Cation Valence Research Articles

Origin of magnetism via cation vacancy defects in non-stoichiometric NiCo2O4 nanoparticles: A synchrotron-based x-ray absorption and x-ray magnetic circular dichroism spectroscopic study

The present study probes the effect of cation distributions in the structural, optical, electronic, and magnetic properties of mixed-valent inverse-spinel NiCo2O4 (NCO) nanoparticles (NPs). NCO NPs were prepared using the sol–gel combustion method and the grain size was obtained in the magnetic exchange length range assumed to be from single-ion anisotropy. The Raman and photoluminescence spectroscopies confirm the presence of an inverse-spinel structure with different oxidation states, and vibrating sample magnetometry clarifies the existence of ferromagnetism with the presence of magnetic anisotropy among the cations. These NPs annealed at a higher grain-growth temperature accumulate ferrimagnetic properties and produce magneto-crystalline anisotropy making NCO an assuring material for spintronic applications. A detailed x-ray absorption spectroscopy and x-ray magnetic circular dichroism studies reveal an indestructible correlation between the distribution of the present cations and the element-specific origin of ferrimagnetic behavior. Ni is found to be accountable for the magnetic moment and electronic conduction, whereas Co is associated mainly with the generation of the magnetic anisotropy even in the polycrystalline NP form. This describes the anti-ferromagnetic coupling between Co and Ni ions that is pivotal in demonstrating the exchange interaction between these cations. The above result signifies the site-dependent cation valence states for the magnetic properties, and the extent of growing conditions are related to such cation-site dysfunction. This depicts further tunability in NCO as a functional oxide material.

Transport of microplastics treated with dielectric barrier discharge (DBD) plasma in saturated porous media

The performance of discharge plasma in treating organic pollutants and micro-organisms in water is impressive. When discharge plasma is used to treat polluted water containing organic pollutants and microorganisms, the presence of a certain amount of microplastics (MPs) in the water is unavoidable due to the complexity of the components contained in the water and the prevalence of MPs. MPs, as one of the pollutants that are difficult to be degraded by discharge plasma, undergo physical and chemical changes that increase their risk in the environment after treatment. Therefore, it is necessary to understand the fate of MPs after being treated with discharge plasma. In this study, the surface morphology of plastics before and after discharge plasma treatment was observed by scanning electron microscopy (SEM). The plastics after discharge plasma treatment were characterized by Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) to determine the changes in oxygen-containing functional groups on the surface. The recovery of microplastics (MPs) in saturated porous media under different physicochemical and plasma oxidation conditions was investigated by column experiments. It has been shown that MPs exhibit increased recovery under conditions of increased flow rate and pH. A decrease in recovery was observed at elevated ionic strength and co-existing cation valence. High voltages and low air flow rates increase the oxidation of MPs by increasing the thermal effects of the dielectric barrier discharge (DBD) plasma system, the amount of reactive oxygen species (ROS) and the intensity of ultraviolet ray (UV) irradiation. The mobility of MPs is enhanced by a combination of these factors. The advection–dispersion equation (ADE) fits the transport data of MPs well. The interaction energy between quartz sand and MPs was calculated using the Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. This study provides a new perspective on the potential risks of discharge plasma in water treatment.

Assembly of MOFs derived Co-Mn bimetallic oxides on SiO2 nanofibrous membrane for indoor air purification

The development of highly efficient air purification materials contributes to acquiring quality indoor air that essential for improving physical health and life comfort. In this work, a Co3O4-CoMn2O4@SiO2 (COCMOS) nanofibrous membranes (NFMs) were prepared by thermal treating Mn-modified ZIF-67@SiO2 NFMs for efficient indoor air purification. The COCMOS NFMs exhibited 99.03 % and 99.999 % dust retention efficiencies for PM0.3 and PM2.5 with a low filtration resistance, respectively. Compared to the Co3O4@SiO2 (COS) NFMs (23 %), the HCHO removal efficiency of COCMOS NFMs was significantly improved at room temperature, reaching over 95 % within 25 min. The characterization results indicated that the thermal treatment of Mn-modified ZIF-67 induced the formation of a Co3O4-CoMn2O4 heterostructure on the surface of COCMOS NFMs. The Mn-Co bimetallic sites in this heterogeneous structure increased the amounts of oxygen vacancies and high valent cations and enhanced the redox properties of COCMOS NFMs, which contributed to its superior performance. This work provided insights on the design and preparation of highly efficient materials for indoor air purification.

