Rational design of high-performance electrocatalysts for hydrogen evolution reaction(HER)is vital for future renewable energy systems.The incorporation of foreign metal ions into catalysts can be an effective approach...Rational design of high-performance electrocatalysts for hydrogen evolution reaction(HER)is vital for future renewable energy systems.The incorporation of foreign metal ions into catalysts can be an effective approach to optimize its performance.However,there is a lack of systematic theoretical studies to reveal the quantitative relationships at the electronic level.Here,we develop a multi-level screening methodology to search for highly stable and active dopants for CoP catalysts.The density functional theory(DFT)calculations and symbolic regression(SR)were performed to investigate the relationship between the adsorption free energy(ΔG_(H^(*)))and 10 electronic parameters.The mathematic formulas derived from SR indicate that the difference of work function(ΔΦ)between doped metal and the acceptor plays the most important role in regulatingΔG_(H^(*)),followed by the d-band center(d-BC)of doped system.The descriptor of HER can be expressed asΔG_(H^(*))=1.59×√|0.188ΔΦ+d BC+0.120|1/2-0.166 with a high determination coefficient(R^(2)=0.807).Consistent with the theoretical prediction,experimental results show that the Al-CoP delivers superior electrocatalytic HER activity with a low overpotential of75 m V to drive a current density of 10 mA cm^(-2),while the overpotentials for undoped CoP,Mo-CoP,and V-CoP are 206,134,and 83 m V,respectively.The current work proves that theΔΦis the most significant regulatory parameter ofΔG_(H^(*))for ion-doped electrocatalysts.This finding can drive the discovery of high-performance ion-doped electrocatalysts,which is crucial for electrocatalytic water splitting.展开更多
Density functional theory(DFT)is used to calculate the most stable structures of Zr_(n)(n=2-5)clusters as well as the adsorption energy values of Zr_(n)(n=2-5)clusters after adsorbing single water molecule.The results...Density functional theory(DFT)is used to calculate the most stable structures of Zr_(n)(n=2-5)clusters as well as the adsorption energy values of Zr_(n)(n=2-5)clusters after adsorbing single water molecule.The results reveal that there is a significant linear relationship between the adsorption energy values and the energy gaps of the Zr_(n)(n=2-5)clusters.Furthermore,the calculations of the reaction paths between Zr_(n)(n=2-5)and single water molecule show that water molecule can react with Zr_(n)(n=2-5)clusters to dissociate,producing hydrogen,and O atoms mix with the clusters to generate Zr_(n)O(n=2-5),all of which are exothermic reactions.According to the released energy,the Zr4 cluster is the most efficient in Zr_(n)(n=2-5)clusters reacting with single water molecule.The natural population analysis(NPA)and density of states(DOS)demonstrate the production of hydrogen and orbital properties in different energy ranges,respectively,jointly forecasting that Zr_(n)O(n=2-5)will probably continue to react with more water molecules.Our findings contribute to better understanding of Zr's chemical reactivity,which can conduce to the development of effective Zr-based catalysts and hydrogen-production methods.展开更多
Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of ...Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of water electrolysis for sustainable hydrogen production.Despite their excellent OER performance,the structural and electronic properties of LDHs,particularly during the OER process,remain to be poorly understood.In this study,a series of LDH catalysts is investigated through in situ X-ray absorption fine structure analyses and density functional theory(DFT) calculations.Our experimental results reveal that the LDH catalyst with equal amounts of Ni and Fe(NF-LDH) exhibits the highest OER activity and catalytic life span when compared with its counterparts having equal amounts of Ni and Co(NC-LDH)and Ni only(Ni-LDH).The NF-LDH shows a markedly enhanced OER kinetics compared to the NC-LDH and the Ni-LDH,as proven by the lower overpotentials of 180,240,and 310 mV,respectively,and the Tafel slopes of 35.1,43.4,and 62.7 mV dec^(-1),respectively.The DFT calculations demonstrate that the lowest overpotential of the NF-LDH is associated with the active sites located at the edge planes of NF-LDH in contrast to those located at the basal planes of Ni-LDH and NC-LDH.The current study pinpoints the active sites on various LDHs and presents strategies for optimizing the OER performance of the LDH catalysts.展开更多
Utilizing the acoustic emission(AE) technique, an experimental investigation into the damage evolution for steel strand under axial tension was described. The damage evolution model for steel stand relating the damage...Utilizing the acoustic emission(AE) technique, an experimental investigation into the damage evolution for steel strand under axial tension was described. The damage evolution model for steel stand relating the damage evolution to acoustic emission parameters was proposed by incorporating the AE rate process theory. The AE monitoring results indicate that damages occur in both elastic and plastic phases of steel strand. In elastic phase, AE signals are mainly sent out from the micro damage due to the surface friction among the wires of steel strand, while in plastic phase, AE signals emitted from the plastic deformation of wires. In addition, the AE cumulative parameters curves closely resemble the loading curve. The AE cumulative parameters curves can well describe the damage evolution process including the damage occurrence and damage development for steel strands. It is concluded that the AE technique is an effective and useful nondestructive technique for evaluating the damage characteristics of steel strand.展开更多
Despite almost half a century of research for theory of mind, its evolutionary origin is largely unknown. This paper proposes that the evolutionary origin of theory of mind starts from the beginning of the human evolu...Despite almost half a century of research for theory of mind, its evolutionary origin is largely unknown. This paper proposes that the evolutionary origin of theory of mind starts from the beginning of the human evolution to form hominins through bipedalism and the mixed habitat. The feet of the early hominins were still adapted for grasping trees rather than walking for long distances and running fast on the ground. The early hominins lived in the mixed habitat of grassy woodland with patches of denser forest, and freshwater springs. The difficulty of walking in the mixed habitat leads to division of labor for the home specialist group (small children, old people, and mothers with small children, and pregnant women) in the safe forest area and the exploration specialist group (young people without the care of small children) in