Pub Date : 2026-03-11DOI: 10.1021/acs.jpcc.5c07952
M. Sarathbavan,C. Kathiresan,Lokeswaran Ravi,K. Kamala Bharathi,Sabyasachi Mukhopadhyay
Conversion-type anode materials show significant potential for advancing next-generation lithium-ion batteries (LIBs). This study involved the synthesis and comprehensive investigation of Li4WO5 and molybdenum-substituted Li4W1–xMoxO5 (x = 0.1, 0.2) regarding their electrochemical properties. Raman spectroscopy and X-ray diffraction validated the establishment of orthorhombic crystal formations. Galvanostatic charge–discharge assessments at 0.1 and 0.3 C demonstrated that molybdenum substitution markedly improved both specific capacity and energy density. The Li4W1–xMoxO5 (x = 0.2) sample exhibited the maximum discharge capacity of 415.16 mAh g–1 and an energy density of 232.48 Wh kg–1 at a rate of 0.1 C. Cyclic voltammetry demonstrated enhanced Li+ transport, with diffusion coefficients aligning with GITT findings. Ex situ SEM study further validated that Mo inclusion improves structural integrity and cycle stability. XPS Studies also indicate the presence of all the elements involved in electrochemical reactions. Upon cycling, the Mo-doped Li4WO5 has superior electrochemical performance, indicating significant potential as a high-energy anode material for improved lithium-ion batteries.
{"title":"Tailoring Lithium-Ion Storage in Li4WO5 through Molybdenum Substitution at Tungsten Sites (x = 0.1, 0.2): Enhanced Electrochemical Performance of a Novel Anode Material","authors":"M. Sarathbavan,C. Kathiresan,Lokeswaran Ravi,K. Kamala Bharathi,Sabyasachi Mukhopadhyay","doi":"10.1021/acs.jpcc.5c07952","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07952","url":null,"abstract":"Conversion-type anode materials show significant potential for advancing next-generation lithium-ion batteries (LIBs). This study involved the synthesis and comprehensive investigation of Li4WO5 and molybdenum-substituted Li4W1–xMoxO5 (x = 0.1, 0.2) regarding their electrochemical properties. Raman spectroscopy and X-ray diffraction validated the establishment of orthorhombic crystal formations. Galvanostatic charge–discharge assessments at 0.1 and 0.3 C demonstrated that molybdenum substitution markedly improved both specific capacity and energy density. The Li4W1–xMoxO5 (x = 0.2) sample exhibited the maximum discharge capacity of 415.16 mAh g–1 and an energy density of 232.48 Wh kg–1 at a rate of 0.1 C. Cyclic voltammetry demonstrated enhanced Li+ transport, with diffusion coefficients aligning with GITT findings. Ex situ SEM study further validated that Mo inclusion improves structural integrity and cycle stability. XPS Studies also indicate the presence of all the elements involved in electrochemical reactions. Upon cycling, the Mo-doped Li4WO5 has superior electrochemical performance, indicating significant potential as a high-energy anode material for improved lithium-ion batteries.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"25 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383826","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}
Pub Date : 2026-03-11DOI: 10.1021/acs.jpcc.5c08294
Shaona Das,Ravi Kiran Dokala,Subhash Thota
We report the influence of Ce3+ substitution on the magnetic structures and phonon dynamics in SmCrO3 perovskites. Magnetic landscapes are spanned by long-range canted antiferromagnetism, AFM with Néel temperatures, TN ∼196 K accompanied by spin-reorientation transitions, TSRPT at 42 K. In Sm0.9Ce0.1CrO3 (SCCO), Ce3+ substitution at Sm3+ sites transforms the weak ferromagnetic (FM) Γ4(Gx,Ay,Fz;FzR) state into the robust AFM Γ1(Ax,Gy,Cz;CzR) configuration through a gradual crossover. Such coexistence of magnetic spin configurations (Γ1(AFM) ⇋ Γ4(WFM)) results in the enhanced high coercive field and a pronounced exchange bias-field, HEB ∼2 kOe. Only-spin driven magneto-crystalline anisotropy of Cr3+ and spin–orbit driven magnetic moment in Sm3+, and Ce3+ exhibits spin-phonon coupling through A1g(6) mode in SCCO are consistent with the temperature dependent spectral features of the isostructural magnetic systems and quite significant in SCCO which is in accordance with the high structural distortion in SCCO. These results demonstrate that site-specific R3+ substitution modulates lattice distortions, spin–phonon coupling, and spin–orbit interactions, offering pathways to optimize perovskites for diverse spintronic applications.