(Invited) Solid/Electrolyte Interface Under Confinement in Divalent Water-in-Salt Electrolytes

Concentrated aqueous electrolytes (water-in-salt electrolytes, WiSEs) have gained increasing attention in the last few years because they display much wider electrochemical stability windows (upwards of 3V) than the thermodynamic limit of water (1.23V), making them exciting candidates for a variety of electrochemical systems including aqueous batteries. Importantly, it is the ions directly at the electrode/electrolyte interface that are key to explaining this unexpected reactivity. The electrode/electrolyte interface is classically thought of as the electrical double layer (EDL), or the ion arrangement at an interface that builds up to neutralize the surface potential. WiSEs present very different EDL structures than do classical dilute electrolytes. However, most work has focused on monovalent WiSEs, primarily motivated by Li-battery applications using lithium bis(trifluoromethylsulphonyl)imide (LiTFSI).In this work, we aim to understand how divalent ions within the WiSE regime alter both the short-range and long-range signatures of the EDL under confinement. For most of the above applications, reactions occur within the pore-space of a porous electrode, which exhibit confined, overlapping EDLs. Therefore, we use confinement as a tool to probe both the short-range layering structure (<10 nm) and electrostatic decay length (~10-100 nm) away from a charged interface with Surface Forces Apparatus (SFA) measurements.Using WiSEs comprising LiTFSI, Zn(TFSI)2, and mixtures of the two salts, we first establish the bulk structure of these electrolytes using Wide Angle X-Ray Scattering and Raman Spectroscopy, which reveal that the anion and cation are closely associated in all electrolytes, regardless of cation valency. Additionally, clusters of ions are formed in all electrolytes, however, the clusters are suppressed with increasing divalent ion fraction. Under confinement, SFA results demonstrate that the thickness of the adsorbed layer of ions at a solid/electrolyte interface grows with increasing divalent ion fraction. Multiple interfacial layers are formed following this adlayer, and these layers seem dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. This work contributes significant fundamental understanding regarding the structure and charge-neutralization mechanism in this class of electrolytes both in the bulk and under confinement at an interface.

Control mechanism of short-term fertilization with cattle manure on the release characteristics of soil colloids in farmland: grain size and physicochemical properties

BackgroundUnderstanding the release characteristics of soil colloids is a prerequisite for studying the co-transport of colloids and pollutants in subsurface environment. As a crucial agricultural management measure, fertilization not only alters the material composition of farmland soil, but also significantly regulates the properties and release patterns of soil colloids. This study systematically investigated the regulatory mechanism of short-term cattle manure fertilization on the macroscopic release and microscopic properties of soil colloids with different particle sizes, providing a theoretical foundation for subsequent research on the fate and transport of agricultural non-point source pollutants.ResultsThe colloids in natural agricultural soil primarily consist of inorganic components. Graded extraction of the colloids has revealed that the combined proportion of colloids with particle sizes of 1–2 μm and 0.45–1 μm accounts for approximately 80.5%. Applying cattle manure inhibits the release of soil colloids, and the content of large particle size (1–2 μm) components increases. The content of organic colloids is increased due to the high total organic carbon (TOC) in cattle manure, particularly those with a particle size less than 1 μm. The characterization of organic colloid components revealed a significant increase in aromatic carbon and oxygen-containing functional groups, while the aliphatic content decreased. The response sequence regarding changes in functional groups within organic colloids induced by fertilization was as follows: –CH3, –CH2 > C–O > –OH > C=C. Fertilization promotes the release of 1:1-type inorganic mineral colloids, increasing the content of poorly crystalline minerals. The retention of aromatic carbon and oxygen-containing functional groups by poorly crystalline mineral colloids served as the primary mechanism leading to their increased content levels. Changes in environmental factors significantly impacted the release and properties of soil colloids. Conditions such as low cationic valence, high ionic strength, and high pH promoted the release of soil colloids.ConclusionsThe short-term fertilization resulted in a reduction in the release of soil colloids and brought about significant alterations in their particle size composition and properties. The findings of this study provide valuable insights into understanding the impact of fertilization-induced colloid release on the environmental behavior of agricultural non-point source pollutants.

