Cationic States Research Articles

Spiro‐buckybowls: Synthesis and Selective Transformations toward Chiral and Nonlinear Optical Polycycles

Integration of spirocycles with buckybowls is a promising strategy to construct three‐dimensional (3D) curved π‐systems and to endow distinctive physicochemical features arising from buckybowls. Herein, a series of carbon‐bridged spiro‐type heterosumanenes (spiro‐HSEs) were synthesized by combining 9,9′‐spirobifluorene and dichalcogenasumanenes (DCSs). It is found that spiro‐conjugation plays an important role in the geometric and electronic structures of spiro‐HSEs. The bowl depth of DCSs moiety becomes larger in the spiro‐HSEs. Owing to the Jahn‐Teller (J‐T) effect, two DCSs segments of spiro‐HSEs have different bowl depths accompanied with the unequal distribution of charge in radical cation state. Taking advantage of the typical reactions of DCSs, selective transformations of spiro‐HSEs have been adopted in accordance to the nature of chalcogen atoms (S, Se, Te) to bestow the value‐added functionalities. The emissive property is enhanced by converting the thiophene rings of S‐doped spiro‐HSE into thiophene S,S‐dioxides. A chiroptical polycycle could be produced by ring‐opening of the edge benzene of Se‐doped spiro‐HSE. The covalent adduct of Te‐doped spiro‐HSE with Br2 forms non‐centrosymmetric halogen‐bonded networks, resulting in the high performance second‐order nonlinear optics (NLO).

Unveiling the Role of Dopants in the Electrochemical Ozone Production Reaction Using Tin Oxide Electrodes

Ozone is a strong oxidizer with promising environmentally friendly applications in water disinfection, air purification, and organic synthesis. The 6-e- electrochemical ozone production (EOP) reaction offers great potential for ozone generation while curbing the formation of harmful by-products compared to other ozone production methods. However, the development of electrochemical ozone production (EOP) catalysts is limited by significant hurdles dictated by thermodynamic limitations. In this work, we develop and validate a comprehensive guideline that outlines a strategic and rational design approach to induce EOP activity in tin oxide. We propose that two things are needed for tin oxide to produce ozone: increased conductivity, achieved with donor dopants, and first-row transition metal (TM) dopants to facilitate hydroperoxyl radical generation through Fenton-like processes. To validate our approach, we picked tantalum, antimony, and tungsten as donor dopants and nickel and cobalt as transition metals. Our results suggest that all combinations of TMs, oxidizable to a cationic state capable of producing hydroperoxyl radicals from hydrogen peroxide, and donor dopants lead to EOP activity in tin oxide.

Structures, energies and vibrational frequencies of the X and A states of haloacetylene cations, HCCX+ (X = F, Cl, Br, I)

Modeling charge migration resulting from the coherent superposition of cation ground and excited states requires information about the potential energy surfaces of the relevant cation states. Since these states are often of the same electronic symmetry as the ground state of the cation, conventional single reference methods such as coupled cluster cannot be used for the excited states. The EOMCCSD-IP (equation of motion coupled cluster with single and double excitations and ionization) is a convenient and reliable “black-box” method that can be used for the ground and excited states of cations, yielding results of CCSD (coupled cluster with singles and double excitation) quality. Charge migration in haloacetylene cations arises from the superposition of the X and A states of HCCX+ (X = F, Cl, Br and I). The geometries, ionization potentials and vibrational frequencies have been calculated by CCSD/cc-pVTZ for neutral HCCX and the X state of HCCX+ and by EOM CCSD-IP/cc-pVTZ for the X and A states of HCCX+. The results agree very well with each other and with experiment. The very good agreement between CCSD and EOMCCSD-IP for the X states demonstrates that EOMCCSD-IP is a suitable method for calculating the structure and properties of ground and excited states for the HCCX cations.

