Trivalent State Research Articles

Electrochemical dissolution of titanium under alternating current polarization to obtain its dioxide

Abstract The titanium electrode was polarized under the influence of alternating current (AC) at 50 Hz. The current density was varied between 100 and 5,000 A m−2. Initially, the titanium electrode oxidized, and then, titanium oxides were reduced during the cathodic half-cycle of the AC. When the cathodic half-cycle changes to the anodic half-cycle, titanium is oxidized to the trivalent state: Ti − 3 e ̄ → Ti 3 + {{\rm{Ti}}-3{\rm{e}}{\rm{̄}}\to {\rm{Ti}}}^{3+} . The direction of the AC changes depending on its frequency, causing the processes occurring on the electrodes to be periodically repeated. The current efficiency of the titanium electrode dissolution depends on the sulfuric acid concentration and electrolyte concentration, reaching up to 63.4% under optimal conditions. Bipolar electrodes were used during AC electrolysis. It was found that the decrease in the mass of titanium electrodes increases almost linearly at first, from 400 to 1,600 A m−2, and then more intensively within the current densities from 1,800 to 2,500 A m−2. It was shown that when using a bipolar electrode, the total mass loss of the electrodes is 1.38 times greater than the total mass loss during polarization without a bipolar electrode. The composition of the titanium dioxide obtained as a result of electrolysis was identified using physico-chemical analysis methods.

Optimal synthetic route for obtaining Co/In layered double hydroxide

Cobalt-indium layered double hydroxides were successfully synthesized via coprecipitation and mechanochemical synthesis with subsequent soft hydrothermal treatment and additional crystallization. The latter method was shown to have advantages over coprecipitation and therefore the mechanochemical route was considered to be optimal for obtaining well-crystallized LDH samples, which do not contain extraneous crystalline phases within the detection limit of X-ray diffraction. The samples were characterized by FTIR spectroscopy, Raman spectroscopy, and transmission electron microscopy. The peroxidase-like activity of the samples was estimated, and the crystal lattice parameters were calculated. The possibility of obtaining cobalt-indium layered double hydroxides with a cationic ratio of Co2+: In3+ = 2 : 1 and 1.5 : 1 was shown. Increasing the aging temperature presumably led to the partial oxidation of cobalt in the samples into trivalent state resulted in the peroxidase-like activity of the samples.

STUDY OF THE BEHAVIOR OF ARSENIC IN COPPER ELECTROLYTE

Abstract. In industrial wastewater, arsenic is most often present in the trivalent state. An analysis of existing purification methods shows that in all cases, with a few exceptions, the most complete removal of arsenic is observed from solutions in which it is in the pentavalent state. This is explained by the significantly lower solubility of arsenates of heavy and alkaline earth metals compared to the corresponding arsenites. The chemical oxidation of As(III) in the following systems was studied: As(III)-H2SO4-H2O, As(III)-MeSO4-H2O, As(III)–H2SO4–MeSO4–H2O (where Me is Cu, Ni, Co, Mn, Zn). The influence of temperature, the amount of transition metal ions, the duration of the experiment, and the concentration of sulfuric acid on the degree of transition of As(III) to As(V) was studied. The effect of catalytic oxidation of As(III) in sulfuric acid solutions was discovered. The maximum degree of oxidation of trivalent arsenic (55-60%) is observed when transition metal salts are introduced into an arsenic solution in the presence of a platinum plate. It has been established that the nature of the studied transition metal salts (Cu2+, Ni2+, Co2+, Mn2+, Zn2+), process duration and temperature do not have a significant effect on the degree of As(III) conversion. The results obtained largely explain the predominance of pentavalent forms of arsenic in production solutions of non-ferrous metallurgy. Key words: copper electrolyte, arsenic, transition metals, catalytic role, instant oxidation effect, activated oxygen.

