Morphology and valence state evolution of Cu:Unraveling the impact on nitric oxide electroreduction

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.

Valence electron structures dependences of structural stability and properties of REX_(3)(RE=rare earth;X=In,Tl)and RE(In,Co)_(3) alloys

Intermetallic compounds REIn_(3)(RE=rare earth)have attracted much attention due to their unique characteristics:crystal field effect,Kondo effect,superconductivity,heavy fermion,and antiferromagnetism,and their cobalt diluted alloys exhibit the ferromagnetic half-metallic characteristics at room temperature.In this study,an empirical electron theory(EET)is employed to investigate systemically the valence electronic structure,the thermal and magnetic properties of REX_(3) and their cobalt diluted alloys for revealing the mechanism of physical properties.The calculated bond length,melting point,and magnetic moment match the experimental ones very well.The study reveals that structural stability and physical properties of REX_(3) and their cobalt dilute alloys are strongly related to their valence electron structures.It is suggested that the structural stability and cohesive energy depend upon the covalent electron,the melting point is modulated by covalent electron pair,and the magnetic moment is originated from 3d magnetic electron.The ferromagnetic characteristics of Co-diluted REIn3 alloys is originated from the introduction of strong ferromagnetic Co atom,but,a competition is caused between the electron transition from valence electron to magnetic electron on d orbit and its reversal electron transformation with increasing the content of cobalt,which results in the formations of diluted magnetic Gd(In,Co)_(3) alloy with minor amount of cobalt and strong magnetic Nd(In,Co)_(3) alloy with doping more Co atoms.

Valence Bands Convergence in p-Type CoSb_(3) through Electronegative Fluorine Filling

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.

Enhanced anomalous Hall effect in kagome magnet YbMn_(6)Sn_(6)with intermediate-valence ytterbium

We report on the magnetization and anomalous Hall effect(AHE)in the high-quality single crystals of the kagome magnet YbMn_(6)Sn_(6),where the spins of the Mn atoms in the kagome lattice order ferromagnetically and the intermediate-valence Yb atoms are nonmagnetic.The intrinsic mechanism plays a crucial role in the AHE,leading to an enhanced anomalous Hall conductivity(AHC)compared with the other rare-earth RMn_(6)Sn_(6)compounds.Our band structure calculation reveals a strong hybridization between the 4f electrons of Yb and conduction electrons.

Equalized Electronegativity Based on the Valence Electrons and Its Application

We take the contribution of all valence electrons into consideration and propose a new valence electrons equilibration method to calculate the equalized electronegativity including molecular electronegativity, group electronegativity, and atomic charge. The ionization potential of alkanes and mono-substituted alkanes, the chemical shift of 1H NMR, and the gas phase proton affinity of aliphatic amines, alcohols, and ethers were estimated. All the expressions have good correlations. Moreover, the Sanderson method and Bratsch method were modified on the basis of the valence electrons equilibration theory. The modified Sanderson method and modified Bratsch method are more effective than their original methods to estimate these properties.

STUDY ON DEGRADATION OF LDPE CATALYZED BY MULTI-VALENCE METALLIC ORGANIC COMPOUNDS AT COMPOST TEMPERATURE

The catalytic effects of the organic compounds of iron,tin and manganese on the degradation of low density polyethylene (LDPE) at compost temperature are discussed.A series of samples were aged in a simulating compost environment.The mechanical properties,viscosity average molecular weight (M η) of PE and hydroperoxide (POOH) concentration in the samples were measured.FT IR and DSC were also applied to characterize some samples.It was shown that the above mentioned metallic organic compounds can catalyze the degradation of LDPE efficiently.After 2 months aging,all samples with catalysts became fragile and the M η of the material decreased dramatically.Furthermore,the concentration of carbonyl and the degree of crystallinity of the material increased with the aging time.

Valence states, impurities and electrocrystallization behaviors during molten salt electrorefining for preparation of high-purity titanium powder from sponge titanium

High-purity titanium powder was prepared by molten salt electrorefining from sponge titanium in NaCl-KCl-TiClx salts. The titanium valence, purity and electrocrystallization during electrolysis process were studied. The XPS analysis showed that the titanium valences are mainly ＋4, ＋3 and ＋2 at the earlier, medium and later stages of electrolysis, respectively. During the electrolysis process, the contents of impurities Si, Cr, Mn, Al vary little, and the contents of impurities Fe, Cu, Ni decrease markedly, while the contents of impurities O, N, H increase obviously. The residual impurities are usually distributed in small tunnel of dendritic crystals. Enhancing the electrolysis temperature and prolonging the electrolysis time can increase the titanium particle size. The TEM analysis showed that the electrodeposited titanium is not a single crystal, but contains many nanostructured grains and subgrains, with grain size of 100-500 nm. The electrolysis mechanisms were also discussed.