Manganese doped La0.8Ba0.2FeO3 perovskite oxide as an efficient electrode material for supercapacitor

In this study, L0.8Ba0.2Fe1-xMnxO3 (LBFM-x, x = 0.0, 0.2, 0.5, 0.8) perovskite materials were synthesized by a Sol-Gel combustion method and were investigated as an electrode material for a supercapacitor device. The morphology, crystalline structure and electrochemical performance of the samples were studied in detail. The active points, where the electrochemical redox reaction takes place to store faradaic energy, are the oxygen vacancies on the surface of perovskite oxides. Partial substitution in the B-site of the perovskite structure, which is directly related to the oxygen vacancy in BO6 octahedral, is effective in optimizing the electrochemical performance. Based on the results of structural analysis, LBFM-0.2 has the highest concentration of oxygen vacancies; thus, it showed a higher electrochemical performance compared to other samples. The supercapacitors prepared with this electrode material should have an acceptably high specific capacitance of 685 F.g−1 at a current density of 2.0 A.g−1. The partial substitution of Mnn+ at the B-site increases the oxidation state of Fe cations and the mobility of oxygen ions through the oxygen vacancy sites. The electrochemical stability of LBFM-0.2, was evaluated by applying long charge-discharge cycles. After 3000 charge-discharge cycles, the supercapacitor was able to maintain about 94 % of its initial capacity.

Targeting Lysosomes: A Strategy Against Chemoresistance in Cancer.

Chemotherapy is still the major method of treatment for many types of cancer. Curative cancer therapy is hampered significantly by medication resistance. Acidic organelles like lysosomes serve as protagonists in cellular digestion. Lysosomes, however, are gaining popularity due to their speeding involvement in cancer progression and resistance. For instance, weak chemotherapeutic drugs of basic nature permeate through the lysosomal membrane and are retained in lysosomes in their cationic state, while extracellular release of lysosomal enzymes induces cancer, cytosolic escape of lysosomal hydrolases causes apoptosis, and so on. Drug availability at the sites of action is decreased due to lysosomal drug sequestration, which also enhances cancer resistance. This review looks at lysosomal drug sequestration mechanisms and how they affect cancer treatment resistance. Using lysosomes as subcellular targets to combat drug resistance and reverse drug sequestration is another method for overcoming drug resistance that is covered in this article. The present review has identified lysosomal drug sequestration as one of the reasons behind chemoresistance. The article delves deeper into specific aspects of lysosomal sequestration, providing nuanced insights, critical evaluations, or novel interpretations of different approaches that target lysosomes to defect cancer.

Synthesis and Characterization of a New Ion Exchange Cellulose -1- Butane Sulphonic Acid (CBSA) Resin and its Application for Removal of Hazardous Metal Ion (Pb2+) from Industrial Waste Water by Batch Method

Objective: The purpose of this work is to develop and evaluate a new cellulose-1-butane sulphonic acid resin and use it for the elimination of hazardous metallic ions from textile industry effluent. Method: In the laboratory, a new cellulose-based resin containing 1- Butane sulphonic acid group has been synthesized. 1-Butane sulphonic acid group has been introduced into cellulose matrix through modified Porath’s method. Findings: Development of cellulose-1-butane sulphonic acid resin based on natural polysaccharides for the removal of lead ions, a dangerous metal, from industrial wastewater. Cellulose -1-Butane sulphonic acid resin's adsorbed metal ions were efficiently eluted using varying strengths of HCl solution. The resin could then be washed with pure, acidic distilled water to restore it to its H+ cationic exchanger state ten times. The hazardous metal ion Pb2+ can be specifically extracted from industrial waste water using the cellulose-1-Butane Sulphonic Acid (CBSA) resin. Novelty: Ion exchange capacity, pH titration, FTIR spectra, elemental analysis, and moisture levels were used to characterize the CBSA resin. At various pH levels, the distribution coefficient value (Kd) of lead metal ions has been methodically investigated using the batch method. Keywords: Effluent, Distribution Coefficient, Resin, Waste Water, Polysaccharide

Geometric and Electronic Properties of P Atom-Doped Al Nanoclusters: Alkaline-like Superatom of P@Al12.

