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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Absorption Correction for Reliable Pair Distribution Functions from Low Energy X-ray Sources

This paper explores the development and testing of a simple absorption correction model for processing powder X-ray diffraction data from Debye−Scherrer geometry laboratory X-ray experiments. This may be used as a preprocessing step before using PDFGETX3 to obtain reliable pair distribution functions (PDFs). Various experimental and theoretical methods for estimating μR were explored, and the most appropriate μR values for correction were identified for different capillary diameters and X-ray beam sizes. We identify operational ranges of μR where a reasonable signal-to-noise ratio is possible after correction. A user-friendly software package, DIFFPY.LABPDFPROC, is presented that can help estimate μR and perform absorption corrections with a rapid calculation for efficient processing.

Absorption↗
DOE OSTI2024

Site Disorder Drives Cyanide Dynamics and Fast Ion Transport in Li 6 PS 5 CN

Halide argyrodite solid-state electrolytes of the general formula Li 6 PS 5 X exhibit complex static and dynamic disorder that plays a crucial role in ion transport processes. Here, we unravel the rich interplay between site disorder and dynamics in the plastic crystal argyrodite Li 6 PS 5 CN and the impact on ion diffusion processes through a suite of experimental and computational methodologies, including temperature-dependent synchrotron powder X-ray diffraction, AC electrochemical impedance spectroscopy, 7 Li solid-state NMR, and machine learning-assisted molecular dynamics simulations. Sulfide and (pseudo)halide site disorder between the two anion sublattices unilaterally improves long-range lithium diffusion irrespective of the (pseudo)halide identity, which demonstrates the importance of site disorder in dictating bulk ionic conductivity in the argyrodite family. Furthermore, we find that anion site disorder modulates the presence and time scales of cyanide rotational dynamics. Ordered configurations of anions enable fast, quasi-free rotations of cyanides that occur on time scales of 10 11 Hz at T = 300 K. In contrast, we find that cyanide dynamics are slow or frozen in Li 6 PS 5 CN when site disorder between the cyanide and sulfide sublattices is present at T = 300 K. We rationalize the observed differences in cyanide dynamics in the context of elastic dipole interactions between neighboring cyanide anions and local strain induced by the configurations of site disorder that may impact the energetic landscape for cyanide rotational dynamics. Through this study, we find that anion disorder plays a decisive role in dictating the extent and time scales of both lithium ion and cyanide dynamics in Li 6 PS 5 CN.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Structural Studies of Alloyed and Nanoparticle Transition Metal Dichalcogenides by Selenium-77 Solid-State Nuclear Magnetic Resonance Spectroscopy

Layered transition metal dichalcogenides (TMDCs) such as MoS 2 , MoSe 2 , and WSe 2 are under intense investigation because they are atomically thin semiconductors with photophysical properties that can be tuned by changing their composition or morphology. Mechanochemical processing has been proposed as a method to obtain alloyed TMDCs in the series Mo 1–x W x S y Se 2–y (x = 0–1; y = 0–2). However, elucidating the chemical transformations occurring at the atomic scale following mechanochemical processing can be challenging because the products are often amorphous or microcrystalline. To address this challenge, we probe TMDC mixing and alloying by using a combination of powder X-ray diffraction, Raman spectroscopy, diffuse reflectance spectroscopy, 77 Se solid-state nuclear magnetic resonance (SSNMR) spectroscopy, and planewave density functional theory (DFT) calculations. The nature of the milling material and reaction atmosphere are shown to be essential factors in limiting the formation of undesired oxide byproducts. We demonstrate acquisition of 77 Se SSNMR spectra using different combinations of Carr-Purcell Meiboom-Gill acquisition (CPMG) pulse sequences, magic angle spinning (MAS), and MAS dynamic nuclear polarization. Further, the combination of SSNMR with the other characterization methods clearly demonstrates that high energy impact ball milling induces molecular level alloying of Mo, W and chalcogen atoms in the family Mo 1–x W x S y Se 2–y . Gauge including projector augmented wave DFT calculations yield accurate 77 Se chemical shift (CS) tensor components. 77 Se SSNMR spectroscopy was also applied to study the structure of WSe 2 nanocrystals intercalated with ethylenediamine. The intercalated WSe 2 nanocrystals exhibit a more positive isotropic 77 Se CS as compared to bulk WSe 2 , however, the 77 Se CS anisotropy is the same, confirming the WSe 2 layers have a similar structure as in their bulk counterparts.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Influence of “Non-Interacting” Flux Concentration in Metallic Flux Growth Synthesis