{"title":"Spin-Reorientation Dynamics and Strong Spin Phonon Coupling in Ce-Substituted SmCrO3","authors":"Shaona Das,Ravi Kiran Dokala,Subhash Thota","doi":"10.1021/acs.jpcc.5c08294","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08294","url":null,"abstract":"We report the influence of Ce3+ substitution on the magnetic structures and phonon dynamics in SmCrO3 perovskites. Magnetic landscapes are spanned by long-range canted antiferromagnetism, AFM with Néel temperatures, TN ∼196 K accompanied by spin-reorientation transitions, TSRPT at 42 K. In Sm0.9Ce0.1CrO3 (SCCO), Ce3+ substitution at Sm3+ sites transforms the weak ferromagnetic (FM) Γ4(Gx,Ay,Fz;FzR) state into the robust AFM Γ1(Ax,Gy,Cz;CzR) configuration through a gradual crossover. Such coexistence of magnetic spin configurations (Γ1(AFM) ⇋ Γ4(WFM)) results in the enhanced high coercive field and a pronounced exchange bias-field, HEB ∼2 kOe. Only-spin driven magneto-crystalline anisotropy of Cr3+ and spin–orbit driven magnetic moment in Sm3+, and Ce3+ exhibits spin-phonon coupling through A1g(6) mode in SCCO are consistent with the temperature dependent spectral features of the isostructural magnetic systems and quite significant in SCCO which is in accordance with the high structural distortion in SCCO. These results demonstrate that site-specific R3+ substitution modulates lattice distortions, spin–phonon coupling, and spin–orbit interactions, offering pathways to optimize perovskites for diverse spintronic applications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"195 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383828","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}
Pub Date : 2026-03-11DOI: 10.1021/acs.jpcc.5c08410
Iga Jankowska,Paweł Ławniczak,Michał Bielejewski,Radosław Pankiewicz,Jadwiga Tritt-Goc
Imidazole-doped chitin oligosaccharide (CHOS-Im) and chitosan (Chitosan-Im) biopolymer composites were investigated as model systems for anhydrous high-temperature proton conduction. Solid-state films were characterized by thermogravimetric analysis (TGA/DTG), electrical impedance spectroscopy (EIS), and variable-temperature 13C and 15N CP MAS NMR. Proton conductivity increases markedly above 100 °C under dry N2, reaching 3 × 10–3 S/m at 150 °C for CHOS-Im and 1 × 10–2 S/m at 130 °C for Chitosan-Im. Solid-state NMR provides direct evidence for proton exchange between imidazole and the polymer functional groups and reveals that thermally activated imidazole reorientation is a key dynamic process governing charge transport. The lower activation energy and increased molecular mobility observed in Chitosan-Im are attributed to acetic acid-induced plasticization, which increases proton accessibility and promotes hydrogen bond network dynamics. These results indicate a direct link between local molecular dynamics and macroscopic proton conductivity under anhydrous high-temperature conditions.
