This paper investigates the verb valency structure of English that is used by English as Foreign Language(EFL)learners from a corpus-driven perspective.Specifically,it focuses on the usage of the verbs“suggest”and“...This paper investigates the verb valency structure of English that is used by English as Foreign Language(EFL)learners from a corpus-driven perspective.Specifically,it focuses on the usage of the verbs“suggest”and“advise”in a selected corpus.By analyzing a sample of written and spoken texts,this study attempts to investigate the similarities and differences in the patterns of verb valency between native English speakers and Chinese EFL learners.The findings of this research can contribute to a better understanding of the challenges faced by Chinese EFL learners in acquiring accurate verb valency structures and provide insights for language teachers in designing effective pedagogical approaches.展开更多
The relationship between bond valence and bond covalency in RMn2O5 (R = La, Pr, Nd.Sm, Eu) has been investigated by a semiempirical method. This method is the generalization of thedielectric description theory of Phil...The relationship between bond valence and bond covalency in RMn2O5 (R = La, Pr, Nd.Sm, Eu) has been investigated by a semiempirical method. This method is the generalization of thedielectric description theory of Phillips. Van Vechten, Levine and Tanaka scheme. The resultsindicate that larger valences usually result in higher bond covalencies, in good agreement with thepoint that the excess charge in the bonding region is the origin of formation of bond covalency.Other factors, such as oxidation state of elements, only make a small contribution to bondcovalency.展开更多
In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond d...In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.展开更多
Change in valency of Nb-oxide in MnO-SiO_2-Nb_2O_5 system was studied with the electrochemical method using ZrO_2 as the solid electrolyte.Thermodynamic analysis has shown that the only possible reaction that could ta...Change in valency of Nb-oxide in MnO-SiO_2-Nb_2O_5 system was studied with the electrochemical method using ZrO_2 as the solid electrolyte.Thermodynamic analysis has shown that the only possible reaction that could take place at the working elec- trode is:2(Nb_2O_5)=2(Nb_2O_4)+O_2 with the a_0 values experimentally evaluated,values of a Nb_2O:/a Nb_2O:were calculated and isoactivity-ratio curves drawn in MnO-SiO_2-Nb_2O_5 triangles at 1418 and 1585K.The simultaneous existence of tetra-and penta-valent Nb mineral constituents in industrial Nb-bearing slags was thus verified experimentally.展开更多
The present paper focuses on a descriptive method of valency-increasing devices in five South Ethio-Semitic languages(Amharic,Harari,Kɨstane,Məsqan,and Endəgaɲ).The five languages were selected for two reasons.The fir...The present paper focuses on a descriptive method of valency-increasing devices in five South Ethio-Semitic languages(Amharic,Harari,Kɨstane,Məsqan,and Endəgaɲ).The five languages were selected for two reasons.The first reason is that conducting a valency study on all South Ethio-Semitic languages would have been impossible.With limited resources and time,it will prove difficult to cover all languages.The second reason is that,except for Amharic,these languages are known for being the least studied.Most of them even lack sufficient recording and description.So this research needs to choose the representative language in each branch.As a result,no explicit theoretical framework is followed;data analysis is guided solely by a descriptive perspective.The study’s data was gathered by consulting native speakers via elicitation.Valency has been considered as both a semantic and syntactic notion.As a semantic notion,it is used to refer to the participants in an event;as a syntactic notion,it is used to indicate the number of arguments in a construction.There are different types of transitivity classes of verbs in the South Ethio-Semitic Language,which is spoken in Ethiopia:intransitive,transitive,and ditransitive.Apart from these,there are verbs that can be used both intransitively and transitively.The facts that provide clear evidence for grammatical relations in South Ethio-Semitic languages are crucial to the study of the concept of valency-increasing devices.As is the case in many languages,South Ethio-Semitic languages possess morphosyntactic means through which the valency of verbs can be adjusted.The application of these morphosyntactic processes decreases or increases the valency of verbs.This article looks at valency-increasing devices in Causative and Applicative South Ethio-Semitic languages.展开更多
Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(...Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(CO_(2)).With a maximal EDA conversion of 82%and EU selectivity of 99%at 160℃ for 2 h,Mn_(2)O_(3) catalysts had the best catalytic activity among them,which was superior to the reported catalysts.In the following order:Mn_(2)O_(3)>MnO_(2)>Mn_(3)O_(4),the catalytic activity for the synthesis of EU from CO_(2) and EDA decreased.Further characterization showed the Mn_(2)O_(3) catalyst possessed a greater Mn^(3+)/Mn4+ratio and more surface oxygen vacancies than the MnO_(2) and Mn_(3)O_(4),which improved its capacity to adsorb and activate CO_(2) and EDA.After four recycling runs,the EDA conversion slightly declined from 82%to 56%on Mn_(2)O_(3) catalyst,while no obvious change in EU selectivity was observed.The loss of surface Ov contents and Mn^(3+)proportion were concluded as main reasons for the decrease in catalytic activity over Mn_(2)O_(3) catalyst.This work demonstrated a metal oxide catalyst that was efficient in producing EU from CO_(2) and EDA.展开更多
The electronic transition emission of Eu<sup>2+</sup> is in close relationship with the crystal-field environment and chemical bond property of Eu<sup>2+</sup> in hosts. The stronger the crysta...The electronic transition emission of Eu<sup>2+</sup> is in close relationship with the crystal-field environment and chemical bond property of Eu<sup>2+</sup> in hosts. The stronger the crystal-field intensity is, the larger the splitting of the 5d level is and the more favourable the broad band emission of d-f transition is. The smaller the covalency is, the smaller the展开更多
Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as high...Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as highly efficient photocatalysts for hydrogen evolution.However,their applications in photocatalytic hydrogen evolution(PHE)are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored.Herein,we excavated a novel NOS photocatalyst of(Me_(2)NH_(2))_(6)In_(10)S_(18)(MIS)with a three-dimensional(3D)structure,and successfully incorporated divalent Co(Ⅱ)and metal Co(0)into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions.As the introduced Co(0)allows for more efficient light utilization and adroitly surficial hydrogen desorption,and meanwhile acts as the‘electron pump’for rapid charge transfer,Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis.With the prolonging of illumination,metal Co(0)gradually escapes from MIS framework,resulting in the decline of PHE performance.By stark contrast,the incorporated Co(Ⅱ)can establish a strong interaction with MIS framework,and simultaneously capture photogenerated electrons from MIS to produce Co(0),which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers.Thus,Co(Ⅱ)-modified MIS exhibits a robust and highly stable PHE activity of~4944μmol/g/h during the long-term photocatalytic reactions,surpassing most of the previously reported In–S framework photocatalysts.This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts,and sheds light on the design of vip confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.展开更多
The recently established theory has built clear connections between hardness and toughness and electron structure involving both valence electron concentration(VEC)and core electron count(CEC)in transition metal nitri...The recently established theory has built clear connections between hardness and toughness and electron structure involving both valence electron concentration(VEC)and core electron count(CEC)in transition metal nitride(TMN)ceramics.However,the underlying deformation mechanisms remain unclear.Herein,we conduct in-depth analysis on microstructure evolution during deformation of the high VEC-CEC solution TiMoN coatings having desired combination of high hardness and toughness.The effects of solid solution,preferred orientation linked with symbiotic compressive stress,grain size and dislocations are systematically discussed.We discover that numerous dislocations have been implanted into the nanocrystals of the TiMoN coating during the high-ionization arc deposition.Using two-beam bright-field imaging,we count the dislocation density and confirm occurrence of dislocation multiplication to form effective plastic deformation,which contributes to significant strain hardening,comparable to solid solution hardening,fine-grain hardening and compressive stress hardening.The improved dislocation activities also play a crucial role in enhancing the toughness by providing extra energy dissipation paths.This work gains new insights into the origins of mechanical properties of ceramic coatings and possibility to tune them via defects.展开更多
Graphene-metal based materials have been utilized in lithium-sulfur(Li–S)batteries owing to their integrated functionalities thus far.However,their synthesis has predominantly relied on wet-chemistry routes,which lim...Graphene-metal based materials have been utilized in lithium-sulfur(Li–S)batteries owing to their integrated functionalities thus far.However,their synthesis has predominantly relied on wet-chemistry routes,which limited their practical activity in Li–S reaction systems.In this study,we introduce a chemical vapor deposition(CVD)-triggered dry-chemistry approach for the preparation of graphene-cobalt(Co)based catalysts.The versatile CVD technique provides a dry and controllable reaction environment,effectively pledging the compact and clean catalytic interfaces between graphene and Co-based components.Additionally,programmed reactions introduce defects such as vacancies and nitrogen heteroatoms into the catalysts.Notably,the graphene layer number and Co valence state can be delicately manipulated by altering the CVD reaction temperature.Specifically,few-layer graphene wrapped Co/Co_(3)O_(4)(FGr-Co/Co_(3)O_(4))prepared at 450 ℃ shows higher catalytic activity than the multi-layer graphene wrapped Co/CoO(MGr-Co/CoO)synthesized at 550 ℃,attributed to its comprehensive control of clean interface,valence distribution range and defects.Leveraging these advantages,the battery with FGr-Co/Co_(3)O_(4)shows favorable working stability with a degradation rate of only 0.08%over 500 cycles at 1.0 C.Furthermore,under an elevated sulfur loading of 6.1 mg cm^(–2),the battery harvests a remarkable areal capacity of 5.9 mA h cm^(–2)along with stable cyclic operation.展开更多
In this work,we proposed a method to enhance the magnetic properties of(Nd,Ce)-Fe-B magnets with Ce/TRE ratios below 25 wt%by introducing a moderate amount of La elements.The segregation behavior of La elements toward...In this work,we proposed a method to enhance the magnetic properties of(Nd,Ce)-Fe-B magnets with Ce/TRE ratios below 25 wt%by introducing a moderate amount of La elements.The segregation behavior of La elements towards grain boundaries(GBs)was utilized to optimize the GB phase structure.Incorporation of La atoms into the main phase induces lattice expansion,leading to an increased formation of Ce^(3+)ions with enhanced magnetic moments.Comparative analysis with the original magnet(La/Ce=0 wt%)demonstrates that the magnet with a La/Ce ratio of 10 wt%exhibits improvements of 0.3%in remanence,12.6%in coercivity,and 0.6%in maximum energy produ ct.These results underscore that the moderate addition of La elements enhances the fluidity of the rare earth-rich phase and optimizes the distribution of lamellar GB,consequently reinforcing the magnetic isolation effect.Furthermore,the promotion of the transformation from Ce^(4+)to Ce^(3+)ons contributes to the comprehensive enhancement of the magnetic properties.This research offers a novel strategy for fabricating high-performance and resource-e fficient sintered magnets based on LaCe alloys.展开更多
Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electr...Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electron numbers between single atoms and adsorbed intermediates(O,N,C,and H)in MXene-anchored SACs(M-Ti_(2)C/M-Ti_(2)CO_(2)).The density functional theory results demonstrated that the sum of the valence electron number(VM)of the interface-doped metal and the valence electron number(VA)of the adsorbed intermediates in M-Ti_(2)C followed the 10-valence electron matching law.Furthermore,based on the 10-valence electron matching law,we deduced that the sum of the valence electron number(k)and VMfor the molecular adsorption intermediate interactions in M-Ti_(2)CO_(2)adhered to the 11-valence electron matching law.Electrostatic repulsion between the interface electrons in M-Ti_(2)CO_(2)and H_(2)O weakened the adsorption of intermediates,Furthermore,we applied the 11-valence electron matching law to guide the design of catalysts for nitrogen reduction reaction,specifically for N_(2)→NNH conversion,in the MTi_(2)CO_(2)structure.The sure independence screening and sparsifying operator algorithm was used to fit a simple three-dimensional descriptor of the adsorbate(R_(2)up to 0.970)for catalyst design.Our study introduced a valence electron matching principle between doped metals(single atoms)and adsorbed intermediates(atomic and molecular)for MXene-based catalysts,providing new insights into the design of high-performance SACs.展开更多
The capacity to predict X-ray transition and K-edge energies in dense finite-temperatur plasmas with high precision is of primary importance for atomic physics of matter under extreme conditions.The dual characteristi...The capacity to predict X-ray transition and K-edge energies in dense finite-temperatur plasmas with high precision is of primary importance for atomic physics of matter under extreme conditions.The dual characteristics of bound and continuum states in dense matter are modeled by a valence-band-like structure in a generalized ion-sphere approach with states that are either bound,free,or mixed.The self-consistent combination of this model with the Dirac wave equations of multielectron bound states allows one to fully respect the Pauli principle and to take into account the exact nonlocal exchange terms.The generalized method allows very high precision without implication of calibration shifts and scaling parameters and therefore has predictive power.This leads to new insights in the analysis of various data.The simple ionization model representing the K-edge is generalized to excitation–ionization phenomena resulting in an advanced interpretation of ionization depression data in near-solid-density plasmas.The model predicts scaling relations along the isoelectronic sequences and the existence of bound M-states that are in excellent agreement with experimental data,whereas other methods have failed.The application to unexplained data from compound materials also gives good agreement without the need to invoke any additional assumptions in the generalized model,whereas other methods have lacked consistency.展开更多
The mechanical,thermodynamic properties and electrical conductivities of L1_(2)-Al_(3)X(X=Zr,Sc,Er,Yb,Hf)structural phases in aluminum conductors were investigated through a first-principles study.The results demonstr...The mechanical,thermodynamic properties and electrical conductivities of L1_(2)-Al_(3)X(X=Zr,Sc,Er,Yb,Hf)structural phases in aluminum conductors were investigated through a first-principles study.The results demonstrate that all structural phases have good alloy-forming ability and structural stability,where Al_(3)Zr is the most superior.Al_(3)Zr,Al_(3)Hf and Al_(3)Sc have enhanced shear and deformation resistance in comparison to other phases.Within the temperature range of 200−600 K,Al_(3)Er and Al_(3)Yb possess the greatest thermodynamic stability,followed by Al_(3)Hf,Al_(3)Zr and Al_(3)Sc.Al_(3)Er and Al_(3)Yb have higher thermodynamic stability than Al_(3)Hf,Al_(3)Zr and Al_(3)Sc.All structural phases exhibit substantial metallic properties,indicating their good electrical conductivity.The electrical conductivities of Al_(3)Hf and Al_(3)Zr are higher than those of Al_(3)Er,Al_(3)Yb and Al_(3)Sc.The covalent bond properties in Al_(3)Sc,Al_(3)Er and Al_(3)Yb enhance the hardness,brittleness and thermodynamic stability of the structural phase.The thermodynamic stability of Al_(3)Sc is significantly reduced by ionic bonds.展开更多
Herein,we established a Zn_(3)(OH)_(2)(V_(2)O_(7))(H_(2)O)_(2)/V-Zn(O,S)Z-scheme heterojunction labeled ZnVO/V-Zn(O,S)with a heterovalent V^(4+)/V^(5+)states and oxygen vacancies in both phases via a one-step in-situ ...Herein,we established a Zn_(3)(OH)_(2)(V_(2)O_(7))(H_(2)O)_(2)/V-Zn(O,S)Z-scheme heterojunction labeled ZnVO/V-Zn(O,S)with a heterovalent V^(4+)/V^(5+)states and oxygen vacancies in both phases via a one-step in-situ hydrolysis method.The NaBH_(4) regulated the ZnVO/V-Zn(O,S)-3 with rich Vo and suitable n(V^(4+))/n(V^(5+))ratio achieved an excellent photocatalytic nitrogen fixation activity of 301.7μmol/(g×h)and apparent quantum efficiency of 1.148%at 420 nm without any sacrificial agent,which is 11 times than that of V-Zn(O,S).The Vo acts as the active site to trap and activate N_(2) molecules and to trap and activate H_(2)O to produce the H for N_(2) molecules photocatalytic reduction.The rich Vo defects can also reduce the competitive adsorption of H_(2)O and N_(2) molecules on the surface active site of the catalyst.The heterovalent vanadium states act as the photogenerated electrons,quickly hopping between V^(4+)and V^(5+)to transfer for the photocatalytic N_(2) reduction reaction.Additionally,the Z-scheme heterojunction effectively minimizes photogenerated carrier recombination.These synergistic effects collectively boost the photocatalytic nitrogen fixation activity.This study provides a practical method for designing Z-scheme heterojunctions for efficient photocatalytic N_(2) fixation under mild conditions.展开更多