the dangerous open area. The different tasks, attitudes, and mentalities in different specialist groups produce theory of mind as the ability to attribute different mental states to different specialist groups. (Uniformity of mind instead of theory of mind is for generalists without division of labor). The early Homo species with the open habitat developed theory of mind for hunter specialist group and gatherer specialist group. The middle Homo species with complex stone tools developed theory of mind for the cooperative specialist groups in the large production of complex stone tools. The late Homo species with complex social interaction developed theory of mind for mind reading to enhance cooperation and to detect cheaters in complex social interaction. For religion, the unusually harsh Upper Paleolithic Period developed theory of mind for imaginary specialists in terms of supernatural power, guidance, and comfort. Therefore, the three general types of theory of mind are for specialists in division of labor, mind reading in complex social interaction, and imaginary specialists in imaginary division of labor under harsh conditions. Self-awareness in the mirror self-recognition test is also explained.展开更多
It is generally cousidered that the mantle creep-flow eurtent is the most important internal cause for erustobody evolution. In fact, the Cause, mantle creep-now current takes place just beneath erustobody. Aeeording ...It is generally cousidered that the mantle creep-flow eurtent is the most important internal cause for erustobody evolution. In fact, the Cause, mantle creep-now current takes place just beneath erustobody. Aeeording to the principle that internal causes of a tning determine its development and evolution, a special attetion should be paid to the basic causea of crustobody evolution. Vnder the guidance of the unbalanced self-organization theory, the authors elueidate that the crustobody system is a far-away thermal balaneed system and an open system, and thete are nonlinear interactions between the essentials, positive feedbacks and frequent fluetuation in the erustobody system. Finally, the following conelusions are drawn: the nonlinear interactions in the erustobody system are the basic formation (main internal cause) for erustobody evolution ; Substance and energy gained from surroundings are the basic conditions (main external cause) of crustobody evolution;and the fluctuations theide the erustobody system are the direct induetive cause of its evolution.展开更多
This paper modifies the Farnes’ unifying theory of dark energy and dark matter which are negative-mass, created continuously from the negative-mass universe in the positive-negative mass universe pair. The first modi...This paper modifies the Farnes’ unifying theory of dark energy and dark matter which are negative-mass, created continuously from the negative-mass universe in the positive-negative mass universe pair. The first modification explains that observed dark energy is 68.6%, greater than 50% for the symmetrical positive-negative mass universe pair. This paper starts with the proposed positive-negative-mass 11D universe pair (without kinetic energy) which is transformed into the positive-negative mass 10D universe pair and the external dual gravities as in the Randall-Sundrum model, resulting in the four equal and separate universes consisting of the positive-mass 10D universe, the positive-mass massive external gravity, the negative-mass 10D universe and the negative-mass massive external gravity. The positive-mass 10D universe is transformed into 4D universe (home universe) with kinetic energy through the inflation and the Big Bang to create positive-mass dark matter which is five times of positive-mass baryonic matter. The other three universes without kinetic energy oscillate between 10D and 10D through 4D, resulting in the hidden universes when D > 4 and dark energy when D = 4, which is created continuously to our 4D home universe with the maximum dark energy = 3/4 = 75%. In the second modification to explain dark matter in the CMB, dark matter initially is not repulsive. The condensed baryonic gas at the critical surface density induces dark matter repulsive force to transform dark matter in the region into repulsive dark matter repulsing one another. The calculated percentages of dark energy, dark matter, and baryonic matter are 68.6 (as an input from the observation), 26 and 5.2, respectively, in agreement with observed 68.6, 26.5 and 4.9, respectively, and dark energy started in 4.33 billion years ago in agreement with the observed 4.71 <span style="white-space:nowrap;">±</span> 0.98 billion years ago. In conclusion, the modified Farnes’ unifying theory reinterprets the Farnes’ equations, and is a unifying theory of dark energy, dark matter, and baryonic matter in the positive-negative mass universe pair. The unifying theory explains protogalaxy and galaxy evolutions in agreement with the observations.展开更多
Magicity,or shell closure,plays an important role in our understanding of complex nuclear phenomena.In this work,we employ one of the state-of-the-art density functional theories,the deformed relativistic Hartree-Bogo...Magicity,or shell closure,plays an important role in our understanding of complex nuclear phenomena.In this work,we employ one of the state-of-the-art density functional theories,the deformed relativistic Hartree-Bogoliubov theory in continuum(DRHBc)with the density functional PC-PK1,to investigate the evolution of the N=20,28,50 shell closures in the 20≤Z≤30 region.We show how these three conventional shell closures evolve from the proton drip line to the neutron drip line by studying the charge radii,two-neutron separation energies,two-neutron gaps,quadrupole deformations,and single-particle levels.In particular,we find that in the 21≤Z≤27 region,the N=50 shell closure disappears or becomes quenched,mainly due to the deformation effects.Similarly,both experimental data and theoretical predictions indicate that the N=28 shell closure disappears in the Mn isotopic chain,mainly due to the deformation effects.The DRHBc theory predicts the existence of the N=20 shell closure in the Ca,Sc,and Ti isotopic chains,but the existing data for the Ti isotopes suggest the contrary,and therefore further research is needed.展开更多