Binding mechanisms of trivalent chromium on colloidal phases from ultramafic systems: Insights from batch experiments and XAS analysis

Understanding the availability and mobility of chromium is a key factor in gaining insight into the fate of chromium and thus essential for assessing the risk of contamination and developing effective remediation strategies. In the natural environment, such as ultramafic systems, which are natural pools of chromium, chromium occurs mostly in the trivalent state (Cr(III)), which is known to have a high affinity for the solid phases such as particles and colloids. However, since Cr(VI) is more toxic, the vast majority of experimental studies focus on its reduction to Cr(III), which is often considered to form (hydr)oxide precipitates due to its poor solubility. Furthermore, while the oxidation state of Cr dictates its geochemical behavior, its interaction with particles and colloids is rarely controlled or monitored. Therefore, the interaction mechanisms between Cr(III) and particles or colloids require further attention. In this study, ten mineral phases (goethite, hematite, pyrolusite, kaolinite, montmorillonite, chlorite, serpentine, fuchsite, amphibole, and chromite) and one organic phase (humic acid), relevant to chromium bearing and carrier phases in ultramafic soils, were investigated to explore their interaction with Cr(III) species. These phases were first characterized by various techniques (including XRD, XRF, SEM, and BET). Adsorption and desorption experiments of Cr(III) on these phases were then carried out, and the distribution of Cr oxidation states in both the aqueous and solid phases was carefully monitored using UV–vis spectroscopy, geochemical speciation modeling, and Cr K-edge XAS spectroscopy. With the exception of pyrolusite, where partial oxidation of Cr(III) to Cr(VI) occurred, Cr(III) was shown to persist as a single oxidation state in all experiments. Desorption analyses showed significantly low desorbed rates, which further confirmed the prevalence of Cr(III). Experimental sorption isotherm data were interpreted using the Langmuir model and its linearized form, which provides important thermodynamic characteristics of adsorbents related to their structural and surface features. This study will provide better constraints for the understanding and prediction of Cr behavior and fate in the environment, especially in ultramafic systems.

Catalytic Effect of Titanium Ions on the Cathodic Reduction of Selenium (VI), Copper (II), Uranium (VI) Ions and Other Metals in an Aqueous Solutions

It is known that catalytic processes are widely applied in the field of organic chemistry; however they also play a significant role in inorganic chemistry. Nonetheless, numerous unresolved issues persist in the technology of inorganic substances and the extraction of metals and nonmetals in their elemental states. This publication aims to consolidate the results of our pioneering research utilizing the redox Ti (IV)–Ti (III) system, which demonstrates a catalytic action on the cathodic reduction of selenium (VI), copper (II), platinum (IV), palladium (IV), bismuth, arsenic (V) ions, uranium (VI), as well as manganese dioxide suspension. It has been demonstrated that in the presence of the redox Ti (IV)–Ti (III) system, hard-to-reduce selenate ions can be reduced at room temperature. The catalytic action of the redox Ti (IV)–Ti (III) system has been reliably demonstrated, and the reaction mechanism has been established. In the electrochemical production of metal powders (Cu, Pt, Pd, Bi) at cathode current densities exceeding the limiting value, a portion of the current is irreversibly lost to the discharge of hydrogen ions. Consequently, the current efficiency (CE) for powder production does not exceed 80 %. We have established that in the presence of titanium (IV) ions, due to their catalytic action, the CE increases by more than 15 %. It has also been shown that during the cathodic polarization of hexavalent uranium its reduction to uranium (IV) in the presence of the catalyst increases by more than 50 %. The reduction of hard-to-reduce arsenate ions in the presence of titanium (IV) ions proceeds with high CE to the active trivalent state, and further reduction can proceed electrochemically. The cathodic reduction of a manganese dioxide suspension was investigated. In the presence of a catalyst — titanium (IV) ions, manganese in this dioxide is reduced to the divalent state with a current efficiency exceeding 90 %.

Mononuclear high-spin iron(III) phthalocyanines

2,9(or 10),16(or 17), 23(or 24)-Tetradecyloxycarbonylphthalocyaninatoiron, FeTDPc, and 2,3,9,10,16,17,23,24-octadecyloxycarbonylphthalocyaninatoiron, FeODPc, were synthesized and characterized. These compounds seem to be in trivalent iron high-spin state in solvents such as chloroform, dichloromethane, benzene, and chlorobenzene, although their counter anion could not be detected by elemental analyses. They react with strong bases such as pyridine and imidazoles to form their mono- and subsequently their di-base complexes with formation constant of >106 and < 200 dm3 mol−1, respectively, in dichloromethane at 20 °C. The resultant mono-adducts appear to be trivalent iron low-spin while the di-base adducts are bivalent iron low-spin state complexes. The addition of ca. 10–30 equivalent of tetrabutylammonium-chloride or -bromide (electrolyte) to the solution containing FeTDPc or FeODPc, causes their spin-state change from iron(III) high to low-spin state. In a solid power state, however, both FeTDPc and FeODPc exist as a mixture of high-spin iron(III)- and intermediate-spin iron(II) species. Strangely, when these compounds are dissolved in polystyrene, i.e. each molecules are isolated from each other, the signals originated from the iron(II) component disappear.