The geometric and electronic characteristics of phosphorus-atom doped aluminum nanoclusters, AlnPm (n = 7-17, m = 1 and 2), were investigated through a combination of experiments and theoretical calculations. The size dependences of the ionization energy (Ei) for AlnPm NCs exhibit a local minimum of 5.37 eV at Al12P1, attributed to an endohedral P@Al12 superatom (SA). This SA originates from an excess electron toward the 2P shell closing (40e), coexisting with an exohedral isomer featuring a vertex P atom. The stability of the endohedral P@Al12 is further enhanced in its cationic state compared to the exohedral isomer, when complexed with a fluorine (F) atom, forming an SA salt denoted as P@Al12+F- with an elevated Ei ranging from 6.42 to 7.90 eV. In contrast, for the anionic Al12P1-, the exohedral form is found to be more stable than the endohedral one using anion photoelectron spectroscopy and calculations. The geometric and electronic robustness of neutral P@Al12 SAs against electron donation and acceptance is discussed in comparison to rare-gas-like Si@Al12 SAs.

Determination of the Electronic Structure, Charge-transfer, and Optical Properties of Neutral, Anionic, and Cationic Perfluoropentacene

Perfluoropentacene ( is an n-type organic semiconductor made by fluorination of p-type semiconductor Pentacene and can find applications in molecular thin film devices. In this work, a theoretical study of Perfluoropentacene was carried out based on density functional theory (DFT) and time dependent (TD-DFT) as implemented in Gaussian 09 package using B3LYP/6-311++G (d, p) and B3LYP/6-31+G(d) basis sets. The electronic, charge transfer, Linear and nonlinear optical properties of the molecule were calculated and reported for the neutral, anionic, and cationic forms of the molecule. The results show that the cationic state of the molecule has the strongest bond length at R(28,32) using the basis sets B3LYP/6-311++G (d,p) and the weakest bond length was found at R(4,6) in the ionic state with 6-31+G (d) basis set. The energy gap obtained for the neutral molecule using 6-31+G (d) and 6-311++G (d,p) basis sets are 2.00eV, 1.99eV respectively. The results show a strong agreement with a previously related work that reported the energy gap as 2.02eV thus indicating high stability of the molecule. Perfluoropentacene has the highest value of chemical hardness of 1.3929eV in its anionic state (Beta MO), so is considered to be harder and more stable than the neutral and cationic. The findings also revealed that with toluene as solvent, the strongest absorption was found at wavelength of 738.38, highest oscillator strength of 0.0599 and the lowest excitation energy of 1.6791eV. The calculated results of polarizability, first and second hyperpolarizability confirm that this molecule is a good non-linear optical material. On the whole, the molecule could be a good material for optoelectronic applications.

Insight from Electrochemical Analysis in the Radical Cation State of a Monopyrrolotetrathiafulvalene-Based [2]Rotaxane.

Mechanically interlocked molecules are a class of compounds used for controlling directional movement when barriers can be raised and lowered using external stimuli. Applied voltages can turn on redox states to alter electrostatic barriers but their use for directing motion requires knowledge of their impact on the kinetics. Herein, we make the first measurements on the movement of cyclobis(paraquat-p-phenylene) (CBPQT4+) across the radical-cation state of monopyrrolotetrathiafulvalene (MPTTF) in a [2]rotaxane using variable scan-rate electrochemistry. The [2]rotaxane is designed in a way that directs CBPQT4+ to a high-energy co-conformation upon oxidation of MPTTF to either the radical cation (MPTTF⋅+) or the dication (MPTTF2+). 1HNMR spectroscopic investigations carried out in acetonitrile at 298 K showed direct interconversion to the thermodynamically more stable ground-state co-conformation with CBPQT4+ moving across the oxidized MPTTF2+ electrostatic barrier. The electrochemical studies revealed that interconversion takes place by movement of CBPQT4+ across both the MPTTF•+ (19.3 kcal mol-1) and MPTTF2+ (18.7 kcal mol-1) barriers. The outcome of our studies shows that MPTTF has three accessible redox states that can be used to kinetically control the movement of the ring component in mechanically interlocked molecules.

