Journal of Molecular Liquids最新文献

{"title":"Solution calorimetry as a method for estimation of enthalpy of mixing of binary mixtures","authors":"Ilnaz T. Rakipov,&nbsp;Artem A. Petrov,&nbsp;Ekaterina A. Titova,&nbsp;Aydar A. Akhmadiyarov","doi":"10.1016/j.molliq.2025.127330","DOIUrl":"10.1016/j.molliq.2025.127330","url":null,"abstract":"<div><div>The work is devoted to developing an approach for estimating the enthalpy of mixing using the classical dissolution calorimetry at infinite dilution method at 298.15 K. The approach is based on the solution enthalpies of binary mixtures (A₁A₂) and their pure (A₁ and A₂) components in an inert solvent (S) medium at infinite dilution. Two systems, n-heptane– chloroform and acetone–chloroform, with different proportions of components, were used to test the proposed approach. The solution enthalpies were measured for the studied binary mixtures in a cyclohexane medium at infinite dilution at 298.15 K. It has been found that the obtained values of mixing enthalpies obtained using the proposed approach are comparable to those reported in the literature values within the measurement error. This approach has considerable perspectives for the determination of mixing enthalpies of more complex systems.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127330"},"PeriodicalIF":5.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impact of brine chemistry on viscoelastic properties and geochemical interactions of low salinity polymer at rock-brine interfaces","authors":"Intisar K. Al-Busaidi ,&nbsp;Rashid S. Al-Maamari ,&nbsp;Mahvash Karimi ,&nbsp;Dawoud Al Mahrouqi ,&nbsp;Hassina Al Hinai","doi":"10.1016/j.molliq.2025.127372","DOIUrl":"10.1016/j.molliq.2025.127372","url":null,"abstract":"&lt;div&gt;&lt;div&gt;Recently, numerous studies have evaluated the efficacy of low salinity polymer (LSP) flooding in sandstone oil reservoirs; however, literature review revealed that the effects of brine chemistry on polymer viscoelasticity, and the subsequent impact on LSP flooding performance need to be clarified. To achieve that, the geochemical interactions of polymer with the rock surface at different brine chemistries and their effects on polymer adsorption and viscosity loss need to be considered. Therefore, the present study aims to investigate the impact of brine chemistry on polymer viscoelasticity, and ion exchange reactions with Boise sandstone cores. A multidimensional experimental approach, including frequency sweep measurements of HPAM polymer solutions at various brine chemistries was employed. Additionally, IC and ICP analyses were conducted for equilibrated brine with Boise rock. Moreover, single-phase displacement experiments were performed to study polymer adsorption and viscosity loss, with effluent analysis carried out using IC and TOC. The results revealed that polymer solutions with low divalent cation (Ca&lt;sup&gt;2+&lt;/sup&gt; or Mg&lt;sup&gt;2+&lt;/sup&gt;) concentrations (2 mM) exhibited longer relaxation times (up to 12 s&lt;sup&gt;−1&lt;/sup&gt;), indicating higher elasticity. However, as the cation concentration increased from 4 mM to 14 mM, the polymer structure stabilized, and additional Ca&lt;sup&gt;2+&lt;/sup&gt; or Mg&lt;sup&gt;2+&lt;/sup&gt; caused a smaller change in relaxation time (decreasing from 1.33 s&lt;sup&gt;−1&lt;/sup&gt; to 0.56 s&lt;sup&gt;−1&lt;/sup&gt;), and consequently, in viscoelasticity. Additionally, salinity had a stronger effect on HPAM polymer viscoelasticity than specific brine composition, with the charge-screening effect from salt concentration being the primary driver of relaxation time reduction. Similarly, the ionic composition of formation brine had minimal impact on the geochemical reactions of Boise rock with or without polymer, except when Ca&lt;sup&gt;2+&lt;/sup&gt; and Mg&lt;sup&gt;2+&lt;/sup&gt; were absent. Moreover, the presence of polymer in the brine was found to affect ion exchange reactions, equilibration processes, and extend the stabilization time during flooding experiments, emphasizing the importance of considering polymer behavior in fluid-rock interactions. Furthermore, the salinity of the makeup brine, rather than polymer concentration, primarily influenced adsorption behavior and injectivity by controlling polymer-rock interactions. Both high salinity polymer (HSP) (5459 ppm) and LSP (545.9 ppm) showed a similar 20 % of viscosity degradation, with delays in viscosity recovery due to polymer adsorption in HSP and salinity changes in LSP, and final degradation driven by increased divalent cation concentration in the water chemistry. These findings emphasize the importance of optimizing polymer formulations based on brine chemistry, managing the salinity of injection water and the presence of divalent cations, and understanding geochemical interactions and flow dynamics to enha","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127372"},"PeriodicalIF":5.