Inducing high-concentration Tb3+ with free oxygen via atomic layer deposition

Precise preparation and control of trivalent states in rare earth metal oxide films are crucial for their optical and magnetic applications. In this study, compact and continuous terbium-doped nanofilms were deposited on silica substrates using atomic layer deposition (ALD). The average nanoparticle size varied from 17.9 to 78.5 nm with increasing growth cycles. X-ray photoelectron spectroscopy showed that the Tb3+/Tb4+ ratio increased from 0.98 to 1.42. A valence reduction mechanism involving free oxygen was introduced to analyze the reasons for the enhanced Tb3+ concentration in the nanofilms. The enhanced photoluminescence of Tb3+ (5D4→7F5) ions and the increased magnetization in terbium oxide nanofilms both reveal that free oxygen ions are the effective active sites responsible for the transition from the tetravalent to the trivalent state, in excellent agreement with theoretical analysis. Size control and free oxygen induction are promising strategies for enhancing the optical and magnetic properties of multivalent rare earth oxides.

Emergence of defects-mediated diluted ferromagnetic semiconductor (ZnS: La3+) Quantum Dots: A versatile platform for optoelectronic and spintronic applications

For the first time, La3+ ions incorporated into semiconductor Zinc Sulfide-Quantum Dots (ZnS-QDs), Zn1-xLaxS, were effectively produced via a straightforward co-precipitation approach, with diverse La ratios (0.00 ≤ x ≤ 0.15 at%). The phase analysis of the acquired QDs, conducted through Raman analysis and X-ray diffractometer (XRD), revealed a singular cubic ZnS structure, devoid of any impurities. Morphology studies by HR-TEM showed a nearly spherical particle with a size of approximately 6.4 nm. X-ray photoelectron spectroscope (XPS) investigation disclosed the significant presence of sulfur vacancies, along with the existence of the trivalent oxidation state of lanthanum (La3+) within the ZnS structure. Optical absorbance studies exhibited that all QDs were positioned approximately at the absorption edges of around 270 nm (4.59 eV), surpassing the bulk ZnS energy gap of 337 nm (3.67 eV), harmonically with the quantum confinement effect. Additionally, a pronounced band gap narrowing was observed with increasing the doping level of La ions, on account of the presence of defects that result in the creation of localized states inside the ZnS band structure. The optical results indicated the capability to fine-tune the optical energy gap, dispersion parameters, and enhance the nonlinear optical parameters, which makes these QDs well-suited for use in optoelectronic devices. Furthermore, the photoluminescence (PL) spectra indicated that the La3+-doped ZnS nanocrystals (NCs) exhibited a wide visible emission band (blue emission) at room temperature, influenced by the La-doping concentration. Besides, the La3+-doped ZnS QDs elucidated ferromagnetic behavior at room temperature, which may be accredited to the vacancy-assisted bound magnetic polaron model. Exploring the intriguing magnetic features of ZnS: La3+ QDs could open avenues for developing innovative spintronic devices.

New insights into the mechanism for Fe coordination promoting photocatalytic reduction of Cr(VI) by graphitic carbon nitride: The boosted transformation of Cr(V) to Cr(III)

Fe coordination is effective to promote photocatalytic Cr(VI) reduction by graphitic carbon nitride (g-C3N4) from wastewater; however, the role of Fe coordination in the Cr intermediate transformation is still unknown. Herein, a Cr intermediate, Cr(V), is detected by electron paramagnetic resonance and its generation and consumption kinetics are constructed for studying the visible-light photocatalytic processes of g-C3N4 and Fe anchored g-C3N4. The inclusion of Fe increased the photocatalytic Cr(VI) removal from 26.8 % to 51.3–85.6 %. The results reveal that Fe coordination of trivalent state can greatly enhance photocatalytic Cr(VI) reduction performance mainly through promoting interfacial electron transfer from g-C3N4 to Cr(V). Compared with pure g-C3N4, increasing Fe(III)/Fe(II) ratio of coordinated Fe species results in 8–11 times of enhancement of photocatalytic Cr(VI) reduction performance, 1–2 times of enhancement of photocatalytic Cr(V) generation, and 8–9 times of enhancement of photocatalytic Cr(V) consumption. This suggests the rate-limiting step for Cr(VI) reduction by g-C3N4-based photocatalysts is the transformation process of Cr(V) to Cr(III) and also illustrates the important role of the coordinated Fe(III) species in the photocatalytic transformation of Cr intermediates. This study deepens the understanding of Fe-coordination-promoted photocatalytic Cr(VI) reduction process and sheds light on developing high-performance g-C3N4-based photocatalysts for Cr(VI) removal from wastewater.