V2O5 Nanospheres with Mixed Vanadium Valences as High Electrochemically Active Aqueous Zinc-Ion Battery Cathode

AV4+-V2O5 cathode with mixed vanadium valences was prepared via a novel synthetic method using VOOH as the precursor,and its zinc-ion storage performance was evaluated.The products are hollow spheres consisting of nanoflakes.The V4+-V2O5 cathode exhibits a prominent cycling performance,with a specific capacity of 140 mAhg-1 after 1000 cycles at 10 A g.1,and an excellent rate capability.The good electrochemical performance is attributed to the presence of V4+,which leads to higher electrochemical activity,lower polarization,faster ion diffusion,and higher electrical conductivity than V2O5 without V4+.This engineering strategy of valence state manipulation may pave the way for designing high-performance cathodes for elucidating advanced battery chemistry.

High valence metals engineering strategies of Fe/Co/Ni-based catalysts for boosted OER electrocatalysis

Electrocatalysis for the oxygen evolution reactions(OER)has attracted much attention due to its important role in water splitting and rechargeable metal-air batteries.Therefore,designing highly efficient and low-cost catalysts for OER process is essential as the conventional catalysts still rely on precious metals.Transition metal-based compounds have been widely investigated as active OER catalysts,and renewed interest in the high valence metals engineered compounds has been achieved for superior catalytic activity and stability.However,an in-depth understanding of the construction strategies and induced effects for the high valence metals engineered catalysts is still lacking and desired.In this review,we have summarized the construction strategies of high valence metals as dopants or formed heterostructures with the iron/cobalt/nickel(Fe/Co/Ni)-based catalysts.Then the induced effects on Fe/Co/Ni-based catalysts by incorporating high valence metals,e.g.,accelerating the surface reconstruction,forming amorphous structure,generating vacancies/defects,and acting as stabilizers,are highlighted.The impacts of high valence metals on OER performance are elucidated based on different elements,including molybdenum(Mo),tungsten(W),cerium(Ce),vanadium(V),chromium(Cr),manganese(Mn),niobium(Nb),zirconium(Zr).The correlations of construction strategies,induced effects,catalytic activity and OER reaction pathways are elaborated.Finally,the remaining challenges for further enhancements of OER performance induced by high valence metals are presented.

Effects of 4f Electron Characteristics and Alternation Valence of Rare Earths on Photosynthesis: Regulating Distribution of Energy and Activities of Spinach Chloroplast

Chloroplasts were isolated from spinach treated with taCl3, CeCl3, and NdCl3. Because of owning 4f electron characteristics and alternation valence, Ce treatment presented the highest enhancement in light absorption, energy transfer from LHC Ⅱ to PS Ⅱ, excitation energy distribution from PS Ⅰ to PS Ⅱ, and fluorescence quantum yield around 680 nm. Compared with Ce treatment, Nd treatment resulted in relatively lower enhancement in these physiological indices, as Nd did not have alternation valence. La treatment presented the lowest enhancement, as La did not have either 4f electron or alternation valence. The increase in activities of whole chain electron transport, PS ⅡDCPIP photoreduction, and oxygen evolution of chloroplasts was of the following order： Ce〉Nd 〉La〉 control. However, the photoreduction activities of spinach PS I almost did not change with La, Ce, or Nd treatments. The results suggested that 4f electron characteristics and alternation valence of rare earths had a close relationship with photosynthesis improvement.

ASTUDY OF VALENCE OF YTTRIUM IN Y_2O_3 Mo CATHODE

The valenceofelementyttrium of Y2 O3 Mocathode materialhasbeenstudied by usingther mal weight analysis, X ray diffraction analysis, Scanning electron microscopy and X rayphotoelectronspectrum . It hasbeen provedthatyttrium oxidecan bereduced by molybdenum carbide. Thereaction between powdered Y2 O3 and Mo2 Ccan happen at 1173 , and Y2 O3may bereduced to metallicyttrium . Afterthepowder mixtureof Y2 O3 and Mo2 Cwasheat treated at1873 K, Yttrium existsin two kinds of chemicalstate- yttrium of zero valence and yttrium ofthreevalences.

