The Journal of Physical Chemistry C最新文献

{"title":"Thermoelectric Performance of Janus Monolayer ZnGeSTe from First-Principles Based Self-Consistent Transport Theory","authors":"Xuelian He, Xianyi Cai, Hongkuan Yuan, Hong Chen","doi":"10.1021/acs.jpcc.4c08445","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08445","url":null,"abstract":"Thermal and electrical transport properties of Janus monolayer ZnGeSTe are investigated using first-principles-based self-consistent transport theory. The temperature-driven phonon dispersion and lattice thermal conductivity (κ_l) are evaluated up to the quartic anharmonicity, and consequently, the κ_l is reduced by 42.36% upon quartic anharmonicity at room temperature. The Seebeck coefficient (<i>S</i>), electrical conductivity (σ), and carrier thermal conductivity (κ_e) are calculated by considering individual carrier lifetimes, and consequently, due to the convergence and dispersion of multiple conduction bands, the large Seebeck coefficient (<i>S</i>) and the high electron mobility contribute to a higher power factor (PF = <i>S</i>²σ) for n-type doping. The optimal figure of merit (zT = PF/(κ_e + κ_l)) monotonically increases with the temperature, and the peak and average zT values are up to 1.16 and 0.79 in the operating temperature range of 500–800 K for n-type doping.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"125 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703632","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":"Surface Electrostatic Potential Roughness: A Crucial Factor Impacting Lithium Diffusion on Curved Transition Metal Dichalcogenide Surfaces","authors":"Jian Chen, Yao Kang, Xudong Wang, Hao Huang, Man Yao","doi":"10.1021/acs.jpcc.4c08731","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08731","url":null,"abstract":"Tuning the nanoscale morphology and structure is a key strategy for enhancing the electrostatic performance of layered transition metal dichalcogenide (TMD) electrodes, where curved structures are inevitably introduced. A comprehensive understanding of the Li-ion diffusion mechanism in curved TMD structures at the atomic scale can guide the high-throughput design of nanoscale electrode materials. By first-principles calculations, we investigated the lithium diffusion in TMDs curved structure and factors resulting in the diffusion barrier variation. Our results demonstrate that the curved structure of TMDs enhances lithium diffusion compared to the planar structure, with the effect of bending on lithium diffusion being influenced by multiple factors. By extracting and analyzing the surface electrostatic potential curve perpendicular to the lithium diffusion path, we introduced the <i>R</i>_Δ<i>q</i>/<i>L</i> parameter to provide a unified explanation for the effect of bending on lithium diffusion, where <i>R</i>_Δ<i>q</i> represents the roughness of the curve and <i>L</i> represents the projected length of the curve. For the same TMDs with varying curvature, the <i>R</i>_Δ<i>q</i>/<i>L</i> perpendicular to the diffusion path is positively correlated with the lithium diffusion barrier on this path. Our results deepen the understanding of the lithium diffusion mechanism for the TMD curved structure and promote the follow-up design of TMD-based electrodes.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"57 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695703","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":"Dissolution Kinetics of Solid Particles and the Role of Aggregation: Vaterite Dissolution","authors":"Morgan P. Milner, Haotian Chen, Jake M. Yang, Richard G. Compton","doi":"10.1021/acs.jpcc.5c01202","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01202","url":null,"abstract":"We report the dissolution kinetics and mechanism of dimeric and larger aggregates of quasi-spherical particles of spherulitic vaterite, CaCO₃, showing that dissolution occurs under thermodynamic control for all species, as seen for the corresponding monomeric species. While the dissolution rate measured via the variation of the projected two-dimensional area with time is, within experimental error, identical for all species, the dissolution time scale required for complete dissolution increases proportionally with particle size. We conclude that the time scale of complete dissolution time scale reflects the extent of aggregation, the solubility of vaterite, and the diffusion coefficient of the dissolved species. Generic inferences on the role of aggregation on the dissolution kinetics of solid particles are drawn.