Nickel molybdate(NiMoO_(4))attracts superior hydrogen desorption behavior but noticeably poor for efficiently driving the hydrogen evolution reaction(HER)in alkaline media due to the sluggish water dissociation step.H...Nickel molybdate(NiMoO_(4))attracts superior hydrogen desorption behavior but noticeably poor for efficiently driving the hydrogen evolution reaction(HER)in alkaline media due to the sluggish water dissociation step.Herein,we successfully accelerate the water dissociation kinetics of NiMoO_(4)for prominent HER catalytic properties via simultaneous in situ interfacial engineering with molybdenum dioxide(MoO_(2))and doping with phosphorus(P).The as-synthesized P-doped NiMoO_(4)/MoO_(2)heterostructure nanorods exhibit outstanding HER performance with an extraordinary low overpotential of-23 m V at a current density of 10 m A cm^(-2),which is highly comparable to the performance of the state-of-art Pt/C coated on nickel foam(NF)catalyst.The density functional theory(DFT)analysis reveals the enhanced performance is attributed to the formation of MoO_(2)during the in situ epitaxial growth that substantially reduces the energy barrier of the Volmer pathway,and the introduction of P that provides efficient hydrogen desorption of Ni MoO_(2).This present work creates valuable insight into the utilization of interfacial and doping systems for hydrogen evolution catalysis and beyond.展开更多
In the semiconductor-based photocatalysts for overall water splitting, loading proper cocatalysts play a crucial role in enhancing the photocatalytic activity. In this work, we have chosen Ni_n/α-Ga_2O_3 as a model a...In the semiconductor-based photocatalysts for overall water splitting, loading proper cocatalysts play a crucial role in enhancing the photocatalytic activity. In this work, we have chosen Ni_n/α-Ga_2O_3 as a model and provided detailed density functional theory calculations to investigate the function of cocatalysts in hydrogen evolution reaction(HER). We have studied the formation and stability of Ni_n(n = 1–4) cluster on two stable surfaces of α-Ga_2O_3(001) and(012). In a Ni_n/α-Ga_2O_3 system, as the Ni 3d states well overlap with O and Ga states, the excited electrons transferred from Ga to Ni may participate in HER. We theoretically predict that introduction of Nincluster on(012) surface can elevate the Fermi level toward the conduction band, which is favorable for the occurrence of HER. Electrochemical computations are used to explore the mechanism of HER. It is found that, in most of Ni_n/α-Ga_2O_3 systems, the active sites of HER are on Ni_n clusters. Loading Ni_n clusters not only importantly reduces the Gibbs free energy of HER but also improves the reaction activity of surface O and Ga sites in HER. Our calculations reasonably explain the experimental observation on significant enhancement of activity for generating hydrogen after loading nickel oxide cocatalysts.展开更多
The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity...The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.展开更多
The surface morphology of Ti-Mg supported catalyst and the polyethylene particles are studied using scanning electron microscope(SEM) technology.The results show that either the catalyst's surface or polymer parti...The surface morphology of Ti-Mg supported catalyst and the polyethylene particles are studied using scanning electron microscope(SEM) technology.The results show that either the catalyst's surface or polymer particle's surface is irregular and has fractal characteristics,which can be described by fractal parameter.The more interesting discovery is that the surface fractal dimension values of the polymer particles vary periodically with the polymerization time.We call this phenomenon fractal evolution,which can be divided into the 'revolution' stage and the 'evolution' stage,And then we present polymerization fractal growing model(PFGM),and successfully describe and /or predict the whole evolving process of the polyethylene particle morphology under the different slurry polymerization(including pre-polymerization) conditions without H2.展开更多
The paper proposes that the four-component structure of political order consists of state, imagination, rule, and accountability whose mental origins are the social brain, theory of mind, the rational brain, and the e...The paper proposes that the four-component structure of political order consists of state, imagination, rule, and accountability whose mental origins are the social brain, theory of mind, the rational brain, and the empirical brain, respectively. The rational brain and the empirical brain are from the thinking brain. This paper posits that in the evolution of political order, the main function of political order is to pacify changed social structure derived from technological revolution. Therefore, the four technological revolutions (the Upper Paleolithic, Agricultural-Bronze, Iron, and Industrial Revolutions) produce the four changed social structures (linked bands, tribe, mega empire, and modern nation, respectively) whose internal conflicts are pacified by the four political revolutions (the imaginative, hierarchical, thinking, bottom-up political revolutions, respectively) to form the four politics (the imaginative egalitarianism, decentralized hierarchical tribalism, centralized top-down thinking, and multilateral bottom-up thinking politics, respectively). In the competitive West originated from Greece and Middle East, the rule of law is the rational rule of competition among competitors, and the accountability of election is the empirical accountability of competition among competitors. In the cooperative East originated from India and China, the rule of relation is the rational rule of cooperation among kin-friends, and the accountability of professional qualification is the empirical accountability of cooperation among kin-friends. For political order, the two viable politics are competitive liberal democracy based on liberty and cooperative well-off democracy (well-off socialism) based on wellbeing. The direction of political order is middle democracy between liberal democracy and well-off democracy based on the multilateral bottom-up thinking politics.展开更多
A common problem in molecular comparative geno- mics is the identification of genes that are under positive, adaptive selection [1]. Such genes are likely to be crucial for speciation, species differentiation, and fun...A common problem in molecular comparative geno- mics is the identification of genes that are under positive, adaptive selection [1]. Such genes are likely to be crucial for speciation, species differentiation, and func- tional specialization. However, discerning the difference between positive selection and relaxation of func- tional constraint can be difficult using current methods. Both processes generally increase the rate of ami- no acid change relative to synonymous changes within coding regions, and unless the amino acid rate is over- whelmingly high across an entire gene, the signature of positive selection can be obscured [2]. Some methodologies do not explicitly determine the difference be- tween a relaxation of functional constraint and positive selection, leaving researchers to determine via other means whether the trajectory of a gene has been specialization or creation of a new function, or removal from the genome via a process of degeneration.展开更多
