Journal of Solid State Chemistry最新文献

{"title":"Ion-selective change storage in three types layered MnO2 films intercalated with different cobalt complexes","authors":"Ryota Sugawara ,&nbsp;Ryosuke Okawa ,&nbsp;Ryo Sasaki ,&nbsp;Mayumi Abe ,&nbsp;Kazuaki Tomono","doi":"10.1016/j.jssc.2025.125659","DOIUrl":"10.1016/j.jssc.2025.125659","url":null,"abstract":"<div><div>In this study, layered MnO₂ films intercalated with three types of cobalt complexes; [Co(en)₃], <em>trans</em>-[Co(en)₂Cl₂], and <em>cis</em>-[Co(en)₂Cl₂] were prepared on FTO substrates, forming [Co(en)₃]@MnO₂, <em>trans</em>-[Co(en)₂Cl₂]@MnO₂, and <em>cis</em>-[Co(en)₂Cl₂]@MnO₂, respectively. XRD, EDS, FT-IR, and Raman results confirmed the preparation of layered MnO₂ films with the respective cobalt complexes in the interlayer. Electrochemical measurements (cyclic voltammetry; CV) in Na₂SO₄ electrolyte showed that [Co(en)₃]@MnO₂ film (262 F/g), <em>trans</em>-[Co(en)₂Cl₂]@MnO₂ film (226 F/g) and <em>cis</em>-[Co(en)₂Cl₂]@MnO₂ film (193 F/g), showing high cycle stability and capacitance. During CV measurements, the cobalt complex in [Co(en)₃]@MnO₂ was deintercalated and replaced by hydrated Na ⁺ ions, whereas in <em>trans</em>-[Co(en)₂Cl₂]@MnO₂ and <em>cis</em>-[Co(en)₂Cl₂]@MnO₂, the cobalt complexes retained in the interlayer. These results suggest that Na⁺ ions intercalation/deintercalation dominated in [Co(en)₃]@MnO₂, while SO₄²⁻ ions intercalation/deintercalation occurred in <em>trans</em>-[Co(en)₂Cl₂]@MnO₂ and <em>cis</em>-[Co(en)₂Cl₂]@MnO₂. The ionic property that Na ⁺ ions diffuse more easily in aqueous solution than SO₄²⁻ ions suggests that the [Co(en)₃]@MnO₂ film has a larger capacitance than the <em>trans</em>-[Co(en)₂Cl₂]@MnO₂ film and the <em>cis</em>-[Co(en)₂Cl₂]@MnO₂ film. Electrochemical impedance spectroscopy (EIS), [Co(en)₃]@MnO₂ exhibited a mixed response of capacitive and diffusive behavior associated with Na ⁺ replacement, with a linear region showing a slope of approximately 60° in the Nyquist plot. <em>trans</em>-[Co(en)₂Cl₂]@MnO₂ and <em>cis</em>-[Co(en)₂Cl₂]@MnO₂ showed two semicircles originating from surface and interlayer reactions, followed by a linear region with a slope of about 80°, reflecting surface-capacitive dominance. These features are consistent with the differences in the slope and phase angle observed in the Bode plots, indicating that the EIS response is influenced by ion diffusivity and interlayer structure.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125659"},"PeriodicalIF":3.5,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Assembly of TM−Containing Polyoxotungstates−Based on Metal−Organic frameworks with catalytic oxidation performances for various sulfides","authors":"Yujiao Hou,&nbsp;Xiaojing Wang,&nbsp;Yifan Cheng,&nbsp;Hongyan Chen,&nbsp;Peilin Han","doi":"10.1016/j.jssc.2025.125655","DOIUrl":"10.1016/j.jssc.2025.125655","url":null,"abstract":"<div><div>The catalytic selectivity oxidation of sulfides to sulfoxides is the central organic reaction for future sustainable development. Herein, two remarkable polyoxotungstates−based on metal−organic frameworks, [{Ag₆(ptz)₄}{PW₁₂O₄₀}]·0.5H₂O and [{Cu₃(ptz)₃}{PW₁₂O₄₀}]·4H₂O (ptz = 5−(4−pridyl)−1H−tetrazole), were deliberately designed and isolated. In compound <strong>1</strong>, the {PW₁₂} polyoxoanions occupy the 1D big rectangular porous original from the 3D Ag−organic framework, constructing a fascinating 3D POMs−based 3D framework. Compound <strong>2</strong> exhibit a glamorous 2D sheet structure comprise of bicapped anions {PW₁₂} and 1D Cu−organic chains. Additionally, two compounds can be severed as the high−efficiency heterogeneous catalysts for the selective oxidation of sulfides. In particularly, compound <strong>1</strong> exhibits satisfying catalytic performance in the oxidation of MPS (conv. 97.5 %; sele. 99 %). Notedly, after five cyclic catalytic reaction, compound <strong>1</strong> maintains excellent catalytic performance and structural stability.