{"title":"Imidazole-Doped Chitin Oligosaccharides and Chitosan Biopolymer Composites for Anhydrous High-Temperature Proton Conduction","authors":"Iga Jankowska,Paweł Ławniczak,Michał Bielejewski,Radosław Pankiewicz,Jadwiga Tritt-Goc","doi":"10.1021/acs.jpcc.5c08410","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08410","url":null,"abstract":"Imidazole-doped chitin oligosaccharide (CHOS-Im) and chitosan (Chitosan-Im) biopolymer composites were investigated as model systems for anhydrous high-temperature proton conduction. Solid-state films were characterized by thermogravimetric analysis (TGA/DTG), electrical impedance spectroscopy (EIS), and variable-temperature 13C and 15N CP MAS NMR. Proton conductivity increases markedly above 100 °C under dry N2, reaching 3 × 10–3 S/m at 150 °C for CHOS-Im and 1 × 10–2 S/m at 130 °C for Chitosan-Im. Solid-state NMR provides direct evidence for proton exchange between imidazole and the polymer functional groups and reveals that thermally activated imidazole reorientation is a key dynamic process governing charge transport. The lower activation energy and increased molecular mobility observed in Chitosan-Im are attributed to acetic acid-induced plasticization, which increases proton accessibility and promotes hydrogen bond network dynamics. These results indicate a direct link between local molecular dynamics and macroscopic proton conductivity under anhydrous high-temperature conditions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"53 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383825","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}
Pub Date : 2026-03-11DOI: 10.1021/acs.jpcc.6c01454
Michal Payuk, Ben Aizenshtein, Dvir Rotem, Lioz Etgar, Danny Porath
Perovskites have a unique crystal structure that allows tunability of physical properties through compositional modifications. Halide perovskites, particularly cesium lead halides (CsPbX3; X = Cl, Br, I), exhibit outstanding optoelectronic properties, with recently demonstrated piezoelectric behavior arising from noncentrosymmetric lattice distortions under mechanical stress or electric fields. While iodine alloying has previously been shown to enhance piezoelectricity in perovskite bulk thin films, its effect in nanoparticles (NPs) remains unexplored. Here, we investigate the intrinsic piezoelectric properties of CsPbBr3 and iodine-alloyed CsPb(Br0.8I0.2)3 in both NP and thin-film morphologies using piezoresponse force microscopy (PFM). To quantify local piezoelectricity, we developed a high-resolution d33 mapping strategy that resolves nanoscale heterogeneity and captures distinct piezoelectric subpopulations. The highest of three observed subpopulations in CsPbBr3 NPs reached 15 ± 4 pm V–1, while CsPb(Br0.8I0.2)3 NPs reached up to 24 ± 6 pm V–1. The alloyed thin-film perovskite exhibited remarkable local d33 coefficients up to 80 ± 17 pm V–1, the highest reported for this material. This work establishes a comparison between iodide alloying effects in CsPbBr3 NPs and thin-film, as well as newfound nanoscale piezoelectric heterogeneity with potential impact on the design of tunable piezoelectric and nanoscale devices.
{"title":"Unraveling Piezoelectric Heterogeneity in All-Inorganic Metal Halide Perovskite Nanoparticles and Thin-Films","authors":"Michal Payuk, Ben Aizenshtein, Dvir Rotem, Lioz Etgar, Danny Porath","doi":"10.1021/acs.jpcc.6c01454","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c01454","url":null,"abstract":"Perovskites have a unique crystal structure that allows tunability of physical properties through compositional modifications. Halide perovskites, particularly cesium lead halides (CsPbX<sub>3</sub>; X = Cl, Br, I), exhibit outstanding optoelectronic properties, with recently demonstrated piezoelectric behavior arising from noncentrosymmetric lattice distortions under mechanical stress or electric fields. While iodine alloying has previously been shown to enhance piezoelectricity in perovskite bulk thin films, its effect in nanoparticles (NPs) remains unexplored. Here, we investigate the intrinsic piezoelectric properties of CsPbBr<sub>3</sub> and iodine-alloyed CsPb(Br<sub>0.8</sub>I<sub>0.2</sub>)<sub>3</sub> in both NP and thin-film morphologies using piezoresponse force microscopy (PFM). To quantify local piezoelectricity, we developed a high-resolution <i>d</i><sub>33</sub> mapping strategy that resolves nanoscale heterogeneity and captures distinct piezoelectric subpopulations. The highest of three observed subpopulations in CsPbBr<sub>3</sub> NPs reached 15 ± 4 pm V<sup>–1</sup>, while CsPb(Br<sub>0.8</sub>I<sub>0.2</sub>)<sub>3</sub> NPs reached up to 24 ± 6 pm V<sup>–1</sup>. The alloyed thin-film perovskite exhibited remarkable local <i>d</i><sub>33</sub> coefficients up to 80 ± 17 pm V<sup>–1</sup>, the highest reported for this material. This work establishes a comparison between iodide alloying effects in CsPbBr<sub>3</sub> NPs and thin-film, as well as newfound nanoscale piezoelectric heterogeneity with potential impact on the design of tunable piezoelectric and nanoscale devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"30 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147440385","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}
