Journal of Solid State Chemistry最新文献

{"title":"FeWO4 nanosheets with enhanced exposed (001) facets for promoting photocatalytic Fenton degradation of organic pollutants","authors":"Yun Wei ,&nbsp;Junpeng Guo ,&nbsp;Chang Liu ,&nbsp;Huihong Lü ,&nbsp;Ye Li","doi":"10.1016/j.jssc.2025.125238","DOIUrl":"10.1016/j.jssc.2025.125238","url":null,"abstract":"<div><div>Crystal faceted engineering has been widely used to improve the performance of photocatalysts, but there is still a lack of a general strategy for the wise design of nanocrystal morphology, and the fast recombination rate of photoinduced carriers seriously hinders the photocatalytic performance. Here, we report a new method to enhance the photocatalytic activity of FeWO₄ through crystal faceted engineering, and investigate the evolution of FeWO₄ morphology. The preparation of three different morphologies of FeWO₄ samples allowed us to carefully investigate the factors that contribute to the intrinsic reactivity of the sample, including H₂O₂ activation and band gap location. The results confirm that the selective exposure of the relatively active facets in the direction of the internal electric field gives the catalyst excellent photoactivity, and the decolorization efficiency of Rhodamine B (RhB) with the main (001) facets reaches 96.5 %, which is higher than that of the nanorods (010), and has excellent performance for the degradation of RhB dyes. Theoretical analysis and EPR trap experiments show that the cycling and photoinduced electron-hole separation efficiency of the coordination unsaturated iron ions is the main reason for the improvement of the photocatalytic activity of the FeWO₄ photofenton system, and the degradation intermediates and pathways of RhB dyes are studied. This work is expected to inform the development of a general approach for the morphology design of photocatalysts.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125238"},"PeriodicalIF":3.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143372072","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":"Machine learning assisted designing of small molecule acceptors with multiple terminal electron-deficient groups and performance prediction for next-generation photovoltaics","authors":"Zunaira Shafiq ,&nbsp;Mudassir Hussain Tahir ,&nbsp;Syed Shoaib Ahmad Shah ,&nbsp;Khalid M. Elhindi ,&nbsp;Munaza Shah Din ,&nbsp;Nadia Akram ,&nbsp;Muhammad Ramzan Saeed Ashraf Janjua","doi":"10.1016/j.jssc.2025.125240","DOIUrl":"10.1016/j.jssc.2025.125240","url":null,"abstract":"<div><div>Small molecule acceptors (SMAs) are extensively used in organic photovoltaics (OPVs) because of their capacity to efficiently receive electrons and enable charge separation. The performance of organic photovoltaic (OPV) devices can be enhanced by designing SMAs with several terminal electron-deficient groups, which will increase their electron-accepting capacity. However, it takes a lot of effort and time to rationally build such complicated molecules. In this work, a strategy for designing novel SMAs with numerous terminal electron-deficient groups is introduced. In order to predict the performance of newly designed SMAs, ML models have been employed that have been trained. Data on the power conversion efficiency (PCE) of 124 solar cell devices is collected. PCE's maximum value is taken into account. To compute molecular descriptors, utilize RDkit. A library of about 200 descriptors has been generated. The chemical similarity of the designed SMAs is studied using cluster plot and heatmap. For this purpose, chemical fingerprints are used. Using this method, thirty SMAs with highest PCE (%) ranges from 9.99 to 9.65 % have been selected.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125240"},"PeriodicalIF":3.