The Journal of Physical Chemistry C最新文献

{"title":"Experimental and Theoretical Investigations on the Structural, Electronic, and Vibrational Properties of β-Bi2Mo2O9 Dibismuth Dimolybdenum","authors":"Raí F. Jucá, José Gadelha da Silva Filho, Lindemberg S. Oliveira, Antônio Joel Ramiro de Castro, Marcelo A. S. Silva, Antonio Sérgio B. Sombra, Pierre Basílio Almeida Fechine, João Maria Soares, Antônio César Honorato Barreto, Paulo T. C. Freire, Gilberto Dantas Saraiva","doi":"10.1021/acs.jpcc.5c04920","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04920","url":null,"abstract":"This study presents a comprehensive structural, vibrational, and electronic investigation of the monoclinic β-Bi₂Mo₂O₉ compound, employing experimental and first-principles approaches. X-ray diffraction combined with Rietveld refinement confirms the crystallization of Bi₂Mo₂O₉ in the P2₁/n space group. Density functional theory calculations within the LDA-D framework reveal a slight underestimation of the lattice parameters and unit cell volume, while preserving local geometries. The vibrational properties were examined through Raman and infrared spectroscopy, supported by group-theory analysis, indicating a rich phonon activity consistent with the complex symmetry and multiatom basis of the monoclinic lattice. Electronic structure calculations identify BMO as an indirect band gap semiconductor with a computed band gap of 2.23 eV, closely matching experimental optical data. Bader charge and electron localization function (ELF) analyses highlight a mixed ionic–covalent bonding character, particularly pronounced in the Mo–O sublattice. Low-temperature Raman spectra (12–300 K) revealed systematic redshifts, peak broadenings, and intensity reductions across low- and high-wavenumber phonon modes, indicative of pronounced anharmonic effects and thermal expansion of the lattice. On the contrary, high-pressure Raman spectra collected up to 9.08 GPa showed a general phonon hardening trend with increasing pressure, attributable to lattice compression. Several Raman modes exhibited anomalous behavior, such as mode appearance, disappearance, and slope changes, pointing to pressure-induced phase transitions and potential symmetry changes.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"58 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306267","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":"Chemistry, Properties, and Patterning of Transparent and Conductive Materials","authors":"Keidy L. Matos, Anthony J. Russo, Adam B. Braunschweig","doi":"10.1021/acs.jpcc.5c05925","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c05925","url":null,"abstract":"Transparent and conductive (T/C) wires and patterns are essential components in modern optoelectronic devices, including touchscreens, solar panels, smart windows, and wearable sensors. These technologies rely on materials that simultaneously transmit visible light, conduct electricity, and can be patterned, requirements that pose substantial chemical, material, and processing challenges. Indium tin oxide, the longstanding industry standard for T/C applications, offers high transparency and low sheet resistance, but suffers from brittleness and restricted stretchability. These limitations have spurred intense research into alternative T/C materials, including metallic nanowires, carbon-based conductors, and conductive polymers, each offering unique advantages related to conductivity, flexibility, environmental stability, and fabrication compatibility. This perspective provides an overview of the properties demanded of T/C materials and recent advances in new T/C chemistry and fabrication techniques used to create T/C patterns.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"3 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145314830","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":"Colloidal Synthesis of Mn2+-Doped SrTiO3 Nanocrystals: B-Site Substitution and Spin-Relaxation Dynamics","authors":"Gaurav Mitra, Kevin R. Kittilstved","doi":"10.1021/acs.jpcc.5c04697","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04697","url":null,"abstract":"We report the colloidal hydrothermal synthesis of a unique nanocrystal (NC) system where Mn²⁺ ions are introduced into SrTiO₃ and appear to substitute at the octahedral Ti⁴⁺ site instead of the A site that has been reported from solid-state syntheses. This observation is supported by electron paramagnetic spectroscopy, where the Mn²⁺ signal has a hyperfine splitting value that is more consistent with Mn²⁺ at the B site in bulk SrTiO₃. We also do not detect