The development of bioinspired catalysts that mimic the nitrogenase enzyme has attracted significant attention for sustainable ammonia synthesis under ambient conditions. In this work, density functional theory (DFT) calculations were employed to design Fe- and Mo-decorated subunene, a newly proposed two-dimensional C–S framework that replicates the Fe–Mo cofactor environment through Fe–S and Mo–S coordination. The resulting single-atom catalysts (SACs) exhibit high structural stability and strong affinity toward molecular nitrogen adsorption. Mo-anchored subunene demonstrates markedly greater N2 activation relative to its Fe analogue, facilitated by enhanced charge transfer and π-backdonation that significantly weakens the N≡N triple bond. Comprehensive analysis, including electronic structure characterization and Gibbs free-energy profiles, reveals that Mo-subunene follows a distal reduction pathway with an exceptionally low overpotential of 0.04 V, while Fe-subunene favors an alternative NRR mechanism with a higher limiting potential of 0.59 V. The well-balanced stabilization of NRR intermediates on the Mo site underpins its superior catalytic performance. Importantly, both Fe- and Mo-decorated subunene systems exhibit high selectivity toward N2 reduction without susceptibility to the competing hydrogen evolution reaction. These findings establish subunene as a robust and efficient platform for mimicking enzymatic N2 fixation and provide new insights into the design of sulfur-coordinated single-atom catalysts for electrochemical ammonia synthesis.
{"title":"Nitrogenase Inspired Nitrogen Reduction on Mo/Fe-Modified Subunene: A Computational Exploration of Bio-Mimetic 2D Catalysis","authors":"Muthupandi Senthilkumar,Venkata Surya Kumar Choutipalli,Karthikraja Esackraj,Naga Venkateswara Rao Nulakani,Kothandaraman Ramanujam,Dalaver Hussain Anjum,Kevin L. Shuford,Muthuramalingam Prakash,Venkatesan Subramanian","doi":"10.1021/acs.jpcc.5c08383","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08383","url":null,"abstract":"The development of bioinspired catalysts that mimic the nitrogenase enzyme has attracted significant attention for sustainable ammonia synthesis under ambient conditions. In this work, density functional theory (DFT) calculations were employed to design Fe- and Mo-decorated subunene, a newly proposed two-dimensional C–S framework that replicates the Fe–Mo cofactor environment through Fe–S and Mo–S coordination. The resulting single-atom catalysts (SACs) exhibit high structural stability and strong affinity toward molecular nitrogen adsorption. Mo-anchored subunene demonstrates markedly greater N2 activation relative to its Fe analogue, facilitated by enhanced charge transfer and π-backdonation that significantly weakens the N≡N triple bond. Comprehensive analysis, including electronic structure characterization and Gibbs free-energy profiles, reveals that Mo-subunene follows a distal reduction pathway with an exceptionally low overpotential of 0.04 V, while Fe-subunene favors an alternative NRR mechanism with a higher limiting potential of 0.59 V. The well-balanced stabilization of NRR intermediates on the Mo site underpins its superior catalytic performance. Importantly, both Fe- and Mo-decorated subunene systems exhibit high selectivity toward N2 reduction without susceptibility to the competing hydrogen evolution reaction. These findings establish subunene as a robust and efficient platform for mimicking enzymatic N2 fixation and provide new insights into the design of sulfur-coordinated single-atom catalysts for electrochemical ammonia synthesis.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383827","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}
Pub Date : 2026-03-10DOI: 10.1021/acs.jpcc.5c08611
Eric Johnsson,Shrinjay Sharma,Arvind Gangoli Rao,David Dubbeldam,Sofia Calero,Thijs J. H. Vlugt