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A DFT-based study on CFBP: Structural, solvent spectroscopic analysis and ligand protein interaction with the antipsychotic characteristics","authors":"Lakshmishri Sekar ,&nbsp;T. Jayavarthanan ,&nbsp;Kumaran Manogaran ,&nbsp;Periandy Sengeny ,&nbsp;V.S.K. Venkatachalapathy ,&nbsp;S. Soundhariya ,&nbsp;T. Sivaranjani ,&nbsp;Stevan Armaković","doi":"10.1016/j.molliq.2025.127361","DOIUrl":"10.1016/j.molliq.2025.127361","url":null,"abstract":"<div><div>This study employs density functional theory (DFT) to investigate the structural, spectroscopic, and pharmacological properties of 4-chloro-4′-fluoro butyrophenone (CFBP). Using the B3LYP method with a 6–311++G(d,p) basis set, we optimized the molecular geometry and analyzed vibrational frequencies. Experimental and theoretical Fourier-transform infrared (FTIR), Raman, and nuclear magnetic resonance (NMR) spectra show strong agreement, validating the computational models. Mulliken population analysis and molecular electrostatic potential mapping reveal charge distribution and reactive sites. Natural bond orbital (NBO) analysis highlights charge delocalization and stabilization energies. HOMO-LUMO gap, UV–Vis spectral transitions, and ADMET profiling confirm the molecule’s electronic and pharmacokinetic properties. Molecular docking studies reveal a binding energy of −5.1 kcal/mol, suggesting strong ligand–protein interaction with potential antipsychotic activity. These findings establish CFBP as a promising candidate for therapeutic applications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127361"},"PeriodicalIF":5.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Research progress on extraction of flavonoids with deep eutectic solvents from natural products","authors":"Hailin Ran ,&nbsp;Hui Li ,&nbsp;Danli Peng ,&nbsp;Yiru Hou ,&nbsp;Yongmei Jiang ,&nbsp;Juxiang Kuang ,&nbsp;Anjun Wang ,&nbsp;Xin Zhang ,&nbsp;Gang Wang","doi":"10.1016/j.molliq.2025.127356","DOIUrl":"10.1016/j.molliq.2025.127356","url":null,"abstract":"<div><h3>Abstract</h3><div>Flavonoid compounds are abundant in natural products and have attracted enduring interest from medical researchers worldwide due to their diverse biological activities, which studies have demonstrated to provide therapeutic benefits for various conditions, including cardiovascular diseases, cancer, and nervous system disorders. Consequently, the extraction of flavonoids from natural sources has become a major research priority. This review provides an overview of the application of Deep eutectic solvents (DESs) in flavonoid extraction, along with key factors influencing extraction efficiency. Furthermore, this research progress on the mechanisms behind the recovery and extraction of flavonoids using DESs. The results of the study provide theoretical basis for the further development and utilization of flavonoids extraction by DESs.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127356"},"PeriodicalIF":5.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143628994","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"HPLC/MALDI-TOF-MS characterization and nutraceutical potential of Seriphedium quettense extracts: A polarity directed solvent extraction and antioxidant kinetics","authors":"Mehwish Shah ,&nbsp;Zheng Linyan ,&nbsp;Muhammad Qasim ,&nbsp;Yemawaysh Zewdie ,&nbsp;Liping Qiu ,&nbsp;Muhammad Ayaz","doi":"10.1016/j.molliq.2025.127349","DOIUrl":"10.1016/j.molliq.2025.127349","url":null,"abstract":"<div><h3>Background</h3><div><em>Seriphedium quettense (S. quettense</em>) is traditionally used against various diseases and is rich in bioactive metabolities Although this plant has several known ethnomedicinal uses, its polarity-guided fingerprinting with kinetic modelling and biological evaluations are not yet been reported.