Cation valency in water-in-salt electrolytes alters the short- and long-range structure of the electrical double layer

Highly concentrated aqueous electrolytes (termed water-in-salt electrolytes, WiSEs) at solid-liquid interfaces are ubiquitous in myriad applications including biological signaling, electrosynthesis, and energy storage. This interface, known as the electrical double layer (EDL), has a different structure in WiSEs than in dilute electrolytes. Here, we investigate how divalent salts [zinc bis(trifluoromethylsulfonyl)imide, Zn(TFSI)2], as well as mixtures of mono- and divalent salts [lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with Zn(TFSI)2], affect the short- and long-range structure of the EDL under confinement using a multimodal combination of scattering, spectroscopy, and surface forces measurements. Raman spectroscopy of bulk electrolytes suggests that the cation is closely associated with the anion regardless of valency. Wide-angle X-ray scattering reveals that all bulk electrolytes form ion clusters; however, the clusters are suppressed with increasing concentration of the divalent ion. To probe the EDL under confinement, we use a Surface Forces Apparatus and demonstrate that the thickness of the adsorbed layer of ions at the interface grows with increasing divalent ion concentration. Multiple interfacial layers form following this adlayer; their thicknesses appear dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. It is likely that in the WiSE regime, electrostatic screening is mediated by the formation of ion clusters rather than individual well-solvated ions. This work contributes to understanding the structure and charge-neutralization mechanism in this class of electrolytes and the interfacial behavior of mixed-electrolyte systems encountered in electrochemistry and biology.

Comparative study of polystyrene microplastic transport behavior in three different filter media: Quartz sand, zeolite, and anthracite

Microplastics (MPs) are emerging contaminants that are attracting increasing interest from researchers, and the safety of drinking water is greatly affected by their transportation during filtration. Polystyrene (PS) was selected as a representative MPs, and three filter media (quartz sand, zeolite, and anthracite) commonly found in water plants were used. The retention patterns of PS-MPs by various filter media under various background water quality conditions were methodically investigated with the aid of DLVO theory and colloidal filtration theory. The results show that the different structures and elemental compositions of the three filter media cause them to exhibit different surface roughnesses and surface potentials. A greater surface roughness of the filter media can provide more deposition sites for PS-MPs, and the greater surface roughness of zeolite and anthracite significantly enhances their ability to inhibit the migration of PS-MPs compared with that of quartz sand. However, surface roughness is not the only factor affecting the migration of MPs. The lower absolute value of the surface potential of anthracite causes the DLVO energy between it and PS-MPs to be significantly lower than that between zeolite and PS-MPs, which results in stronger retention of PS-MPs by anthracite, which has a lower surface roughness, than zeolite, which has a higher surface roughness. The transport of PS-MPs in the medium is affected by the combination of the surface roughness of the filter media and the DLVO energy. Under the same operating conditions, the retention efficiencies of the three filter materials for PS-MPs followed the order of quartz sand < zeolite < anthracite. Additionally, the conditions of the solution markedly influenced the transport ability of PS-MPs within the simulated filter column. The transport PS-MPs in the simulated filter column decreased with increasing solution ionic strength and cation valence. Naturally, dissolved organic matter promoted the transfer of PS-MPs in the filter layer, and humic acid had a much stronger facilitating impact than fulvic acid. The study findings might offer helpful insight for improving the ability of filter units ability to retain MPs.