Hydroisomerization of alkane isomers is an important step in the manufacture of current kerosene and sustainable aviation fuels. Zeolites are used as acid catalysts in this process. It is therefore important to have predictions of the adsorption capacity or maximum loading of hydrocarbons in zeolites. Here, a cascade model using machine learning models is used to predict the maximum loading of alkane isomers in zeolites. The cascade is composed of a gradient-boosted tree classifier stage that predicts whether adsorption occurs and a regressor predicting the value of the maximum loading. The final data set consists of 45 different adsorbates (both linear and branched alkanes up to C16) and 97 different zeolite structures, resulting in 4365 data points. Descriptors include information on the geometry and topology of zeolite channels as well as the shape and size of the adsorbates. Extra composite descriptors are also present to provide the physical basis for predictions. Multiple regressors of different natures are considered: support vector regressors, gradient-boosted trees, extreme gradient-boosted trees, and the TabPFN pretrained model. TabPFN yields the highest generalization performance and the lowest error. An interpretability analysis using SHAP reveals that the most influential descriptors are physically meaningful, highlighting steric and volumetric constraints as the primary factors controlling the prediction of qmax. It is shown that despite both the classifier and the regressor being insensitive to random splits in data, the regressor is prone to overfitting at low fractions of data withheld for testing. The cascade model is compared to an Artificial Neural Network for training and resource efficiency. Despite training being longer for the neural network, the final model is lighter in both memory and storage. This work is built on our previous research in predicting the Henry coefficients of long-chain alkanes in zeolites. Using this previous model and the findings of this work, one could construct the adsorption isotherm for any alkane, thus enabling the analysis of adsorption behavior of alkane mixtures using IAST.
{"title":"Predicting the Maximum Loading in Zeolites for Hydroisomerization Applications: A Machine Learning Approach","authors":"Eric Johnsson,Shrinjay Sharma,Arvind Gangoli Rao,David Dubbeldam,Sofia Calero,Thijs J. H. Vlugt","doi":"10.1021/acs.jpcc.5c08611","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08611","url":null,"abstract":"Hydroisomerization of alkane isomers is an important step in the manufacture of current kerosene and sustainable aviation fuels. Zeolites are used as acid catalysts in this process. It is therefore important to have predictions of the adsorption capacity or maximum loading of hydrocarbons in zeolites. Here, a cascade model using machine learning models is used to predict the maximum loading of alkane isomers in zeolites. The cascade is composed of a gradient-boosted tree classifier stage that predicts whether adsorption occurs and a regressor predicting the value of the maximum loading. The final data set consists of 45 different adsorbates (both linear and branched alkanes up to C16) and 97 different zeolite structures, resulting in 4365 data points. Descriptors include information on the geometry and topology of zeolite channels as well as the shape and size of the adsorbates. Extra composite descriptors are also present to provide the physical basis for predictions. Multiple regressors of different natures are considered: support vector regressors, gradient-boosted trees, extreme gradient-boosted trees, and the TabPFN pretrained model. TabPFN yields the highest generalization performance and the lowest error. An interpretability analysis using SHAP reveals that the most influential descriptors are physically meaningful, highlighting steric and volumetric constraints as the primary factors controlling the prediction of qmax. It is shown that despite both the classifier and the regressor being insensitive to random splits in data, the regressor is prone to overfitting at low fractions of data withheld for testing. The cascade model is compared to an Artificial Neural Network for training and resource efficiency. Despite training being longer for the neural network, the final model is lighter in both memory and storage. This work is built on our previous research in predicting the Henry coefficients of long-chain alkanes in zeolites. Using this previous model and the findings of this work, one could construct the adsorption isotherm for any alkane, thus enabling the analysis of adsorption behavior of alkane mixtures using IAST.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"79 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383837","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}