</div></div><div><h3>Materials and Methods</h3><div>In this study, we performed polarity-directed extraction of fractions from <em>S. quettense</em> and samples were subjected to HPLC/MALDI-TOF MS analysis, total phenolic and flavonoids contents (TPC/TFC) following standard procedures. Furhter, we elucidated the inhibitory potentials of samples towards various oxidants, free radicals, microbial strains, and cancer cell lines to assess their potential use in nutraceuticals.</div></div><div><h3>Results</h3><div>Considerable amount of phenolic acids such as gallic acid (GA) and citric acid (CA) were found in the MeOH extract (0.5 and 16 µg/mg GA equivalent respectively). Moreover, flavonoids such as QU were abundantly found in the ethyl acetate (EA) extract (1.9 µg/mg QE equivalent). Highest TFC was found in EA and CL extracts (130.46 and 81.08 µg QE/mg respectively), while the highest TPC was observed in MeOH + WT extract (108.67 µg GA/mg). Extracts rich in phenolic acids revealed strong antioxidant capacity. In particular, the MeOH extract showed high activity (IC₅₀ = 5.48 µg/mL) in diphenylpicryl hydrazine (DPPH) free-radical scavenging assays. The MeOH + EtOH and MeOH + WT extracts exhibited considerable antibacterial activity against <em>Pseudomonas aeruginosa</em> and <em>Bacillus subtilis</em> (IC₅₀ = 11.1 and 11 µg/mL, respectively)<em>.</em> The extracts also demonstrated in vitro cytotoxicity against the HeLa cervical cancer cell line, with the NH extract demonstrating a high activity of IC₅₀ = 14.29 µg/mL. The CL extract demonstrated significant antifungal activity (DIZ = 11 ± 0.03) against <em>Mucor</em> species. The hemocompatibility results revealed that all extracts were safe. The structural-bioactivity relationship showed neuroprotective and anti-aging activity of the combination of different classes of phytochemicals in these extracts.</div></div><div><h3>Conclusions</h3><div>Our findings indicate that <em>S. quettense</em> plant extracts contain bioactive secondary metabolites which might contribute towards the pharmacological potentials of the plant. Further detailed studies are required to elucidate the molecular mechanism of these results and its potential applications in nutraceutical sector.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127349"},"PeriodicalIF":5.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143628915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Analytical expression for Poisson’s equation in relation to a bispherical pore and examination of influence of the pore wall’s concave and convex structure on the EDL capacitance curve","authors":"Samaneh Safdaar,&nbsp;Ezzat Keshavarzi","doi":"10.1016/j.molliq.2025.127365","DOIUrl":"10.1016/j.molliq.2025.127365","url":null,"abstract":"<div><div>The effects of the convex and concave walls of a bispherical pore of a porous electrode of an EDL supercapacitor on the amount of capacitance have been investigated. The classical density functional theory in the framework of the primitive model, PM has been used. Also, the analytical solution for Poisson’s equation has been presented. The different accumulation of ions at the pore’s concave (outer) and convex (inner) walls leads to varying charge storage values and, consequently, the amount of EDL capacitance. The entropy effect causes the counterion accumulation at the concave wall to be greater than that at the convex wall; however, the energy effect, which is imposed by the electrode potential, effects on that. The amount of counterion adsorption directly affects the wall’s EDL capacitance, which has been thoroughly investigated for both concave and convex walls. Our results indicate that the concave wall’s capacitance is always larger than the convex wall’s. Finally, the effect of ion size and electrolyte concentration on the value of capacitance has also been studied; results show a camel-bell curve transition with concentration.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127365"},"PeriodicalIF":5.