Effect of cation species on pressure-driven electrokinetic energy conversion in charged conical nanochannels

Electrokinetic energy conversion (EEC) offers a promising avenue for transforming elusive natural energy into electric power, showing a wide application spectrum. Unlike prevalent studies that chiefly utilize symmetrical electrolyte solution (e.g., KCl) and uniformly structured negatively charged nanochannels for EEC, this paper delves into a thorough examination of EEC characteristics—streaming current, streaming potential, and output power—in both positively and negatively charged conical nanochannels with symmetrical and asymmetric (CaCl2 and LaCl3) electrolytes solutions. Operating under the assumption that the electrolyte solutions (KCl, CaCl2, and LaCl3) possess equivalent ionic strength and, thereby, a common Debye length, our findings reveal a significant dependency of EEC characteristics and their regulation parameters on the electrolyte type, nanochannel charge polarity, and ionic strength. As the ionic strength increases, both the streaming current and output power initially rise to a peak before subsequently declining, with the ionic strength at the peak being influenced by the cation valence: lower valence leads to lower ionic strength. In asymmetric electrolyte scenarios, optimal EEC characteristic is observed in positively charged conical nanochannels under a reverse pressure difference, attributed to the ion-selective and ionic concentration distribution in the charged conical nanochannels. Moreover, the complex behaviors of the regulation parameters of EEC characteristics are unveiled. Notably, a tri-valent electrolyte's regulation parameters exceed those of a bi-valent electrolyte, indicating that ionic valence asymmetry enhances the regulation effects on EEC in conical nanochannels.

Oxygen potential measurement of U0.85Am0.15O2 at 1473, 1573, and 1673 K

Oxygen potential data of U0.85Am0.15O2−x were measured at 1473, 1573, and 1673 K by thermogravimetry. In U1−yAnyO2−x, where An stands for Pu or Am, and for a given value of “y” and Oxygen/Metal ratio, the oxygen potential of U1−yAmyO2−x is higher than that of U1−yPuyO2−x. The valence of cations in the hypostoichiometric region is similar to that of Nd-doped UO2. At the stoichiometric composition, it is estimated to be Am3+, U4+, and U5+ (for charge compensation of Am3+) in the stoichiometric composition. The experimental data were analyzed using a defect chemistry model, and a relationship connecting the oxygen-to-metal ratio, the temperature, and the equilibrium oxygen partial pressure was proposed.

Probing the Long- and Short-Range Structural Chemistry in the C-Type Bixbyite Oxides Th0.40Nd0.48Ce0.12O1.76, Th0.47Nd0.43Ce0.10O1.785, and Th0.45Nd0.37Ce0.18O1.815 via Synchrotron X-ray Diffraction and Absorption Spectroscopy.

The long- and short-range structural chemistry of the C-type bixbyite compounds Th0.40Nd0.48Ce0.12O1.76, Th0.47Nd0.43Ce0.10O1.785, and Th0.45Nd0.37Ce0.18O1.815 is systematically examined using synchrotron X-ray powder diffraction (S-PXRD), high-energy resolution fluorescence detection X-ray absorption near edge (HERFD-XANES), and extended X-ray absorption fine structure spectroscopy (EXAFS) measurements supported by electronic structure calculations. S-PXRD measurements revealed that the title compounds all form classical C-type bixbyite structures in space group Ia3̅ that have disordered cationic crystallographic sites with further observation of characteristic superlattice reflections corresponding to oxygen vacancies. Despite the occurrence of oxygen vacancies, HERFD-XANES measurements on the Ce L3-edge revealed that Ce incorporates as Ce4+ into the structures but involves local distortion that resembles cluster behavior and loss of nearest-neighbors. In comparison, HERFD-XANES measurements on the Nd L3-edge supported by electronic structure calculations reveal that Nd3+ adopts a local coordination environment similar to the long-range C-type structure while providing charge balancing for the formation of oxygen defects. Th L3-edge EXAFS analysis reveals shorter average Th-O distances in the title compounds in comparison to pristine ThO2 in addition to shorter Th-O and Th-Ce distances compared to Th-Th or Ce-Ce in the corresponding F-type binary oxides (ThO2 and CeO2). These distances are further found to decrease with the increased Nd content of the structures despite simultaneous observation of the overall lattice structure progressively expanding. Linear combination calculations of the M-O bond lengths are used to help explain these observations, where the role of oxygen defects, via Nd3+ incorporation, induces local bond contraction and enhanced Th cation valence, leading to the observed increased lattice expansion with progressive Nd3+ incorporation. Overall, the investigation points to the significance of dissimilar cations exhibiting variable short-range chemical behavior and how it can affect the long-range structural chemistry of complex oxides.