Decomposition of Hydrogen Peroxide in Presence of DimethylglyoximatoNickel Complexes as Catalysts: Catalase-Like Activity

The development in coordination chemistry in recent years raise hopes that synthetically produced metal complexes could mimic many biochemical systems widely found in nature. There is a certain analogy between nature and organometallic systems. A large number of biological metal complexes are known, including oxygen carriers like hemoglobin in the blood, which contains a ferrous ion; respiratory enzymes; those involved in protein hydrolysis; and vitamin B12, which is only active in the presence of cobalt in the trivalent state. The Nickel (III), in addition to Fe-S clusters, was an essential component in hydrogenases. Since then, nickel (III) complexes have been used as models for studying the catalytic function of certain enzymes (hydrogenases). In this context, a study on the catalytic ability of dimethylglyoximato-nickel complexes as peroxiredoxases in the dismutation or oxidation of hydrogen peroxide was conducted. The results were discussed, commented upon, and a reaction mechanism was proposed. The results seem encouraging, regarding the effect of the complexation on catalase- like activity.

Hard X-ray nanoprobe to study the emission properties of Ce-doped YAG wafer by using XEOL and TR-XEOL

In this study, the valent state, emission properties, and decay lifetime of Ce-doped yttrium aluminum garnet (Y3Al5O12, YAG) wafer have been probed using X-ray absorption (XAS), X-ray excited optical luminescence (XEOL), and time-resolved XEOL (TR-XEOL). The XAS spectrum demonstrates that Ce ions are in the trivalent state, and the XEOL spectrum exhibits typical 5 d1-4f1(2F5/2) and 5 d1-4f1(2F7/2) transitions of Ce3+ ions, with emission peaks at ∼528 nm and 582 nm, respectively. From the TR-XEOL measurements, the decay lifetimes of 5 d1-4f1(2F5/2) and 5 d1-4f1(2F7/2) transitions are about ∼90 ns and ∼100 ns, respectively. We found that the reabsorption effects will not only make the 5 d1-4f1(2F7/2) transitions have longer decay lifetime, but also the higher emission intensity. By comparison with photoluminescence (PL) and time-resolved PL using a pulsed laser at 375 nm, we found that the emission spectra and decay lifetime of Ce-doped YAG (111) wafer are different when using X-ray irradiation. The longer decay lifetime measured by TR-XEOL compared TR-PL are caused by high X-ray dose irradiation. In addition, high X-ray doses provided by the nano-focus X-ray beam will be influenced the emission behaviors of Ce-doped YAG (111) wafer. Which phenomena have been demonstrated by using time-dependent XEOL with irradiation for 10 h. These peculiar emission behaviors observed with a hard X-ray nanoprobe may be able to provide important information on quantum technologies and scintillators used in hard X-ray detectors.

Hydrothermal Synthesis of a Valence State Constant High-Entropy Perovskite Sr(TiZrHfVNb)O3 with Improved Photoresponsiveness.

A vanadium ion valence state constant high-entropy perovskite system was synthesized using the hydrothermal method with a trivalent vanadium ion as the vanadium source. The B-site of the perovskite crystal lattice was loaded with five atoms in equal proportions. We tried to synthesize the Sr(TiZrHfVNb)O3 high-entropy system using different methods. However, the valence state of the vanadium ion could only be kept constant using the hydrothermal process in the valence balanced high-entropy composition system. There was significant vanadium element segregation and second phase in the Sr(TiZrHfVNb)O3 system prepared using the solid-state reaction process. Also, obvious vanadium ion valence state ascending from V3+ to V5+ appeared in this high-entropy system with an increase in calcination temperature. Inconspicuous vanadium element segregation appeared at 900 °C, the significant segregation phenomenon and second phase appeared at 1200 °C, and the particle size increased with the temperature. This meant that the high-entropy value could not only stabilize the crystal phase, but also stabilize the ionic valence state. Moreover, the constant trivalent vanadium ion valence state could provide coordinated performance with a wide optical response range and a low band gap for the high-entropy system. This suggests that the system might grow a potential ceramic material for optical applications.