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125655"},"PeriodicalIF":3.5,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145047146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A flexible linker-based indium frameworks as highly efficient catalysts for carbon dioxide conversion","authors":"Sheli Zhang ,&nbsp;Yuerong Yan ,&nbsp;Huijie Shan ,&nbsp;Yunchang Fan ,&nbsp;Haibao Zhu","doi":"10.1016/j.jssc.2025.125650","DOIUrl":"10.1016/j.jssc.2025.125650","url":null,"abstract":"<div><div>The chemical fixation of carbon dioxide (CO₂) represents a viable strategy to achieve carbon neutrality. However, the conversion of CO₂ is still limited by the lack of efficient heterogeneous catalysts. To address this problem, a flexible linker-based metal-organic frameworks were synthesized using hard Lewis acid indium as metal center (In-MOFs) and their catalytic performance for the CO₂ cycloaddition with epoxides in the absence of solvent and co-catalyst was evaluated. Experimental results revealed that In-MOFs exhibited great catalytic activity (cyclic carbonate yield, 97.2 %) and selectivity (&gt;98 %) for the cycloaddition of CO₂ and epichlorohydrin (ECH) under mild conditions (80 °C for 5 h, 0.1 MPa CO₂) due to the strong Lewis acidity of In (III), which significantly lowered energy barrier of epoxide ring opening and the insertion of CO₂, consequently promoting the CO₂ cycloaddition reaction.</div><div>These results suggested that the In-MOFs exhibited promising potential as catalysts for the CO₂ chemical fixation and may provide a new approach for the fabrication of MOFs-based catalysts for the CO₂ conversion.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125650"},"PeriodicalIF":3.5,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145047148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of high-temperature treatment with orthophosphoric acid on the phase composition, elemental composition, microstructure and electrical properties of calcium sulfate hemihydrate","authors":"Ivan Nikulin,&nbsp;Tatiana Nikulicheva,&nbsp;Vitaly Vyazmin,&nbsp;Oleg Ivanov,&nbsp;Nikita Anosov,&nbsp;Olga Telpova","doi":"10.1016/j.jssc.2025.125656","DOIUrl":"10.1016/j.jssc.2025.125656","url":null,"abstract":"<div><div>Citrogypsum, which is waste product of biochemical production of citric acid, has been applied to prepare bulk samples of calcium sulfate hemihydrate, CaSO₄∙0.5H₂O. The samples were undergone to high-temperature (95 °C) treatment in 85 wt% aqueous solution of orthophosphoric acid at different treatment times, <em>t</em>_<em>h</em> (<em>t</em>_<em>h</em> = 1; 3; 5; 7; 10 and 15 min). Due to interaction between CaSO₄∙0.5H₂O and H₂O from aqueous solution, at first treatment stage, the starting calcium sulfate hemihydrate quickly (at <em>t</em>_<em>h</em> &lt; 1 min) and completely transforms into calcium sulfate dihydrate, CaSO₄∙2H₂O. With further increase in <em>t</em>_<em>h</em>, phase composition of the samples changes from single-phased state with monoclinic CaSO₄∙2H₂O structure at <em>t</em>_<em>h</em> = 1min to two-phased state at <em>t</em>_<em>h</em> &gt; 1 min, in which new phase of calcium sulfate hemihydrate CaSO₄∙0.5H₂O with pseudo-trigonal structure is gradually forming from phase CaSO₄∙2H₂O. Formation of two-phased state is related to phase transformation, originated from partial removal of crystallization water molecules from the CaSO₄·2H₂O structure. During the acid treatment, in the samples content of Ca and S decrease, and content of P increases. These changes in elemental composition are governed by mechanisms of cation exchange (via partial replacement of Ca²⁺ cation by two H⁺ ions) and anion exchange (via partial replacement of acid group (SO₄)^2- by acid residue (HPO₄)^2-). Electrical properties of the samples were examined by analyzing of room-temperature voltage-current dependencies, recording at 50 Hz. Electrical conductivity of the samples are gradually increasing with increasing <em>t</em>_<em>h</em>. This effect can be related to appearance of mobile H⁺ ions in structure of the samples. Highest value of the conductivity is ∼0.058 S∙m⁻¹ for <em>t</em>_<em>h</em> = 15 min. Increase in the conductivity is accompanied by gradual increase in relaxational current contribution into total electric current. This feature can be originated from formation of acid residues (PO₄)^3-, which partially replace acid residue (SO₄)^2- in the CaSO₄ structure of the acid treated samples.