yet they all agree well with the experimentally measured curve. In the area near the planar strain state, the predicted curves and experimentally measured curve are very close. The predicted curve based on the Hosford yield function is more accurate under the tension-compression strain states described in the left part of the FLC, while the accuracy is better for the predicted curve based on Hill＇48 yield function under the tension-tension strain states shown in the right part.展开更多
In order to understand the laws of motion for supercavitating vehicle better, simplified equations for longitudinal motion of supercavitating vehicle were derived. Then the corresponding simulation software for trajec...In order to understand the laws of motion for supercavitating vehicle better, simplified equations for longitudinal motion of supercavitating vehicle were derived. Then the corresponding simulation software for trajectory of supereavitating vehicle was programmed, by which the theoretical predicted trajectories of the supercavitating vehicle at different velocities were obtained. It was found that the predicted trajectories at low speed and without cavitation on the vehicle in theory agreed well with those in experiments, and the theoretical predicted trajectories at high speed and with supercavity on the vehicle correctly reflected the motion laws of the supercavitating vehicle. The influences of various parameters of eavitator and rudder on the underwater trajectory were compared and analyzed, which can provide a guide for the design of hydrodynamic distribution and gross parameters of the supereavitating weapons.展开更多
Interface chemical modulation strategies are considered as promising method to prepare electrocatalysts for the urea oxidation reaction(UOR).However,conventional interface catalysts are generally limited by the inhere...Interface chemical modulation strategies are considered as promising method to prepare electrocatalysts for the urea oxidation reaction(UOR).However,conventional interface catalysts are generally limited by the inherent activity and incompatibility of the individual components themselves,and the irregular charge distribution and slow charge transfer ability between interfaces severely limit the activity of UOR.Therefore,we optimized and designed a Ni_(2)P/CoP interface with modulated surface charge distribution and directed charge transfer to promote UOR activity.Density functional theorycalculations first predict a regular charge transfer from CoP to Ni_(2)P,which creates a built-in electric field between Ni_(2)P and CoP interface.Optimization of the adsorption/desorption process of UOR/HER reaction intermediates leads to the improvement of catalytic activity.Electrochemical impedance spectroscopy and ex situ X-ray photoelectron spectroscopy characterization confirm the unique mechanism of facilitated reaction at the Ni_(2)P/CoP interface.Electrochemical tests further validated the prediction with excellent UOR/HER activities of 1.28 V and 19.7 mV vs.RHE,at 10 mA cm^(-2),respectively.Furthermore,Ni_(2)P/CoP achieves industrial-grade current densities(500 mA cm^(−2))at 1.75 V and 1.87 V in the overall urea electrolyzer(UOR||HER)and overall human urine electrolyzer(HUOR||HER),respectively,and demonstrates considerable durability.展开更多
Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3...Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3)N_(4)(N,S-g-C_(3)N_(4))is elaborately designed on the basis of theoretical predictions of first-principle density functional theory(DFT).The calculated Gibbs free energy of adsorbed hydrogen(ΔGH∗)for N,S-g-C_(3)N_(4) at the N-doping active sites is extremely close to zero(0.01 eV).Inspired by the theoretical predictions,the N,S-g-C_(3)N_(4) is successfully fabricated through ammonia-rich pyrolysis synthesis strategy,in which ammonia is in-situ obtained by pyrolyzing melamine.Subsequent characterizations indicate that the N,S-g-C_(3)N_(4) possesses high specific surface area,outstanding light utilization,good hydrophilicity,and efficient carrier transfer efficiency.Consequently,the N,S-g-C_(3)N_(4) displays an extremely high H2 evolution rate of 8269.9μmol g−1 h−1,achieves an apparent quantum efficiency(AQE)of 3.24%,and also possesses outsatnding durability.Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap,but also induce charge redistribution to facilitate hydrogen adsorption,thus promoting the photocatalytic HER process.Moreover,femtosecond transient absorption(fs-TA)spectroscopy further corroborates the efficient photogenerated carrier transport of N,S-g-C_(3)N_(4).This research highlights a promising and reliable strategy to achieve superior photocatalytic activity,and exhibits significant guidance for precise designing high-efficiency photocatalysts.展开更多
Two-dimensional(2D)materials such as metal chalcogenides have great potential as cathode catalyst materials for lithium oxygen batteries(LOBs)due to their large specific surface area and stable chemical properties.How...Two-dimensional(2D)materials such as metal chalcogenides have great potential as cathode catalyst materials for lithium oxygen batteries(LOBs)due to their large specific surface area and stable chemical properties.However,thus far,due to the lack of theoretical prediction methods,huge load on catalytic synthesis and performance evaluation is concerned.Herein,we reported a theoretical method for 2D metal chalcogenides as catalysts for LOBs using first principles density functional theory(DFT)calculations.We extracted key parameters that affect the overpotential,including Li-X bond energy(X represents chalcogen elements)and catalyst lattice constant,and theoretically predicted the catalytic performance.The DFT calculation results indicate that MoS_(2)with appropriate Li-X bond energy and lattice constant has the lowest theoretical overpotential,and its cyclic stability should be higher than other materials under the same conditions.Significantly,we experimentally validated the theoretical predictions presented above.The experimental results shows that pure MoS_(2)with 2H phase can stably work for more than 220 cycles at a current density of 500 mA/g,and the actual overpotential is lower than other metal chalcogenides.This work provides a swift pathway to accelerate searching high performance catalytic in LOBs.展开更多