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"99 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703618","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":"Surface Electrostatic Potential Roughness: A Crucial Factor Impacting Lithium Diffusion on Curved Transition Metal Dichalcogenide Surfaces","authors":"Jian Chen,&nbsp;Yao Kang,&nbsp;Xudong Wang,&nbsp;Hao Huang and Man Yao*,&nbsp;","doi":"10.1021/acs.jpcc.4c0873110.1021/acs.jpcc.4c08731","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08731https://doi.org/10.1021/acs.jpcc.4c08731","url":null,"abstract":"<p >Tuning the nanoscale morphology and structure is a key strategy for enhancing the electrostatic performance of layered transition metal dichalcogenide (TMD) electrodes, where curved structures are inevitably introduced. A comprehensive understanding of the Li-ion diffusion mechanism in curved TMD structures at the atomic scale can guide the high-throughput design of nanoscale electrode materials. By first-principles calculations, we investigated the lithium diffusion in TMDs curved structure and factors resulting in the diffusion barrier variation. Our results demonstrate that the curved structure of TMDs enhances lithium diffusion compared to the planar structure, with the effect of bending on lithium diffusion being influenced by multiple factors. By extracting and analyzing the surface electrostatic potential curve perpendicular to the lithium diffusion path, we introduced the <i>R</i>_Δ<i>q</i>/<i>L</i> parameter to provide a unified explanation for the effect of bending on lithium diffusion, where <i>R</i>_Δ<i>q</i> represents the roughness of the curve and <i>L</i> represents the projected length of the curve. For the same TMDs with varying curvature, the <i>R</i>_Δ<i>q</i>/<i>L</i> perpendicular to the diffusion path is positively correlated with the lithium diffusion barrier on this path. Our results deepen the understanding of the lithium diffusion mechanism for the TMD curved structure and promote the follow-up design of TMD-based electrodes.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 13","pages":"6074–6082 6074–6082"},"PeriodicalIF":3.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758890","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":"DFT Insights into Hydrogen Spillover Mechanisms: Effects of Metal Species, Size, and Support","authors":"Cheng-Hsi Yeh, Ho Viet Thang, Yves Ira A. Reyes, Carmine Coluccini, Hsin-Yi Tiffany Chen","doi":"10.1021/acs.jpcc.4c08097","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08097","url":null,"abstract":"Hydrogen spillover is a crucial mechanism in heterogeneous catalysis. Herein, density functional theory calculations were conducted to study the metal–support interactions (MSI) and the hydrogen spillover mechanisms in terms of metal size, metal species, and support effects using single-atom (M₁) and four-atom cluster (M₄) models of Ru, Ni, and Pt, supported on anatase TiO₂(101), rutile TiO₂(110), MgO(100), MgO(110), and graphene. For M₁ systems, the binding energies (<i>E</i>_b) vary widely across different M₁ species and substrate surfaces. In contrast to M₁ systems whose MSI are affected by metal type, those supported M₄ models are determined primarily by the support: r-TiO₂(110) &gt; a-TiO₂(101) &gt; MgO(110) &gt; MgO(100) &gt; graphene. Thermodynamically favorable hydrogen spillover on oxide-supported M₁ models required hydrogen coverages (θ) of ∼6 ML, whereas counterpart M₄ systems require ∼3 ML. Therefore, oxide-supported cluster catalysts can facilitate favorable hydrogen spillover better than single-atom catalysts; hydrogen spillover to TiO₂ is more favorable than to MgO. In contrast, no favorable hydrogen spillover was observed on graphene-supported M₁ and M₄ models. Despite considering the same route, different hydrogen spillover mechanisms are observed depending on the support: (i) on reducible TiO₂, hydrogen spills over as a proton with the electron transferred to the support; (ii) on nonreducible MgO, hydrogen spills over as a proton but the electron remains localized to the bound metal; (iii) on graphene, hydrogen spills over as a neutral hydrogen atom. Notably, supported M₄ models with stronger MSI are predicted to exhibit a more facile hydrogen spillover from both thermodynamic and kinetic perspectives, particularly when considering the same metal species across different supports. These detailed insights are expected to advance the understanding of hydrogen spillover on catalysts, which will be valuable for their future design and development.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"57 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703616","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":"Consequences of Magneto-Electrical Coupling in Multiferroic VSe2/Sc2CO2 Heterostructures","authors":"Himangshu Sekhar Sarmah, Subhradip Ghosh","doi":"10.1021/acs.jpcc.4c08598","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08598","url":null,"abstract":"Two-dimensional van der Waals heterostructures are potential game changers both in understanding the fundamental physics and in the realization of various devices that exploit magnetism on the nanoscale. Multiferroic heterostructures comprising a two-dimensional ferroelectric and a two-dimensional ferromagnet are ideal candidates for the electrical control of properties of the