The influence of bond valence on bond covalence in Lal-xCaxCrO3(x = 0.0, 0.1, 0.2, 0.3) has been studied by using semi empirical method. This method is the extortion of the dialectic description theory proposed by Phi...The influence of bond valence on bond covalence in Lal-xCaxCrO3(x = 0.0, 0.1, 0.2, 0.3) has been studied by using semi empirical method. This method is the extortion of the dialectic description theory proposed by Phillips, Van Vetches, Levine and Tanaka (PVLT). In the calculation of bond valence, two schemes were adopted. The first is the equal-valence scheme, and the second is Bond Valence Sums (BVS) scheme. Bath schemes suggest that for the title compound bond covalence be mainly influenced by bond valence, and insensitive to the Ca doping level. Generally speaking, larger bond valences usually result in higher bond covalence's.展开更多
Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption...Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption and waste gas emissions.To address this,electrocatalytic nitric oxide reduction reaction(NORR)has emerged as a promising strategy to bridge NH3consumption to NH3production,harnessing renewable electricity for a sustainable future.Copper(Cu)stands out as a prominent electrocatalyst for NO reduction,given its exceptional NH3yield and selectivity.However,a crucial aspect that remains insufficiently explored is the effects of morphology and valence states of Cu on the NORR performance.In this investigation,we synthesized CuO nanowires(CuO-NF)and Cu nanocubes(Cu-NF)as cathodes through an in situ growth method.Remarkably,CuO-NF exhibited an impressive NH3yield of 0.50±0.02 mg cm^(-2)h^(-1)at-0.6 V vs.reversible hydrogen electrode(RHE)with faradaic efficiency of29,68%±1,35%,surpassing that of Cu-NF(0.17±0.01 mg cm^(-2)h^(-1),16.18%±1.40%).Throughout the electroreduction process,secondary cubes were generated on the CuO-NF surface,preserving their nanosheet cluster morphology,sustained by an abundant supply of subsurface oxygen(s-O)even after an extended duration of 10 h,until s-O depletion ensued.Conversely,Cu-NF exhibited inadequate s-O content,leading to rapid crystal collapse within the same timeframe.The distinctive current-potential relationship,akin to a volcano-type curve,was attributed to distinct NO hydrogenation mechanisms.Further Tafel analysis revealed the exchange current density(i0)and standard heterogeneous rate constant(k0)for CuO-NF,yielding 3.44×10^(-6)A cm^(-2)and 3.77×10^(-6)cm^(-2)s^(-1)when NORR was driven by overpotentials.These findings revealed the potential of CuO-NF for NO reduction and provided insights into the intricate interplay between crystal morphology,valence states,and electrochemical performance.展开更多
Band convergence is considered to be a strategy with clear benefits for thermoelectric performance,generally favoring the co-optimization of conductivity and Seebeck coefficients,and the conventional means include ele...Band convergence is considered to be a strategy with clear benefits for thermoelectric performance,generally favoring the co-optimization of conductivity and Seebeck coefficients,and the conventional means include elemental filling to regulate the band.However,the influence of the most electronegative fluorine on the CoSb_(3) band remains unclear.We carry out density-functional-theory calculations and show that the valence band maximum gradually shifts downward with the increase of fluorine filling,lastly the valence band maximum converges to the highly degenerated secondary valence bands in fluorine-filled skutterudites.展开更多
Cu^(+)-doped alkali borosilicate glasses with different Na_(2)O contents were prepared by the melting method,and the effects of different R values(R=Na_(2)O/B_(2)O_(3))on the structure,ion presence state and luminesce...Cu^(+)-doped alkali borosilicate glasses with different Na_(2)O contents were prepared by the melting method,and the effects of different R values(R=Na_(2)O/B_(2)O_(3))on the structure,ion presence state and luminescence properties of Cu^(+)-doped alkali borosilicate glasses were investigated.The analysis by FT-IR and Raman spectroscopy shows that,with the increase of R value of the glass,the[BO_(3)]in the structure of Cu^(+)-doped alkali borosilicate glass transforms into[BO_(4)]and the number of non-bridging oxygen in the glass network appears to be slightly increased.The absorption spectra and EPR analysis reveal that the Cu^(+)content in the glass gradually decreases and the Cu^(2+)content gradually increases as the R value of the glass increases.XPS and PL tests further indicate that the transformation of the octahedral coordination structure of Cu^(+)to the octahedral coordination structure of Cu^(2+)and the cubic coordination structure of Cu^(+)occurs in the glass as the R value of the glass increases.This transformation can effectively reduce the concentration quenching phenomenon of Cu^(+)and improve the fluorescence luminescence intensity of the glass samples.Meanwhile,the samples were found to have luminescence tunability as well as good thermal stability.展开更多
文摘This paper investigates the verb valency structure of English that is used by English as Foreign Language(EFL)learners from a corpus-driven perspective.Specifically,it focuses on the usage of the verbs“suggest”and“advise”in a selected corpus.By analyzing a sample of written and spoken texts,this study attempts to investigate the similarities and differences in the patterns of verb valency between native English speakers and Chinese EFL learners.The findings of this research can contribute to a better understanding of the challenges faced by Chinese EFL learners in acquiring accurate verb valency structures and provide insights for language teachers in designing effective pedagogical approaches.