In situ experiments probing the mechanisms of flux growth synthesis above 1100 °C, though challenging, enable direct observation of synthetic pathways, products, and metastable phases. In this study, in situ powder X-ray diffraction of flux growth synthesis up to 1200 °C was employed to investigate the role of Sn flux in the synthesis of praseodymium cobalt germanides. We demonstrate that metallic fluxes, with minimal incorporation into the target compounds, significantly influence the reaction products of flux growth synthesis of intermetallic compounds. Furthermore, the validation of in situ experiments with bulk synthesis is also presented.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Thermodynamic and Kinetic Mechanisms Governing the Synthesis of Nickel-Poor Cathodes

A deeper understanding of the thermodynamics and kinetics governing the lithiation and layering mechanisms of NMC cathode materials (LiNixMnyCozO 2 , where x + y + z = 1) offers valuable insights for enhancing synthesis methods and improving cathode performance. By employing atomistic and mesoscale approaches informed by in situ powder X-ray diffraction (PXRD) experiments, critical parameters for comprehending lithiation and layering processes and reaction rates were identified. The mesoscale approach captured the evolution of the phases and crystallite size observed in the in situ PXRD, revealing the differences in reaction rates with the use of different lithium salts and starting precursors. Ab initio molecular dynamics (AIMD) underscored the importance of vacancies and structural defects in promoting ion mobility and facilitating the nucleation of a layered domain. This nucleation disrupts the symmetry of disordered phases, ultimately creating a strained phase that serves as a buffer between layered and disordered regions. The lithiation and layering processes reflect a dynamic balance between the thermodynamic drive for a low-energy layered structure and the kinetic of diffusion, which is influenced by temperature and lithium vacancy concentration. Overall, reaction mechanisms are driven by the inherent defects of the intermediate phase that differ for NMC cathode materials. The lithium salts impact the rates of lithiation and layering, with a much slower process for Li 2 CO 3 .

25 ENERGY STORAGE↗
DOE OSTI2025

Role of Ammonium Hydroxide on Glucose Oxidase Immobilized in Metal–Azolate Framework-7 Enzyme Activity

Enzymes are nature’s catalysts, but their instability outside native environments limits practical applications. Metal–organic frameworks (MOFs) offer a promising platform for enzyme immobilization, enhancing stability, and reusability through their tunable porosity and crystallinity. While ZIF-based MOFs have been extensively studied, metal azolate framework-7 (MAF-7) remains largely unexplored for biomimetic mineralization. Its hydrophilic character makes it a promising alternative for enzyme encapsulation; however, the role of essential basic modulators such as ammonium hydroxide (NH 4 OH) on enzyme structure and function has not been investigated. Here, in this study, we examine the NH 4 OH mediated synthesis of glucose oxidase within MAF-7 using powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cryogenic transmission electron microscopy (cryo-TEM), and enzyme assays. Our results show that NH 4 OH modulates crystal morphology, enzyme activity, and nucleation behavior, with higher concentrations leading to partial enzyme denaturation and reduced catalytic performance. By integrating time-resolved cryo-TEM with activity assays, we uncover how modulator concentration impacts early stage crystallization and enzyme folding, a mechanistic insight not previously demonstrated in MOF systems. These findings highlight modulator chemistry as a critical, underexplored variable in MOF synthesis, advancing rational design strategies for enzyme@MOFs (E@MOF) beyond ZIFs and toward more tunable, biocompatible frameworks like MAF-7.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Cs X Si 15 P 21 ( X = Sn or Pb): Polar Noncentrosymmetric Si–P Frameworks Stabilized by Covalent X –P Bonding