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125656"},"PeriodicalIF":3.5,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Application of Heywang model to the apparent PTCR effect in water-adsorbing layered materials","authors":"Phieraya Pulphol ,&nbsp;Saichon Sriphan ,&nbsp;Kanokwan Chaithaweep ,&nbsp;Naratip Vittayakorn ,&nbsp;Tosapol Maluangnont","doi":"10.1016/j.jssc.2025.125657","DOIUrl":"10.1016/j.jssc.2025.125657","url":null,"abstract":"<div><div>Surface proton/hydroxide conduction predominates at ambient conditions prior to levelling off at elevated temperatures due to water evaporation and subsequent loss of charge carriers. This water-induced charge transport results in the “apparent” positive temperature coefficient of resistivity (PTCR) effect. Herein, we show that Heywang model typical of classical ferroelectric PTCR ceramics is applicable to a wide range of water-adsorbing layered materials (0.17–4.76 wt% H₂O). Several examples include layered alkali titanates with negatively-charge sheets; one van der Waals material (g‒C₃N₄) with neutral sheets; and a NiFe layered double hydroxide with positively-charge sheets. The linear log <em>ρ</em>_DC vs (<em>ε</em>′_DC<em>T</em>)^-1 plots (<em>ρ</em>_DC = static resistivity, <em>ε</em>′_DC = static dielectric permittivity, and <em>T</em> temperature) are observed from 25 to 250 °C where resistivity and dielectric permittivity varied up to five orders of magnitude. Using Cs₂Ti₆O₁₃ as a representative sample, the density of acceptor states at the grain boundary <em>N</em>_s (the exact nature to be elucidated) is ∼10¹⁰-10¹¹ cm^-2, slightly dependent on the heating/cooling rates (0.5, 2 and 5 °C·min^-1). Complex plane analyses show that capacitances at grain/grain boundaries alike are constant regardless of temperatures, but resistances in both cases peak at 150–200 °C. While rigorous theoretical basis is yet to be constructed, the observed linearity suggests that there could be a common foundation between these two classes of PTCR materials which have been treated separately so far.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125657"},"PeriodicalIF":3.5,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106685","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Controlled hydrothermal synthesis of highly crystalline tetragonal BaTiO3 nanocrystals with uniform size distribution","authors":"Jinmiao Wen ,&nbsp;Chenlu Jia ,&nbsp;Yin Zhao ,&nbsp;Canyang Wang ,&nbsp;Shuai Yuan ,&nbsp;Yi Wang ,&nbsp;Meihong Zhang ,&nbsp;Liyi Shi","doi":"10.1016/j.jssc.2025.125652","DOIUrl":"10.1016/j.jssc.2025.125652","url":null,"abstract":"<div><div>Highly dispersed tetragonal phase BaTiO₃ nanoparticles were synthesized via a hydrothermal method. The effects of TiO₂ precursor and hydrothermal media on the phase transformation and microstructure of BaTiO₃ nanocrystals were investigated. Additionally, the time-dependent evolution of nucleation and crystal growth was elucidated. A key influencing factor of this method is the use of a well-crystallized TiO₂ as the precursor, combined with ammonia-based reaction media; this combination not only promotes nucleation but also inhibits OH defect formation during crystal growth. Consequently, superior tetragonality and narrow particle size distribution of BaTiO₃ nanoparticles can be achieved. Furthermore, atomic-scale internal and surface structure were investigated using high-angle annular dark field scanning transmission electron microscopy. Ferroelectric and piezoelectric properties of the prepared samples were examined based on their polarization characteristics using piezoelectric responsive force microscopy, further confirming the high tetragonality of the as-prepared BaTiO₃ nanoparticles.