Electrochemically-Driven Reversible Catch and Release of Rare Earth Elements

The sustainable recovery of critical materials, such as rare earth elements (REEs), from dilute and non-traditional sources is pivotal for securing a reliable domestic supply. Using environmentally friendly methods is necessary to maximize the economic and sustainability benefits. One of the most promising approaches is the electrochemically controlled recovery of REEs, which becomes even more compelling when integrated with renewable energy sources. We developed a groundbreaking electroactive material with an exceptional affinity for REEs in their trivalent state. This material demonstrates a remarkable ability for highly reversible binding and release of REEs, controlled by the redox state of the material. We will present the REE recovery system's design principles and performance characteristics, mainly focusing on its efficacy in extracting REEs from dilute sources and structure-property relationships.

Revealing the atomic and electronic mechanism of human manganese superoxide dismutase product inhibition

Human manganese superoxide dismutase (MnSOD) is a crucial oxidoreductase that maintains the vitality of mitochondria by converting superoxide (O2●−) to molecular oxygen (O2) and hydrogen peroxide (H2O2) with proton-coupled electron transfers (PCETs). Human MnSOD has evolved to be highly product inhibited to limit the formation of H2O2, a freely diffusible oxidant and signaling molecule. The product-inhibited complex is thought to be composed of a peroxide (O22−) or hydroperoxide (HO2−) species bound to Mn ion and formed from an unknown PCET mechanism. PCET mechanisms of proteins are typically not known due to difficulties in detecting the protonation states of specific residues that coincide with the electronic state of the redox center. To shed light on the mechanism, we combine neutron diffraction and X-ray absorption spectroscopy of the product-bound, trivalent, and divalent states of the enzyme to reveal the positions of all the atoms, including hydrogen, and the electronic configuration of the metal ion. The data identifies the product-inhibited complex, and a PCET mechanism of inhibition is constructed.

Characterization of Kazakhstan’s Clays by Mössbauer Spectroscopy and X-ray Diffraction

Studies of the mineralogical composition were carried out, and the features of the clays from the deposits of Kazakhstan were established using Mössbauer spectroscopy (MS) and X-ray diffraction analysis (XRD). According to the XRD results, all the samples were mixed-layer clays of the kaolinite–illite type. The lattice parameters of the kaolinite were determined, and it was shown that its structure was disordered and contained a certain amount of impurity in some of the clay samples. A special feature of two of the samples was the additionally identified muscovite polytype 2M1. The spectra of the iron-containing clays were amenable to being resolved into separate components, with similar Mössbauer parameters of the kaolinite, muscovite, illite, and glauconite. The oxidation state of the iron was determined using MS. The predominant part of paramagnetic iron in most samples was in the trivalent state. The primary minerals contributing to Fe2+ were illite and muscovite. The results obtained during the study of the clay samples with complex mineralogical compositions using MS and XRD methods both complemented one another and were found to be in good agreement.

Trivalent Cation Defect Optimization Spin State of Nickel(II) in NiFe-Layered Double Hydroxide Nanosheets for Oxygen Evolution

Trivalent Cation Defect Optimization Spin State of Nickel(II) in NiFe-Layered Double Hydroxide Nanosheets for Oxygen Evolution

Separation of terbium as a first step towards high purity terbium-161 for medical applications.

Terbium-161 is a medical radiolanthanide that has a beta decay energy and half-life similar to that of lutetium-177, which makes it a promising alternative for therapeutic purposes. The production route using an enriched gadolinium-160 target necessitates the purification of terbium-161 from the untransmuted target material as well as from its stable decay product, dysprosium-161. The separation of neighbouring lanthanides is challenging due to their similar chemical properties and prominent trivalent oxidation states. In this work, the aim is to change the oxidation state of terbium, resulting in the altering of chemical properties that ease the intragroup separation. To this end, a novel separation method is investigated, involving the electrochemical oxidation of terbium (3+) to terbium (4+) followed by anion exchange chromatography. The electrolysis conditions are set to the highest achievable conversion rate, followed by a dilution step during which the pH and electrolyte concentration are slightly lowered to obtain conditions that are compatible with the separation method. XAS analysis is done to characterize the carbonato complex of both oxidation states and to further elucidate the separation mechanism. The results show that the separation approach of combining electrochemical oxidation with anion exchange chromatography is promising for the purification of 161Tb for medical use.