文摘The relationship between bond valence and bond covalency in RMn2O5 (R = La, Pr, Nd.Sm, Eu) has been investigated by a semiempirical method. This method is the generalization of thedielectric description theory of Phillips. Van Vechten, Levine and Tanaka scheme. The resultsindicate that larger valences usually result in higher bond covalencies, in good agreement with thepoint that the excess charge in the bonding region is the origin of formation of bond covalency.Other factors, such as oxidation state of elements, only make a small contribution to bondcovalency.
文摘In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.
文摘Change in valency of Nb-oxide in MnO-SiO_2-Nb_2O_5 system was studied with the electrochemical method using ZrO_2 as the solid electrolyte.Thermodynamic analysis has shown that the only possible reaction that could take place at the working elec- trode is:2(Nb_2O_5)=2(Nb_2O_4)+O_2 with the a_0 values experimentally evaluated,values of a Nb_2O:/a Nb_2O:were calculated and isoactivity-ratio curves drawn in MnO-SiO_2-Nb_2O_5 triangles at 1418 and 1585K.The simultaneous existence of tetra-and penta-valent Nb mineral constituents in industrial Nb-bearing slags was thus verified experimentally.
文摘The present paper focuses on a descriptive method of valency-increasing devices in five South Ethio-Semitic languages(Amharic,Harari,Kɨstane,Məsqan,and Endəgaɲ).The five languages were selected for two reasons.The first reason is that conducting a valency study on all South Ethio-Semitic languages would have been impossible.With limited resources and time,it will prove difficult to cover all languages.The second reason is that,except for Amharic,these languages are known for being the least studied.Most of them even lack sufficient recording and description.So this research needs to choose the representative language in each branch.As a result,no explicit theoretical framework is followed;data analysis is guided solely by a descriptive perspective.The study’s data was gathered by consulting native speakers via elicitation.Valency has been considered as both a semantic and syntactic notion.As a semantic notion,it is used to refer to the participants in an event;as a syntactic notion,it is used to indicate the number of arguments in a construction.There are different types of transitivity classes of verbs in the South Ethio-Semitic Language,which is spoken in Ethiopia:intransitive,transitive,and ditransitive.Apart from these,there are verbs that can be used both intransitively and transitively.The facts that provide clear evidence for grammatical relations in South Ethio-Semitic languages are crucial to the study of the concept of valency-increasing devices.As is the case in many languages,South Ethio-Semitic languages possess morphosyntactic means through which the valency of verbs can be adjusted.The application of these morphosyntactic processes decreases or increases the valency of verbs.This article looks at valency-increasing devices in Causative and Applicative South Ethio-Semitic languages.
基金supported by the National Natural Science Foundation of China(No.22278041)the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(No.2022-K78)+1 种基金Jiangsu Province Key Laboratory of Fine Petrochemical Engineering(No.KF2107)the Advanced Catalysis and Green Manufacturing Collab-orative Innovation Center(No.ACGM2022-10-07)。
文摘Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(CO_(2)).With a maximal EDA conversion of 82%and EU selectivity of 99%at 160℃ for 2 h,Mn_(2)O_(3) catalysts had the best catalytic activity among them,which was superior to the reported catalysts.In the following order:Mn_(2)O_(3)>MnO_(2)>Mn_(3)O_(4),the catalytic activity for the synthesis of EU from CO_(2) and EDA decreased.Further characterization showed the Mn_(2)O_(3) catalyst possessed a greater Mn^(3+)/Mn4+ratio and more surface oxygen vacancies than the MnO_(2) and Mn_(3)O_(4),which improved its capacity to adsorb and activate CO_(2) and EDA.After four recycling runs,the EDA conversion slightly declined from 82%to 56%on Mn_(2)O_(3) catalyst,while no obvious change in EU selectivity was observed.The loss of surface Ov contents and Mn^(3+)proportion were concluded as main reasons for the decrease in catalytic activity over Mn_(2)O_(3) catalyst.This work demonstrated a metal oxide catalyst that was efficient in producing EU from CO_(2) and EDA.
基金Project supported by the National Natural Science Foundation of China.
文摘The electronic transition emission of Eu<sup>2+</sup> is in close relationship with the crystal-field environment and chemical bond property of Eu<sup>2+</sup> in hosts. The stronger the crystal-field intensity is, the larger the splitting of the 5d level is and the more favourable the broad band emission of d-f transition is. The smaller the covalency is, the smaller the
基金financial supports provided by the Natural Science Foundation of Fujian Province(No.2024J01195)the National Nature Science Foundation of China(No.21905279)+1 种基金Sanming University(Nos.22YG11 and PYT2201)the Education Scientific Research Project of Youth Teachers in the Education Department of Fujian Province(No.JAT220351).