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125652"},"PeriodicalIF":3.5,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046641","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural disorder and symmetry of nickel oxalate dihydrate affected by synthesis conditions","authors":"Anatolii V. Korneev,&nbsp;Mariya A. Kuzmina,&nbsp;Alina R. Izatulina,&nbsp;Olga V. Frank-Kamenetskaya","doi":"10.1016/j.jssc.2025.125641","DOIUrl":"10.1016/j.jssc.2025.125641","url":null,"abstract":"<div><div>Nickel oxalate dihydrate α-NiC₂O₄∙2H₂O (space group <em>C</em>2/<em>c</em>) belongs to a family of oxalates with general formula M²⁺(C₂O₄)∙2H₂O (M = Fe, Mn, Mg, Zn, Ni, Co), known as humboldtine group minerals. To elucidate patterns of structural disorder we have synthesized Ni-oxalate dihydrate from water solution in a wide range of conditions (pH = 1.5–9.5, Ni/C₂O₄ = 0.17–4, T = 25–200 °C) and explored the synthesis products using powder X-ray diffraction including Rietveld refinement and scanning electron microscopy with EDX-spectroscopy. It was revealed that structural disorder of NiC₂O₄∙2H₂O affects the diffraction patterns and unit cell parameters. We have found an entire series of monoclinic structures, different by their degree of disorder. Excess of oxalate ions, weak-alkaline pH and especially temperature of crystallization medium are positively affecting the ordering of monoclinic nickel oxalate structure. There is an inverse correlation between structure disorder and its deviation from orthorhombic symmetry. Structural mechanisms of transitions between space groups <em>Cccm</em>, <em>Fddd</em> and <em>C</em>2/<em>c</em> in Ni(C₂O₄)∙2H₂O oxalates (polymorphism, desymmetrization) have been suggested. The study contributes to our understanding of crystal chemistry of humboldtine group oxalates and could be used in biotechnologies in future.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125641"},"PeriodicalIF":3.5,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145061220","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrothermal synthesis and growth of stable strontium apatite for radioactive salt waste immobilization","authors":"Xiaoliang Gou ,&nbsp;Maobiao Ran ,&nbsp;Shunzhang Chen ,&nbsp;Yi Liu ,&nbsp;Guoqing Gu ,&nbsp;Xiaoyan Shu ,&nbsp;Fen Luo ,&nbsp;Congcong Ding ,&nbsp;Xirui Lu","doi":"10.1016/j.jssc.2025.125648","DOIUrl":"10.1016/j.jssc.2025.125648","url":null,"abstract":"<div><div>Safe management of chloride-rich radioactive salt waste produced during molten-salt dry reprocessing of spent nuclear fuel is essential for the sustainable deployment of advanced nuclear energy systems. Although ⁹⁰SrCl₂ represents only a minor mass fraction, its high specific activity and decay heat dominate short-term thermal management. In this work, a low temperature hydrothermal synthesis of Sr₅(PO₄)₃Cl effectively immobilized Sr and about 10 % of Cl, while the remaining Cl was released as NaCl. Over a 10-h hydrothermal process, the step-like growth of crystalline and partially disordered domains promotes enhanced crystallinity and increased particle size of the Sr₅(PO₄)₃Cl solidified form, thereby improving its chemical durability. The well-crystallized product exhibits a mass loss of less than 1.8 <em>wt</em>.% at 1000 °C, and normalized leach rate of Sr²⁺ is 3.5 × 10⁻⁶ gm⁻²d⁻¹ after 28 d in deionized water at 90 °C. Reliable thermal and chemical stability confirm that low-temperature hydrothermal processing is an energy-efficient strategy for conditioning ⁹⁰SrCl₂ chloride wastes prior to geological disposal.