Metal silicon phosphides composed of earth-abundant Si and P tend to exhibit semiconducting properties and adopt diverse crystal structures with relatively small additions of structure-directing elements. The potential of silicon phosphide materials in nonlinear optical applications has been hindered by the inability to systematically produce noncentrosymmetric structures with such a flexible framework. Here, in this work, two isostructural compounds with a novel noncentrosymmetric structure were made possible by the inclusion of elements with stereochemically active lone pairs (Sn 2+ and Pb 2+ ). The structures were determined through single-crystal and synchrotron powder X-ray diffraction. Analysis of chemical bonding in real space through the electron localization function revealed stereochemically active Pb 2+ and Sn 2+ species in a trigonal pyramidal coordination with {Pb/Sn}–P bonds. Such covalent bonding between Pb and P is quite uncommon in extended solids and has been reported in a few rare instances. Band structure calculations and linear optical measurements confirm the semiconducting nature of Cs X Si 15 P 21 ( X = Sn or Pb). The synthesis was optimized to yield high-purity polycrystalline samples. The nonlinear optical properties show promising second-harmonic generation (SHG) coefficients from the Kurtz–Perry method. First-principles calculations of the nonlinear optical properties support the experimentally determined SHG values and provide moderate values of birefringence, suggesting Cs X Si 15 P 21 could be phase-matchable and practical nonlinear optical materials in the mid-IR region.

crystal structure↗
DOE OSTI2026

Thin-Film Stabilization and Magnetism of η -Carbide-Type Iron Nitrides

Transition-metal nitrides in ..eta..-carbide-type structures exhibit unusual bonding motifs and proximity to magnetic instabilities. Yet they remain unexplored in thin-film form due to the difficulty of stabilizing nitrogen-poor ternaries among competing phases. Here, we report the thin-film synthesis and phase-stability mapping of the ..eta..-nitride systems Fe-W-N and Fe-Mo-N. Amorphous Fe-M-N (M = W, Mo) combinatorial libraries deposited by reactive cosputtering crystallize upon rapid thermal annealing, enabling systematic identification of synthesis windows as a function of composition and annealing temperature. Using laboratory powder X-ray diffraction and synchrotron grazing incidence wide-angle X-ray scattering, we establish that Fe 3 Mo 3 N-based ..eta..-carbide phases form over a substantially broader compositional and thermal range than W-based compositions, where ..eta.. structures are stabilized only when the films are Fe-rich. These trends are rationalized using mixed chemical-potential vs composition phase diagrams that capture the narrow nitrogen chemical-potential stability of ..eta..-nitrides. Magnetic measurements reveal that ferromagnetism is induced in Fe-rich Fe 3.54 Mo 2.46 N with a small exchange-bias-like response that is absent in Fe 3 W 3 N-based compositions, highlighting the sensitivity of magnetic behavior to modest deviations from stoichiometry. This work establishes practical thin-film synthesis routes for ..eta..-nitride materials and demonstrates how composition can be tuned to access emergent magnetic phenomena in these complex nitrides.

36 MATERIALS SCIENCE↗
DOE OSTI2024

“Mn 3 AlN” is Really Mn 4 N

We investigate the synthesis of antiperovskite “Mn 3 AlN” using the published synthesis procedure, as well as several new reaction pathways. In each case, only a combination of antiperovskite Mn 4 N and Mn 5 Al 8 or precursors is obtained. The identity of the obtained antiperovskite phase is unambiguously determined to be Mn4N via synchrotron powder X-ray diffraction (SPXRD), X-ray absorption spectroscopy (XAS), and magnetometry. The experimental results are further supported by thermochemical calculations informed by density functional theory (DFT), which find Mn 3 AlN to be metastable versus decomposition into Mn and AlN. The DFT-based calculations also predict an antiferromagnetic ground state for Mn3AlN. This directly contradicts the previously reported ferromagnetic behavior of "Mn 3 AlN". Instead, the observed magnetic behavior is consistent with ferrimagnetic Mn 4 N. We examine the data in the original publication and conclude that the compound reported to be Mn 3 AlN is in fact Mn 4 N.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Synthesis of Layered Gold Tellurides AuSbTe and Au 2 Te 3 and Their Semiconducting and Metallic Behavior

Previous studies on natural samples of pampaloite (AuSbTe) revealed the crystal structure of a potentially cleavable and/or exfoliable material, while studies on natural and synthetic montbrayite (Sb-containing Au 2 Te 3 ) claimed various chemical compositions for this low-symmetry compound. Few investigations of synthetic samples have been reported for both materials, leaving much of their chemical, thermal, and electronic characteristics unknown. Here, in this study, we investigate the stability, electronic properties, and synthesis of the gold antimony tellurides AuSbTe and Au 1.9 Sb 0.46 Te 2.64 (montbrayite). Differential thermal analysis and in situ powder X-ray diffraction revealed that AuSbTe is incongruently melting, while Au 1.9 Sb 0.46 Te 2.64 is congruently melting. Calculations of the band structures and four-point resistivity measurements showed that AuSbTe is a semiconductor and Au 1.9 Sb 0.46 Te 2.64 a metal. Various synthesis attempts confirmed the limited stable chemical composition of Au 1.9 Sb 0.46 Te 2.64 , identified successful methods to synthesize both compounds, and highlighted the challenges associated with single-crystal synthesis of AuSbTe.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Developing Lanthanide-Nitrate Cluster Chemistry toward Rare Earth Separations