Non-renewable fossil fuels have led to serious problems such as global warming,environmental pollution,etc.Oxygen electrocatalysis including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)plays a cent...Non-renewable fossil fuels have led to serious problems such as global warming,environmental pollution,etc.Oxygen electrocatalysis including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)plays a central role in clean energy conversion,enabling a number of sustainable processes for future air battery technologies.Fluorine,as the most electronegative element(4.0)not only can induce more efficient regulation for the electronic structure,but also can bring more abundant defects and other novel effects in materials selection and preparation for favorable catalysis with respect to the other nonmetal elements.However,an individual and comprehensive overview of fluorine-containing functional materials for oxygen electrocatalysis field is still blank.Therefore,it is very meaningful to review the recent progresses of fluorine-containing oxygen electrocatalysts.In this review,we first systematically summarize the controllable preparation methods and their possible development directions based on fluorine-containing materials from four preparation methods.Due to the strong electron-withdrawing properties of fluorine,its control of the electronic structure can effectively enhance the oxygen electrocatalytic activity of the materials.In addition,the catalytic enhancement effect of fluorine on carbonbased materials also includes the prevent oxidation and the layer peeling,and realizes the precise atomic control.And the catalytic improvement mechanism of fluorine containing metal-based compounds also includes the hydration of metal site,the crystal transformation,and the oxygen vacancy induction.Then,based on their various dimensions(0D–3D),we also have summarized the advantages of different morphologies on oxygen electrocatalytic performances.Finally,the prospects and possible future researching direction of F-containing oxygen electrocatalysts are presented(e.g.,novel pathways,advanced methods for measurement and simulation,field assistance and multi-functions).The review is considered valuable and helpful in exploring the novel designs and mechanism analyses of advanced fluorine-containing electrocatalysts.展开更多
To unify the four known fundamental forces and provide an explanation for the origin and the evolution of the universe are two long-term goals of theoretical physics. Here a “universe collapse model” has been propos...To unify the four known fundamental forces and provide an explanation for the origin and the evolution of the universe are two long-term goals of theoretical physics. Here a “universe collapse model” has been proposed. The universe consists of Matter and No-matter. No-matter is the universal energy that constructs a consistent universe field, presenting a spiral wave motion at the speed of light at the small scale. The partial collapse of the universal energy forms the particles of the universal energy in a variety of sizes, which are called as the elementary particles. These elementary particles form atom and matter, which construct the galaxies. The collapse of the universe field induces the formation of the universe collapse potential (UCP) and universe collapse force (UCF), and the later is represented by four different aspects of the fundamental forces at the large or small scales. The mathematical equation and the derivation of UCP and UCF are described, and possible experimental tests are also suggested. Therefore, this new model may give a novel explanation for the unification of four fundamental forces and the origin and the evolution of the universe.展开更多
Designing multicomponent integration catalysts(MICs)has been a promising strategy for improving electrocatalytic hydrogen evolution reaction(HER)due to the highly active interfaces as well as electronic synergy.Nevert...Designing multicomponent integration catalysts(MICs)has been a promising strategy for improving electrocatalytic hydrogen evolution reaction(HER)due to the highly active interfaces as well as electronic synergy.Nevertheless,many fundamental questions such as their actual active species and the influence on long-term stability remain to be answered.Herein,we present the structural evolution from a pseudotri-component electrocatalyst of nitrogen-doped carbon supported nickel/vanadium nitride/vanadium oxide(Ni-VN-V_(2)O_(3)/NC)nanorods to the heterostructural nickel/vanadium nitride(Ni-VN/NC)nanosheets during chemical or electrochemical processes.The self-reconstructed Ni-VN/NC exhibits a robust stability under alkaline conditions,while maintaining initial efficient HER activity with a low overpotential of 76 mV at the current density of 10 mA cm^(-2).Theoretical calculations and quasi-in-situ spectroscopic technology unveil the redistribution of electrons on the synergistic active interface,which synchronously optimizes the affinities for hydrogen,hydroxide,and water molecules,thereby remarkably accelerating the HER kinetics by reducing the barrier of Volmer step.展开更多
基金Financial support from the National Natural Science Foundation of China(21676216)the Special project of Shaanxi Provincial Education Department(20JC034)+1 种基金GHfund B(202202022563)Hefei Advanced Computing Center。
文摘Rational design of high-performance electrocatalysts for hydrogen evolution reaction(HER)is vital for future renewable energy systems.The incorporation of foreign metal ions into catalysts can be an effective approach to optimize its performance.However,there is a lack of systematic theoretical studies to reveal the quantitative relationships at the electronic level.Here,we develop a multi-level screening methodology to search for highly stable and active dopants for CoP catalysts.The density functional theory(DFT)calculations and symbolic regression(SR)were performed to investigate the relationship between the adsorption free energy(ΔG_(H^(*)))and 10 electronic parameters.The mathematic formulas derived from SR indicate that the difference of work function(ΔΦ)between doped metal and the acceptor plays the most important role in regulatingΔG_(H^(*)),followed by the d-band center(d-BC)of doped system.The descriptor of HER can be expressed asΔG_(H^(*))=1.59×√|0.188ΔΦ+d BC+0.120|1/2-0.166 with a high determination coefficient(R^(2)=0.807).Consistent with the theoretical prediction,experimental results show that the Al-CoP delivers superior electrocatalytic HER activity with a low overpotential of75 m V to drive a current density of 10 mA cm^(-2),while the overpotentials for undoped CoP,Mo-CoP,and V-CoP are 206,134,and 83 m V,respectively.The current work proves that theΔΦis the most significant regulatory parameter ofΔG_(H^(*))for ion-doped electrocatalysts.This finding can drive the discovery of high-performance ion-doped electrocatalysts,which is crucial for electrocatalytic water splitting.