Synergistic Hydrogen Peroxide‐Driven Cation Valence Regulation and La/O Co‐Doped SnS‐Based Oxysulfide Catalyst for Efficient Catalytic Reduction of Toxic Organics and Cr(VI) Under Dark

AbstractA novel La/O co‐doped SnS oxysulfide catalyst (labeled SnLaOS) with heterovalent tin states and sulfur vacancy defects is successfully synthesized for effective catalytic reduction of toxic organics heavy metal ions with NaBH4 in the dark. La/O co‐doped and hydrogen peroxide‐driven SnLaOS catalyst with suitable heterovalent Sn2+/Sn4+ states and sulfur vacancy defects exhibited excellent catalytic reduction capability. The 100 mL 20 ppm of 4‐nitrophenol (4‐NP) and 50 ppm of rhodamine‐B (RhB), methylene blue (MB), methyl orange (MO), and Cr(VI) solution are entirely reduced by 5 mg SnLaOS‐3 within 10, 12, 12, 16, and 14 min, respectively, with durable stability. Synergistic transition metal La3+‐cation and O2−‐anion co‐doped SnS adjusted the energy bandgap and introduced sulfur vacancy defects, and the hydrogen peroxide‐driven regulated the SnLaOS with suitable Sn4+/Sn2+ states ratio. The sulfur vacancies in SnLaOS provide active sites for adsorbed proton for pollutants reduction, and heterovalent Sn2+/Sn4+ states in SnLaOS facilitates electrons efficient transfer through electron hopping between Sn2+ and Sn4+ for pollutants reduction. This study provides a novel efficient catalyst for the water pollutants treatment.

NiFe layered double hydroxide nanosheets self assembled and etched by phosphotungstic acid for the enhanced oxygen evolution reaction

Poor conductivity and low reaction kinetics of layered double hydroxides (LDHs) hindered their large-scale applications as catalysts in the oxygen evolution reactions (OER). The composites with vacancies, high valence cations and 3D gradient pore structures were synthesized by the ionic exchange, delamination and self-assembly methods. The nanoclusters [PW12O40]3- were successfully intercalated into the interlayers of LDHs due to the static attraction. Meanwhile, the partial metal cations in the layers were etched by its conjugate acid. The molar ratios of Ni:Fe and acid:LDH need to be modulated to achieve the optimum catalytic performances. The composite 1:4PW12–Ni3Fe exhibited a lower overpotential 270 mV at 10 mA cm−2, superior kinetics (43 mV dec−1), better conductivity (2.68 Ω cm−2) and larger turnover frequency (3.59 s−1) than the bulk and nanosheet counterparts with reevesite-like structure. [PW12O40]3- more effectively reduced the overpotentials of LDHs than other interlayer anions (e.g.WO4−, B4O72− and CnH2n+1SO42−). The favourable electrocatalytic performances were attributed to the synergistic effects. The vacancies provided new active centers with high intermediate adsorption energy. The high valances cations induced electronic coupling and spatial charge redistribution. 3D gradient pore structures with a large electrochemical active surface area exposed active sites and provided a convenient path for transferring masses and charges.