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143350774","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":"Sb-doped kagome antiferromagnet FeGe: Superlattice structure and spin-reorientation transition","authors":"Zhaodi Lin ,&nbsp;Chenfei Shi ,&nbsp;Xiaofan Xu ,&nbsp;Qiyuan Liu ,&nbsp;Ji-Yong Liu ,&nbsp;Wanting Yang ,&nbsp;Jinhu Yang ,&nbsp;Baojuan Kang ,&nbsp;Shixun Cao ,&nbsp;Jin-Ke Bao","doi":"10.1016/j.jssc.2025.125243","DOIUrl":"10.1016/j.jssc.2025.125243","url":null,"abstract":"<div><div>Kagome lattice, a two-dimensional corner-sharing triangle network, can be realized in a real material and thus host many interesting physical phenomena. Charge density wave, anomalous Hall effect and antiferromagnetism have been discovered in a typical kagome material FeGe. Here, we report the effects of Sb doping on its crystal structure, magnetic and electrical transport properties. Charge density wave is suppressed completely by only a doping level of <em>x</em> = 0.05 in FeGe_1-<em>x</em>Sb_<em>x</em>. A <span><math><mrow><msqrt><mn>3</mn></msqrt><mo>×</mo><msqrt><mn>3</mn></msqrt><mo>×</mo><mn>2</mn></mrow></math></span> superlattice is realized at room temperature when the doping level of Sb reaches <em>x</em> = 0.12. The structure distortion of the supercell for the Fe kagome and Ge honeycomb planes are unveiled from single crystal x-ray diffraction measurements. Sb doping can only suppress the A-type antiferromagnetism mildly in FeGe, and induce a spin-reorientation transition when the doping level <em>x</em> is 0.1 or larger. The spin-reorientation transition can be modulated by the doping level as well as the external magnetic field in FeGe_1-<em>x</em>Sb_<em>x</em>. No detectable transport or thermodynamic signals can be identified for the spin-reorientation transition, indicating a subtle change in the electronic structure or magnetic entropy.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125243"},"PeriodicalIF":3.2,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143394619","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":"Crystal growth and magnetic evolution of antiferromagnetic topological insulator Zn-doped MnBi2Te4","authors":"Zhenduo Fan ,&nbsp;Haohang Xu ,&nbsp;Jinggeng Zhao ,&nbsp;Yaohui Zhang ,&nbsp;Xianjie Wang ,&nbsp;Yu Sui ,&nbsp;Zhe Lv ,&nbsp;Jian Liu ,&nbsp;Sida Jiang ,&nbsp;Zhiguo Liu","doi":"10.1016/j.jssc.2025.125242","DOIUrl":"10.1016/j.jssc.2025.125242","url":null,"abstract":"<div><div>As the first intrinsic magnetic topological insulator, MnBi₂Te₄ has provided a material platform for the realization of various novel physical phenomena arising from the interaction between magnetism and band topology. Here, transition element Zn<em>-</em>doped MnBi₂Te₄ crystals of millimeter size, synthesized by using self-flux method, are reported. With increasing Zn content, the hexagonal lattice shrinks, and the Raman frequencies show a red shift. All samples undergo a transition from A<em>-</em>type antiferromagnetic (A<em>-</em>AFM) to canted antiferromagnetic (CAFM) to ferromagnetic (FM) under magnetic field. The antiferromagnetic ordering temperature slightly increases from 24.2 K for MnBi₂Te₄ to 25.2 K for Mn_0.75Zn_0.25Bi₂Te₄. The transition field from AFM to CAFM decreases from 3.4 T for <em>x</em> = 0–3.07 T for <em>x</em> = 0.25. Isothermal magnetization data suggest that the single<em>-</em>ion anisotropy of Mn²⁺ decrease and the interlayer magnetic interaction increase slightly due to the diluted magnetic ions and unit cell shrinkage. Samples Mn_0.9Zn_0.1Bi₂Te₄ and Mn_0.8Zn_0.2Bi₂Te₄ show metallic conduction with a cusplike anomaly at around <em>T</em>_<em>N</em> ≈ 24 K, corresponding to a long<em>-</em>range antiferromagnetic (AFM) transition. The increase of <em>T</em>_<em>N</em> and decrease of transition field (<span><math><mrow><msubsup><mi>H</mi><mi>c</mi><mrow><mi>S</mi><mi>F</mi></mrow></msubsup></mrow></math></span>) upon Zn doping, make it possible to manipulate magnetic and electrical properties in topological insulators by non<em>-</em>magnetic element substitution, which is of great significance for further application in quantum information storage and spintronics.