文摘Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as highly efficient photocatalysts for hydrogen evolution.However,their applications in photocatalytic hydrogen evolution(PHE)are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored.Herein,we excavated a novel NOS photocatalyst of(Me_(2)NH_(2))_(6)In_(10)S_(18)(MIS)with a three-dimensional(3D)structure,and successfully incorporated divalent Co(Ⅱ)and metal Co(0)into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions.As the introduced Co(0)allows for more efficient light utilization and adroitly surficial hydrogen desorption,and meanwhile acts as the‘electron pump’for rapid charge transfer,Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis.With the prolonging of illumination,metal Co(0)gradually escapes from MIS framework,resulting in the decline of PHE performance.By stark contrast,the incorporated Co(Ⅱ)can establish a strong interaction with MIS framework,and simultaneously capture photogenerated electrons from MIS to produce Co(0),which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers.Thus,Co(Ⅱ)-modified MIS exhibits a robust and highly stable PHE activity of~4944μmol/g/h during the long-term photocatalytic reactions,surpassing most of the previously reported In–S framework photocatalysts.This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts,and sheds light on the design of vip confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.
基金supported by the Distinguished Young Scholars of China(No.52025014)Natural Science Foundation of Zhejiang Province(No.LQ23E010002)Innovation 2025 Major Project of Ningbo(Nos.2022Z011 and 2023Z022).
文摘The recently established theory has built clear connections between hardness and toughness and electron structure involving both valence electron concentration(VEC)and core electron count(CEC)in transition metal nitride(TMN)ceramics.However,the underlying deformation mechanisms remain unclear.Herein,we conduct in-depth analysis on microstructure evolution during deformation of the high VEC-CEC solution TiMoN coatings having desired combination of high hardness and toughness.The effects of solid solution,preferred orientation linked with symbiotic compressive stress,grain size and dislocations are systematically discussed.We discover that numerous dislocations have been implanted into the nanocrystals of the TiMoN coating during the high-ionization arc deposition.Using two-beam bright-field imaging,we count the dislocation density and confirm occurrence of dislocation multiplication to form effective plastic deformation,which contributes to significant strain hardening,comparable to solid solution hardening,fine-grain hardening and compressive stress hardening.The improved dislocation activities also play a crucial role in enhancing the toughness by providing extra energy dissipation paths.This work gains new insights into the origins of mechanical properties of ceramic coatings and possibility to tune them via defects.
基金support of the National Natural Science Foundation of China(Grant No.52172239,52202038,and 52402247)the Innovative Funds Plan of Henan University of Technology(Grant No.2020ZKCJ07)the Natural Science Foundation of Shandong Province(Grant No.ZR2022QE081)。
文摘Graphene-metal based materials have been utilized in lithium-sulfur(Li–S)batteries owing to their integrated functionalities thus far.However,their synthesis has predominantly relied on wet-chemistry routes,which limited their practical activity in Li–S reaction systems.In this study,we introduce a chemical vapor deposition(CVD)-triggered dry-chemistry approach for the preparation of graphene-cobalt(Co)based catalysts.The versatile CVD technique provides a dry and controllable reaction environment,effectively pledging the compact and clean catalytic interfaces between graphene and Co-based components.Additionally,programmed reactions introduce defects such as vacancies and nitrogen heteroatoms into the catalysts.Notably,the graphene layer number and Co valence state can be delicately manipulated by altering the CVD reaction temperature.Specifically,few-layer graphene wrapped Co/Co_(3)O_(4)(FGr-Co/Co_(3)O_(4))prepared at 450 ℃ shows higher catalytic activity than the multi-layer graphene wrapped Co/CoO(MGr-Co/CoO)synthesized at 550 ℃,attributed to its comprehensive control of clean interface,valence distribution range and defects.Leveraging these advantages,the battery with FGr-Co/Co_(3)O_(4)shows favorable working stability with a degradation rate of only 0.08%over 500 cycles at 1.0 C.Furthermore,under an elevated sulfur loading of 6.1 mg cm^(–2),the battery harvests a remarkable areal capacity of 5.9 mA h cm^(–2)along with stable cyclic operation.
基金Project supported by the National Natural Science Foundation of China(52071004,52301228,51971005,52171168)the Program of Top Disciplines Construction in Beijing(PXM2019_014204_500031)the International Research Cooperation Seed Fund of Beijing University of Technology(2021B23)。
文摘In this work,we proposed a method to enhance the magnetic properties of(Nd,Ce)-Fe-B magnets with Ce/TRE ratios below 25 wt%by introducing a moderate amount of La elements.The segregation behavior of La elements towards grain boundaries(GBs)was utilized to optimize the GB phase structure.Incorporation of La atoms into the main phase induces lattice expansion,leading to an increased formation of Ce^(3+)ions with enhanced magnetic moments.Comparative analysis with the original magnet(La/Ce=0 wt%)demonstrates that the magnet with a La/Ce ratio of 10 wt%exhibits improvements of 0.3%in remanence,12.6%in coercivity,and 0.6%in maximum energy produ ct.These results underscore that the moderate addition of La elements enhances the fluidity of the rare earth-rich phase and optimizes the distribution of lamellar GB,consequently reinforcing the magnetic isolation effect.Furthermore,the promotion of the transformation from Ce^(4+)to Ce^(3+)ons contributes to the comprehensive enhancement of the magnetic properties.This research offers a novel strategy for fabricating high-performance and resource-e fficient sintered magnets based on LaCe alloys.