any higher-valent Mn³⁺ or Mn⁴⁺ by any spectroscopic method in the Mn:SrTiO₃ NCs. The spin-relaxation dynamics of the Mn²⁺ dopants before and after introducing Ti³⁺ defects into the SrTiO₃ NCs through photodoping is also studied qualitatively using continuous-wave EPR power saturation studies at 100 K. We observe broadening of the Mn²⁺ EPR line widths consistent with cross-relaxation between Ti³⁺ and Mn²⁺ up to room temperature. This result is similar to but less efficient than our previous demonstration of accelerated spin relaxation of Cr³⁺ after photodoping Cr³⁺:SrTiO₃ NCs. This weaker cross-relaxation results from the larger difference in Landé <i>g</i> factors that results in a larger energy mismatch between the Mn²⁺ and Ti³⁺ EPR transitions in an applied magnetic field.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"195 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306261","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":"First-Principles Investigation of Naphyne as an Ultra-High-Capacity Anode Material for Potassium-Ion Battery","authors":"Nirmal Barman, Utpal Sarkar","doi":"10.1021/acs.jpcc.5c04816","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04816","url":null,"abstract":"Potassium-ion batteries (KIBs) are gaining attention as a cost-effective and sustainable alternative to lithium-ion batteries, primarily due to the natural abundance of potassium and its favorable electrochemical characteristics. Despite these advantages, the development of highly efficient anode materials remains a significant challenge, mainly because of the large ionic radius of the K⁺ ion, which tends to induce structural instability in conventional anode materials. In this context, we employ first-principles calculation based on density functional theory (DFT) to evaluate the potential of <i>naphyne</i>, a novel two-dimensional (2D) polyaromatic alkyne-based carbon structure, as a high-performance anode material for KIBs. Our computational analysis reveals that naphyne offers an ultrahigh theoretical capacity of 1487.53 mAh/g, significantly outperforming conventional anodes like graphite (273 mAh/g) and other reported anode materials. This superior theoretical storage capability arises from its ability to stably accommodate up to 48 potassium ions in the K₄₈C₇₂ unit via multilayer adsorption, with average adsorption energies ranging from −0.881 to −0.133 eV per adsorbed K-ion. Moreover, naphyne exhibits a low potassium-ion diffusion barrier (0.37 eV) and high diffusion coefficient (up to 5.502 × 10^–7 cm²/s), supporting rapid K-ion transport and excellent rate capability. The structure undergoes minimal structural deformations (≤0.65% along <i>a</i>, ≤ 0.73% along <i>b</i> and ≤ 1.38% area expansion) upon potassiation, indicating robust structural stability under cycling conditions. Notably, potassium adsorption also induces a transition in the electronic structure from semiconducting to metallic behavior, thereby enhancing the material’s electronic conductivity and facilitating fast charge transfer. With an average low open-circuit voltage (OCV) of approximately 0.37 V, naphyne presents a balanced electrochemical profile suitable for high energy density storage. Collectively, these findings highlight naphyne as a promising and transformative anode material for the advancement of next-generation, sustainable potassium-ion battery technologies.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"40 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145314828","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":"First-Principles Prediction of Two-Dimensional Be Allotropes and Alkaline-Earth Analogues (Mg, Ca, Sr, and Ba): from Hexagonal 2D Beryllenes to IIA Xenes","authors":"Heng Zhang, Frédéric Guégan, Sylvain Pitié, Busheng Wang, Congxin Xia, Gilles Frapper","doi":"10.1021/acs.jpcc.5c06483","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c06483","url":null,"abstract":"The chemical space of two-dimensional (2D) elemental beryllium (beryllene) was systematically explored via an <i>ab initio</i> evolutionary algorithm, revealing a rich polymorphism. We identified eight distinct allotropes (α: <i>P</i>6/<i>mmm</i>, <i>Z</i> = 1; β: <i>P</i>3̅<i>m</i>1, <i>Z</i> = 2; γ: <i>P</i>6̅<i>m</i>2, <i>Z</i> = 3; δ: <i>P</i>3̅<i>m</i>1, <i>Z</i> = 3; ε: <i>P</i>2/<i>m</i>, <i>Z</i> = 8; ζ: <i>Pmma</i>, <i>Z</i> = 4; η: <i>P</i>4/<i>mmm</i>, <i>Z</i> = 3; θ: <i>P</i>2/<i>m</i>, <i>Z</i> = 5) exhibiting excellent thermodynamic, mechanical, dynamical, and thermal stability. The ε-, ζ-, η-, and θ-beryllene phases are newly predicted. Analysis