Inductive effect of cationic equivalent substitution tuning europium valence in Na2Zr1-xHfxSiO5:Eu phosphors for WLEDs

The realization of Eu3+ reduction and its reduction mechanism have become focal points in the field of WLED phosphor research. In this study, the reduction of Eu3+ was successfully achieved through cationic substitution strategy by replacing Zr4+ with Hf4+ in Na2ZrSiO5:Eu3+. The effects of substituting Hf4+ for Zr4+ on the phase, crystal structure, and luminescence properties of Na2Zr1-xHfxSiO5:Eu0.03 (0 ≤ x ≤ 1) were thoroughly investigated based on Rietveld refinement, spectral data, DFT calculation and electronegativity of ions. Comprehensive consideration was given to the effect of site size change and site reducibility on Eu3+ reduction. The results demonstrate that the reduction of Eu3+ in Na2Zr1-xHfxSiO5:Eu0.03 is attributed to the alteration in inducible effect caused by cationic substitution and the enhancement in site reducibility rather than changes in site size. Therefore, the cationic substitution strategy based on induction effect presents a novel approach for achieving Eu3+ reduction and offers a new insight into developing and modifying Eu2+-activated phosphors.

Constructing surface protective film of V-Se-O to promote zinc ion storage by surface oxygen implantation strategy

Interfacial chemical modification is an effective strategy to adjust the strong Coulombic ion-lattice interactions with high valence cations experienced by electrode materials, facilitating the reaction kinetic. In this paper, a simple and fast surface oxygen implantation strategy was designed to adjust the electronic structure of stainless steel (SS) supported vanadium diselenide (VSe2) nanosheets and form a surface protective film, which effectively accelerates the reaction kinetics of Zn2+ and extends the cycle life of the battery. It is demonstrated that the conductivity, pseudocapacitance and specific capacity can be tuned by selectively introducing oxygen species to the surface, which provides an important reference for the design of electrodes with controlled surface chemistry. Density functional theory (DFT) calculations also confirm that the electronic structure can be adjusted by surface oxygen injection strategy, which not only improves the conductivity, but also adjusts the adsorption energy, thus providing favorable conditions for zinc ion storage. Benefiting from the selenium vacancies and pores generated by the removal of part of selenium, and the oxide film formed on the surfaces, the VSe2-xOx-SS-30 electrode showed higher specific capacity (188.4 mAh/g at 0.5 A g−1 after 50 cycles), better rate performance (107.1 mAh/g at 4 A g−1) and more satisfactory cycling stability (83.1 mAh/g at 5 A g−1 after 1800 cycles) than VSe2-SS electrode. Importantly, the flexible quasi-solid-state VSe2-xOx-SS-30//Zn battery also exhibits high specific capacity and excellent environmental adaptability. Furthermore, the zinc (de)intercalation and transformation reactions mechanism was revealed by some ex-situ/in-situ techniques.

Efficiency of Cr3+ → Cr4+ conversion in YSAG:Cr ceramics

In this study, we investigated the influence of the position and quantitative content of scandium in YSAG:Cr on the efficiency of chromium cation valence conversion. YSAG:Cr ceramic powders were synthesized using the chemical precipitation method. It was determined that the microstructure of ceramics and the luminescent properties of YSAG:Cr4+ depend on the predominant position of scandium, whether it replaces octahedral or dodecahedral positions in the garnet crystal lattice. An increase in Scdod content contributed to a decrease in grain size and a shift of the emission peak of Cr4+ ions towards the short-wavelength region. Conversely, an increase in Scoct content led to an increase in grain size and a shift of the maximum of the luminescent band towards the long-wavelength region. It was found that increasing the quantitative content of scandium in the octahedral position in the garnet structure by up to 50 % enhances the efficiency of the conversion of Cr3+ to Cr4+, while an increase in the proportion of Scdod resulted in a decrease in conversion efficiency.