ferromagnets, which can lead to nonvolatile memory devices, for example. Relatively new but immensely promising two-dimensional materials, MXene and transition metal dichalcogenides, can be effectively combined to achieve the goal, as both have flexibilities in their structures and compositions that are tunable. In this work, using density functional theory, we have investigated the magneto-electric coupling-driven transitions in the electronic ground states of VSe₂/Sc₂CO₂ bilayer and trilayer heterostructures. Our results demonstrate that the change in the ferroelectric polarization in the MXene layer leads to changes in the spin-polarized band structures of the magnetic component VSe₂ enabling a semiconductor to half-metal transition in these heterostructures. We propose several applications of this magneto-electric coupling in these multiferroic heterostructures that can lead to the efficient operation of field effect transistors and achieve nonvolatility in memory devices at the nanoscale.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"9 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695596","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":"Zero-Valent Iron Inside Carbon Nanocube as an Efficient Peroxymonosulfate Activator toward Catalytic Oxidation of Organic Pollutants","authors":"Xinyue Li, Shuang Jin, Yi Wang, Zhimin Cui, Zhe Chen","doi":"10.1021/acs.jpcc.4c08677","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08677","url":null,"abstract":"The agglomeration tendency of nano zero-valent iron (Fe⁰) limits its practical applications toward catalytic oxidation of organic pollutants. Herein, an in situ encapsulation of polydopamine on the surface of Prussian blue (PB) nanocubes followed by a confined reduction treatment strategy was presented to confine the zero-valent iron nanoparticles (Fe⁰) inside hollow carbon nanocube (Fe⁰@C) as an efficient peroxymonosulfate (PMS) activator toward catalytic oxidation of toxic organic contaminants. The catalytic results showed that 100% degradation of bisphenol A (BPA) could be completed within 5 min with Fe⁰@C nanocube as a catalyst to activate PMS. This delicately designed Fe⁰@C nanocube displayed a superior kinetic rate constant compared with the pure Fe⁰ nanoparticles (4.2-fold). Experimental evidence revealed that the generation of multiple reactive oxygen species in the nanocubes played a vital role for the significantly enhanced catalytic efficiency for organic contaminants. Both SO₄^•–, •O₂^–, and •OH dominated radical processes, and nonradical pathways involving ¹O₂ were accounted for PMS activation and organic contaminant degradation. The superior catalytic performance was attributed to a carbon layer with large specific surface area and highly dispersed Fe⁰ nanoparticles to provide abundant active sites, distinct nanocube structure to concentrate the reactant molecules within a confined space, and an excellent electron/mass transport property.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"8 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677977","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 First-Principles Study of n-Type Defects and Cobalt Doping on Magnetic and Optical Properties of ZnS Nanowires: Implications for Spintronic and Photovoltaic Applications","authors":"Muhammad Sheraz Khan, Bingsuo Zou","doi":"10.1021/acs.jpcc.5c00109","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00109","url":null,"abstract":"Diluted magnetic semiconductors (DMSs) are promising candidates for advanced spintronic and photovoltaic applications due to their induced ferromagnetism, spin-dependent interactions, and elevated Curie temperatures. However, the underlying mechanisms of ferromagnetism and the dynamics of optical emission in these materials remain incompletely understood due to their complex microstructural and compositional properties. In this study, we employed density functional theory (DFT) calculations to explore the optoelectronic and magnetic properties of Co-doped ZnS nanowires, with and without structural defects such as Zn interstitial doping (<i>I</i>_Zn) and sulfur vacancy (<i>V</i>_S) or iodine codoping. Our results show that in defect-free ZnS nanowires, Co ions, whether substitutional or interstitial, exhibit antiferromagnetic (AFM) coupling. However, the presence of structural defects or iodine codoping introduces additional electron carriers that interact with the <i>d</i>-states of Co ions, leading to the formation of bound magnetic polarons (BMPs) and, consequently, strong ferromagnetic (FM) coupling between Co ions. Notably, the defective Co-doped ZnS nanowires exhibit a Curie temperature exceeding room temperature, which is crucial for practical device applications. Optical analysis reveals that substitutional Co-doped ZnS has a <i>d–d</i> transition peak at 1.92 eV and a fundamental band-gap peak at 3.56 eV, while interstitial Co doping results in a <i>d–d</i> transition peak at 1.78 eV and a