Chemphyschem最新文献_第8页

Machine Learning Study of Methane Activation by O-Centered Radicals over Metal Oxide Clusters. 金属氧化物簇上o中心自由基活化甲烷的机器学习研究。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-08-18 DOI: 10.1002/cphc.202500274

Ying Xu, Zi-Yu Li, Yu-Ting Xiao, Yu-Zhe Hu, Qi Yang, Xiao-Nan Wu, Sheng-Gui He

{"title":"Machine Learning Study of Methane Activation by O-Centered Radicals over Metal Oxide Clusters.","authors":"Ying Xu, Zi-Yu Li, Yu-Ting Xiao, Yu-Zhe Hu, Qi Yang, Xiao-Nan Wu, Sheng-Gui He","doi":"10.1002/cphc.202500274","DOIUrl":"10.1002/cphc.202500274","url":null,"abstract":"Methane activation, a \"holy grail\" in chemistry, is crucial for producing value-added chemicals. Metal oxide clusters (MOCs) that activate methane through oxygen-centered radicals (O•-) have been extensively studied. However, a systematic and quantitative understanding of the electronic factors that govern the reactivity of the O•- radicals toward methane is still missing. Herein, a machine learning model has been developed to quantitatively describe the reactivity of MOCs toward CH4 by incorporating 17 newly obtained experimental reaction rate constants alongside data accumulated from the literature, a total of 107 in number, as well as descriptors derived from density functional theory calculations. Utilizing the back propagation artificial neural network algorithm, the model described with only two key features-unpaired spin density (UPSD) and local charge (QL)-is capable of predicting CH4 activation reactivity of O•- containing MOCs across a wide range of metal elements and cluster compositions. Further investigations indicate that a feature related to the detachment or attachment of electrons can replace QL while UPSD is irreplaceable. By using artificial intelligence, this study has made a big step forward in understanding methane activation by reactive oxygen species.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500274"},"PeriodicalIF":2.2,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144871692","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}

引用次数: 0

Structure and Dynamics of Water and Ions at Quartz (101) and (001) Surfaces under Applied Electric Fields from Molecular Simulations 分子模拟应用电场作用下石英（101）和（001）表面水和离子的结构和动力学。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-08-14 DOI: 10.1002/cphc.202401147

Pauline G. Simonnin, Sebastien N. Kerisit, Timothy C. Johnson, Kevin M. Rosso

{"title":"Structure and Dynamics of Water and Ions at Quartz (101) and (001) Surfaces under Applied Electric Fields from Molecular Simulations","authors":"Pauline G. Simonnin, Sebastien N. Kerisit, Timothy C. Johnson, Kevin M. Rosso","doi":"10.1002/cphc.202401147","DOIUrl":"10.1002/cphc.202401147","url":null,"abstract":"Electrical double layer (EDL) models are commonly adopted as a framework for understanding electrokinetic properties at mineral-fluid interfaces but the dynamics of ion and water mobilities are typically not well known. Extending the previous work performed at equilibrium conditions, here it is examined how applied electric fields induce mobilities of monovalent and divalent ions at hydroxylated quartz (001) and (101) interfaces with various electrolyte solutions (NaCl, KCl, and CaCl2). The simulations reveal how the diffusion coefficients depend on the orientation and magnitude of the applied electric field, with a particularly strong effect for fields applied parallel to the quartz surfaces. While the effect in perpendicular applied fields is more subtle, nonetheless the disruption of the water in the first layers at the surface with corresponding effects on wettability is observed. The details of EDL ion drift mobilities are found to be strongly correlated to the silanol density and crystallographic orientation at the interface. The findings shed light on the complex interplay between local and external forces affecting how these interfaces respond in applied field applications that include electrical impedance spectroscopy, electroosmotic flow, and ζ -potential measurements.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144854729","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}

引用次数: 0

Mesophase Properties and Molecular Order of Shape Anisometrically Divergent Thiophene Mesogens 形状不一等发散型噻吩中间体的介相性质和分子顺序。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-08-13 DOI: 10.1002/cphc.202500233

Bathini Veeraprakash, Gallelli Pratap, Nitin P. Lobo, Krishna V. Ramanathan, Tanneru Narasimhaswamy