基金funded by the National Natural Science Foundation of China(61701288,51706128)the Natural Science Basic Research Program of Shaanxi Province(2021JM-485)+2 种基金the Key Scientific Research Project of Shaanxi Provincial Education Department(20JS019)the High-level Achievement Cultivation Project of Collaborative Innovation Center for Comprehensive Development of Qinba Biological Resources(QBXT-17-8)the Postgraduate Innovation Project of Shaanxi University of Technology(SLGYCX2410).
文摘Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electron numbers between single atoms and adsorbed intermediates(O,N,C,and H)in MXene-anchored SACs(M-Ti_(2)C/M-Ti_(2)CO_(2)).The density functional theory results demonstrated that the sum of the valence electron number(VM)of the interface-doped metal and the valence electron number(VA)of the adsorbed intermediates in M-Ti_(2)C followed the 10-valence electron matching law.Furthermore,based on the 10-valence electron matching law,we deduced that the sum of the valence electron number(k)and VMfor the molecular adsorption intermediate interactions in M-Ti_(2)CO_(2)adhered to the 11-valence electron matching law.Electrostatic repulsion between the interface electrons in M-Ti_(2)CO_(2)and H_(2)O weakened the adsorption of intermediates,Furthermore,we applied the 11-valence electron matching law to guide the design of catalysts for nitrogen reduction reaction,specifically for N_(2)→NNH conversion,in the MTi_(2)CO_(2)structure.The sure independence screening and sparsifying operator algorithm was used to fit a simple three-dimensional descriptor of the adsorbate(R_(2)up to 0.970)for catalyst design.Our study introduced a valence electron matching principle between doped metals(single atoms)and adsorbed intermediates(atomic and molecular)for MXene-based catalysts,providing new insights into the design of high-performance SACs.
基金supported by the NSFC under Grant Nos.11374315 and 12074395the Invited Scientist Program of CNRS at Ecole Polytechnique,Palaiseau,France。
文摘The capacity to predict X-ray transition and K-edge energies in dense finite-temperatur plasmas with high precision is of primary importance for atomic physics of matter under extreme conditions.The dual characteristics of bound and continuum states in dense matter are modeled by a valence-band-like structure in a generalized ion-sphere approach with states that are either bound,free,or mixed.The self-consistent combination of this model with the Dirac wave equations of multielectron bound states allows one to fully respect the Pauli principle and to take into account the exact nonlocal exchange terms.The generalized method allows very high precision without implication of calibration shifts and scaling parameters and therefore has predictive power.This leads to new insights in the analysis of various data.The simple ionization model representing the K-edge is generalized to excitation–ionization phenomena resulting in an advanced interpretation of ionization depression data in near-solid-density plasmas.The model predicts scaling relations along the isoelectronic sequences and the existence of bound M-states that are in excellent agreement with experimental data,whereas other methods have failed.The application to unexplained data from compound materials also gives good agreement without the need to invoke any additional assumptions in the generalized model,whereas other methods have lacked consistency.
基金National Natural Science Foundation of China (No. 52274403)。
文摘The mechanical,thermodynamic properties and electrical conductivities of L1_(2)-Al_(3)X(X=Zr,Sc,Er,Yb,Hf)structural phases in aluminum conductors were investigated through a first-principles study.The results demonstrate that all structural phases have good alloy-forming ability and structural stability,where Al_(3)Zr is the most superior.Al_(3)Zr,Al_(3)Hf and Al_(3)Sc have enhanced shear and deformation resistance in comparison to other phases.Within the temperature range of 200−600 K,Al_(3)Er and Al_(3)Yb possess the greatest thermodynamic stability,followed by Al_(3)Hf,Al_(3)Zr and Al_(3)Sc.Al_(3)Er and Al_(3)Yb have higher thermodynamic stability than Al_(3)Hf,Al_(3)Zr and Al_(3)Sc.All structural phases exhibit substantial metallic properties,indicating their good electrical conductivity.The electrical conductivities of Al_(3)Hf and Al_(3)Zr are higher than those of Al_(3)Er,Al_(3)Yb and Al_(3)Sc.The covalent bond properties in Al_(3)Sc,Al_(3)Er and Al_(3)Yb enhance the hardness,brittleness and thermodynamic stability of the structural phase.The thermodynamic stability of Al_(3)Sc is significantly reduced by ionic bonds.
文摘Herein,we established a Zn_(3)(OH)_(2)(V_(2)O_(7))(H_(2)O)_(2)/V-Zn(O,S)Z-scheme heterojunction labeled ZnVO/V-Zn(O,S)with a heterovalent V^(4+)/V^(5+)states and oxygen vacancies in both phases via a one-step in-situ hydrolysis method.The NaBH_(4) regulated the ZnVO/V-Zn(O,S)-3 with rich Vo and suitable n(V^(4+))/n(V^(5+))ratio achieved an excellent photocatalytic nitrogen fixation activity of 301.7μmol/(g×h)and apparent quantum efficiency of 1.148%at 420 nm without any sacrificial agent,which is 11 times than that of V-Zn(O,S).The Vo acts as the active site to trap and activate N_(2) molecules and to trap and activate H_(2)O to produce the H for N_(2) molecules photocatalytic reduction.The rich Vo defects can also reduce the competitive adsorption of H_(2)O and N_(2) molecules on the surface active site of the catalyst.The heterovalent vanadium states act as the photogenerated electrons,quickly hopping between V^(4+)and V^(5+)to transfer for the photocatalytic N_(2) reduction reaction.Additionally,the Z-scheme heterojunction effectively minimizes photogenerated carrier recombination.These synergistic effects collectively boost the photocatalytic nitrogen fixation activity.This study provides a practical method for designing Z-scheme heterojunctions for efficient photocatalytic N_(2) fixation under mild conditions.