基金Project supported by the Open Research Fund of Computational Physics Key Laboratory of Sichuan Province,Yibin University,China(Grant No.YBXYJSWL-ZD-2020-005)the Student’s Platform for Innovation and Entrepreneurship Training Program,China(Grant No.S202110616084)。
文摘Density functional theory(DFT)is used to calculate the most stable structures of Zr_(n)(n=2-5)clusters as well as the adsorption energy values of Zr_(n)(n=2-5)clusters after adsorbing single water molecule.The results reveal that there is a significant linear relationship between the adsorption energy values and the energy gaps of the Zr_(n)(n=2-5)clusters.Furthermore,the calculations of the reaction paths between Zr_(n)(n=2-5)and single water molecule show that water molecule can react with Zr_(n)(n=2-5)clusters to dissociate,producing hydrogen,and O atoms mix with the clusters to generate Zr_(n)O(n=2-5),all of which are exothermic reactions.According to the released energy,the Zr4 cluster is the most efficient in Zr_(n)(n=2-5)clusters reacting with single water molecule.The natural population analysis(NPA)and density of states(DOS)demonstrate the production of hydrogen and orbital properties in different energy ranges,respectively,jointly forecasting that Zr_(n)O(n=2-5)will probably continue to react with more water molecules.Our findings contribute to better understanding of Zr's chemical reactivity,which can conduce to the development of effective Zr-based catalysts and hydrogen-production methods.
基金supported by the National Research Foundation of Korea (NRF-2022R1C1C1004171)supported by the National Science Foundation (Grant number ACI1548562)。
文摘Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of water electrolysis for sustainable hydrogen production.Despite their excellent OER performance,the structural and electronic properties of LDHs,particularly during the OER process,remain to be poorly understood.In this study,a series of LDH catalysts is investigated through in situ X-ray absorption fine structure analyses and density functional theory(DFT) calculations.Our experimental results reveal that the LDH catalyst with equal amounts of Ni and Fe(NF-LDH) exhibits the highest OER activity and catalytic life span when compared with its counterparts having equal amounts of Ni and Co(NC-LDH)and Ni only(Ni-LDH).The NF-LDH shows a markedly enhanced OER kinetics compared to the NC-LDH and the Ni-LDH,as proven by the lower overpotentials of 180,240,and 310 mV,respectively,and the Tafel slopes of 35.1,43.4,and 62.7 mV dec^(-1),respectively.The DFT calculations demonstrate that the lowest overpotential of the NF-LDH is associated with the active sites located at the edge planes of NF-LDH in contrast to those located at the basal planes of Ni-LDH and NC-LDH.The current study pinpoints the active sites on various LDHs and presents strategies for optimizing the OER performance of the LDH catalysts.
基金Projects(51308073,51378081)supported by the National Natural Science Foundation of ChinaProject(20124316120002)supported by PhD Programs Foundation of Ministry of Education of China+1 种基金Project(12KB02)supported by the Key Laboratory for Safety Control of Bridge Engineering of Ministry of Education of ChinaProject(14JJ3087)supported by the Science Foundation of Hunan Province,China
文摘Utilizing the acoustic emission(AE) technique, an experimental investigation into the damage evolution for steel strand under axial tension was described. The damage evolution model for steel stand relating the damage evolution to acoustic emission parameters was proposed by incorporating the AE rate process theory. The AE monitoring results indicate that damages occur in both elastic and plastic phases of steel strand. In elastic phase, AE signals are mainly sent out from the micro damage due to the surface friction among the wires of steel strand, while in plastic phase, AE signals emitted from the plastic deformation of wires. In addition, the AE cumulative parameters curves closely resemble the loading curve. The AE cumulative parameters curves can well describe the damage evolution process including the damage occurrence and damage development for steel strands. It is concluded that the AE technique is an effective and useful nondestructive technique for evaluating the damage characteristics of steel strand.