{"title":"Mesophase Properties and Molecular Order of Shape Anisometrically Divergent Thiophene Mesogens","authors":"Bathini Veeraprakash, Gallelli Pratap, Nitin P. Lobo, Krishna V. Ramanathan, Tanneru Narasimhaswamy","doi":"10.1002/cphc.202500233","DOIUrl":"10.1002/cphc.202500233","url":null,"abstract":"The shape anisometrically variant thiophene mesogens are investigated by 13C NMR spectroscopy for the structural and orientational information in the liquid crystalline phase. These mesogens feature thiophene positioned at different locations within the core unit and include distinct substitutions. The mesogenic core is built with phenyl and thiophene rings directly connected or joined via linking units. Depending on the structure of the core unit, the occurrence of nematic and smectic C mesophases is recognized. The 1D and 2D 13C NMR studies in the liquid crystalline phase reveal interesting orientational information. The 13C1H dipolar couplings measured by the 2D separated local field technique offer precise structural information about thiophene and its orientation concerning the long molecular axis. The large variation in the magnitude of 13C1H dipolar couplings of thiophene is found to be extremely sensitive to molecular shape and is analyzed with respect to individual ring geometries. Thus, for a rod-like mesogen, the thiophene ring main order parameter in the nematic phase is 0.45, whereas, for a mesogen with a flexible spacer, it decreases to 0.17 in the same phase. In contrast, the thiophene main order parameter for bent-core mesogen reaches 0.82 in the smectic C phase.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144844755","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}

引用次数: 0

Oxygen-Vacancy-Driven Persistent Luminescence in Mn2+-Doped MgGeO3: Insights from X-Ray Absorption Fine Structure Spectroscopy 氧空位驱动的Mn2+掺杂MgGeO3的持续发光：来自x射线吸收精细结构光谱的见解。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-08-13 DOI: 10.1002/cphc.202500207

Sherry Cao, Yihong Liu, Ruoxin Deng, Clement Lee, Lijia Liu

{"title":"Oxygen-Vacancy-Driven Persistent Luminescence in Mn2+-Doped MgGeO3: Insights from X-Ray Absorption Fine Structure Spectroscopy","authors":"Sherry Cao, Yihong Liu, Ruoxin Deng, Clement Lee, Lijia Liu","doi":"10.1002/cphc.202500207","DOIUrl":"10.1002/cphc.202500207","url":null,"abstract":"Mn2+-doped MgGeO3 (MMGO) is a near-infrared-emitting persistent luminescence (PersL) phosphor. Its low luminescence decay has been linked to vacancies within the MgGeO3 host, likely associated with Ge, although no direct correlations have been confirmed. In this study, the Ge K-edge X-ray absorption fine structure (XAFS) spectroscopy is employed to investigate a series of MMGO submicron-sized particles with varying afterglow durations. These samples are synthesized using a recently developed hydrothermal method, where it is found that the PersL duration is related to the annealing temperature and the presence of codopants. It is first demonstrated that the XAFS spectra obtained using an in-house XAFS spectrometer are comparable in quality to those acquired at synchrotron facilities. Analysis of the local Ge environment of the MMGO shows that the PersL duration is directly related to the Ge–O coordination number. Additionally, the introduction of Li+ extends the PersL duration of MMGO but does not alter the Ge–O coordination. The findings provide insights into the structural mechanisms driving luminescence and highlight the capability of in-house XAFS systems to deliver high-quality data for advanced materials research.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202500207","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144844756","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}

引用次数: 0

Artificial Intelligence-Driven Optimization of Gaussian Orbital Expansions via Evolutionary Computing: Applications to Confined Atoms and Molecules 基于进化计算的高斯轨道展开的人工智能驱动优化：在受限原子和分子中的应用。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-08-13 DOI: 10.1002/cphc.202500107

Victor García, Manuel Fernández

引用次数: 0

Simplification of the Fermi–Löwdin Self-Interaction Correction Method for Efficient Self-Interaction-Free Density Functional Calculations 简化Fermi-Löwdin自相互作用修正方法的有效自相互作用无密度泛函计算。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-08-12 DOI: 10.1002/cphc.202500086