The high economic value of extra virgin olive oil (EVOO) makes it susceptible to adulteration with lower-cost oils, necessitating rapid and reliable analytical methods for authenticity assessment. In this work, a Raman spectroscopic approach combined with a multiscale Fusion Convolutional Residual Attention Network (MSF-CRAN) is developed for the identification and quantification of EVOO adulteration. Model interpretability is enhanced through the integration of SHapley Additive Explanations (SHAP), enabling the analysis of spectral feature contributions. To address limited sample availability in multicomponent adulteration systems, binary, ternary, and higher-order blended samples were prepared, and data set expansion was achieved using spectral feature transfer and generative adversarial networks (GANs). The proposed MSF-CRAN model demonstrates excellent performance, achieving 100% classification accuracy for adulteration identification and high quantitative accuracy for ternary mixtures with an R2 of 0.991 and a mean absolute error (MAE) of 0.0181. The results highlight the robustness and generalization capability of the proposed framework for the Raman-based analysis of complex multicomponent systems.
{"title":"Interpretable Deep Learning Framework Enables Authentication and Quantification of Olive Oil Adulteration by Raman Spectroscopy","authors":"Xue-Yang Xiong,Huan Chen,Jia-Sheng Lin,Fan-Li Zhang","doi":"10.1021/acs.jpcc.6c00601","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c00601","url":null,"abstract":"The high economic value of extra virgin olive oil (EVOO) makes it susceptible to adulteration with lower-cost oils, necessitating rapid and reliable analytical methods for authenticity assessment. In this work, a Raman spectroscopic approach combined with a multiscale Fusion Convolutional Residual Attention Network (MSF-CRAN) is developed for the identification and quantification of EVOO adulteration. Model interpretability is enhanced through the integration of SHapley Additive Explanations (SHAP), enabling the analysis of spectral feature contributions. To address limited sample availability in multicomponent adulteration systems, binary, ternary, and higher-order blended samples were prepared, and data set expansion was achieved using spectral feature transfer and generative adversarial networks (GANs). The proposed MSF-CRAN model demonstrates excellent performance, achieving 100% classification accuracy for adulteration identification and high quantitative accuracy for ternary mixtures with an R2 of 0.991 and a mean absolute error (MAE) of 0.0181. The results highlight the robustness and generalization capability of the proposed framework for the Raman-based analysis of complex multicomponent systems.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"39 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383836","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}
Pub Date : 2026-03-10DOI: 10.1021/acs.jpcc.5c08190
Denis V. Zhuravlev,Sergei A. Vasilkov,Ilia A. Elagin,Vladimir A. Chirkov,Oleg V. Levin
The reliability of extracting the electrical conductivity of electroactive polymer films from cyclic voltammetry (CV) on interdigitated electrodes (IDEs) is assessed using a data-driven, physics-based modeling framework. Pseudo-two-dimensional simulations replicate the IDE geometry and timing of the CV protocols. A porous-layer model that couples Butler–Volmer interfacial kinetics, radial diffusion of dopant anions within polymer globules, and lateral current flow in the IDE reproduces the salient voltammetric features. However, at typical scan rates, conductivity inferred from IDE current differences departs from the equilibrium value: pronounced hysteresis emerges, twin peaks develop, and occasional unphysical negative values appear. Analysis attributes the discrepancies to overpotential, spatially nonuniform doping across the film thickness, and uncompensated transient faradaic contributions to the current difference. Two accuracy-oriented protocols are evaluated: slowing the scan toward a quasi-equilibrium regime and employing staircase voltammetry with step holds until current stabilization. Both approaches recover conductivities consistent with the equilibrium relation and substantially reduce hysteresis. The workflow provides actionable guidance for obtaining reliable conductivity parameters for modeling and designing potentioresistive protective layers in lithium-ion cells and is transferable to other electrochemical systems that require an accurate description of conducting polymers.