High-Entropy CeNbO4+δ-Based Ceramics with Ultrahigh Comprehensive Thermosensitive Performances.

Next-generation advanced high-temperature sensors rely heavily on negative temperature coefficient thermosensitive ceramics with low cost, small volume, high sensitivity, and fast response. However, thus far, the enormous challenge of achieving ultrahigh stability and accuracy has become a critical bottleneck restricting the development of thermosensitive ceramics in high-temperature sensor applications. Here, we propose a high-entropy strategy to design a "cation valence self-equilibrium" system in CeNbO4+δ-based ceramics introducing redox couple compensation and ultrahigh density dislocations to solve the problem of temperature-dependent oxygen nonstoichiometry that restricts the performances of high-temperature thermosensitive ceramics. Ferroelastic domains are generated by enhancing the configurational entropy at both A and B sites, resulting in a dramatic increase of dislocation density to >1010 mm-2, which ultimately optimizes the thermosensitive performances. Extreme temperature measurement accuracy with R2 as high as 999.98‰ and RSS as low as 0.011 and high-temperature stability with ΔR/R0 as low as 0.23% after aging at 873 K for 1000 h are realized in high-entropy CeNbO4+δ-based ceramics, indicating a breakthrough in the comprehensive performances of thermosensitive ceramics. This work opens up an effective way to design thermosensitive materials with ultrahigh comprehensive performance to meet the requirements of advanced high-temperature sensors.

Mo6+ bifunctional substitution of P2-type manganese oxide for high performance sodium-ion batteries

Due to its cost-effectiveness and high specific capacity, P2-type manganese (Mn) oxide is considered a highly promising cathode material for sodium ion batteries (SIBs). However, the practical application of this material is hindered by poor cyclic stability caused by the phase transition of P2-P’2 due to the Jahn-Teller effect of Mn3+ at low voltage and significant volume changes at high voltage. In this study, we utilized Mo6+ dual-function P2-Na0.67Mn0.99Mo0.01O1.997(PO4)0.0008 (NMMPO-1) to achieve exceptional magnification performance and cycle stability. Advanced electron microscopy and X-ray diffraction analysis revealed that Mo6+ acts as a pillar in replacing interlayer Na+ sites within the P2 phase, resulting in extended layer spacing and a stable crystal structure. Additionally, Mo6+ substitution for Mn3+ weakens the Jahn-Teller distortion effect of Mn3+. Ex-situ X-ray diffraction experiments demonstrated that NMMPO-1 effectively inhibits the P2-P’2 phase transition at low voltage while minimizing volume changes during charge–discharge cycles. Overall, our modified NMMPO-1 exhibits excellent cycle stability with 144.55 mA h g−1 after 100 cycles at 0.5C, retaining 83 % capacity retention rate, along with impressive rate performance achieving capacity of 100.57 mA h g−1 at 5C. Furthermore, NMMPO-1 demonstrates superior air stability compared to unmodified samples when exposed to air over multiple cycles. Moreover, through detailed analysis using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic intermittent titration technique (GITT) curves; it is observed that NMMPO-1 possesses enhanced Na+ diffusion capacity and kinetic properties compared to other materials. This research provides novel insights into the role of substituting high valence cations in layered Mn oxide materials which can contribute towards designing improved performance for future sodium ion battery applications.

Finely tuning cobalt valence in Co3O4 lattice through chromium substitution: Regulating the charge transfer and oxygen vacancies for oxygen evolution and methanol oxidation reaction