Selim Romero, Yoh Yamamoto, Tunna Baruah, Rajendra R. Zope

{"title":"Simplification of the Fermi–Löwdin Self-Interaction Correction Method for Efficient Self-Interaction-Free Density Functional Calculations","authors":"Selim Romero, Yoh Yamamoto, Tunna Baruah, Rajendra R. Zope","doi":"10.1002/cphc.202500086","DOIUrl":"10.1002/cphc.202500086","url":null,"abstract":"Fermi–Löwdin orbital self-interaction-correction (FLOSIC) method uses symmetric orthogonalized Fermi orbitals as localized orbitals in one-electron SIC schemes. In FLOSIC, a set of Fermi orbital descriptors (FOD) defines the FLOs and is obtained by energy minimization. Determination of optimal FODs is a computationally very demanding task. Herein, simplification of the FLOSIC calculations by removing self-interaction error from a set of selected orbitals of interest (SOSIC) is proposed. This approach is illustrated by choosing a set of valence orbitals as active orbitals. The results of a wide range of properties obtained using the valence SOSIC (vSOSIC) scheme are compared against the Perdew–Zunger SIC results. The two methods agree within a few percent for the majority of the properties. The mean absolute error in the vertical detachment energy of water cluster anions with vSOSIC-Perdew–Burke–Ernzerhof (PBE) against benchmark CCSD(T) results is only 15 meV making vSOSIC-PBE an excellent alternative to the CCSD(T) for the case. The calculation on the [Cu<math></math>Cl<math></math>]2− complex demonstrates that the FOD optimization in vSOSIC is substantially smoother and faster. Assessment of the performance of SIC-r<math></math>SCAN shows that it performs similarly to the SIC-Strongly Constrained and Appropriately Normed functional (SCAN) for most properties, but for atomization energies, SIC-r<math></math>SCAN outperforms SIC-SCAN.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 18","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144820693","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}

引用次数: 0

Plasmonics for Chemical Transformation: From Fundamentals to the Cutting-Edge Applications 等离子体化学转化：从基础到前沿应用。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-08-11 DOI: 10.1002/cphc.202401102

Dev Kumar Thapa, Soumava Biswas

{"title":"Plasmonics for Chemical Transformation: From Fundamentals to the Cutting-Edge Applications","authors":"Dev Kumar Thapa, Soumava Biswas","doi":"10.1002/cphc.202401102","DOIUrl":"10.1002/cphc.202401102","url":null,"abstract":"Plasmonic nanostructures, leveraging the phenomenon of localized surface plasmon resonance, have emerged as transformative tools in chemical catalysis by enabling reaction pathways inaccessible to conventional approaches. This review consolidates the fundamental principles of plasmonics and highlights recent advancements in their application to sustainable chemical transformations, such as CO2 reduction, selective oxidation, and hydrogenation. Notably, the innovative use of plasmon-induced hot carriers and field enhancement effects in overcoming reaction barriers, achieving unprecedented reaction selectivity and efficiency under mild conditions, is explored. The review underscores significant contributions, including the strategic coupling of plasmonic metals with defect-engineered supports, facilitating charge separation, and enabling selective product formation. The review introduces the potential of chiral plasmonic nanostructures for asymmetric synthesis, a frontier yet to be fully explored. Additionally, the review also explores the potential of alternative, cost-effective materials like aluminum and magnesium for use in plasmonic systems. Furthermore, key challenges in plasmonics, such as reducing energy losses and improving scalability have been discussed.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144820692","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}

引用次数: 0

Probing Facet Specific Interaction of 2-Propanol and CoFe2O4 at Near-Ambient Conditions 近环境条件下探测2-丙醇和CoFe2O4的面特异性相互作用。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-08-11 DOI: 10.1002/cphc.202500095

Anupam Bera, Soma Salamon, Heiko Wende, Steffen Franzka, Eckart Hasselbrink, Stéphane Kenmoe

{"title":"Probing Facet Specific Interaction of 2-Propanol and CoFe2O4 at Near-Ambient Conditions","authors":"Anupam Bera, Soma Salamon, Heiko Wende, Steffen Franzka, Eckart Hasselbrink, Stéphane Kenmoe","doi":"10.1002/cphc.202500095","DOIUrl":"10.1002/cphc.202500095","url":null,"abstract":"The interaction between 2-propanol and low-index facets of cobalt ferrite thin films under near-ambient conditions has been studied using surface-sensitive vibrational sum frequency spectroscopy (vSFS) and ab initio molecular dynamics (AIMD) simulations. The experimental and theoretical findings suggest that 2-propanol undergoes molecular and dissociative adsorption on different facets of CoFe2O4. Dissociation was found to be more prevalent on the (111) surface than on the (001) surface. Under dry conditions, the active regions on the (111) surface consist of Co2+–O2–propoxide–Fe3+ bridges. In contrast, the Co2+ surface atoms are inactive on the (001) surface under dry conditions. The Fe3+ surface atoms are the preferred adsorption sites. Molecular water plays a detrimental role because it competitively adsorbs onto the active sites with 2-propanol, inhibiting its decomposition. Moreover, OH groups with a lower concentration promote the formation of 2-propoxide. These results contrast with our recent study in which 2-propanol remained molecularly adsorbed on the Co3O4 (001) surface. These findings underscore the ambivalent role of hydroxyl groups on surfaces and also highlight the importance of dissociation state and water concentration as critical parameters for 2-propanol activation.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 17","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144815901","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}