{"title":"Limitations of Cyclic Voltammetry on Interdigitated Electrodes for Evaluating Polymer Conductivity","authors":"Denis V. Zhuravlev,Sergei A. Vasilkov,Ilia A. Elagin,Vladimir A. Chirkov,Oleg V. Levin","doi":"10.1021/acs.jpcc.5c08190","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08190","url":null,"abstract":"The reliability of extracting the electrical conductivity of electroactive polymer films from cyclic voltammetry (CV) on interdigitated electrodes (IDEs) is assessed using a data-driven, physics-based modeling framework. Pseudo-two-dimensional simulations replicate the IDE geometry and timing of the CV protocols. A porous-layer model that couples Butler–Volmer interfacial kinetics, radial diffusion of dopant anions within polymer globules, and lateral current flow in the IDE reproduces the salient voltammetric features. However, at typical scan rates, conductivity inferred from IDE current differences departs from the equilibrium value: pronounced hysteresis emerges, twin peaks develop, and occasional unphysical negative values appear. Analysis attributes the discrepancies to overpotential, spatially nonuniform doping across the film thickness, and uncompensated transient faradaic contributions to the current difference. Two accuracy-oriented protocols are evaluated: slowing the scan toward a quasi-equilibrium regime and employing staircase voltammetry with step holds until current stabilization. Both approaches recover conductivities consistent with the equilibrium relation and substantially reduce hysteresis. The workflow provides actionable guidance for obtaining reliable conductivity parameters for modeling and designing potentioresistive protective layers in lithium-ion cells and is transferable to other electrochemical systems that require an accurate description of conducting polymers.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"199 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383832","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}
Multilayered synthetic antiferromagnets (SAFs) are artificial three-dimensional (3D) architectures engineered to create novel, complex, and stable spin textures. Noninvasive and quantitative nanoscale magnetic imaging of the two-dimensional stray field profile at the sample surface is essential for understanding the fundamental properties of the spin-structure and being able to tailor them to achieve new functionalities. However, the deterministic detection of spin textures and their quantitative characterization at the nanoscale remain challenging. Here, we use nitrogen-vacancy scanning probe microscopy (NV-SPM) under ambient conditions to perform the first quantitative vector-field magnetometry measurements in the multilayered SAF [(Co/Pt)5/Co/Ru]3/(Co/Pt)6. We investigate the static and dynamic nanoscale properties of antiferromagnetic domains with boundaries hosting “one-dimensional” ferromagnetic stripes with ∼100 nm of width and periodic modulation of the magnetization. By employing NV-SPM measurements in different imaging modes and involving NV-probes with various crystallographic orientations, we demonstrate distinct fingerprints emerging from GHz-range spin noise and constant stray fields on the order of several mT. This provides quantitative insights into the structure of domains and domain walls, as well as, into magnetic noise associated with thermal spin-waves. Our work opens up new opportunities for quantitative vector-field magnetometry of modern magnetic materials with tailored 3D spin textures and stray field profiles, and potentially novel spin-wave dispersions─in a quantitative and noninvasive manner, with exceptional magnetic sensitivity and nanometer scale spatial resolution.