of the electron localization function at Be₃ centers in the β and γ phases proves to be consistent with 3-center-2-electron bonding rather than electride character. Additionally, thirty-two stable bulk-derived 2D slabs were identified, with the (001) slabs demonstrating superior experimental feasibility due to their low formation enthalpies (0.069–0.799 eV/atom) and cleavage energies (0.089–0.113 eV/Ų). Extending these eight beryllene allotropes to other Group IIA metals yielded 16 new 2D Xenes (magnesene, calcene, strontene, barene) within the γ, δ, ε, and ζ prototypes. This work underscores the polymorphism of 2D Group IIA metals and provides critical theoretical insights into their synthesis.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"47 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Combined Theoretical and Experimental Investigation on an Fe-Doped Bi2Se3 Topological Insulator","authors":"Ravi Kumar, D. S. Sisodiya, Kritika Vijay, Soma Banik, Shashwati Sen, P. D. Babu, Dibyendu Bhattacharyya","doi":"10.1021/acs.jpcc.5c03940","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c03940","url":null,"abstract":"Research on magnetic ion doping in topological insulators (TIs) such as Bi₂Se₃ is rapidly advancing due to its technological potential and relevance to fundamental physics. In this study, a detailed investigation has been carried out on an Fe-doped Bi₂Se₃ system through ab initio density functional theory (DFT) calculation and X-ray absorption spectroscopy (XAS) and angle-resolved photoelectron spectroscopy (ARPES) measurements on Fe-doped Bi₂Se₃ single crystals. Formation energy calculations indicate that Fe preferentially occupies interstitial sites in the van der Waals gap, a finding supported by the XAS and ARPES measurements. The simulated electronic band structure reveals that interstitial Fe doping preserves the bandgap of pristine Bi₂Se₃, while substitutional doping at Bi sites reduces it. The presence of Se vacancies in the system, as obtained from DFT simulations, has also been corroborated by XAS measurements. Thus, the above combined theoretical and experimental investigations have offered significant insight into a transition metal-doped TI system, which is important for both technological applications and exploration of exotic fundamental physical phenomena.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"550 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306260","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":"From Chaos to Control: Advancing Laser-Based Nanomaterial Synthesis through Mechanisms, Materials, and Applications","authors":"Anna R. Ziefuss,&nbsp;, ,&nbsp;Stephan Barcikowski,&nbsp;, and ,&nbsp;Katharine Moore Tibbetts*,&nbsp;","doi":"10.1021/acs.jpcc.5c06365","DOIUrl":"10.1021/acs.jpcc.5c06365","url":null,"abstract":"","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 41","pages":"18377–18379"},"PeriodicalIF":3.2,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145295929","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":"Selective Observation of Edge-Specific Electronic States and Chemical Reactivity of Laser-Cut MoS2 Surfaces","authors":"Fumihiko Ozaki, Shuntaro Tani, Shunsuke Tanaka, YoungHyun Choi, Kozo Mukai, Wataru Osada, Masafumi Horio, Takanori Koitaya, Susumu Yamamoto, Iwao Matsuda, Taisuke Ozaki, Mitsuaki Kawamura, Masahiro Fukuda, Yohei Kobayashi, Jun Yoshinobu","doi":"10.1021/acs.jpcc.5c04876","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04876","url":null,"abstract":"The edge sites of molybdenum disulfide (MoS₂) are recognized as active sites for various catalytic reactions. However, selective spectroscopic investigation of edge-specific electronic states and surface reactions has been challenging due to the difficulty in preparing edge surfaces with sufficiently large and well-defined areas. In this study, we report a novel method for fabricating MoS₂ edge surfaces by the ultrashort laser pulse cutting of bulk crystals. This approach enables selective spectroscopic characterization of the edge surface via microscopic X-ray photoelectron spectroscopy (XPS) under ultrahigh-vacuum and ambient-pressure (AP) conditions. Valence band photoelectron spectra show a density of states at the Fermi level only on the edge surface. van der Waals density functional theory calculations indicate that the zigzag-structured edge surfaces exhibit metallic properties regardless of sulfur defects. Moreover, the Mo 3d XPS spectra of the edge surface reveal components corresponding to coordinatively unsaturated Mo atoms. Using AP-XPS under water vapor, we demonstrate