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125648"},"PeriodicalIF":3.5,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145047149","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hybrid antioxidant based on exfoliated layered double hydroxides nanosheets with improved thermal stabilizing effects for polypropylene","authors":"Qian Zhang ,&nbsp;Guifu Zuo ,&nbsp;Yuchen Yue ,&nbsp;Jingran Zhang ,&nbsp;Fabrice Leroux ,&nbsp;Pinggui Tang ,&nbsp;Yongjun Feng","doi":"10.1016/j.jssc.2025.125640","DOIUrl":"10.1016/j.jssc.2025.125640","url":null,"abstract":"<div><div>An antioxidant (AO) agent, 3-(3,5-ditertbutyl-4-hydroxyphenyl) propionate anions (DBHP), intercalated between layered double hydroxides (DBHP-LDH) was prepared by coprecipitation method and then a part was delaminated in toluene to form exfoliated DBHP-LDH nanosheets. Both types of DBHP-LDH compositions, powder and exfoliated nanosheets were characterized by XRD, SEM and TEM, and subsequently incorporated into polypropylene (PP) as AO filler to improve the thermal stability of PP. The addition of DBHP-LDH affected the crystallization and melting behaviour as well as transmittance of PP, giving rise to its crystallinity improved but its transparency reduced. It was found that by incorporating either DBHP-LDH powder or exfoliated DBHP-LDH nanosheets the thermal decomposition temperatures and thermal aging resistance of PP were enhanced. Interestingly, between the two hybrid systems, it is however the exfoliated DBHP-LDH nanosheets that showed a better stabilizing effect for PP. This is attributed to the better dispersion regarding the exfoliated DBHP-LDH nanosheets, thus providing a more efficient radical scavenging capability. Even with its pronounced interface between PP chains and highly exposed nanosheets, about 30 % of DBHP was released from the exfoliated DBHP-LDH/PP compared to about 20 % DBHP migrated out of the conventional DBHP-LDH/PP films after 132 h test. This shows that the organic AO agent is well tethered to hydroxyl-bearing LDH nanosheets, thus opening new route to design functionalized filler for polymer from exfoliated LDH hybrid layers.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125640"},"PeriodicalIF":3.5,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modelling of oxygen diffusion in perovskite-type neodymium strontium ferrite Nd0.3Sr0.7FeO3-δ by application of molecular dynamics","authors":"Wolfgang Preis","doi":"10.1016/j.jssc.2025.125653","DOIUrl":"10.1016/j.jssc.2025.125653","url":null,"abstract":"<div><div>The diffusion of oxygen in Nd_0.3Sr_0.7FeO_3-δ (NSF37) with <em>δ</em> = 0.35 (space group: <span><math><mrow><mi>P</mi><mi>m</mi><mover><mn>3</mn><mo>‾</mo></mover><mi>m</mi></mrow></math></span>) was modelled in the temperature range from 2000 to 873 K by means of molecular dynamics (MD). The Nd and Sr atoms on the A-site sublattice as well as the oxygen vacancies on the oxygen sublattice were distributed randomly. The MD simulations yielded the trajectories as well as mean square displacements of oxygen atoms, resulting in vacancy self-diffusion coefficients which showed a non-Arrhenius type temperature dependence. The activation energy increased from 0.9 to 1.2 eV with decreasing temperature. The radial pair distribution functions, computed for Nd – O and Sr – O correlations, indicated the formation of defect interactions (preferential residence of vacancies in the vicinity of Sr) which might give rise to the variation of the activation energy. Moreover, the effect of symmetrical Σ13 (320) grain boundaries on the oxygen transport in NSF37 was investigated in detail. In particular, the effective oxygen self-diffusion coefficient (comprising both bulk and grain boundary regions) was determined as a function of temperature ranging from 1673 to 873 K. When the interfaces were equilibrated properly at 1673 K, leading to amorphous interfacial regions, the grain boundaries were clearly blocking for the oxygen transport. If, however, the equilibration at 1673 K was omitted (largely preventing the amorphization of the grain boundaries), fast grain boundary diffusion could be observed at low temperatures. At 873 K the grain boundary diffusion coefficient exceeded the bulk diffusivity by a factor of 2–3.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125653"},"PeriodicalIF":3.5,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}