fundamental band-gap peak at 3.47 eV. Interstitial Co doping reduces the band gap from 3.5 to 3.47 eV, whereas substitutional Co doping increases it to 3.56 eV. Structural defects or iodine codoping in the substitutional Co-doped ZnS nanowires introduce optical bands in the infrared, visible, and ultraviolet regions, enhancing optical absorption efficiency. The study indicates that in the FM state, the <i>d–d</i> transition peaks of the Co ions and the fundamental band-gap transition are lower in energy compared to the AFM state. These findings underscore the potential of Co-doped ZnS nanowires with tailored structural modifications for next-generation spintronic devices and high-performance photovoltaic systems, where enhanced magnetic and optical properties are critical for device efficiency and reliability.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"96 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695599","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":"Thin Polymer Electrolytes with 3D Nanofiber Skeletons Enabling High-Performance Solid-State Lithium Metal Batteries","authors":"Lehao Liu,&nbsp;Rubing Xu,&nbsp;Jiaxin Tu,&nbsp;Rongmin Zhou,&nbsp;Jinshan Mo,&nbsp;Tianrong Yang,&nbsp;Qian Zhao,&nbsp;Mengxuan Zhang,&nbsp;Dongmei Zhang and Meicheng Li*,&nbsp;","doi":"10.1021/acs.jpcc.5c0081410.1021/acs.jpcc.5c00814","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00814https://doi.org/10.1021/acs.jpcc.5c00814","url":null,"abstract":"<p >Polymer electrolytes are extensively utilized in solid-state batteries due to their high flexibility, excellent interfacial contact with the electrodes, and low cost. However, they suffer from issues such as large thickness, low room-temperature ionic conductivity, and poor mechanical properties. In this study, we employ an environmentally friendly and straightforward vacuum filtration method to obtain a thin poly(ethylene oxide) (PEO)–aramid nanofiber (ANF)–LiTFSI composite electrolyte film with a small thickness of 25–42 μm. Compared with the solution-casting method, the rapid vacuum filtration process leads to the formation of a 3D interpenetrating ANF network structure and also a continuous ion conduction pathway at the PEO/ANF interfaces. Consequently, the thin composite electrolyte exhibits a high room-temperature ionic conductivity of 3.27 × 10^–5 S cm^–1 and a high strength of 5.19 MPa, which is 26 times that of the solution-casted PEO–LiTFSI electrolyte. Furthermore, the thin electrolyte shows excellent lithium dendrite suppression capability, and the thin electrolyte-containing lithium metal batteries deliver a capacity retention of 78% after 180 cycles with an average Coulombic efficiency of 99.9%. The thin electrolyte with the 3D nanofiber skeleton developed in this work possesses great potential for high-performance lithium metal batteries.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 13","pages":"6138–6147 6138–6147"},"PeriodicalIF":3.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758773","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":"Thin Polymer Electrolytes with 3D Nanofiber Skeletons Enabling High-Performance Solid-State Lithium Metal Batteries","authors":"Lehao Liu, Rubing Xu, Jiaxin Tu, Rongmin Zhou, Jinshan Mo, Tianrong Yang, Qian Zhao, Mengxuan Zhang, Dongmei Zhang, Meicheng Li","doi":"10.1021/acs.jpcc.5c00814","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00814","url":null,"abstract":"Polymer electrolytes are extensively utilized in solid-state batteries due to their high flexibility, excellent interfacial contact with the electrodes, and low cost. However, they suffer from issues such as large thickness, low room-temperature ionic conductivity, and poor mechanical properties. In this study, we employ an environmentally friendly and straightforward vacuum filtration method to obtain a thin poly(ethylene oxide) (PEO)–aramid nanofiber (ANF)–LiTFSI composite electrolyte film with a small thickness of 25–42 μm. Compared with the solution-casting method, the rapid vacuum filtration process leads to the formation of a 3D interpenetrating ANF network structure and also a continuous ion conduction pathway at the PEO/ANF interfaces. Consequently, the thin composite electrolyte exhibits a high room-temperature ionic conductivity of 3.27 × 10^–5 S cm^–1 and a high strength of 5.19 MPa, which is 26 times that of the solution-casted PEO–LiTFSI electrolyte. Furthermore, the thin electrolyte shows excellent lithium dendrite suppression capability, and the thin electrolyte-containing lithium metal batteries deliver a capacity retention of 78% after 180 cycles with an average Coulombic efficiency of 99.9%. The thin electrolyte with the 3D nanofiber skeleton developed in this work possesses great potential for high-performance lithium metal batteries.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"61 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677978","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}