引用次数: 0

2D Piezoelectric Covalent Organic Frameworks: Construction, Characterization, and Potential Applications 二维压电共价有机框架：结构、表征和潜在应用。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-08-11 DOI: 10.1002/cphc.202500148

Qianfeng Gu, Xiangqian Lu, Wei Qin, Qichun Zhang

{"title":"2D Piezoelectric Covalent Organic Frameworks: Construction, Characterization, and Potential Applications","authors":"Qianfeng Gu, Xiangqian Lu, Wei Qin, Qichun Zhang","doi":"10.1002/cphc.202500148","DOIUrl":"10.1002/cphc.202500148","url":null,"abstract":"2D piezoelectric covalent organic frameworks (2D p-COFs) represent a transformative class of materials merging structural precision, symmetry breaking, dynamic covalent chemistry, and electromechanical functionality. Unlike inorganic piezoelectrics (e.g., ZnO, perovskites) or conventional polymers, 2D p-COFs leverage their atomically ordered, noncentrosymmetric architectures to achieve efficient mechanical-to-electrical energy conversion while offering tunable structure, permanent porosity, and stability. Given the successful examples set by fluoropolymer-based energy harvesters, grafting fluorine-substituted alkyl chains onto COFs can facilitate dipole alignment and generate net spontaneous polarization, thereby inducing piezoelectricity. Recent advances in synthesis—fluorinated side-chain functionalization and hybrid system designs—have enabled large piezoelectric coefficients and high open-circuit voltages in nanogenerators. This review delves into the core principles of piezoelectricity, construction methodologies, the characterization of distinctive properties, and the burgeoning applications of 2D p-COFs in energy harvesting, catalysis, and sensing, while also facing challenges associated with scalability and stability.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144820690","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}

引用次数: 0

Conservation of the Total Order of the Axial SiSi and N → Si Bonds in Oligosilanylsilatranes 低聚硅烷中轴向Si - Si键和N→Si键总序的守恒。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-08-11 DOI: 10.1002/cphc.202500230

Elena F. Belogolova, Evgeniya P. Doronina, Judith Baumgartner, Christoph Marschner, Viatcheslav V. Jouikov

{"title":"Conservation of the Total Order of the Axial SiSi and N → Si Bonds in Oligosilanylsilatranes","authors":"Elena F. Belogolova, Evgeniya P. Doronina, Judith Baumgartner, Christoph Marschner, Viatcheslav V. Jouikov","doi":"10.1002/cphc.202500230","DOIUrl":"10.1002/cphc.202500230","url":null,"abstract":"Structural data from X-ray diffractometry (XRD) of oligosilanylsilatranes with a common coordination center SiSiO3N are used to map the SN2 substitution pathway at silatrane SiIV atom using the Bürgi–Dunitz method of structural correlation (MSC). A classical hyperbola-like reaction coordinate is featured using the nonlinear least squares method. This representation perfectly corresponds to the ideal MSC pattern imposed by the conservation of the total order of the axial bonds in silatranes. At the analytical level, it describes the inverse relationship of the internuclear distances SiSi and N → Si of the axial fragment N → SiSi and provides an experimental (XRD) support for the presence of a covalent contribution in the dative contact N → Si in oligosilanylsilatranes. Theoretical bond orders determined by various methods are analyzed from the point of view of their ability to describe the inverse relation between the axial 3c4e bonds of the oligosilanylsilatrane unit and the conservation of their overall order. The nature of N → Si bond in oligosilanylsilatranes is considered within orbital and quantum-topological approaches.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 19","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202500230","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144820691","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}

引用次数: 0