{"title":"Nanoscale NV-Center Magnetometry of a Synthetic Three-Dimensional Spin Texture","authors":"Ricardo Javier Peña Román,Sandip Maity,Fabian Samad,Dinesh Pinto,Simon Josephy,Andrea Morales,Attila Kákay,Klaus Kern,Olav Hellwig,Aparajita Singha","doi":"10.1021/acs.jpcc.6c00518","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c00518","url":null,"abstract":"Multilayered synthetic antiferromagnets (SAFs) are artificial three-dimensional (3D) architectures engineered to create novel, complex, and stable spin textures. Noninvasive and quantitative nanoscale magnetic imaging of the two-dimensional stray field profile at the sample surface is essential for understanding the fundamental properties of the spin-structure and being able to tailor them to achieve new functionalities. However, the deterministic detection of spin textures and their quantitative characterization at the nanoscale remain challenging. Here, we use nitrogen-vacancy scanning probe microscopy (NV-SPM) under ambient conditions to perform the first quantitative vector-field magnetometry measurements in the multilayered SAF [(Co/Pt)5/Co/Ru]3/(Co/Pt)6. We investigate the static and dynamic nanoscale properties of antiferromagnetic domains with boundaries hosting “one-dimensional” ferromagnetic stripes with ∼100 nm of width and periodic modulation of the magnetization. By employing NV-SPM measurements in different imaging modes and involving NV-probes with various crystallographic orientations, we demonstrate distinct fingerprints emerging from GHz-range spin noise and constant stray fields on the order of several mT. This provides quantitative insights into the structure of domains and domain walls, as well as, into magnetic noise associated with thermal spin-waves. Our work opens up new opportunities for quantitative vector-field magnetometry of modern magnetic materials with tailored 3D spin textures and stray field profiles, and potentially novel spin-wave dispersions─in a quantitative and noninvasive manner, with exceptional magnetic sensitivity and nanometer scale spatial resolution.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"52 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383768","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}
Crystalline porous materials, such as covalent organic frameworks (COFs), have emerged as promising candidates for photocatalytic and optoelectronic applications due to their tunable architecture and capacity to mitigate charge recombination. The incorporation of highly aromatic organic building blocks that promote self-assembly and columnar growth enables the formation of COFs with a controlled layer thickness. However, the influence of interlayer stacking on the structural and optoelectronic behaviors of these materials remains poorly understood. In this work, we combine experimental and theoretical approaches to elucidate the stacking-induced evolution of perylene–Zn–porphyrin COFs. Spectroscopic and microscopic analyses, supported by density functional theory (DFT) calculations, reveal that self-assembly through AA stacking markedly modifies both the geometry and electronic structure. The transition from nonplanar 2D architectures to planar multilayered frameworks results in reduced band gaps, inversion of the frontier crystalline orbital delocalization, and a shift of absorption dominance toward the porphyrin units. These findings demonstrate that controlled layer stacking is a viable strategy to tailor the electronic and optical properties of stacked 2D COFs, paving the way for their integration into high-performance optoelectronic devices.
{"title":"Stacking Effects on the Optoelectronic Properties of 2D Perylene-Zn-Porphyrin-Based COFs","authors":"Valentin Diez-Cabanes,Sergio de-la-Huerta-Sainz,Elisabeth Escamilla,Pedro A. Marcos,Alfredo Bol-Arreba,Kathryn McCarthy,Roberto González-Gómez,Santiago Aparicio,Pau Farràs","doi":"10.1021/acs.jpcc.5c08341","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08341","url":null,"abstract":"Crystalline porous materials, such as covalent organic frameworks (COFs), have emerged as promising candidates for photocatalytic and optoelectronic applications due to their tunable architecture and capacity to mitigate charge recombination. The incorporation of highly aromatic organic building blocks that promote self-assembly and columnar growth enables the formation of COFs with a controlled layer thickness. However, the influence of interlayer stacking on the structural and optoelectronic behaviors of these materials remains poorly understood. In this work, we combine experimental and theoretical approaches to elucidate the stacking-induced evolution of perylene–Zn–porphyrin COFs. Spectroscopic and microscopic analyses, supported by density functional theory (DFT) calculations, reveal that self-assembly through AA stacking markedly modifies both the geometry and electronic structure. The transition from nonplanar 2D architectures to planar multilayered frameworks results in reduced band gaps, inversion of the frontier crystalline orbital delocalization, and a shift of absorption dominance toward the porphyrin units. These findings demonstrate that controlled layer stacking is a viable strategy to tailor the electronic and optical properties of stacked 2D COFs, paving the way for their integration into high-performance optoelectronic devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"6 10 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383830","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}
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