A longstanding discrepancy between theoretical predictions and experimental observations on the highpressurestructural transformations of lanthanum mononitride(LaN)has posed challenges for understandingthe behavior of...A longstanding discrepancy between theoretical predictions and experimental observations on the highpressurestructural transformations of lanthanum mononitride(LaN)has posed challenges for understandingthe behavior of heavy transition metal mononitrides.Here,we systematically investigate the structural evolutionof LaN under high pressure using first-principles calculations combined with angle-dispersive synchrotron X-raydiffraction,identifying the phase transition sequence and corresponding phase boundaries.Analyses of energetics,kinetic barriers,and lattice dynamics reveal distinct mechanisms driving these transitions.These results clarifythe structural stability of LaN and offer guidance for studying other heavy transition metal mononitrides withcomplex electronic behavior under extreme conditions.展开更多
Carbyne delivers various excellent properties for the existence of the larger number of sp-hybridized carbon atoms.Here,a 3D well-defined porous carbon material germanium-carbdiyne(Ge-CDY)which is comprised of only sp...Carbyne delivers various excellent properties for the existence of the larger number of sp-hybridized carbon atoms.Here,a 3D well-defined porous carbon material germanium-carbdiyne(Ge-CDY)which is comprised of only sp-hybridized carbon atoms bridging by Ge atoms has been developed and investigated.The unique diamond-like structure constructed by linear butadiyne bonds and sp 3-hybridized Ge atoms ensures the stability of Ge-CDY.The large percentage of conjugated alkyne bonds composed of sp-C guarantees the good conductivity and the low band gap,which were further confirmed experimentally and theoretically,endowing Ge-CDY with the potential in electrochemical applications.The well-defined 3D carbon skeleton of Ge-CDY provides abundant uniform nanopores,which is suitable for metal ions storage and diffusion.Further half-cell evaluation also demonstrated Ge-CDY exhibited an excellent performance in lithium storage.All those indicating sp-hybridized carbon-based materials can exhibit great potential to possess excellent properties and be applied in the field of energy,electronic,and so on.展开更多
Failure mechanism and impact resistance of a human porous cranium are studied in detail by means of theoretical and numerical methods.It is hypothesized that pore distribution of a cranium directly affects cranial ene...Failure mechanism and impact resistance of a human porous cranium are studied in detail by means of theoretical and numerical methods.It is hypothesized that pore distribution of a cranium directly affects cranial energy absorption,and a stretched beam model and a real beam model are taken as the example for the verification.Meanwhile,for the purpose of comparison with numerical results,a theoretical model is also proposed for the prediction of residual velocity and contact force of the impactor for an impacted skull.Compared with the real beam model,the stretched beam model containing through-thickness pores is easily deformed under the impact,thereby buffering well the external impact energy.The energy absorption efficiency of both the stretched beam model and real beam model is concerned with the threshold velocity for penetration which is directly related to the size of the structural damage area.Overall,there is good agreement between numerical and theoretical results.In addition,the effect of structural geometric parameters(shape and size of the impactor)on the impact resistance of the skull bone is theoretically investigated.The study provides reference for the evaluation of the energy absorption and failure mechanism of the skull under impact loads.展开更多
Rationally regulating the adsorption strength of reaction intermediates on the surface of copper-based electrocatalysts would influence the product selectivity in the electrochemical CO_(2)reduction reaction(eCO_(2)RR...Rationally regulating the adsorption strength of reaction intermediates on the surface of copper-based electrocatalysts would influence the product selectivity in the electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,theoretical screening results reveal that among the twelve metals,Mg,Al,Cr,Mn,Fe,Co,Ni,Zn,Sn,Bi,Mo and Ce,the introduction of the metals Bi,Ce,Mg and Mn into CuOOH nanosheets not only modulates the Cu active center,but also leads to a certain degree of conformational distortion,resulting in an increased occupation of electrons in the antibonding state and accelerating the formation of the ratedetermining step ^(*)HCOO.In situ spectroscopies combined with theoretical calculations confirm that Bi atoms modulate the electronic structure of Cu and enhance CO_(2)activation,while Cu sites promote the adsorption of ^(*)HCOO intermediate,significantly increasing the formation of HCOOH with Faradaic efficiency exceeding 90%on the CuBiOOH.Moreover,the introduction of Mn into CuOOH nanosheets can induce the formation of key intermediates(^(*)CHO and ^(*)CO),leading to enhanced asymmetric C–C coupling to generate ethanol.Our work provides deep insights into the structural regulation strategy of Cu sites at the atomic scale for converting CO_(2)to liquid chemical products.展开更多