In-situ optimizing the valence configuration of vanadium sites in NiV-LDH nanosheet arrays for enhanced hydrogen evolution reaction

Developing the highly active, cost-effective, environmental-friendly, and ultra-stable nonprecious electrocatalysts for hydrogen evolution reaction(HER) is distinctly indispensable for the large-scale practical applications of hydrolytic hydrogen production. Herein, we report the synthesis of well-integrated electrode, NiV layered double hydroxide nanosheet array grown in-situ on porous nickel foam(abbreviated as in-NiV-LDH/NF) via the facile one-step hydrothermal route. Interestingly, the valence configuration of vanadium(V) sites in such NiV-LDH are well dominated by the innovative use of NF as the reducing regulator, achieving the reassembled in-NiV-LDH/NF with a high proportion of trivalent V ions(V3+), and then an enhanced intrinsic electrocatalytic HER activity. The HER testing results show that the in-NiVLDH/NF drives the current densities of 10 and 100 mA cm-2 at extremely low overpotentials of 114 and 245 mV without iR-compensation respectively, even outperforms commercial 20 wt% Pt/C at the large current density of over 80 mA cm-2 in alkaline media, as well as gives robust catalytic durability of at least 100 h in both alkaline and neutral media. More importantly, this work provides a fresh perspective for designing bimetal(oxy) hydroxides electrocatalysts with efficient hydrogen generation.

Boosting the cell performance of the SiO_(x)@C anode material via rational design of a Si-valence gradient

Relieving the stress or strain associated with volume change is highly desirable for high-performance SiOx anodes in terms of stable solid electrolyte interphase(SEI)-film growth.Herein,a Si-valence gradient is optimized in SiOx composites to circumvent the large volume strain accompanied by lithium insertion/extraction.SiO_(x)@C annealed at 850℃ has a gentle Si-valence gradient along the radial direction and excellent electrochemical performances,delivering a high capacity of 506.9 mAh g^(−1) at 1.0 A g^(−1) with a high Coulombic efficiency of~99.8%over 400 cycles.Combined with the theoretical prediction,the obtained results indicate that the gentle Si-valence gradient in SiO_(x)@C is useful for suppressing plastic deformation and maintaining the inner connection integrity within the SiO_(x)@C particle.Moreover,a gentle Si-valence gradient is expected to form a stress gradient and affect the distribution of dangling bonds,resulting in local stress relief during the lithiation/delithiation process and enhanced Li-ion kinetic diffusion.Furthermore,the lowest interfacial stress variation ensures a stable SEI film at the interface and consequently increases cycling stability.Therefore,rational design of a Si-valence gradient in SiOx can provide further insights into achieving high-performance SiOx anodes with large-scale production.

High valence state of Ni and Mo synergism in NiS_(2);MoS_(2)hetero-nanorods catalyst with layered surface structure for urea electrocatalysis

High valence state species are significant in the energy-relevant electrochemical oxidation reactions.Herein,the high active state of Ni^(3+)formation induced by Mo^(6+)and their efficient synergism in NiS_(2)-MoS_(2)hetero-nanorods powder catalyst with the rough layered structure are demonstrated,as proof of concept,for the urea-assisted water electrolysis.This catalyst can be derived from the sulfidation of NiMoO_(4) nanorods that can realize individual metal sulfides sufficiently mixing at a domain size in the nanoscale which creates lots of active sites and nanointerfaces.The high valence state of Mo^(6+)and Ni^(3+)formation and increased conductive phase of 1 T MoS_(2)in the hetero-nanorods compared to the counterpart pure phases are revealed by spectral study and microscopic analysis;high electrochemical surface area and active site exposure are found due to the nano-interface formation and layered rough nanosheets over the surface of nanorods.They show much higher catalytic performance than their pure phases for urea oxidation,including high catalytic activity,stability,charge transfer ability and catalytic kinetics resulting from more active Ni^(3+)species formation and electronic synergism of high valence metals.Transformation of 1 T MoS_(2)to Mo^(6+)and increased amount of Mo^(6+)and Ni^(3+)after stability test indicate their involvement and synergism for the catalysis reaction.The current work offers a novel understanding of the synergistic effect based on the high valence state synergism for heterogeneous catalysts in electrocatalysis.

Effect of Valence Electron Structure on Temper Process and Hardness of the Supersaturated Carburized Layer

By measuring the hardness of carburized layer of a new type supersaturated carburizing steel （35Cr3SiMnMoV） at different temper temperature for 2 h, the relationship curve between the carburized layer hardness and the temper temperature is established. The result indicates that the hardness goes down firstly, then up and down, just like a wave consistent with the temperature increase. A secondary hardening peak appears at 570 ℃ or so. Based on Empirical Election Theory （EET） of Solids and Molecules, the valence electron structures （VESs） containing α-Fe-C, α-Fe-C-Me segregation structure units and carbide are calculated. The laws of temper process and hardness change with the temper temperature are explained, and the fact that reconstruction of θ-Fe3C is prior to that of special carbide at high tempering is analyzed with the phase structure formation factor, S, being taken into consideration. Therefore, the laws of temper process and hardness change of supersaturated carburized layer at different temper temperature can be traced back to valence electron structure （VES） level of alloy phase.