In this intriguing study, our central focus revolves around efficiency of the Oxygen Evolution Reaction (OER) and methanol oxidation Reaction (MOR) through a captivating approach: harnessing the power of cobalt valence modulation in Cobaltite (Co3O4), achieved by the enchanting substitution of chromium (Cr). By seamlessly integrating chromium atoms into the crystal lattice of Co3O4, our ultimate aim is to orchestrate a remarkable transformation in the potential-determining step of the OER, resulting in a symphony of improved catalytic performance. This substitution is done by utilizing simple sol-gel method at low temperatures. This gentle adjustment of cation valence states creates oxygen vacancies on the spinel surface, achieving an ideal ion ratio of Co2+/Co3+. The formation of spinel oxides has been confirmed by a comprehensive range of precise physicochemical techniques including, Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), High Resolution Transmission Electron Microscopy (HRTEM), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS), Brunauer–Emmett–Teller (BET) technique and Raman spectroscopy. The presence of oxygen vacancy has been verified with Electron Paramagnetic Resonance (EPR) spectroscopy. The spinel oxide, Cr1.5Co1.5O4 displays superior activity for OER with current density of 100 mA/cm2 at the overpotential of only 413 mV. Our findings highlight the significance of cobalt valence control in promoting OER/MOR activity, paving the way for advanced electrocatalytic systems with enhanced energy conversion capabilities.

Fluorinated silane self-assembled monolayer modification of V2O5 for enhanced hole injection and device efficiency

This study introduces a new approach to enhance hole injection in organic light-emitting diodes (OLEDs) by modifying the energy band alignment. This enhancement is achieved by incorporating gap states near the Fermi level through the application of a 1H,1H,2H,2H-perfluorooctyltriethoxysilane self-assembled monolayer (F8SAM) coating on V2O5. Compared to thermally evaporated V2O5, the F8SAM coating induces greater oxygen deficiency, reducing the V2O5 (V5+) content from 84.2 % to 76.9 % and increasing the VO2 (V4+) content from 15.7 % to 23.0 %. This modification causes both the highest occupied molecular orbital and gap state levels to move closer to the Fermi level, facilitated by increased oxygen vacancies, high carrier concentration, and delocalized free electrons. The alteration in the gap state provides a more accessible pathway for efficient hole injection, as confirmed in optoelectronic green light devices, which demonstrate a wavelength of 530 ± 5 nm. Significantly, devices incorporating a double-layer hole-injection layer exhibit a 5-fold increase in maximum luminance, a 1.6-fold increase in current efficiency, and a 1.7-fold increase in power efficiency compared to devices with an unmodified V2O5 film. The enhanced performance is attributed to the well-aligned F8SAM on V2O5, which increases the density of hole states and thereby improves device performance. This study demonstrates a practical method for modulating the cation valence state of V2O5, offering a pathway toward improved hole injection and, consequently, more efficient and functional OLED devices.

Reaction mechanism and kinetics for Pt/C and Au/C catalyzed aqueous phase glycerol oxidation to various carboxylic acids

Fundamental understanding of heterogeneously catalytic aerobic oxidation of polyol is highly desirable for sustainable and efficient chemical synthesis. Herein, based on the purpose of exploring the selectivity of various carboxylic acids on Pt-Au catalysts with different ratios, we conducted a comprehensive investigation into the reaction pathways of glycerol oxidation over pristine Pt/C and Au/C catalysts via experiments, kinetics analysis and DFT calculations. Structural characterizations revealed that Pt/C exhibits a higher metallic state and more d electrons, thus tending to strongly adsorb OH– and promote oxygen activation. Conversely, the weak oxygen activation of Au/C could be attributed to fewer cationic high valence state and d electrons. Furthermore, the Langmuir-Hinshelwood kinetic model and DFT calculations indicate both catalysts exhibit obvious differences in product distribution. Specifically, Pt demonstrated higher selectivity towards lactic acid by facilitating dehydration of C-OH in glyceraldehyde and promoting timely desorption of lactic acid species. In contrast, Au displayed more glycolic acid products caused by strengthening oxidative cleavage of C-C bond in glyceric acid. Expanding to bimetallic catalysts, it was observed that catalysts with higher Au content exhibit enhanced selectivity towards the oxidation of glyceric acid to glycolic acid, while those with a higher Pt ratio demonstrate increased selectivity for the oxidation of glycerol to lactic acid. These findings provide valuable insights for guiding the design and optimization of this catalytic process to achieve targeted product generation.