The present study focuses on the prediction of acoustic absorption performance of a perforated plate with air jets by theoretical calculations. In addition, we experimentally measured the flow rate, internal pressure,...The present study focuses on the prediction of acoustic absorption performance of a perforated plate with air jets by theoretical calculations. In addition, we experimentally measured the flow rate, internal pressure, acoustic pressure, and transfer function using an acoustic impedance tube. The normal incidence absorption coefficient was calculated from the measured transfer function using transfer function methods. We investigated the influences of background air space, flow velocity, thickness, aperture rate, and aperture diameter of a perforated plate on the acoustic absorption characteristics. The frequency characteristics of the acoustic absorption coefficient showed a maximum value at a local frequency. As the background air space increased, the peak frequency of acoustic absorption characteristics decreased. As the flow velocity passing through the apertures increased, the peak level of the acoustic absorption coefficient also increased. The theoretical results agreed well with the experimental ones qualitatively.展开更多
CoS_(2) is considered to be a promising electrocatalyst for hydrogen evolution reaction(HER).However,its further widespread applications are hampered by the unsatisfactory activity due to relatively high chemisorption...CoS_(2) is considered to be a promising electrocatalyst for hydrogen evolution reaction(HER).However,its further widespread applications are hampered by the unsatisfactory activity due to relatively high chemisorption energy for hydrogen atom.Herein,theoretical predictions of first-principles calculations reveal that the introduction of a Cl-terminated MXenes-Ti_(3)CNCl_(2) can significantly reduce the HER potential of CoS_(2)-based materials and the Ti_(3)CNCl_(2)@CoS_(2) core–shell nanostructure has Gibbs free energy of hydrogen adsorption(|ΔGH|)close to zero,much lower than that of the pristine CoS_(2) and Ti_(3)CNCl_(2).Inspired by the theoretical predictions,we have successfully fabricated a unique Ti_(3)CNCl_(2)@CoS_(2) core–shell nanostructure by ingeniously coupling CoS_(2) with a Cl-terminated MXenes-Ti_(3)CNCl_(2).Interface-charge transfer between CoS_(2) and Ti_(3)CNCl_(2) results in a higher degree of electronic localization and a formation of chemical bonding.Thus,the Ti_(3)CNCl_(2)@CoS_(2) core–shell nanostructure achieves a significant enhancement in HER activity compared to pristine CoS_(2) and Ti_(3)CNCl_(2).Theoretical calculations further confirm that the partial density of states of CoS_(2) after hybridization becomes more non-localized,and easier to interact with hydrogen ions,thus boosting HER performance.In this work,the success of oriented experimental fabrication of high-efficiency Ti_(3)CNCl_(2)@CoS_(2) electrocatalysts guided by theoretical predictions provides a powerful lead for the further strategic design and fabrication of efficient HER electrocatalysts.展开更多
The electroplating industry is the main source of 6:2 chlorinated polyfluorinated ether sulfonate(6:2 Cl-PFESA)pollution,which presents risks to human health and the environment.It is therefore crucial to develop effe...The electroplating industry is the main source of 6:2 chlorinated polyfluorinated ether sulfonate(6:2 Cl-PFESA)pollution,which presents risks to human health and the environment.It is therefore crucial to develop effective 6:2 Cl-PFESA degradation techniques.Persulfate oxidation is a potential treatment method for 6:2 Cl-PFESA due to its outstanding oxidative degradability following the generation of the sulfate radical(SO_(4)^(•−))and hydroxyl radical(•OH).It has proven difficult to acquire a full understanding of the reaction mechanism and formation of intermediate(IM)products through conventional experimental studies because they are costly and time-consuming.Therefore,a theoretical analysis method based on density functional theory(DFT)calculations was applied.The DFT results showed that electron transfer for the degradation of 6:2 Cl-PFESA could be initiated by the protonated sulfate radical(HSO_(4)•,ΔG≠SET=9.16 kcal/mol),rather than SO4•−(ΔG≠SET=41.60 kcal/mol).After desulfonation,the reaction underwent stepwise decarboxylation cycles under the action of•OH,leading to the elimination of the CF_(2) units until there was complete mineralization into HCl,HF,and CO_(2).Furthermore,the IMs and the end products of 6:2 Cl-PFESA were evaluated using ECOSAR and TEST software.The low bioaccumulation of the short-chain IMs meant that they could be considered safe in terms of ecotoxicity and health effects.This research determined the theoretical and mechanistic basis of the effects of persulfate in the treatment of water containing 6:2 Cl-PFESA,and its structural analogues.展开更多
基金funded by the Master,Ph D Scholarship Programme of Vingroup Innovation Foundation(VINIF),code VINIF.2023.Th S.118。
文摘Understanding and predicting droplet breakup is essential in droplet-based microfluidic systems,as it enables precise control over droplet manipulation for various applications.In this study,droplet breakup behavior in a T-junction microchannel is investigated under the influence of microchannel geometry using three-dimensional numerical simulations.A theoretical model is developed based on the balance between surface tension and viscous drag forces acting on the droplet,incorporating the effects of geometric parameters on droplet length.This model predicts the critical Capillary number required for breakup to occur.The theoretical predictions are validated using both previous research data and the present numerical simulations.The results show that the model accurately predicts the transition between breakup and non-breakup regimes.Specifically,an increase in sidearm length ratio inhibits droplet breakup and leads to an asymmetric breakup regime.Furthermore,increasing the outlet-to-inlet width ratio also reduces the likelihood of droplet breakup.These findings provide a predictive framework for understanding and controlling droplet dynamics in microfluidic T-junctions,with potential applications in lab-on-a-chip technologies.