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125242"},"PeriodicalIF":3.2,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143377722","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":"Exploring crystal field influences on optical spectra of 3d7 (Ni3+ vs Co2+) ions in cubic pyrochlores A2Ti2O7 (A = Y, Gd) and layered-hexagonal MCl2 (M = Cd, Mg) for potential optoelectronic applications","authors":"Yatramohan Jana ,&nbsp;Anwesha Biswas ,&nbsp;Dinabandhu Halder ,&nbsp;Shankhanil Sarkar ,&nbsp;Czesław Rudowicz","doi":"10.1016/j.jssc.2025.125241","DOIUrl":"10.1016/j.jssc.2025.125241","url":null,"abstract":"<div><div>Herein we utilize computational methods for crystal field (CF) parameter (CFP) modelling to analyse experimental energy levels obtained from optical spectra of transition metal (TM) ions doped in crystalline hosts. These methods enable assessing the influence of structural distortions and chemical environments on the CF energy levels and thus optical properties of host-dopant systems. As a case study, we selected Ni³⁺ and Co²⁺(3d⁷) ions doped into: (a) cubic pyrochlores A₂Ti₂O₇ (A = Y, Gd), and (b) layered-hexagonal MCl₂ (M = Cd, Mg). The interplay of octahedral and trigonal CF, and spin-orbit coupling leads to low-spin ²E_g for Ni³⁺ and high-spin ⁴T_1g ground states for Co²⁺, impacting the optical properties of doped hosts. Semiempirical approaches: exchange charge model (ECM) and superposition model (SPM), are employed. For CFP modelling in titanates, the symmetry adapted axis system is adopted, whereas in chlorides - the modified crystallographic axis system. The predicted CF energy levels and <em>g</em>-factors compare well with experimental data. Ni³⁺ ion shows stronger cubic CF with larger CFPs and smaller distortions than Co²⁺ ion. For Co²⁺ ions across hosts, the SPM predicts more accurate CFPs and thus the CF energy levels than ECM. The behaviour of Co²⁺ differs substantially from that of other TM ions in doped hosts. Due to strong absorption/emission in the visible and infrared wavelength region, these hosts are promising for fabrication of infrared laser and sensor devices. This work highlights importance of fine-tuning structural properties and chemical environment, thus offering deeper insights into the structural and optical properties of the studied systems. The results may be useful for designing other TM ions doped hosts tailored for specific technological applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125241"},"PeriodicalIF":3.2,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143350777","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":"Co3O4@C nanocomposites derived from the thermal decomposition of Co-based metal-organic frameworks for lithium storage","authors":"Li Wang ,&nbsp;Jun Chen ,&nbsp;Huan Yang ,&nbsp;Haitao Dong ,&nbsp;Yang Yu ,&nbsp;Jingwen Sun ,&nbsp;Jingquan Sha","doi":"10.1016/j.jssc.2025.125239","DOIUrl":"10.1016/j.jssc.2025.125239","url":null,"abstract":"<div><div>To address the homogeneous dispersion in the preparation process of transition metal oxides and to overcome significant volume expansion issues during charging and discharging in lithium-ion batteries, thermal decomposition of metal-organic frameworks (MOFs) emerges as a promising approach for obtaining carbon-supported composite nanomaterials comprising transition metal oxides. Herein, a Co-based MOF, namely Co₆(TBA)₄(H⁺)₂(H₂O)₂(Py) (Co-TBA) was fabricated from hydrothermal synthesis with Co(NO₃)₂·6H₂O and 4,4′,4″-s-triazine-2,4,6-tricarbonic acid (TBA) as starting materials. Subsequently, homogenous thermal decomposition of Co-TBA was performed to obtain Co₃O₄@C nanocomposites. The resulting Co₃O₄@C nanomaterials exhibited approximately a sixteen-fold increase in discharge specific capacity (777.5 mAh g⁻¹) during cycling tests at a high current density of 1.0 A g⁻¹ compared to that of Co-TBA (47.4 mAh g⁻¹). The galvanostatic intermittent titration technique revealed that Co₃O₄@C exhibited significantly enhanced ion diffusion rates (10⁻¹⁰-10⁻¹³) compared to Co-TBA (10⁻¹⁴-10⁻¹⁷). Moreover, the Co₃O₄@C nanocomposite exhibits the hybrid supercapacitor-battery behavior confirmed by the analysis results of cyclic voltammetry kinetic analysis.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125239"},"PeriodicalIF":3.2,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143136618","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":"Deciphering the commensurately modulated monoclinic phase of Rb2ZnCl4 at low temperatures","authors":"Surya Rohith Kotla ,&nbsp;Sitaram Ramakrishnan ,&nbsp;Achim M. Schaller ,&nbsp;Toms Rekis ,&nbsp;Claudio Eisele ,&nbsp;Jin-Ke Bao ,&nbsp;Leila Noohinejad ,&nbsp;Geoffroy de Laitre ,&nbsp;Marc de Boissieu ,&nbsp;Sander van Smaalen","doi":"10.1016/j.jssc.2025.125226","DOIUrl":"10.1016/j.jssc.2025.125226","url":null,"abstract":"<div><div>The ferroelectric phase III of