Enhanced magnetic behavior of LaFeO3 by co-doping with Nd3+ and V5+ substitution (La0.8Nd0.2Fe0.95V0.05O3)

To enhance the quality of applications of LaFeO3 (LFO) as a magnetoelectric multiferroic through the improvement of magnetic behaviour, co-doping of Nd3+ (20 %) and V5+ (5 %) was considered for partial substitution in place of La3+ and Fe3+, respectively. Co-doped sample of La0.8Nd0.2Fe0.95V0.05O3 (LNFVO) was prepared by solid state reaction method. Rietveld analysis of X-ray diffractograms confirmed the formation as well as successful incorporation of dopants (Nd3+ and V5+) in La3+ and Fe3+ sites of the distorted perovskite structure with Pbnm space group. Morphological features including information related to crystallographic phase were examined by TEM. Distortion due to co-doping helped to achieve the stated objectives. Valence states of dopants and host cations were explored by analyzing XPS observations. Detailed magnetic measurements in the temperature range starting from 300 K down to 2 K suggested that magnetic property was drastically enhanced compared to that of the undoped, which was attributed to mismatch of valence states, ionic diameters etc. between dopants with host cations. The doped sample showed antiferromagnetic to ferromagnetic transition at and below 19 K. All such findings related to magnetic property would be quite attractive for the improvement of multiferroic applications as the low value of magnetization of pristine sample of LFO restrict it to become a good magnetoelectric multiferroic.

First Structured Uranium‐Based Monoliths Produced via Vat Photopolymerization for Nuclear Applications

AbstractUranium plays an unquestionable role in the framework of nuclear physics, biology, and radiopharmacy. Moreover, uranyl ion UO22+ offers an immense variety of applications due to the unique photosensitivity of its complexes. The excited state of uranyl cation is indeed accessible under ultraviolet‐visible (UV–vis) light, readily producing radical species UO22+* upon light irradiation. Herein, an innovative synthesis protocol is presented to explore the use of uranyl cations as photocatalyst systems for photocurable sol–gel‐based formulations, coupling the photochemical reactions of uranyl cations with photopolymerization‐based additive manufacturing processes. Additive manufacturing has nowadays revolutionized the production of complex structures with arbitrary geometries and has opened up enticing opportunities for innovative technological breakthroughs and highly tailorable systems. The fabrication of micro‐architected components is shown via vat photopolymerization, namely, the Digital Light Processing technique, and ‐3D) printed parts are converted into uranium dicarbide (UC2)/carbon nanocomposite upon carbothermal reduction. This uranyl‐mediated additive manufacturing process constitutes the first application of the synergistic role of uranyl motifs in a photopolymer platform, demonstrating for the first time the possibility to directly pattern uranium‐based materials in complex structures.

Cation-exchange-induced structural and chemical modulation of transition metal spinel sulfides to enhance their oxygen evolution performance

Transition metal spinels are promising oxygen evolution reaction (OER) catalysts; however, their rational design has been impeded by their inherent elemental and structural complexities. To alleviate these issues, this paper describes the role of cation exchange in developing active OER catalysts whose chemical and structural features are tailored while their morphology and crystal structure are maintained for enabling a systematic comparison. Through cation exchange, pre-synthesized Co3S4 spinel nanoparticles (NPs) transform into (NixCo3−x)S4 NPs with compositions ranging from Co-rich to Ni-rich phases. Apart from stoichiometry, the atomic disorder and chemical state of the metal cations are amended through excessive interdiffusion and interstitial site preference of the cations, evidently helping boost the catalytic activity. Specifically, (Ni1.2Co1.8)S4—which exhibits an optimal Ni/Co ratio, high structural disorder, and distinct surface chemical states—shows excellent OER performance (overpotential at 10 mA/cm2: 298 mV). In-depth analyses including in situ Raman spectroscopy and DFT calculations indicate that (Ni1.2Co1.8)S4 gradually transforms into OER-active Co/NiOOH—which has a unique electronic structure with strong reaction-intermediate-adsorbing characteristics—during the OER cycles. Overall, the study findings underscore the potency of cation exchange as a tool for controlling structural and chemical features, thereby helping explore complex catalyst materials while enhancing their activity.