基金Project(51375328)supported by the National Natural Science Foundation of ChinaProject(20143009)supported by Graduates Innovation Project of Shanxi Province,ChinaProject(2015-036)supported by Shanxi Scholarship Council of China
文摘A theoretical prediction on forming limit diagram（FLD） of AZ31 magnesium alloy sheet was developed at warm temperatures based on the M-K theory. Two different yield criteria of von Mises and Hill＇48 were applied in this model. Mechanical properties of AZ31 magnesium alloy used in the prediction were obtained by uniaxial tensile tests and the Fields-Backofen equation was incorporated in the analysis. In addition, experimental FLDs of AZ31 were acquired by conducting rigid die swell test at different temperatures to verify the prediction. It is demonstrated from a comparison between the predicted and the experimental FLDs at 473 K and 523 K that the predicted results are influenced by the type of yield criterion used in the calculation, especially at lower temperatures. Furthermore, a better agreement between the predicted results and experimental data for AZ31 magnesium alloy sheet at warm temperatures was obtained when Hill＇48 yield criterion was applied.
基金supported by the NSFC(no 40473024 and 40343019)Project of the 11th and 10th Five-Year Research and Development of International Seabed(noDYXM-115-02-1-11,PY105-01-04-13 and DY 105-01-02-1)+2 种基金Project of Key Laboratory of Marginal Sea Geology,Guangzhou Institute of Geochemistry and South China Sea Institute of Oceanology,CAS(no MSGL08-01,MSGLCAS03-4)Specialized Research Fund for the Doctoral Program of Higher Education(no 20040558049)the Fundamental Research Funds for the Central Universities
文摘In the present study,the modified Sverjensky-Molling equation,derived from a linear-free energy relationship,is used to predict the Gibbs free energies of formation of crystalline phases ofα-MOOH （with a goethite structure）andα-M_2O_3（with a hematite structure）from the known thermodynamic properties of the corresponding aqueous trivalent cations（M^（3＋））.The modified equation is expressed asΔG_（f,M_VX）~0=a_（M_VX）ΔG_（0,M^（3＋））^（0）＋b_（M_VX）＋β_（M_VXγM^（3＋））,where the coefficients a_（M_VX）,b_（M_VX）,andβ_（M_VX） characterize a particular structural family of M_VX（M is a trivalent cation[M^（3＋）]and X represents the remainder of the composition of solid）;γ^（3＋）is the ionic radius of trivalent cations（M^（3＋））;ΔG_（f,M_VX）~0 is the standard Gibbs free energy of formation of M_vX;andΔG_（n,M^（3＋））~0 is the non-solvation energy of trivalent cations（M^（3＋））.By fitting the equation to the known experimental thermodynamic data,the coefficients for the goethite family（α-MOOH）are a_（M_VX）=0.8838,b_（M_VX）=-424.4431（kcal/mol）,andβ_（M_VX）=115（kcal/ mol.（？））,while the coefficients for the hematite family（α-M_2O_3）are a_（M_VX）=1.7468,b_（M_VX）=-814.9573（kcal/ mol）,andβ_（M_VX）=278（kcal/mol.（？））.The constrained relationship can be used to predict the standard Gibbs free energies of formation of crystalline phases and fictive phases（i.e.phases that are thermodynamically unstable and do not occur at standard conditions）within the isostructural families of goethite（α-MOOH）and hematite（α-M_2O_3）if the standard Gibbs free energies of formation of the trivalent cations are known.
基金supported by the National Natural Science Foundation of China(No.21373132,No.21603133)the Education Department of Shaanxi Provincial Government Research Projects(No.16JK1142,No.16JK1134)the Scientific Research Foundation of Shaanxi University of Technology for Recruited Talents(No.SLGKYQD2-13,No.SLGKYQD2-10,No.SLGQD14-10)
文摘In this work,the photovoltaic properties of BFBPD-PC61 BM system as a promising high-performance organic solar cell（OSC） were theoretically investigated by means of quantum chemistry and molecular dynamics calculations coupled with the incoherent charge-hopping model.Moreover,the hole carrier mobility of BFBPD thin-film was also estimated with the aid of an amorphous cell including 100 BFBPD molecules.Results revealed that the BFBPD-PC61 BM system possesses a middle-sized open-circuit voltage of 0.70 V,large short-circuit current density of 17.26 mA ·cm^-2,high fill factor of 0.846,and power conversion efficiency of 10%.With the Marcus model,in the BFBPD-PC61 BM interface,the exciton-dissociation rate,kdis,was predicted to be 2.684×10^13 s^-1,which is as 3-5 orders of magnitude large as the decay（radiative and non-radiative） one（10-8-10^10s^-1）,indicating a high exciton-dissociation efficiency of 100% in the BFBPD-PC61 BM interface.Furthermore,by the molecular dynamics simulation,the hole mobility of BFBPD thin-film was predicted to be as high as 1.265 × 10^-2 cm-2·V^-1·s^-1,which can be attributed to its dense packing in solid state.