Analysis of Transition Mechanism of Cubic Boron Nitride Single Crystals under High Pressure-High Temperature with Valence Electron Structure Calculation

The possibilities of hexagonal boron nitride(hBN) and lithium boron nitride(Li_3BN_2) transition into cubic boron nitride(cBN) under synthetic pressure 5.0 GPa and synthetic temperature 1700 K are analyzed with the use of the empirical electron theory of solids and molecules. The relative differences in electron density are calculated for dozens of bi-phase interfaces hBN/cBN, Li_3BN_2/cBN. These relative differences of hBN/cBN are in good agreement with the first order of approximation(<10%), while those of Li_3BN_2/cBN are much greater than 10%.This analysis suggests that Li_3BN_2 is impossible to be intermediate phase but is a catalyst and cBN should be directly transformed by hBN.

A STUDY OF TEMPERATURE-DEPENDENT VALENCE BOND STRUCTURE OF TITANIUM

On the basis of energy and shape method for the determination of the valence bond （ VB ） structures of crystal, the valence bond structure of titanium is redetermined at room temperature and calculated in the whole temperature range of 0-1943K. The outer shell electronic distribution of Ti is ec^29907. （sc^0.4980 ＋ dc^2.4927） ef^1.0098 in crystal. The temperature dependences of the VB structures of hcp and bcc phases are the same. The VB structures of hcp and bcc phases monotonically increase or decrease with the increase in temperature, but show discontinuous changes at the phase-transformation temperature 1155K.

Quick valence analysis method of vanadium toward accurate toxicity assessment of vanadium-containing hazardous wastes

In order to develop a quick, efficient and sensitive valence analysis method of vanadium(Ⅴ), the highperformance liquid chromatography(HPLC) was utilized to separate and quantify EDTA-complexed Ⅴ(Ⅲ), Ⅴ(Ⅳ) and Ⅴ(Ⅴ) ions. The influence of EDTA, TBAOH, solution pH and organic modifier on retention behavior of V-EDTA complexes was investigated. Complexed Ⅴ(Ⅲ), Ⅴ(Ⅳ) and Ⅴ(Ⅴ) ions can be separated and quantified in 5 min, with detection limits of 0.04 mg/L Ⅴ(Ⅲ), 0.07 mg/L Ⅴ(Ⅳ), and 0.06 mg/L Ⅴ(Ⅴ), respecti vely. The established method is applied to analyzing the hazardous waste of V-Cr-bearing reducing slag and results demonstrate 49.94% of its Ⅴ element to be toxic Ⅴ(Ⅴ). This work opens a new avenue for quick and accurate toxicity assessment of hazardous wastes containing multivalent heavy metals.

Coherence of the Even-Odd Rule with an Effective-Valence Isoelectronicity Rule for Chemical Structural Formulas: Application to Known and Unknown Single-Covalent-Bonded Compounds

Ions or molecules are said to be isoelectronic if they are composed of different elements but have the same number of electrons, the same number of covalent bonds and the same structure. This criterion is unfortunately not sufficient to ensure that a chemical structure is a valid chemical compound. In a previous article, a procedure has been described to draw 2D valid structural formulas: the even-odd rule. This rule has been applied first to single-bonded molecules then to single-charged single-bonded ions. It covers hypovalent, hypervalent or classic Lewis’ octet compounds. The funding principle of the even-odd rule is that each atom of the compound possesses an outer-shell filled only with pairs of electrons. The application of this rule guarantees validity of any single-covalent-bond chemical structure. In the present paper, this even-odd rule and its electron-pair criterion are checked for coherence with an effective-valence isoelectronic rule using numerous known compounds having single-covalent-bond connections. The test addresses Lewis’ octet ions or molecules as well as hypovalent and hypervalent compounds. The article concludes that the even-odd rule and the effective-valence isoelectronicity rule are coherent for known single-covalent-bond chemical compounds.

Novel Phenomenon on Valence Unvariation of Doping Ion in Yb:YAG Transparent Ceramics Using MgO Additives

Yb：YAG nanopowders were synthesized by the alcohol-water co-precipitatlon method adding MgO as sintering additives. Appropriate amount of MgO adding can restrict the agglomeration and reduce the particle size of Yb：YAG powders. When the MgO content was 0.04wt%, well-dispersed Yb：YAG powders with ellipsoidal particles of less than 100 nm diameter were obtained. The experimental results showed the valence variation of doping ion Yb〉 would not appear when adding MgO as sintering additives, so ceramics showed colorless transparent instead of green due to Yb^2＋ color center using traditional SiO2 as additives. The transmission of the sintered Yb：YAG ceramics can reach 80.6% even without annealing. Ceramic morphology showed that the grains had uniform-distribution with the size of 10 iam or so, and no impurity and pore existed in the grain boundary and crystalline while using optimal sintering conditions.