Rb<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>ZnCl<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> is stable below <span><math><msub><mrow><mi>T</mi></mrow><mrow><mi>c</mi></mrow></msub></math></span> = 192 K. It is known to be a threefold superstructure of the centrosymmetric high-temperature structure, with space group <span><math><mrow><mi>P</mi><msub><mrow><mn>2</mn></mrow><mrow><mn>1</mn></mrow></msub><mi>c</mi><mi>n</mi></mrow></math></span>. Below <span><math><msub><mrow><mi>T</mi></mrow><mrow><mi>L</mi></mrow></msub></math></span> = 70 K, phase IV exists as a sixfold superstructure. We report the crystal structure of phase IV with monoclinic symmetry <span><math><mrow><mi>C</mi><mi>c</mi></mrow></math></span> (b unique), while a structure model with symmetry <span><math><mrow><mi>P</mi><mi>n</mi></mrow></math></span> (c unique) leads to an almost equally good, yet significantly worse fit to the diffraction data. Employing the superspace approach to these commensurately modulated structures results in modulation waves that follow the two-dimensional irreducible representation <span><math><msub><mrow><mi>T</mi></mrow><mrow><mn>1</mn></mrow></msub></math></span> of <span><math><mrow><mi>P</mi><msub><mrow><mn>2</mn></mrow><mrow><mn>1</mn></mrow></msub><mi>c</mi><mi>n</mi></mrow></math></span>, albeit with different order parameter directions defining <span><math><mrow><mi>C</mi><mi>c</mi></mrow></math></span> and <span><math><mrow><mi>P</mi><mi>n</mi></mrow></math></span> symmetries, consistent with the literature. Standard tools of crystal-chemical analysis indicate that the sixfold superstructure is more stable than the threefold superstructure of phase III. However, crystal-chemical arguments cannot distinguish between the correct superstructure model with space group <span><math><mrow><mi>C</mi><mi>c</mi></mrow></math></span> (<span><math><mi>b</mi></math></span> unique) and the incorrect superstructure model with symmetry <span><math><mrow><mi>P</mi><mi>n</mi></mrow></math></span> (<span><math><mi>c</mi></math></span> unique) for phase IV. New crystal chemical tools are required, in order to attain a meaningful understanding of superstructure formation.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125226"},"PeriodicalIF":3.2,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143377792","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Properties of low-density SiO2 aerogels prepared based on the phase separation method","authors":"Lili Wang,&nbsp;Hongkai Zhao,&nbsp;Lei Chen,&nbsp;Haiyan Wang,&nbsp;Zhaotao Sun,&nbsp;Shunyu Cui","doi":"10.1016/j.jssc.2025.125237","DOIUrl":"10.1016/j.jssc.2025.125237","url":null,"abstract":"<div><div>To solve the problems of frequent solvent substitution and the high cost of modifiers in the process of aerogel preparation, this study proposed a modification method based on the combination of one-pot technology and phase separation technology, using polyoxydisiloxane (PEDS) as a precursor, with a small amount of n-hexane and Hexamethyldisiloxane(HMDSO) added in-situ, and n-hexane as the aging solution, followed by the addition of trimethylchlorosilane (TMCS), and trimethylethoxysilane (TMES) mixed in one pot for modification, after the end of modification to the mixed solution to the silicon ratio of 2.1 of water, water molecules were weakened by the role of the mutual solubility between ethanol and n-hexane, breaking the ternary phase equilibrium. The upward migration of hexane droplets was observed by microscopy, which led to the precipitation of ethanol from the system. Finally, a low-density SiO₂ aerogel powder was prepared by drying at atmospheric pressure and room temperature. Therefore, the phase separation method can be used to dry the gel under atmospheric pressure, avoiding the need for multiple solvent substitutions and hydrophobic modification in the traditional method. Under the most economical conditions for the use of pharmaceuticals, the silica aerogel powder synthesised by TMCS and TMES at a molar ratio of 1:2 can have a density as low as 0.0785g/cm³, a thermal conductivity as low as 0.0223 W/(m∙K), and a specific surface area as high as 837m²/g. Therefore, the phase separation method opens up a new pathway for the high-efficiency synthesis of silica aerogel powders, which makes aerogel products play a greater role in the field of thermal insulation.