文摘Four isomers of the three-dimensionally connected bare boron cationic cluster B were investigated by using ab initio molecular orbital theory at the HF/6-31G level. The results show that the D5h symmetric isomer of B is a possible isomer candidate of its stable geometries with closed structure.
基金the financial support from National Natural Science Foundation of China(NSFC Grants No.12002277 and No.52401010)Natural Sciences and Engineering Research Council of Canada(NSERC)Discovery grant(RGPIN-2023-03628)McGill’s William Dawson Scholar fund.
文摘CONSPECTUS:Dislocation loops(DLs),characterized by closed dislocation lines,are a category of defects of vital importance in determining the mechanical properties of metals,particularly under extreme conditions,such as irradiation,severe plastic deformation,and hydrogen embrittlement.These loops,more intricate than simple dislocations,exhibit far more intricate reaction and evolution pathways arising from the loop type transformation and the associated planar fault transition.This can significantly alter dislocation activities contributing to dislocation channels and complex dislocation networks,which are closely linked to crack initiation and propagation during fracture.Understanding the transformation of DLs is crucial for the development of materials capable of withstanding harsh environments,including those encountered in nuclear reactors,aerospace applications,and hydrogen-rich environments.This Account delves into the computational advancements in studying DL transformations in FCC,HCP,and BCC metals.Traditional simulations often struggle to capture the complexity of DL structures and interactions.To overcome these limitations,a novel computational approach has been developed,enabling precise construction and analysis of DLs.Not only does it automatically account for necessary atom addition or deletion,it is also generic and versatile,applicable for any arbitrary DL morphology with planar fault or fault combination in both pristine metal and complex alloy systems.The new construction approach of DLs provides a critical enabler for studying the transformation of DLs across different crystal structures.In high-symmetry FCC metals,these transformations involve complex unfaulting driven by Shockley and Frank loop interactions,influenced by variations in stress,temperature,and radiation.Meanwhile,HCP metals,with a lower crystal symmetry,exhibit more complex DL transformations due to high anisotropy in the slip systems,variation in Burgers vectors,and different planar faults.Unlike pristine FCC and HCP lattices,ordered intermetallic systems like L12-Ni3Al experience a disruption of translational symmetry within the lattice.The ordered nature of these alloys complicates DL interacting with line dislocation,causing asymmetrical shearing and looping mechanisms.BCC metals,in contrast,exhibit different DL evolution due to the lack of stable stacking faults,leading to stronger interactions with impurities such as carbon and hydrogen.In particular,the interaction between DLs and hydrogen in BCC metals is a critical aspect worth investigating as it can cause severe damage in BCC materials under irradiation,hydrogen embrittlement,and intense deformation.This Account highlights the complex nature of DL transformation in metals under extreme environments and recent computational advances.Differences in the evolution of DLs across crystal structures and their interactions with cracks and solute elements are critical areas for future research.Key challenges include extending DL transformation theories to ordered lattice structures,developing machine-learning-based interatomic potentials,and refining multiscale models to better capture the dynamic behavior of DLs.These efforts will help develop more accurate predictive models,leading to materials with improved resistance to deformation and fracture in harsh environments.
基金This work was supported by the National Natural Science Foundation of China （Nos. 21373132, 21502109）, and the Doctor Research Start Foundation of Shaanxi University of Technology （Nos. SLGKYQD2-13, SLGKYQD2-10, SLGQD14-10）, and the Education Department of Shaanxi Provincial Gov- ernment Research Projects （No. 16JK1142）.
文摘Designing and synthesizing high-performable electron donor materials are very important for fabricating organic solar cell devices with high power conversion efficiency （PCE）. In this work, quantum chemical and molecular dynamics calculations coupled with the Marcus-Hush charge transfer model were used to investigate the photovoltaic properties of 4Cl-BPPQ/PC61BM. Results reveal that 4Cl-BPPQ/PCrlBM system theoretically possesses a large open-circuit voltage （1.29 V）, high fill factor （0.90）, and over 9% PCE. Moreover, calculations also reveal that the 4Cl-BPPQ/PC61BM system has a middle-sized exciton binding energy （0.492 eV）, but relatively small charge-dissociation and charge-recombination reorganization energies （0.345 eV and 0.355 eV）. Based on the 4CI-BPPQ/PC61BM complex, the charge-dissociation rate constant, kdis, is estimated to be as large as 6.575× 10^12 s^-1, while the charge-recombination one, krec, is very small （〈 1.0 s^-1） under the same condition due to the very small driving force （AGree=-1.900 eV）. In addition, by means of an amorphous cell containing one hundred 4C1-BPPQ molecules, the hole carrier mobility of 4CI-BPPQ solid is estimated as high as 3.191 × 10^-3 cm^2·V^-1·s^-1. In brief, our calculation shows that 4Cl-BPPQ/PC61BM system is a very promising organic solar cell system, and is worth of making further device research by experiments.