文摘Despite almost half a century of research for theory of mind, its evolutionary origin is largely unknown. This paper proposes that the evolutionary origin of theory of mind starts from the beginning of the human evolution to form hominins through bipedalism and the mixed habitat. The feet of the early hominins were still adapted for grasping trees rather than walking for long distances and running fast on the ground. The early hominins lived in the mixed habitat of grassy woodland with patches of denser forest, and freshwater springs. The difficulty of walking in the mixed habitat leads to division of labor for the home specialist group (small children, old people, and mothers with small children, and pregnant women) in the safe forest area and the exploration specialist group (young people without the care of small children) in the dangerous open area. The different tasks, attitudes, and mentalities in different specialist groups produce theory of mind as the ability to attribute different mental states to different specialist groups. (Uniformity of mind instead of theory of mind is for generalists without division of labor). The early Homo species with the open habitat developed theory of mind for hunter specialist group and gatherer specialist group. The middle Homo species with complex stone tools developed theory of mind for the cooperative specialist groups in the large production of complex stone tools. The late Homo species with complex social interaction developed theory of mind for mind reading to enhance cooperation and to detect cheaters in complex social interaction. For religion, the unusually harsh Upper Paleolithic Period developed theory of mind for imaginary specialists in terms of supernatural power, guidance, and comfort. Therefore, the three general types of theory of mind are for specialists in division of labor, mind reading in complex social interaction, and imaginary specialists in imaginary division of labor under harsh conditions. Self-awareness in the mirror self-recognition test is also explained.
文摘It is generally cousidered that the mantle creep-flow eurtent is the most important internal cause for erustobody evolution. In fact, the Cause, mantle creep-now current takes place just beneath erustobody. Aeeording to the principle that internal causes of a tning determine its development and evolution, a special attetion should be paid to the basic causea of crustobody evolution. Vnder the guidance of the unbalanced self-organization theory, the authors elueidate that the crustobody system is a far-away thermal balaneed system and an open system, and thete are nonlinear interactions between the essentials, positive feedbacks and frequent fluetuation in the erustobody system. Finally, the following conelusions are drawn: the nonlinear interactions in the erustobody system are the basic formation (main internal cause) for erustobody evolution ; Substance and energy gained from surroundings are the basic conditions (main external cause) of crustobody evolution;and the fluctuations theide the erustobody system are the direct induetive cause of its evolution.
文摘This paper modifies the Farnes’ unifying theory of dark energy and dark matter which are negative-mass, created continuously from the negative-mass universe in the positive-negative mass universe pair. The first modification explains that observed dark energy is 68.6%, greater than 50% for the symmetrical positive-negative mass universe pair. This paper starts with the proposed positive-negative-mass 11D universe pair (without kinetic energy) which is transformed into the positive-negative mass 10D universe pair and the external dual gravities as in the Randall-Sundrum model, resulting in the four equal and separate universes consisting of the positive-mass 10D universe, the positive-mass massive external gravity, the negative-mass 10D universe and the negative-mass massive external gravity. The positive-mass 10D universe is transformed into 4D universe (home universe) with kinetic energy through the inflation and the Big Bang to create positive-mass dark matter which is five times of positive-mass baryonic matter. The other three universes without kinetic energy oscillate between 10D and 10D through 4D, resulting in the hidden universes when D > 4 and dark energy when D = 4, which is created continuously to our 4D home universe with the maximum dark energy = 3/4 = 75%. In the second modification to explain dark matter in the CMB, dark matter initially is not repulsive. The condensed baryonic gas at the critical surface density induces dark matter repulsive force to transform dark matter in the region into repulsive dark matter repulsing one another. The calculated percentages of dark energy, dark matter, and baryonic matter are 68.6 (as an input from the observation), 26 and 5.2, respectively, in agreement with observed 68.6, 26.5 and 4.9, respectively, and dark energy started in 4.33 billion years ago in agreement with the observed 4.71 <span style="white-space:nowrap;">±</span> 0.98 billion years ago. In conclusion, the modified Farnes’ unifying theory reinterprets the Farnes’ equations, and is a unifying theory of dark energy, dark matter, and baryonic matter in the positive-negative mass universe pair. The unifying theory explains protogalaxy and galaxy evolutions in agreement with the observations.
基金Supported in part by the National Natural Science Foundation of China(NSFC)(11975041,11961141004)Xiang-Xiang Sun is supported in part by NSFC(12205308)the Deutsche Forschungsgemeinschaft(DFG)and NSFC through the funds provided to the Sino-German Collaborative Research Center TRR110"Symmetries and the Emergence of Structure in QCD"(NSFC Grant No.12070131001,DFG Project-ID 196253076)。
文摘Magicity,or shell closure,plays an important role in our understanding of complex nuclear phenomena.In this work,we employ one of the state-of-the-art density functional theories,the deformed relativistic Hartree-Bogoliubov theory in continuum(DRHBc)with the density functional PC-PK1,to investigate the evolution of the N=20,28,50 shell closures in the 20≤Z≤30 region.We show how these three conventional shell closures evolve from the proton drip line to the neutron drip line by studying the charge radii,two-neutron separation energies,two-neutron gaps,quadrupole deformations,and single-particle levels.In particular,we find that in the 21≤Z≤27 region,the N=50 shell closure disappears or becomes quenched,mainly due to the deformation effects.Similarly,both experimental data and theoretical predictions indicate that the N=28 shell closure disappears in the Mn isotopic chain,mainly due to the deformation effects.The DRHBc theory predicts the existence of the N=20 shell closure in the Ca,Sc,and Ti isotopic chains,but the existing data for the Ti isotopes suggest the contrary,and therefore further research is needed.