that water molecules dissociate on the edge surface at room temperature, where the unsaturated Mo atoms serve as the active sites for water dissociation. The present edge preparation method offers a versatile platform for studying the intrinsic physical and chemical properties of edge surfaces of van der Waals-layered materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"9 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145295540","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":"Operando Raman Spectroscopic Analysis for Electrolyte/Electrode Interface Reaction in Lithium–Sulfur Batteries with Sparingly Solvating Electrolyte","authors":"Hikari Watanabe, Nana Arai, Yui Kawana, Erika Otani, Jihae Han, Yasuhiro Umebayashi","doi":"10.1021/acs.jpcc.5c04154","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04154","url":null,"abstract":"Understanding electrolyte/electrode interface reactions during battery operation is essential for the development and optimization of next-generation secondary batteries. There have been many reports on the discharge reaction mechanism in lithium sulfur batteries, which are next-generation secondary batteries. However, most of these reports are related to the sulfur reduction reaction, which is strongly affected by the electrolyte system. Here, we investigated not only the active material sulfur but also the electrolyte near the interface during discharging using <i>operando</i> Raman spectroscopic methods to reveal the discharge behavior in a Lithium sulfur battery with sulfolane (SL)-based concentrated electrolyte and lithium-glyme solvate ionic liquid (Li-G SIL). We have succeeded in experimentally demonstrating that the concentration polarization of Li⁺ occurs significantly in the Li-G SIL system with a low Li⁺ transference number. This is consistent with the fact that the intermediate products differ: the intermediates produced in the SL-based electrolyte system contain Li⁺, whereas in the G4-based electrolyte system, the chemical species containing Li⁺ is hardly confirmed. We believe that the difference in the Li⁺ concentration at the interface affects the overvoltage of the battery.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306271","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":"Voltage-Induced Degradation of PTB7 with Atmospheric Exposure and the Contributions of Simultaneous Exposure to Light","authors":"Thomas J. Blackburn, Sarah M. Tyler, Jeanne E. Pemberton","doi":"10.1021/acs.jpcc.5c05633","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c05633","url":null,"abstract":"Previous studies of organic semiconductor (OSC) degradation have focused primarily on photochemical processes, which are thought to be the main cause of shortened device lifetimes. However, OSC optoelectronic devices operate through charge generation, charge mobility through the active layer material, and/or charge recombination that require the presence of an electric field across the device for charge harvesting or injection. The presence of moving charges in these devices implies the presence of polaron forms in the OSC that may have vastly different chemical reactivity than the neutral OSC. Despite the critical role of the electric field in generating, collecting, and mobilizing charge carriers in OSC active layers, the contributions that these charges make to OSC degradation is not well understood. The role of device voltage as a contributor to OSC degradation is studied here for films of poly[[4,8-bis[(2-ethylhexyl)oxy] benzo[1,2-<i>b</i>:4,5-<i>b</i>′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-<i>b</i>]thiophenediyl]] (PTB7) using infrared reflectance–absorbance spectroscopy and X-ray photoelectron spectroscopy. It is proposed that the application of voltage across thin film OSCs under dark ambient atmosphere conditions, in combination with doping by atmospheric O₂, leads to the generation of superoxide anions that degrade the film through pathways different from those of purely photodegradative processes in which singlet oxygen is proposed to be the predominant player. PBT7 films exposed simultaneously to (light + voltage) host both reactive oxygen species with initial degradation pathways apparently directed to the more reactive polaron sites generated by the applied voltage. These results demonstrate that the effects of applied voltage must be considered when understanding degradation processes in OPVs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"89 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145295542","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}