基金co-supported by National Natural Science Foundation of China (No.50905008)Fund of National Engineering and Research Center for Commercial Aircraft Manufacturing (No.SAMC12-JS-15-008)
文摘The Forming Limit Curve （FLC） of the third generation aluminum-lithium （Al-Li） alloy 2198-T3 is measured by conducting a hemispherical dome test with specimens of different widths. The theoretical prediction of the FLC of 2198-T3 is based on the M-K theory utilizing respectively the von Mises, Hill＇48, Hosford and Barlat 89 yield functions, and the different predicted curves due to different yield functions are compared with the experimentally measured FLC of 2198-T3. The results show that though there are differences among the four predicted curves, yet they all agree well with the experimentally measured curve. In the area near the planar strain state, the predicted curves and experimentally measured curve are very close. The predicted curve based on the Hosford yield function is more accurate under the tension-compression strain states described in the left part of the FLC, while the accuracy is better for the predicted curve based on Hill＇48 yield function under the tension-tension strain states shown in the right part.
文摘In order to understand the laws of motion for supercavitating vehicle better, simplified equations for longitudinal motion of supercavitating vehicle were derived. Then the corresponding simulation software for trajectory of supereavitating vehicle was programmed, by which the theoretical predicted trajectories of the supercavitating vehicle at different velocities were obtained. It was found that the predicted trajectories at low speed and without cavitation on the vehicle in theory agreed well with those in experiments, and the theoretical predicted trajectories at high speed and with supercavity on the vehicle correctly reflected the motion laws of the supercavitating vehicle. The influences of various parameters of eavitator and rudder on the underwater trajectory were compared and analyzed, which can provide a guide for the design of hydrodynamic distribution and gross parameters of the supereavitating weapons.
文摘Interface chemical modulation strategies are considered as promising method to prepare electrocatalysts for the urea oxidation reaction(UOR).However,conventional interface catalysts are generally limited by the inherent activity and incompatibility of the individual components themselves,and the irregular charge distribution and slow charge transfer ability between interfaces severely limit the activity of UOR.Therefore,we optimized and designed a Ni_(2)P/CoP interface with modulated surface charge distribution and directed charge transfer to promote UOR activity.Density functional theorycalculations first predict a regular charge transfer from CoP to Ni_(2)P,which creates a built-in electric field between Ni_(2)P and CoP interface.Optimization of the adsorption/desorption process of UOR/HER reaction intermediates leads to the improvement of catalytic activity.Electrochemical impedance spectroscopy and ex situ X-ray photoelectron spectroscopy characterization confirm the unique mechanism of facilitated reaction at the Ni_(2)P/CoP interface.Electrochemical tests further validated the prediction with excellent UOR/HER activities of 1.28 V and 19.7 mV vs.RHE,at 10 mA cm^(-2),respectively.Furthermore,Ni_(2)P/CoP achieves industrial-grade current densities(500 mA cm^(−2))at 1.75 V and 1.87 V in the overall urea electrolyzer(UOR||HER)and overall human urine electrolyzer(HUOR||HER),respectively,and demonstrates considerable durability.
基金supported by the National Natural Science Foun-dation of China(No.62004143)the Key R&D Program of Hubei Province(No.2022BAA084)the Natural Science Foundation of Hubei Province(No.2021CFB133).
文摘Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3)N_(4)(N,S-g-C_(3)N_(4))is elaborately designed on the basis of theoretical predictions of first-principle density functional theory(DFT).The calculated Gibbs free energy of adsorbed hydrogen(ΔGH∗)for N,S-g-C_(3)N_(4) at the N-doping active sites is extremely close to zero(0.01 eV).Inspired by the theoretical predictions,the N,S-g-C_(3)N_(4) is successfully fabricated through ammonia-rich pyrolysis synthesis strategy,in which ammonia is in-situ obtained by pyrolyzing melamine.Subsequent characterizations indicate that the N,S-g-C_(3)N_(4) possesses high specific surface area,outstanding light utilization,good hydrophilicity,and efficient carrier transfer efficiency.Consequently,the N,S-g-C_(3)N_(4) displays an extremely high H2 evolution rate of 8269.9μmol g−1 h−1,achieves an apparent quantum efficiency(AQE)of 3.24%,and also possesses outsatnding durability.Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap,but also induce charge redistribution to facilitate hydrogen adsorption,thus promoting the photocatalytic HER process.Moreover,femtosecond transient absorption(fs-TA)spectroscopy further corroborates the efficient photogenerated carrier transport of N,S-g-C_(3)N_(4).This research highlights a promising and reliable strategy to achieve superior photocatalytic activity,and exhibits significant guidance for precise designing high-efficiency photocatalysts.
基金supported by the National Natural Science Foundation of China(Grant No.U21A2054,52262032,52273285,51961011,52173094)Scientific Research and Technology Development Program of Guangxi(Grant No.AA23062070).
文摘Two-dimensional(2D)materials such as metal chalcogenides have great potential as cathode catalyst materials for lithium oxygen batteries(LOBs)due to their large specific surface area and stable chemical properties.However,thus far,due to the lack of theoretical prediction methods,huge load on catalytic synthesis and performance evaluation is concerned.Herein,we reported a theoretical method for 2D metal chalcogenides as catalysts for LOBs using first principles density functional theory(DFT)calculations.We extracted key parameters that affect the overpotential,including Li-X bond energy(X represents chalcogen elements)and catalyst lattice constant,and theoretically predicted the catalytic performance.The DFT calculation results indicate that MoS_(2)with appropriate Li-X bond energy and lattice constant has the lowest theoretical overpotential,and its cyclic stability should be higher than other materials under the same conditions.Significantly,we experimentally validated the theoretical predictions presented above.The experimental results shows that pure MoS_(2)with 2H phase can stably work for more than 220 cycles at a current density of 500 mA/g,and the actual overpotential is lower than other metal chalcogenides.This work provides a swift pathway to accelerate searching high performance catalytic in LOBs.