Nitrate-decorated hexamers with a [Ln 6 (μ 6 -O)(μ 3 –OH) 8 ] 8+ core have been reported for nearly every lanthanide ion and are used as precursors for the assembly of functional metal–organic frameworks. Yet, few studies have examined the correlation between the solution and solid-state species, and the formation of mixed-metal clusters. Toward this end, a series of homo- and heterometal lanthanide nitrate hexamers was prepared via pH adjustment of aqueous lanthanide nitrate solutions. Examination of the homometallic europium solutions using Small Angle X-ray Scattering and nESI-MS showed that lower order complexes dominate lanthanide speciation in nitrate media. Yet, powder X-ray diffraction data of the precipitated phase confirmed the formation of [Ln 6 (μ 6 -O)(μ 3 -OH) 8 (NO 3 ) 6 (H 2 O) 12 ]·2(NO 3 )·n(H 2 O), Ln 6 , for Ln = Eu and Tb. For heterometal systems, analysis of the solid-state product by ICP–MS showed the selective incorporation of the heavier rare earths into Ln 6 . Selectivity was quantified by calculating an average separation factor, which is defined as the ratio of recovery factors of both metals. Further examination of the luminescence behavior of mixed metal [Tb 6–x Eu x (μ 6 -O)(μ 3 -OH) 8 (NO 3 ) 6 (H 2 O) 12 ]·2(NO 3 )·n(H 2 O), with x = 1.1–3.6, showed that the relative intensities of the peaks at 489 nm (terbium, 5 D 4 → 7 F 6 ) and 690 nm (europium, 5 D 0 → 7 F 4 ) trend with the percent incorporation of europium and terbium into the cluster.

anions↗
DOE OSTI2026

Itinerant Magnetism in Hydride-Synthesized CaCo 12 B 6

A new compound in the underexplored Ca–Co–B phase space has been discovered, validating high-throughput computations from the Open Quantum Materials Database, which predicted thermodynamic stability for CaCo 12 B 6 in the SrNi 12 B 6 structure type. The synthetic effects of different boron precursors and the advantages of using CaH 2 instead of Ca metal were demonstrated by the short synthesis duration and high purity of CaCo 12 B 6 , in contrast with traditional synthesis routes. Powder X-ray diffraction (PXRD) confirmed that CaCo 12 B 6 shares the SrNi 12 B 6 structure ( R $\bar{3}$m (#166), a = 9.469(4) Å, c = 7.468(2) Å, Z = 3) and is water- and air-stable. High-temperature in situ PXRD indicates that CaCo 12 B 6 is stable below 1050 K under vacuum in a silica capillary. CaCo 12 B 6 decomposes between 693 and 773 K during spark-plasma sintering. Density functional theory calculations indicate that CaCo 12 B 6 is metallic with a ferromagnetic ground state. X-ray absorption near-edge spectroscopy and Bader charge analysis indicate that Co atoms in CaCo 12 B 6 lack ionic character. Magnetometry reveals room-temperature paramagnetism with μ eff = 1.7(1)μ B per Co atom and a Weiss constant of +190(10)K. Ferromagnetic ordering occurs below 172(1)K, resulting in a saturation moment of 0.46 μ B per Co atom. Our findings demonstrate that the hydride route is a viable strategy for discovery of new ternary alkaline-earth-transition metal borides analogous to rare-earth-containing counterparts.