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143637578","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the biomedical and photocatalytic properties of copper(II) imidazole complex-functionalized TiO2 nanoparticles","authors":"Devanshi Chhabria ,&nbsp;Ganeshraja Ayyakannu Sundaram ,&nbsp;Dhanraj Ganapathy ,&nbsp;Prabhalakshmi Balasubramaniyan","doi":"10.1016/j.molliq.2025.127368","DOIUrl":"10.1016/j.molliq.2025.127368","url":null,"abstract":"<div><div>The development of multifunctional nanoparticles (NPs) with enhanced biological and photocatalytic activities is crucial for biomedical and environmental applications. This study investigates the biomedical and photocatalytic potential of TiO₂ NPs grafted with a copper(II) imidazole complex, focusing on cytotoxicity, anti-inflammatory, antioxidant, and photocatalytic properties. The Cu-TiO₂ NPs exhibited significant biological and photocatalytic enhancements. Cytotoxicity assays on NSCLC cell lines revealed dose-dependent effects, with 47 % cytotoxicity at 300 µg/mL, increasing to 72 % at 500 µg/mL. Anti-inflammatory assessments via BSA denaturation assays showed 19 % inhibition at 100 µg/mL, rising to 78 % at 500 µg/mL, nearing cholecalciferol’s 84 %. The antioxidant capacity, measured through DPPH radical scavenging, demonstrated 42 % inhibition at 300 µg/mL and 68 % at 500 µg/mL, significantly surpassing the Cu(II) precursor complex but slightly below ascorbic acid’s 84 %. Photocatalytic degradation of Rhodamine B under UV irradiation achieved 86.4 % efficiency within 60 min, exceeding TiO₂ (45.4 %) and the RhB blank (14.7 %), with kinetic analysis confirming a pseudo-first-order reaction (k = 0.033 min⁻¹ for Cu-TiO₂ vs. 0.011 min⁻¹ for TiO₂). Phenol degradation tests further demonstrated 70 % removal efficiency, highlighting wastewater treatment potential. Notably, radical scavenger studies identified hydroxyl radicals (<img>OH) as the primary reactive species, confirming the environmentally safe mechanism of photocatalysis. Importantly, the Cu-TiO₂ NPs have the added advantage of being biocompatible, making them a promising candidate for environmental remediation without negatively impacting living organisms. These findings underscore the significant cytotoxic, anti-inflammatory, antioxidant, and photocatalytic capabilities of Cu-TiO₂ nanoparticles, emphasizing their potential for cancer therapy, inflammation management, oxidative stress reduction, and environmental remediation, with future in vivo studies and mechanistic explorations essential to optimizing their therapeutic efficacy and photocatalytic performance.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127368"},"PeriodicalIF":5.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143628919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Glyphosate and AMPA sorption onto synthetic iron (oxyhydr)oxides: A comparative study","authors":"Alana Deduck Cicilinski ,&nbsp;Vander Freitas Melo ,&nbsp;Patricio Peralta-Zamora","doi":"10.1016/j.molliq.2025.127303","DOIUrl":"10.1016/j.molliq.2025.127303","url":null,"abstract":"<div><div>Glyphosate (GLY) and its metabolite AMPA are highly soluble in water, potentially facilitating their transport through soil. However, the strong reactivity of their phosphonic and carboxylic groups promotes interactions with organic and inorganic soil components, significantly limiting mobility and effectively preventing leaching. This study evaluates the sorption of GLY and AMPA on synthetic colloids, specifically goethite (Gt, α-FeOOH), hematite (Hm, α-Fe₂O₃) and ferrihydrite (Fh, Fe₅HO₈·4H₂O). The sorption of GLY and AMPA on Fe oxides is kinetically favored, being mainly controlled by the intraparticle diffusion process. AMPA generally fits better to the Freundlich model, indicating electrostatic interactions and the formation of outer-sphere complexes. In contrast, GLY aligns more closely with the Langmuir-Freundlich or Langmuir model, suggesting specific chemical interactions, likely involving ligand exchange between the oxygen of the phosphonic group and the biprotonated ferric hydroxyl group (Fe–OH₂^+0.5). The results indicate that Fe oxides exhibit similar adsorption capacities for GLY.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127303"},"PeriodicalIF":5.