基金supported by the Natural Science Foundation of China(Grant Nos.T2325013,12474004,and 52288102)the National Key Research and Development Program of China(Grant No.2021YFA1400503)the Program for Jilin University Science and Technology Innovative Research Team。
文摘A longstanding discrepancy between theoretical predictions and experimental observations on the highpressurestructural transformations of lanthanum mononitride(LaN)has posed challenges for understandingthe behavior of heavy transition metal mononitrides.Here,we systematically investigate the structural evolutionof LaN under high pressure using first-principles calculations combined with angle-dispersive synchrotron X-raydiffraction,identifying the phase transition sequence and corresponding phase boundaries.Analyses of energetics,kinetic barriers,and lattice dynamics reveal distinct mechanisms driving these transitions.These results clarifythe structural stability of LaN and offer guidance for studying other heavy transition metal mononitrides withcomplex electronic behavior under extreme conditions.
基金This study was supported by the National Natural Science Foundation of China (21701182,51822208,21771187,21790050,and 21790051)the Frontier Science Research Project (QYZDB-SSW-JSC052)+1 种基金the Chinese Academy of Sciences,the Taishan Scholars Program of Shandong Province (tsqn201812111)Institute Research Project (QIBEBT ZZBS 201809).
文摘Carbyne delivers various excellent properties for the existence of the larger number of sp-hybridized carbon atoms.Here,a 3D well-defined porous carbon material germanium-carbdiyne(Ge-CDY)which is comprised of only sp-hybridized carbon atoms bridging by Ge atoms has been developed and investigated.The unique diamond-like structure constructed by linear butadiyne bonds and sp 3-hybridized Ge atoms ensures the stability of Ge-CDY.The large percentage of conjugated alkyne bonds composed of sp-C guarantees the good conductivity and the low band gap,which were further confirmed experimentally and theoretically,endowing Ge-CDY with the potential in electrochemical applications.The well-defined 3D carbon skeleton of Ge-CDY provides abundant uniform nanopores,which is suitable for metal ions storage and diffusion.Further half-cell evaluation also demonstrated Ge-CDY exhibited an excellent performance in lithium storage.All those indicating sp-hybridized carbon-based materials can exhibit great potential to possess excellent properties and be applied in the field of energy,electronic,and so on.
基金This study was funded in part by the National Natural Science Foundation of China(Grant 12002107)the National Postdoctoral Program for Innovative Talents(Grant BX20190101)+3 种基金the China Postdoctoral Science Foundation(Grant 2019M661268)the Heilongjiang Postdoctoral Financial Assistance(Grant LBH-Z19061)The present work was also supported in part by Alexander von Humboldt Foundation(Grant 1155520)(University of Siegen,Germany)the Science and Technology on Advanced Composites in Special Environment Laboratory,Young Elite Scientist Sponsorship Program by CAST(Grant YESS20160190).
文摘Failure mechanism and impact resistance of a human porous cranium are studied in detail by means of theoretical and numerical methods.It is hypothesized that pore distribution of a cranium directly affects cranial energy absorption,and a stretched beam model and a real beam model are taken as the example for the verification.Meanwhile,for the purpose of comparison with numerical results,a theoretical model is also proposed for the prediction of residual velocity and contact force of the impactor for an impacted skull.Compared with the real beam model,the stretched beam model containing through-thickness pores is easily deformed under the impact,thereby buffering well the external impact energy.The energy absorption efficiency of both the stretched beam model and real beam model is concerned with the threshold velocity for penetration which is directly related to the size of the structural damage area.Overall,there is good agreement between numerical and theoretical results.In addition,the effect of structural geometric parameters(shape and size of the impactor)on the impact resistance of the skull bone is theoretically investigated.The study provides reference for the evaluation of the energy absorption and failure mechanism of the skull under impact loads.
基金supported by the Natural Science Foundation of Jilin Province(20220101051JC)the National Natural Science Foundation of China(22075099)。
文摘Rationally regulating the adsorption strength of reaction intermediates on the surface of copper-based electrocatalysts would influence the product selectivity in the electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,theoretical screening results reveal that among the twelve metals,Mg,Al,Cr,Mn,Fe,Co,Ni,Zn,Sn,Bi,Mo and Ce,the introduction of the metals Bi,Ce,Mg and Mn into CuOOH nanosheets not only modulates the Cu active center,but also leads to a certain degree of conformational distortion,resulting in an increased occupation of electrons in the antibonding state and accelerating the formation of the ratedetermining step ^(*)HCOO.In situ spectroscopies combined with theoretical calculations confirm that Bi atoms modulate the electronic structure of Cu and enhance CO_(2)activation,while Cu sites promote the adsorption of ^(*)HCOO intermediate,significantly increasing the formation of HCOOH with Faradaic efficiency exceeding 90%on the CuBiOOH.Moreover,the introduction of Mn into CuOOH nanosheets can induce the formation of key intermediates(^(*)CHO and ^(*)CO),leading to enhanced asymmetric C–C coupling to generate ethanol.Our work provides deep insights into the structural regulation strategy of Cu sites at the atomic scale for converting CO_(2)to liquid chemical products.