基金Project supported by Laboratory of Rare Earth Chemistry and Physics and Applied Chemistry Research Centre of Changchun, China
文摘The influence of bond valence on bond covalence in Lal-xCaxCrO3(x = 0.0, 0.1, 0.2, 0.3) has been studied by using semi empirical method. This method is the extortion of the dialectic description theory proposed by Phillips, Van Vetches, Levine and Tanaka (PVLT). In the calculation of bond valence, two schemes were adopted. The first is the equal-valence scheme, and the second is Bond Valence Sums (BVS) scheme. Bath schemes suggest that for the title compound bond covalence be mainly influenced by bond valence, and insensitive to the Ca doping level. Generally speaking, larger bond valences usually result in higher bond covalence's.
基金supported by the Fundamental Research Funds for the Central Universities(FRF-EYIT-23-07)。
文摘Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption and waste gas emissions.To address this,electrocatalytic nitric oxide reduction reaction(NORR)has emerged as a promising strategy to bridge NH3consumption to NH3production,harnessing renewable electricity for a sustainable future.Copper(Cu)stands out as a prominent electrocatalyst for NO reduction,given its exceptional NH3yield and selectivity.However,a crucial aspect that remains insufficiently explored is the effects of morphology and valence states of Cu on the NORR performance.In this investigation,we synthesized CuO nanowires(CuO-NF)and Cu nanocubes(Cu-NF)as cathodes through an in situ growth method.Remarkably,CuO-NF exhibited an impressive NH3yield of 0.50±0.02 mg cm^(-2)h^(-1)at-0.6 V vs.reversible hydrogen electrode(RHE)with faradaic efficiency of29,68%±1,35%,surpassing that of Cu-NF(0.17±0.01 mg cm^(-2)h^(-1),16.18%±1.40%).Throughout the electroreduction process,secondary cubes were generated on the CuO-NF surface,preserving their nanosheet cluster morphology,sustained by an abundant supply of subsurface oxygen(s-O)even after an extended duration of 10 h,until s-O depletion ensued.Conversely,Cu-NF exhibited inadequate s-O content,leading to rapid crystal collapse within the same timeframe.The distinctive current-potential relationship,akin to a volcano-type curve,was attributed to distinct NO hydrogenation mechanisms.Further Tafel analysis revealed the exchange current density(i0)and standard heterogeneous rate constant(k0)for CuO-NF,yielding 3.44×10^(-6)A cm^(-2)and 3.77×10^(-6)cm^(-2)s^(-1)when NORR was driven by overpotentials.These findings revealed the potential of CuO-NF for NO reduction and provided insights into the intricate interplay between crystal morphology,valence states,and electrochemical performance.
基金supported by the National Natural Science Foundation of China (Grant Nos.52171220,92163212,and 92163119)the Research Funding of Wuhan Polytechnic University (Grant No.2022RZ059)the National Innovation and Entrepreneurship Training Program for College Students (Grant No.S202310497202)。
文摘Band convergence is considered to be a strategy with clear benefits for thermoelectric performance,generally favoring the co-optimization of conductivity and Seebeck coefficients,and the conventional means include elemental filling to regulate the band.However,the influence of the most electronegative fluorine on the CoSb_(3) band remains unclear.We carry out density-functional-theory calculations and show that the valence band maximum gradually shifts downward with the increase of fluorine filling,lastly the valence band maximum converges to the highly degenerated secondary valence bands in fluorine-filled skutterudites.
基金Funded by the Key R&D Projects in Hubei Province of China(No:2020BAB061)。
文摘Cu^(+)-doped alkali borosilicate glasses with different Na_(2)O contents were prepared by the melting method,and the effects of different R values(R=Na_(2)O/B_(2)O_(3))on the structure,ion presence state and luminescence properties of Cu^(+)-doped alkali borosilicate glasses were investigated.The analysis by FT-IR and Raman spectroscopy shows that,with the increase of R value of the glass,the[BO_(3)]in the structure of Cu^(+)-doped alkali borosilicate glass transforms into[BO_(4)]and the number of non-bridging oxygen in the glass network appears to be slightly increased.The absorption spectra and EPR analysis reveal that the Cu^(+)content in the glass gradually decreases and the Cu^(2+)content gradually increases as the R value of the glass increases.XPS and PL tests further indicate that the transformation of the octahedral coordination structure of Cu^(+)to the octahedral coordination structure of Cu^(2+)and the cubic coordination structure of Cu^(+)occurs in the glass as the R value of the glass increases.This transformation can effectively reduce the concentration quenching phenomenon of Cu^(+)and improve the fluorescence luminescence intensity of the glass samples.Meanwhile,the samples were found to have luminescence tunability as well as good thermal stability.