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125237"},"PeriodicalIF":3.2,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143300003","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":"Supramolecular crystalline material based on uranyl(V) and γ-cyclodextrin formed by photoreduction and irradiation reduction","authors":"Shijie Xiong ,&nbsp;Jianyuan Qi ,&nbsp;Qiwei Wu,&nbsp;Xinghai Shen","doi":"10.1016/j.jssc.2025.125236","DOIUrl":"10.1016/j.jssc.2025.125236","url":null,"abstract":"<div><div>Actinide supramolecular materials exhibit unique electronic properties and functions, offering great opportunities for application. However, the uranyl(V) based crystalline materials are reported scarcely due to the instability of uranyl(V). Herein, we report on the preparation and structural characterization of supramolecular crystalline materials composed of uranyl, γ-cyclodextrin (γ-CD) and Cs⁺ for the first time. The experimental results show that uranyl is activated in an asymmetric four-coordination microstructure with strong ligand to metal charge transfer (LMCT) in the prepared crystalline. Simulated calculation reveals that the crystalline has a high surface charge density of 0.15 C/m², which benefits the conversion of uranyl(VI) to uranyl(V). Subsequently, photoreduction and γ-irradiation reduction are explored to achieve efficient reduction from uranyl(VI) to uranyl(V), yielding reduction ratios of 73 % and 88 %, respectively. In the obtained supramolecular crystalline, the uranyl(V) in majority can coexist stably with minor uranyl(VI) in γ-CD environment because of restricted coordination. After reduction, the bandgap of crystalline is decreased from 2.85 to 1.92 eV due to the stronger LMCT effect. Furthermore, the characteristic <em>g</em>-factors of uranyl(V) at 2.005 and 2.020 suggest the existence of magnetism of the crystalline at room temperature.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125236"},"PeriodicalIF":3.2,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143300002","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":"The effect of hydrogen bonding on the magnetism quantum behavior of doped Co-MOFs","authors":"Zhenjun Fan ,&nbsp;Haoming Ning ,&nbsp;Zhenyu Mi ,&nbsp;Zhilin Xu ,&nbsp;Tianyi Gao ,&nbsp;Zhirui Sun ,&nbsp;Xiaohui Song","doi":"10.1016/j.jssc.2025.125207","DOIUrl":"10.1016/j.jssc.2025.125207","url":null,"abstract":"<div><div>In this paper, the low temperature magnetic behavior of doped Co based metal-organic frameworks (MOFs) single-crystals [(CH₃)₂NH₂]Co_1-xM_x[HCOO]₃ (DMCo_1-xM_xF) with M = Mg, Zn, Mn, Ni and x = 0.1–0.5 were systematically investigated. It was found that the long-range interactions between magnetic ions were effectively modulated by the type of doping ions, with antiferromagnetic phase transition temperature of 18.5 K for DMCo_0.8Ni_0.2F, 13.5 K for DMCo_0.8Mn_0.2F, 14.5 K for DMCo_0.9Zn_0.1F and 12 K for DMCo_0.7Mg_0.3F. Abnormally large coercive fields and hysteresis loss in Mg- or Zn- doping samples reveal the existence of single-ion quantum magnets in Co-based MOFs after non-magnetic doping. The coexistence of both long-range magnetic order and individual single-ion quantum magnets was further confirmed by quantum step behavior observed in the low-temperature hysteresis loop for non-magnetic doping (Mg, Zn) samples. A systematic analysis of the changes in bond length, bond angle, and vibrational spectrum of the samples indicates that the enhancement of hydrogen bonding is beneficial for increasing the anisotropy of magnetic single ions, leading to an increase in magnetic hysteresis and coercive fields, exhibiting quantum tunneling behavior of magnetic single ions. For the magnetic doping (Mn, Ni) samples, complex magnetic behavior is exhibited due to competition between magnetic ions. Our research indicates that doping can effectively regulate the quantum behavior of magnetic ions. The strength of hydrogen bonds has a significantly impacts on spin reversal and interactions.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125207"},"PeriodicalIF":3.2,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143377096","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}