Precisely quantifying bulk transition metal valence evolution in conventional battery electrode by inverse partial fluorescence yield

Precisely quantifying transition metal(TM) redox in bulk is a key to understand the fundamental of optimizing cathode materials in secondary batteries. At present, the commonly used methods to probe TM redox are hard X-ray absorption spectroscopy(hXAS) and soft X-ray absorption spectroscopy(sXAS).However, they are both facing challenges to precisely quantify the valence states of some transition metals such as Mn. In this paper, Mn-L iPFY(inverse partial fluorescence yield) spectra extracted from Mn-L m RIXS(mapping of resonant inelastic X-ray scattering) is adopted to quantify Mn valence states. Mn-L i PFY spectra has been considered as a bulk-sensitive, non-distorted probe of TM valence states.However, the exact precision of this method is still unclear in quantifying practical battery electrodes.Herein, a series of LiMn_(2)O_(4) electrodes with different charge and discharge states are prepared. Based on their electrochemical capacity(generally considered to be very precise), the precision of Mn iPFY in quantifying bulk Mn valence state is confirmed, and the error range is unraveled. Mn-L mRIXS iPFY thus is identified as one of the best methods to quantify the bulk Mn valence state comparing with hXAS and sXAS.

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.

Novel ternary metals-based telluride electrocatalyst with synergistic effects of high valence non-3d metal and oxophilic Te for pH-universal hydrogen evolution reaction

Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline HER kinetics.Here,we design ternary transition metals-based nickel telluride(Mo WNi Te)catalysts consisting of high valence non-3d Mo and W metals and oxophilic Te as a first demonstration of non-precious heterogeneous electrocatalysts following the bifunctional mechanism.The Mo WNi Te showed excellent HER catalytic performance with overpotentials of 72,125,and 182 mV to reach the current densities of 10,100,and 1000 mA cm^(-2),respectively,and the corresponding Tafel slope of 47,52,and 58 mV dec-1in alkaline media,which is much superior to commercial Pt/C.Additionally,the HER performance of Mo WNi Te is well maintained up to 3000 h at the current density of 100 mA cm^(-2).It is further demonstrated that the Mo WNi Te exhibits remarkable HER activities with an overpotential of 45 mV(31 mV)and Tafel slope of 60 mV dec-1(34 mV dec-1)at 10 mA cm^(-2)in neutral(acid)media.The superior HER performance of Mo WNi Te is attributed to the electronic structure modulation,inducing highly active low valence states by the incorporation of high valence non-3d transition metals.It is also attributed to the oxophilic effect of Te,accelerating water dissociation kinetics through a bifunctional catalytic mechanism in alkaline media.Density functional theory calculations further reveal that such synergistic effects lead to reduced free energy for an efficient water dissociation process,resulting in remarkable HER catalytic performances within universal pH environments.

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.

Roles of Oxygen Vacancy and Lower Valence Metallic Ion in Direct Decomposition of NO over La_（2－x）（Sr，Th）_xCuO_（4±λ）

Two systems of La_(2-x)Sr_xCuO_(4±λ) and La_(2-x)Th_xCuO_(4±λ) mixed oxides with K_2NiF_4structure were synthesized.The compositions and structures of the catalysts were characterized by means of XRD,XPS,chemical analysis and so on.The catalytic behavior for the direct decomposition of NO has been investigated.The results show that the catalytic activity is closely related to the oxygen vacancy and lower valence metallic ion in the direct decomposition of NO.The presence of oxygen vacancy is necessary for mixed oxide to have steady activity in NO decomposition.

Origion of Band-like and Atom-like Features of the Valence Band Auger Emission from Thansition Metals

The occurrence of both band-like and atom-like Auger spectra involving valence band electron of d-transition metals is discussed based on the two-step model of the Auger electron emission, i.e.an initial core-hole is first generated and the Auger transition occurs between the core-hole andthe valence states, The occupied vaIence states relax to screen the core-hole which results in a redistribution of the valence electrons, The electronic states concerned by the Auger transitionare calculated by the FLAPW method. There is a clear relation between band-like and atom-like features of the spectra and the different responses of these metals to the existence of a core-hole.