Bi(III)‐based oxide semiconductors with ambipolar doping: (Na, K)BiO2

AbstractBi(III)‐based oxides are emerging as important semiconductors for future electronic applications. Through hybrid density functional theory calculations and defect analysis, we demonstrate that ABi(III)O2 (A = Na or K) is a promising wide‐band‐gap bipolar semiconductor. Our calculations predict ABiO2 to have a large band gap of 1.97 eV for NaBiO2 and 2.77 eV for KBiO2. Unlike widely‐used oxide semiconductors such as In2O3 and ZnO, the spatially extended cation states (Bi 6s) of ABiO2 significantly contribute to the valence band maximum, enhancing p‐type dopability. We indeed show that potential acceptors, such as SrBi, produce shallow levels. In addition, n‐type doping is found to be possible through the extrinsic doping of heterovalent elements such as Te and F. The band‐structure analysis reveals that ABiO2 has small effective masses for electrons and holes (< 1m0 where m0 is the electron rest mass), indicating favorable electron and hole transport properties.

Crystal structure, composition and valence state of cations in mixed-valence A1-xCdxMnO3 (A=Pr, La) ceramics

Abstract Complex manganites A1−xCdxMnO3 (A = Pr, La) are synthesized by solid state reaction method. X-ray diffraction, scanning electron microscopy and energy-dispersive analysis are applied to study their crystal structure, surface morphology, elemental and phase composition. X-ray photoelectron spectroscopy (XPS) methods are used to study the charge states of Pr and La cations, as well as to quantify the fractions of coexisting Mn3+ and Mn4+ ions. La3d-, La4d-, Pr4d- и Mn2p-spectra of La3+, Pr3+, Mn3+ and Mn4+ ions are calculated in the isolated–ion approximation with accounting for multiplet splitting and charge transfer effect. Good agreement with the experiment is obtained. The relative fractions of trivalent and tetravalent manganese ions in La0.45Cd0.78Mn0,9O2.86 and Pr0.50Cd0.76Mn0.86O2.88 samples are determined by fitting the Mn2p spectra by superposition of experimental spectra containing only Mn3+, and only Mn4+ ions; they were found to be 0.71Mn3+/0.29Mn4+ and 0.54Mn3+/0.46Mn4+, respectively.

Determination of GaN nanosensor for scavenging of toxic heavy metal ions (Mn2+, Zn2+, Ag+, Au3+, Al3+, Sn2+) from water: Application of green sustainable materials by molecular modeling approach

Gallium nitride nanocage (GaN_NC) can select toxic heavy metals from water. Therefore, it has been found a selective competition for metal cations in the GaN_NC. The electromagnetic and thermodynamic attributes of heavy metals cations-trapped gallium nitride nanocage (GaN_NC) was depicted by material modeling. The data display that heavy metals cations-trapped in the GaN_NC system are resistant materials, with the firm adsorption zone in the center of the cage. Furthermore, charge transfer from GaN_NC to the heavy metals cations demonstrates clear n-type adsorbing manner. The encapsulation of heavy metals cations occurs via chemisorption. In this article, the behavior of trapping of heavy metal ions of Mn2+, Zn2+, Ag+, Au3+, Al3+ and Sn2+ by gallium nitride nanocone for sensing the water metal cations was observed. The nature of covalent features for these complexes has represented the analogous energy amount and vision of the PDOS for the p states of N and d states of heavy metal cations of Mn2+, Zn2+, Ag+, Au3+, Al3+ and Sn2+ through water treatment. The partial density of states (PDOS) can also evaluate an appointed charge group between Mn2+, Zn2+, Ag+, Au3+, Al3+, Sn2+ and GaN_NC which indicate the most stable complex of metallic visage and a certain degree of covalent specifications between heavy metals cations and gallium nitride nanocage. Furthermore, the NMR analysis indicated the notable peaks surrounding metal elements of Mn2+, Zn2+, Ag+, Au3+, Al3+ and Sn2+ through the trapping in the GaN_NC during ion detection and removal from water; however, it can be seen some fluctuations in the chemical shielding treatment of isotropic and anisotropy tensors. Based on the results in this research, the selectivity of metal ion adsorption by gallium nitride nanocage (ion sensor) has been approved as: Ag+ ˃ Au3+ ˃ Mn2+ ≫ Zn2+ ˃ Sn2+ ˃ Al3+. Using quantum theory of atoms in molecules (QTAIMs) method, intermolecular interactions and corresponding parameters at critical bonding points were also investigated.

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.

Effect of Organic Cation Adsorption on Ion-Transport Selectivity in a Cation-Permselective Nanopore Membrane.