基金supported by JSPS KAKENHI Grant Numbers JP17K06232
文摘The present study focuses on the prediction of acoustic absorption performance of a perforated plate with air jets by theoretical calculations. In addition, we experimentally measured the flow rate, internal pressure, acoustic pressure, and transfer function using an acoustic impedance tube. The normal incidence absorption coefficient was calculated from the measured transfer function using transfer function methods. We investigated the influences of background air space, flow velocity, thickness, aperture rate, and aperture diameter of a perforated plate on the acoustic absorption characteristics. The frequency characteristics of the acoustic absorption coefficient showed a maximum value at a local frequency. As the background air space increased, the peak frequency of acoustic absorption characteristics decreased. As the flow velocity passing through the apertures increased, the peak level of the acoustic absorption coefficient also increased. The theoretical results agreed well with the experimental ones qualitatively.
基金supported by the National Natural Science Foundation of China(No.62004143)the Central Government Guided Local Science and Technology Development Special Fund Project(No.2020ZYYD033)+3 种基金the Natural Science Foundation of Hubei Province(No.2021CFB133)the Opening Fund of Key Laboratory of Rare Mineral,Ministry of Natural Resources(No.KLRM-KF 202005)the Opening Fund of Key Laboratory for Green Chemical Process of Ministry of Education of Wuhan Institute of Technology(No.GCP202101)the Innovation Project of Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education(No.LCX2021003).
文摘CoS_(2) is considered to be a promising electrocatalyst for hydrogen evolution reaction(HER).However,its further widespread applications are hampered by the unsatisfactory activity due to relatively high chemisorption energy for hydrogen atom.Herein,theoretical predictions of first-principles calculations reveal that the introduction of a Cl-terminated MXenes-Ti_(3)CNCl_(2) can significantly reduce the HER potential of CoS_(2)-based materials and the Ti_(3)CNCl_(2)@CoS_(2) core–shell nanostructure has Gibbs free energy of hydrogen adsorption(|ΔGH|)close to zero,much lower than that of the pristine CoS_(2) and Ti_(3)CNCl_(2).Inspired by the theoretical predictions,we have successfully fabricated a unique Ti_(3)CNCl_(2)@CoS_(2) core–shell nanostructure by ingeniously coupling CoS_(2) with a Cl-terminated MXenes-Ti_(3)CNCl_(2).Interface-charge transfer between CoS_(2) and Ti_(3)CNCl_(2) results in a higher degree of electronic localization and a formation of chemical bonding.Thus,the Ti_(3)CNCl_(2)@CoS_(2) core–shell nanostructure achieves a significant enhancement in HER activity compared to pristine CoS_(2) and Ti_(3)CNCl_(2).Theoretical calculations further confirm that the partial density of states of CoS_(2) after hybridization becomes more non-localized,and easier to interact with hydrogen ions,thus boosting HER performance.In this work,the success of oriented experimental fabrication of high-efficiency Ti_(3)CNCl_(2)@CoS_(2) electrocatalysts guided by theoretical predictions provides a powerful lead for the further strategic design and fabrication of efficient HER electrocatalysts.
基金This work was supported by the National Natural Science Foundation of China(Grant No.U20A20146,Grant No.52200198)the Natural Science Foundation of Shandong Province(Grant No.ZR2021QB186).
文摘The electroplating industry is the main source of 6:2 chlorinated polyfluorinated ether sulfonate(6:2 Cl-PFESA)pollution,which presents risks to human health and the environment.It is therefore crucial to develop effective 6:2 Cl-PFESA degradation techniques.Persulfate oxidation is a potential treatment method for 6:2 Cl-PFESA due to its outstanding oxidative degradability following the generation of the sulfate radical(SO_(4)^(•−))and hydroxyl radical(•OH).It has proven difficult to acquire a full understanding of the reaction mechanism and formation of intermediate(IM)products through conventional experimental studies because they are costly and time-consuming.Therefore,a theoretical analysis method based on density functional theory(DFT)calculations was applied.The DFT results showed that electron transfer for the degradation of 6:2 Cl-PFESA could be initiated by the protonated sulfate radical(HSO_(4)•,ΔG≠SET=9.16 kcal/mol),rather than SO4•−(ΔG≠SET=41.60 kcal/mol).After desulfonation,the reaction underwent stepwise decarboxylation cycles under the action of•OH,leading to the elimination of the CF_(2) units until there was complete mineralization into HCl,HF,and CO_(2).Furthermore,the IMs and the end products of 6:2 Cl-PFESA were evaluated using ECOSAR and TEST software.The low bioaccumulation of the short-chain IMs meant that they could be considered safe in terms of ecotoxicity and health effects.This research determined the theoretical and mechanistic basis of the effects of persulfate in the treatment of water containing 6:2 Cl-PFESA,and its structural analogues.