Principle for the Working of the Lithium-Ion Battery

The technological advances in Lithium-ion batteries have created many new applications, including electric vehicles. In this short note, we shall explain in simple terms the basic physics why and how it is possible to have high energy capacity in Lithium-ion batteries. However, heating has been a common problem and without appropriate design, they might give fire and explosion as reported.

First-principle study of the structural,electronic,and optical properties of SiC nanowires

We preform first-principle calculations for the geometric, electronic structures and optical properties of SiC nanowires（NWs）. The dielectric functions dominated by electronic interband transitions are investigated in terms of the calculated optical response functions. The calculated results reveal that the SiC NW is an indirect band-gap semiconductor material except at a minimum SiC NW（n = 12） diameter, showing that the NW（n = 12） is metallic. Charge density indicates that the Si–C bond of SiC NW has mixed ionic and covalent characteristics： the covalent character is stronger than the ionic character, and shows strong s–p hybrid orbit characteristics. Moreover, the band gap increases as the SiC NW diameter increases. This shows a significant quantum size and surface effect. The optical properties indicate that the obvious dielectric absorption peaks shift towards the high energy, and that there is a blue shift phenomenon in the ultraviolet region. These results show that SiC NW is a promising optoelectronic material for the potential applications in ultraviolet photoelectron devices.

Synthesis and Investigation of the Activity of Cu-Cr-Co/Al2O3/Al-Catalysts in the Microwave Radiation-Stimulated Reaction Joint Deep Oxidation of Hydrocarbons and Carbon Monoxide

This article shows main principles and presents ideas described in the scientific and technical literature, on the mechanism of interaction of microwave radiation with a solid phase materials, which were used as a basis of creation of new perspective, energy efficient and environmentally safe technologies of preparation of heterogeneous catalysts for the reactions which were carried out under the influence of electro-magnetic radiation of microwave radiation. Author’s research results confirm possibilities of practical use of proposed method of hydrothermal oxidation of industrial low-dispersing of aluminum powders with presence of bulk phase of Al(ОН)3·nH2O, with further thermal treatment in microwave field for acquisition of armored А1/А12О33 compositions, which effectively consume energy of microwave radiation. Due to the textured characteristics and thermo-transforming ability, synthesized components can be used as potential universal bearings of catalysts for reactions stimulated by electromagnetic radiation of (2.45 GHz) microwave frequency.

Peracetic acid catalytic activation using Co_(3)O_(4) nanocluster decorated graphitic carbon nitride for cefapirin degradation in water

This study innovated cobalt-based catalytic nanocomposites(CCNs)for the heterogeneous activation of peracetic acid(PAA),a green and efficient advanced oxidation process for removing antibiotics from water.Commercial Co_(3)O_(4) catalysts exhibit limited activity due to stable electronic structures.To overcome this,CCNs were synthesized using a one-step condensation method,incorporating a size control strategy that anchors Co_(3)O_(4) nanoclusters within 4‒5 nm onto six-fold cavity of g-C3N4,simultaneously modifying the coordination environment of Co.This alteration significantly enhances the adsorption energy of PAA and catalytic activity compared to commercial Co_(3)O_(4).The improved performance of CCN2,in particular,is attributed to a shift in the cobalt d band center towards the Fermi level,facilitating electron delocalization and transfer,enhancing Co‒O bonding,and accelerating PAA decomposition.CCN2’s superior activity,with a cefapirin(CFP)degradation kinetic rate constant(k1=0.760 min^(−1))~11 times that of PAA direct oxidation(k1=0.070 min^(−1))and~5 times that of commercial Co_(3)O_(4)/PAA system(k1=0.164 min^(−1)),is due to its ability to generate dominant reactive species for antibiotic degradation,including alkoxy radicals(CH3C(=O)OO•),high valence metal(Co^(Ⅳ)(=O)^(2+)),and singlet oxygen(^(1)O_(2)),with the latter two being crucial for the degradation process.The degradation of CFP involved three mechanisms,including direct oxidation by PAA,decarboxylation,and open-ring reactions at nitrogen sites.This research provides insights into developing high-activity catalysts for efficient PAA activation and antibiotic removal,leveraging the strategy of shifting the transition metal d band center.