A key knowledge gap in the emerging field of nanofluidics concerns how the ionic composition and ion-transport properties of a nanoconfined solution differ from those of a contacting bulk solution. We and others have been using potentiometric concentration cells, where a nanopore or nanotube membrane separates salt solutions of differing concentrations to explore this issue. The membranes studied contained a fixed pore/tube wall anionic charge, which ideally would prohibit anions and salt from entering the pore/tube-confined solution. We have been investigating experimental conditions that allow for this ideally permselective cation state to be achieved. Results of potentiometric investigations of a polymeric nanopore membrane (10 ± 2 nm-diameter pores) with anionic charge due to carbonate are presented here. While studies of this type have been reported using alkaline metal and alkaline earth cations, there have been no analogous studies using organic cations. This paper uses a homologous series of tetraalkylammonium ions to address this knowledge gap. The key result is that, in contrast to the inorganic cations, the ideal cation-permselective state could not be obtained under any experimental conditions for the organic cations. We propose that this is because these hydrophobic cations adsorb onto the polymeric pore walls. This makes ideality impossible because each adsorbed alkylammonium must bring a charge-balancing anion, Cl-, with it into the nanopore solution. The alkylammonium adsorption that occurred was confirmed and quantified by using surface contact angle measurements.

Tunability of domain structure in partially inverse spinels NiAl2O4

Re-arrangement of cationic distribution in partially inverse spinel NiAl2O4 by using chemical pressure perturbation is studied. Structural, impedance and magnetic analysis suggest presence of regions/domains inside the grain/bulk with same lattice arrangement but varying in cationic oxidation state. Perturbing the cationic distribution in the grain via low concentrations of ambivalence substituent rearranges the cationic distribution across these domains within the partially inverse spinel lattice without disturbing the crystal structure. A comprehensive explanation on the origin & tunability of cationic distribution within the partially-inverse lattice is proposed.

Electrochemical charge storage performance of (Mn, Ni, Mo, Co, Fe)3O4 high entropy oxide nanoparticles produced via thermal plasma route

Highly complex high entropy metal oxides (HEOs) have several unique characteristics, such as more active sites and material stability that improve the electrochemical charge storage capacity. In this study, HEOs (Mn, Ni, Mo, Co, Fe)3O4 nanoparticles were synthesized using a thermal plasma route and its electrochemical energy storage performance was studied with two distinct electrolytes such as 1 M KOH and NaOH. The X-ray diffraction analysis revealed the phase pure spinel structured HEOs with crystalline size ranging from 13 to 29 nm. Scanning electron microscopy and electron dispersive X-ray spectroscopy results revealed the quasi-spherical morphology and uniform distribution of constitutional cations in the as-synthesized HEOs. The X-ray photoelectron spectroscopy results identified the oxidation states of cations in spinel HEOs. The charge/discharge studies of as-synthesized HEOs showed a specific capacitance of 215 F g-1 /26.9 mAh g-1 at a current density of 2 A g-1 in 1 M KOH electrolyte which is 156 % greater than 1 M NaOH electrolyte. Furthermore, a high capacitance retention of 91 % was achieved after completing 3000 cycles at 10 A g-1 current density which indicates that the HEOs have excellent charge/discharge reversibility. Electrochemical impedance spectroscopy revealed that the solution and charge transfer resistances of HEOs electrodes were 1.04 and 3.2 Ω, respectively. This novel synthesis strategy attempts to overcome the difficulties experienced by established methods for bulk manufacture of phase pure HEOs since thermal plasma method is a rapid and a single-step approach for the bulk production of nanomaterial.

Operando double-edge high-resolution X-ray absorption spectroscopy study of BiVO4 photoanodes.

High energy resolution fluorescence detected X-ray absorption spectroscopy is a powerful method for probing the electronic structure of functional materials. The X-ray penetration depth and photon-in/photon-out nature of the method allow operando experiments to be performed, in particular in electrochemical cells. Here, operando high-resolution X-ray absorption measurements of a BiVO4 photoanode are reported, simultaneously probing the local electronic states of both cations. Small but significant variations of the spectral lineshapes induced by the applied potential were observed and an explanation in terms of the occupation of electronic states at or near the band edges is proposed.