基金supported by the National Natural Science Foundation of China(21875292 and 51902103)Hunan Provincial Natural Science Foundation(2019JJ50037 and 2021JJ30087)+1 种基金Natural Science Foundation of Guangdong Province(2020A1515010798)the Hunan Joint International Laboratory of Advanced Materials and Technology for Clean Energy(2020CB1007)。
文摘Nickel molybdate(NiMoO_(4))attracts superior hydrogen desorption behavior but noticeably poor for efficiently driving the hydrogen evolution reaction(HER)in alkaline media due to the sluggish water dissociation step.Herein,we successfully accelerate the water dissociation kinetics of NiMoO_(4)for prominent HER catalytic properties via simultaneous in situ interfacial engineering with molybdenum dioxide(MoO_(2))and doping with phosphorus(P).The as-synthesized P-doped NiMoO_(4)/MoO_(2)heterostructure nanorods exhibit outstanding HER performance with an extraordinary low overpotential of-23 m V at a current density of 10 m A cm^(-2),which is highly comparable to the performance of the state-of-art Pt/C coated on nickel foam(NF)catalyst.The density functional theory(DFT)analysis reveals the enhanced performance is attributed to the formation of MoO_(2)during the in situ epitaxial growth that substantially reduces the energy barrier of the Volmer pathway,and the introduction of P that provides efficient hydrogen desorption of Ni MoO_(2).This present work creates valuable insight into the utilization of interfacial and doping systems for hydrogen evolution catalysis and beyond.
基金financially supported by the National Natural Science Foundation of China under Grants 21473183 and 21303079
文摘In the semiconductor-based photocatalysts for overall water splitting, loading proper cocatalysts play a crucial role in enhancing the photocatalytic activity. In this work, we have chosen Ni_n/α-Ga_2O_3 as a model and provided detailed density functional theory calculations to investigate the function of cocatalysts in hydrogen evolution reaction(HER). We have studied the formation and stability of Ni_n(n = 1–4) cluster on two stable surfaces of α-Ga_2O_3(001) and(012). In a Ni_n/α-Ga_2O_3 system, as the Ni 3d states well overlap with O and Ga states, the excited electrons transferred from Ga to Ni may participate in HER. We theoretically predict that introduction of Nincluster on(012) surface can elevate the Fermi level toward the conduction band, which is favorable for the occurrence of HER. Electrochemical computations are used to explore the mechanism of HER. It is found that, in most of Ni_n/α-Ga_2O_3 systems, the active sites of HER are on Ni_n clusters. Loading Ni_n clusters not only importantly reduces the Gibbs free energy of HER but also improves the reaction activity of surface O and Ga sites in HER. Our calculations reasonably explain the experimental observation on significant enhancement of activity for generating hydrogen after loading nickel oxide cocatalysts.
基金Changjiang Scholars Program of the Ministry of Education,Grant/Award Number:Q2018270Outstanding Youth Funding of Anhui Province,Grant/Award Number:OUFAH 1908085J10+2 种基金Jiangsu Students'Innovation and Entrepreneurship Training Program,Grant/Award Number:202111117079YNatural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200044National Natural Science Foundation of China,Grant/Award Numbers:NSFC 21671004,NSFC 21975001,NSFC U1904215。
文摘The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.
基金Supported by the National Natural Science Foundation of China (No. 29706010, No. 20203016).
文摘The surface morphology of Ti-Mg supported catalyst and the polyethylene particles are studied using scanning electron microscope(SEM) technology.The results show that either the catalyst's surface or polymer particle's surface is irregular and has fractal characteristics,which can be described by fractal parameter.The more interesting discovery is that the surface fractal dimension values of the polymer particles vary periodically with the polymerization time.We call this phenomenon fractal evolution,which can be divided into the 'revolution' stage and the 'evolution' stage,And then we present polymerization fractal growing model(PFGM),and successfully describe and /or predict the whole evolving process of the polyethylene particle morphology under the different slurry polymerization(including pre-polymerization) conditions without H2.
文摘The paper proposes that the four-component structure of political order consists of state, imagination, rule, and accountability whose mental origins are the social brain, theory of mind, the rational brain, and the empirical brain, respectively. The rational brain and the empirical brain are from the thinking brain. This paper posits that in the evolution of political order, the main function of political order is to pacify changed social structure derived from technological revolution. Therefore, the four technological revolutions (the Upper Paleolithic, Agricultural-Bronze, Iron, and Industrial Revolutions) produce the four changed social structures (linked bands, tribe, mega empire, and modern nation, respectively) whose internal conflicts are pacified by the four political revolutions (the imaginative, hierarchical, thinking, bottom-up political revolutions, respectively) to form the four politics (the imaginative egalitarianism, decentralized hierarchical tribalism, centralized top-down thinking, and multilateral bottom-up thinking politics, respectively). In the competitive West originated from Greece and Middle East, the rule of law is the rational rule of competition among competitors, and the accountability of election is the empirical accountability of competition among competitors. In the cooperative East originated from India and China, the rule of relation is the rational rule of cooperation among kin-friends, and the accountability of professional qualification is the empirical accountability of cooperation among kin-friends. For political order, the two viable politics are competitive liberal democracy based on liberty and cooperative well-off democracy (well-off socialism) based on wellbeing. The direction of political order is middle democracy between liberal democracy and well-off democracy based on the multilateral bottom-up thinking politics.