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143591864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrospinning of gelatin fine fibers loaded with hop waste extract: Development, characterization, and application as antioxidant chitosan bilayer films","authors":"Aline Oliveira Silva Iahnke,&nbsp;Micheli Legemann Monte,&nbsp;Tito Roberto Sant’Anna Cadaval,&nbsp;Luiz Antonio Almeida Pinto","doi":"10.1016/j.molliq.2025.127364","DOIUrl":"10.1016/j.molliq.2025.127364","url":null,"abstract":"<div><div>The present work demonstrated the potential of recovering bioactive compounds from hop waste extract using green solvents and incorporating them into fine gelatin fibers. The fine fibers were deposited on chitosan films, producing a bilayer film. Afterward, the bilayer film was characterized and applied as an antioxidant. Hop waste extract was characterized by lipid content, total phenolic content, and total flavonoid content. The extract was a good source of flavonoids (&gt;8.4 mg QE g⁻¹). Electrospinning solutions were characterized by viscosity and electrical conductivity. Fine gelatin fibers loaded with hop waste extract as a source of an antioxidant agent were developed using the electrospinning method. The operational conditions were conducted under 22.4 kV, needle tip-to-collector distance of 13.75 cm, and flow rate of 1.2 mL h⁻¹). Electrospinning of pure gelatin and gelatin incorporated with hop waste extract solutions was formed on the chitosan films. The fibers obtained by the electrospinning process were evaluated by the properties of thickness, color, morphology, thermal stability, functional groups, and hop extract incorporation efficiency. Bilayer films were characterized by thickness, tensile strength, elongation-at-break, water vapor permeability, and morphology. The antioxidant activity against the DPPH radical of fibers loaded with bioactive compounds improved by 71.1 % compared to the pure gelatin fiber. Selected electrospinning solutions were collected on chitosan films to produce antioxidant bilayer films. Compared to the pure chitosan film, the bilayer film elongation increased by 65 %, and antioxidant activity increased by 85 %.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127364"},"PeriodicalIF":5.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143610010","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical behavior of molybdenum ions and their coordination structures in NaCl-KCl melt containing fluoride ions","authors":"Huakui Zhang ,&nbsp;Zepeng Lv ,&nbsp;Shaolong Li ,&nbsp;Jilin He ,&nbsp;Kun Yang ,&nbsp;Yong Fan ,&nbsp;Jianxun Song","doi":"10.1016/j.molliq.2025.127375","DOIUrl":"10.1016/j.molliq.2025.127375","url":null,"abstract":"<div><div>In the process of electrolytic extraction and refining of molybdenum metal, molybdenum ions exhibit diverse valence states and are involved in complex coordination reactions with various electrolyte ions, leading to intricate forms of existence and electrochemical behavior. In this study, the electrolyte composition was adjusted by precisely controlling the addition of fluoride ions, allowing for an in-depth investigation of their influence on the reduction kinetics of Mo(V) ions and the coordination environment within the molten salt. The introduction of fluoride ions was observed to streamline the reduction mechanism of high-valent molybdenum ions, simplifying their previously complex multi-step reduction pathway to a more efficient single-step process. The initial reaction of Mo(V) ions under varying concentrations of fluoride ions was identified as a diffusion-controlled reversible process, with the diffusion coefficient decreasing as fluoride ion concentration increased. Moreover, fluoride ions demonstrate greater polarizability than chloride ions, facilitating the formation of stable coordination compounds with molybdenum ions, as evidenced by XPS analysis and first-principles molecular dynamics methods. As fluoride ion concentration increases, the coordination structure of molybdenum progressively shifts from Mo–Cl to Mo–F bonds, thereby influencing the charge transfer and ion diffusion dynamics of high-valent molybdenum ions. This study provides valuable new insights for the selection of electrolytes in the molten salt electrolytic extraction and refining process of molybdenum metal.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127375"},"PeriodicalIF":5.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}