Synthesis, structure, and magnetic properties of lanthanide(III) complexes incorporating a tris-chelate cobalt(III) complex as a metalloligand

A series of CoIII–LnIII–CoIII trinuclear complexes [Ln{Co(Hmtimn)3}2](NO3)3 were prepared by following a simple one-pot synthesis method, mixing an unsymmetrical bidentate ligand 2-(2-imidazolinyl)-6-methoxypheol (H2mtimn) with Co(NO3)2·6H2O and LnX3· 6H2O (where Ln = La, Ce, Pr, Nd, Gd or Dy and X = NO3 − or Cl−) in methanolic solution in the presence of triethylamine in air. In the reaction mixture, this leads to the in situ formation of a tris-chelate CoIII metalloligand unit, which can coordinate LnIII ions through the interactions of phenolato- and methoxy-O donors. X-ray structural analysis revealed that the CoIII metalloligand functions as a rigid tripodal ligand to coordinate to a LnIII ion by six oxygen donors. The two metalloligands in the complex exhibit homochiral aggregation (ΔΔ or ΛΛ) upon coordination to the LnIII ion. The coordination of the central LnIII ion was found to be a distorted icosahedral geometry. Magnetic susceptibility measurements reveal that both cobalt and central lanthanide ions exist in trivalent states.

Newly developed CeO2 and Gd2O3-reinforced borosilicate glasses from municipal waste ash and their optical, structural, and gamma-ray shielding properties

From the useless municipal solid waste (MSW) ashes, CeO2, Gd2O3 and CeO2 + Gd2O3 doped borosilicate glasses were organized via melting-quenching procedure. Various optical, structural, physical and radiation shielding parameters were examined towards the influence of 100 kGy of γ-radiation. UV–visible NIR spectra revealed UV peaks at 351, 348 and 370 nm corresponding to the trivalent states of Ce3+ and Gd3+ ions, while, photoluminescence (PL) spectra displayed asymmetric broad excitations of Ce3+ and Gd3+ ions due to 4f → 5d transitions, and emission intense bands at 412, 434, and 417 nm. CIE chromaticity shows that Gd3+ ions increase the luminescence of Ce3+. FTIR absorption bands revealed an overlapping between tetrahedral groups of silicate (SiO4), with trigonal (BO3) and tetrahedral (BO4) units of borate. The influence of 100 kGy obtains quite reduction in UV–visible NIR and PL peaks, large stability in FTIR and ESR spectra, and stability of thermal expansion coefficient (CTE) as well. The whole data revealed optical, structural and physical stability of glasses after irradiation besides an enhancement in microhardness owing to more structural compactness and high bonding connectivity. Radiation shielding parameters from Phy-X/PSD program showed higher values of mass (MAC) and linear attenuation coefficients (LAC), and effective atomic number (Zeff) in the order of; glass Ce+Gd > glass Ce > glass Gd. Ce + Gd doped glass revealed also the lowest half value layer (HVL) comparing to other shielding commercial concretes. The study recommends the beneficial and economical use of the useless MSW ash to produce CeO2 and/or Gd2O3 borosilicate glasses with hopeful radiation shielding features.

Exploring the Limits of Fe-Rich Chemistries in Na-Based CaFe2O4-Type Postspinel Oxides.

Structural trends, physical properties, and electrochemical performances of the NaFexRu2-xO4 system have been investigated. Synthesis attempts using both conventional solid-state routes and high-pressure methods were explored for the compositional range 1.0 ≤ x ≤ 1.67. Based on Rietveld refinements against powder X-ray diffraction data, analyses of 57Fe Mössbauer spectroscopy data, and elemental analysis by electron microprobe, the existence of a confined compositional solid solution (1 ≤ x ≤ 1.3) adopting the CaFe2O4-type postspinel structure is demonstrated. This is contrasted with the NaFexTi2-xO4 system, for which no evidence of a solid solution is observed. However, for all explored synthetic routes of NaFexRu2-xO4 compositions, a trivalent iron oxidation state is maintained. Structural analysis and qualitative bond valence energy landscape models reveal that the progressive integration of iron into the postspinel framework results in narrowed sodium ion diffusion channels, restricting electrochemical deintercalation of sodium. Consequently, the CaFe2O4-type iron-rich compounds explored in this study demonstrate limited potential as positive electrode materials for sodium batteries. It is expected that this fundamental insight will help guide the exploration of alternative NaM2O4-based positive electrode materials with similar structure types.