文摘A common problem in molecular comparative geno- mics is the identification of genes that are under positive, adaptive selection [1]. Such genes are likely to be crucial for speciation, species differentiation, and func- tional specialization. However, discerning the difference between positive selection and relaxation of func- tional constraint can be difficult using current methods. Both processes generally increase the rate of ami- no acid change relative to synonymous changes within coding regions, and unless the amino acid rate is over- whelmingly high across an entire gene, the signature of positive selection can be obscured [2]. Some methodologies do not explicitly determine the difference be- tween a relaxation of functional constraint and positive selection, leaving researchers to determine via other means whether the trajectory of a gene has been specialization or creation of a new function, or removal from the genome via a process of degeneration.
基金supported by the National Natural Science Foundation of China,China(52203066,51973157,51673148 and 51678411)the Science and Technology Plans of Tianjin,China(19PTSYJC00010)+3 种基金China Postdoctoral Science Foundation Grant,China(2019M651047)the Tianjin Research Innovation Project for Postgraduate Students,China(2020YJSB062)the Tianjin Municipal College Student’Innovation And Entrepreneurship Training Program,China(202110058052)the National Innovation and Entrepreneurship Training Program for College Students,China(202110058017)。
文摘Non-renewable fossil fuels have led to serious problems such as global warming,environmental pollution,etc.Oxygen electrocatalysis including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)plays a central role in clean energy conversion,enabling a number of sustainable processes for future air battery technologies.Fluorine,as the most electronegative element(4.0)not only can induce more efficient regulation for the electronic structure,but also can bring more abundant defects and other novel effects in materials selection and preparation for favorable catalysis with respect to the other nonmetal elements.However,an individual and comprehensive overview of fluorine-containing functional materials for oxygen electrocatalysis field is still blank.Therefore,it is very meaningful to review the recent progresses of fluorine-containing oxygen electrocatalysts.In this review,we first systematically summarize the controllable preparation methods and their possible development directions based on fluorine-containing materials from four preparation methods.Due to the strong electron-withdrawing properties of fluorine,its control of the electronic structure can effectively enhance the oxygen electrocatalytic activity of the materials.In addition,the catalytic enhancement effect of fluorine on carbonbased materials also includes the prevent oxidation and the layer peeling,and realizes the precise atomic control.And the catalytic improvement mechanism of fluorine containing metal-based compounds also includes the hydration of metal site,the crystal transformation,and the oxygen vacancy induction.Then,based on their various dimensions(0D–3D),we also have summarized the advantages of different morphologies on oxygen electrocatalytic performances.Finally,the prospects and possible future researching direction of F-containing oxygen electrocatalysts are presented(e.g.,novel pathways,advanced methods for measurement and simulation,field assistance and multi-functions).The review is considered valuable and helpful in exploring the novel designs and mechanism analyses of advanced fluorine-containing electrocatalysts.
文摘To unify the four known fundamental forces and provide an explanation for the origin and the evolution of the universe are two long-term goals of theoretical physics. Here a “universe collapse model” has been proposed. The universe consists of Matter and No-matter. No-matter is the universal energy that constructs a consistent universe field, presenting a spiral wave motion at the speed of light at the small scale. The partial collapse of the universal energy forms the particles of the universal energy in a variety of sizes, which are called as the elementary particles. These elementary particles form atom and matter, which construct the galaxies. The collapse of the universe field induces the formation of the universe collapse potential (UCP) and universe collapse force (UCF), and the later is represented by four different aspects of the fundamental forces at the large or small scales. The mathematical equation and the derivation of UCP and UCF are described, and possible experimental tests are also suggested. Therefore, this new model may give a novel explanation for the unification of four fundamental forces and the origin and the evolution of the universe.
基金supported by the National Natural Science Foundation of China(21901089,21901088,22161021 and 91622105)the Jiangxi Provincial Department of Science and Technology(20192BBEL50017,20172BCB22008 and 20192ACB20013)+1 种基金the support of Jiangxi Province(jxsq2018106041)the‘‘Young Elite Scientists Sponsorship Program”by CAST。
文摘Designing multicomponent integration catalysts(MICs)has been a promising strategy for improving electrocatalytic hydrogen evolution reaction(HER)due to the highly active interfaces as well as electronic synergy.Nevertheless,many fundamental questions such as their actual active species and the influence on long-term stability remain to be answered.Herein,we present the structural evolution from a pseudotri-component electrocatalyst of nitrogen-doped carbon supported nickel/vanadium nitride/vanadium oxide(Ni-VN-V_(2)O_(3)/NC)nanorods to the heterostructural nickel/vanadium nitride(Ni-VN/NC)nanosheets during chemical or electrochemical processes.The self-reconstructed Ni-VN/NC exhibits a robust stability under alkaline conditions,while maintaining initial efficient HER activity with a low overpotential of 76 mV at the current density of 10 mA cm^(-2).Theoretical calculations and quasi-in-situ spectroscopic technology unveil the redistribution of electrons on the synergistic active interface,which synchronously optimizes the affinities for hydrogen,hydroxide,and water molecules,thereby remarkably accelerating the HER kinetics by reducing the barrier of Volmer step.