diffraction↗
DOE OSTI2026

From Serendipity to Exploration: Synthesis and Properties of PtSiSb

PtSiSb is a compound with covalent Si–Sb bonds, which are relatively rare instances in solid-state materials. The original report on PtSiSb indicates synthetic challenges for the isolation of single-phase samples, as well as potential discrepancies in the predicted electronic structure and experimental transport properties. In this work, we considered PtSiSb as a case study with the objective of demonstrating the importance of synthesis as a bridge between theoretical predictions and experimental properties. Using guidance from in situ powder X-ray diffraction, the synthesis of single-phase polycrystalline samples was developed, allowing further experimental characterization of transport and catalytic properties. Thermal conductivity and heat capacity demonstrated anomalous behavior, indicating an unconventional phonon scattering mechanism in PtSiSb. Charge transport measurements indicated semimetallic behavior. Hydrogen evolution reaction (HER) tests in acidic electrolyte revealed that the PtSiSb cathode needs an overpotential η 10 = 120 mV to achieve a current density j = −10 mA/cm 2 . This is lower activity than elemental Pt but comparable to known and active transition-metal phosphide HER catalysts, such as CoP, with η 10 = 93 mV when measured at identical conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Post-Mortem Characterization of Cerium Speciation in Molten Calcium Chloride

Abstract Advancing radiochemistry and nuclear materials science requires understanding actinide interactions with molten salts, which are used in next-generation nuclear reactors and for processing of actinides to recover useful fissile material. Understanding chemical interactions of actinides with molten salts has been limited by challenges in developing spectroscopic and X-ray techniques that are compatible with the high temperatures necessary to study molten salts. In this work, interactions of CeO2 (serving as a nonradioactive surrogate for uranium and plutonium) with CaCl2 are characterized following heating. Scanning electron microscopy indicates CeO2 morphological changes from small (<1 μm) particles to 3–5 μm sheets. Powder X-ray diffraction and infrared and Raman spectroscopies show the formation of CeOCl at higher (850–1050 °C) temperatures. In the absence of a chemical reducing agent, it was found that a high-temperature, low-oxygen environment is the key to the formation of oxychloride and that oxychloride formation is inhibited by annealing the CeO2 starting material. Lastly, thermal analysis revealed lowering of the melting point of CaCl2 after heating with CeO2. In all, this work identifies applicable spectroscopic techniques to target studies of heavy elements in molten salt environments and highlights the relationship between chemical speciation and melting behavior, a key thermophysical property.

Kelly, Sheridon N. [Lawrence Livermore National La↗
DOE OSTI2024

Effect of Pressure on Crystal Structure and Phonon Density of States of FeSi

The strongly correlated material FeSi displays several unusual thermal, magnetic, and structural properties under varying pressure-temperature (P-T) conditions. It is a potential thermoelectric alloy and a material with several geochemical implications as a possible constituent at the Earth's core-mantle boundary (CMB). Previous theoretical studies predicted a pressure-induced B20-B2 transition at ambient temperature below 40 GPa; however, experimentally, the structural transition is observed only at high P-T conditions. In this study, we have performed high-pressure powder X-ray diffraction (XRD) up to 90 GPa and Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements up to 120 GPa to understand the phase stability and lattice dynamics. Our study provides evidence for a non-hydrostatic stress-induced B20-B2 transition in FeSi at around 36 GPa. We deduced the Fe partial phonon density of states (PDOS) and thermal parameters from NRIXS measurements up to 120 GPa and compared them with density functional theory (DFT) calculations. Furthermore, the computations show pressure-induced metallization and the band gap closing around 12 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Carbon-Mediated Oxygen Vacancy Creation at Hematite Interfaces

Nanoscale iron oxides (e.g., hematite (a-Fe 2 O 3 )) have unique properties, such as enhanced chemical reactivity and high surface area, when compared with their bulk counterparts. These nanoscale surfaces can be more reactive due to the presence of defects (e.g., oxygen vacancies). In this work, we probed the surface chemistry of bulk and nanoscale hematite via X-ray photoelectron spectroscopy, electron microscopy, and powder X-ray diffraction. Oxygen exposure and vacuum annealing experiments were conducted to add or remove oxygen vacancies and remove adventitious carbon. In the absence of the oxygen annealing step, vacuum annealing resulted in partial reduction of Fe(III) to Fe(II) on all hematite surfaces. This was a size-dependent effect with the extent of reduction increasing as the crystallite size decreased. In addition, the atomic concentrations of carbon increased on all iron oxide surfaces after vacuum annealing. Oxygen annealing almost completely removed carbon from sample surfaces, and no Fe(III) reduction was observed in the absence of carbon. Under these conditions, the results reveal that carbonaceous material enhances oxygen vacancy formation, which then facilitates the reduction of Fe(III) on hematite surfaces. We provide new insights into the mechanisms of Fe(III) reduction on both bulk and nanoscale hematite surfaces and establish the major role of carbon in oxygen vacancy formation.

Zengotita, Frances E. [University of Notre Dame, I↗
DOE OSTI2025

Demonstration of MgCr 2– x Mn x O 4 Spinel Oxide Cathodes in High-Voltage Mg Batteries

Solid-solution oxide spinels with high redox voltages and facile Mg 2+ mobility have been identified as promising candidates for practical, high-voltage cathodes in Mg batteries. In this work, we discuss the development of MgCr 2-x Mn x O 4 [x = 0.5, 1, 1.2] solid-solution spinel oxides as a cathode material and their electrochemical performance paired with an Mg anode in a full cell. This work presents the first demonstration of full cells with these materials. Mg-Cr-Mn spinel oxides with varying Cr and Mn contents were synthesized using alternative synthetic routes for optimal electrochemical performance. High-resolution synchrotron powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (NMR) spectroscopy, and electron microscopy showed that these different synthetic routes resulted in changes in structures and particle morphologies, which in turn affect the electrochemical performance. Particularly, the urea coprecipitation synthetic route resulted in high-surface-area particles that enabled lower overpotentials and increased discharge capacity. The high surface area also resulted in expedited structural degradation caused by the irreversible migration of Mg 2+ into normally vacant 16c sites in the spinel lattice. This structural degradation was lessened by using a hydrosauna-urea synthesis method, which decreased the Mg/Mn inversion ratio while retaining high-surface-area particles with good cycling performance. Furthermore, our findings highlight the necessity for high surface area or nanostructured spinel oxide cathodes with minimized Mg-Mn inversion to enable spinel oxide cathodes in Mg full cells.

Mg anode↗
DOE OSTI2025

From Structure to Function: Zn/Mn-Modified Maghemite as an Advanced Nanoplatform for Magnetic Hyperthermia and Radionuclide Therapy

The development of nanoplatforms capable of efficient heat generation and stable radionuclide delivery is essential for effective bimodal cancer therapy. Here, in this study, binary (Fe–M) and ternary (Fe–M–M′) metal oxide nanoparticles were synthesized via a polyol method optimized to produce flower-like γ-Fe 2 O 3 (maghemite) structures, with M and M′ representing Zn and/or Mn. Comprehensive structural and magnetic characterization was conducted to explain the relationship between composition, defect structure, and hyperthermic performance. The analyses revealed that cation substitution induced an Fe-site vacancy, primarily at octahedral positions, leading to local structural distortions, as confirmed by powder X-ray diffraction and pair distribution function analysis. The optimized composition, with Zn/Mn/Fe = 0.040:0.182:1, exhibited the highest concentration of vacancies and structural disorder. These vacancies altered the bonding environment, enhancing magnetic interactions at tetrahedral sites while weakening those at the octahedral positions. The resulting multicore nanoflowers (20–63 nm; core size 13–18 nm) displayed strong heating performance, with intrinsic loss power ranging from 0.34 to 5.77 nHm 2 kg –1 . The optimized sample achieved a temperature increase of 30 °C within 2 min and a specific absorption rate of 369 W g –1 . This composition was further coated with citrate (CA) and successfully radiolabeled with 177 Lu, achieving a radiolabeling yield of 92.7% and excellent stability, thus forming a robust nanoplatform for combined magnetic hyperthermia and radionuclide therapy. Biological evaluation of the optimized S5 composition revealed selective cytotoxicity toward HeLa and LS174 cells, while toxicity was significantly lower to A549, A375, and normal MRC-5 cells. Citrate coating of S5 nanoparticles (S5@CA) drastically reduced their cytotoxicity across all tested cell lines (IC 50 > 200 μg mL –1 ), confirming their enhanced biocompatibility for therapeutic applications. In HeLa cells subjected to magnetic hyperthermia, the viability decreased to approximately 84% after 30 min and 61% after 60 min of treatment, demonstrating the sustained hyperthermic effect at a controlled working temperature of 48 °C. These results underscore the effectiveness of cation substitution and vacancy engineering in tailoring the functional properties of maghemite-based nanomaterials for advanced multimodal cancer therapies.

36 MATERIALS SCIENCE↗