The Journal of Physical Chemistry C最新文献

{"title":"BA2SnI4 as a Promising 2D Ruddlesden–Popper Perovskite for Optoelectronic Applications","authors":"J. F. Dalmedico,&nbsp;D. N. Silveira,&nbsp;Carlos Maciel O. Bastos,&nbsp;C. R. C Rêgo,&nbsp;Alexandre Cavalheiro Dias,&nbsp;D. Guedes-Sobrinho and Maurício J. Piotrowski*,&nbsp;","doi":"10.1021/acs.jpcc.5c0170710.1021/acs.jpcc.5c01707","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01707https://doi.org/10.1021/acs.jpcc.5c01707","url":null,"abstract":"<p >Lead-free two-dimensional (2D) hybrid metal halide perovskites (MHPs) emerge as promising eco-friendly alternatives to lead-based counterparts, offering excellent thermodynamic stability and environmental compatibility despite lower solar harvesting efficiency. Nonetheless, the dearth of research on tin-based MHPs illustrates the difficulties in their optoelectronic characterization. Herein, we present a computational protocol that integrates <i>ab initio</i> and semiempirical approaches to investigate the electronic, optical, and excitonic properties of the scarcely explored BA₂SnI₄, where BA represents butylammonium. We apply a cost-effective computational framework that combines a maximally localized Wannier function tight-binding (MLWF-TB) method for electronic states with the Bethe–Salpeter equation (BSE) for excitonic properties. To improve the accuracy of the electronic band gap, we employ a relativistic quasi-particle correction (DFT-1/2) within the density functional theory (DFT) framework, which also includes van der Waals corrections and spin–orbit coupling effects. Our findings reveal that replacing Pb with Sn weakens exciton binding, leading to lower exciton binding energies and improved charge extraction efficiency. These results indicate a band gap of 2.0 eV, an exciton ground state energy of 1.85 eV, and an exciton binding energy of 150 meV. The BSE calculations also predict a redshift in absorption, extending the spectral response further into the visible range, compared to the independent particle approximation (IPA). 2D RP BA₂SnI₄ perovskite is a promising photovoltaic material since even in ultrathin films smaller than 0.25 μm, this material can achieve PCE values near 25%, close to the Shockley–Queisser limit. Although Sn-based 2D MHPs present advantageous features, more work is required to resolve manufacturing issues and enhance performance stability.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 21","pages":"9646–9655 9646–9655"},"PeriodicalIF":3.3,"publicationDate":"2025-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpcc.5c01707","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165980","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}

{"title":"BA2SnI4 as a Promising 2D Ruddlesden–Popper Perovskite for Optoelectronic Applications","authors":"J. F. Dalmedico, D. N. Silveira, Carlos Maciel O. Bastos, C. R. C Rêgo, Alexandre Cavalheiro Dias, D. Guedes-Sobrinho, Maurício J. Piotrowski","doi":"10.1021/acs.jpcc.5c01707","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01707","url":null,"abstract":"Lead-free two-dimensional (2D) hybrid metal halide perovskites (MHPs) emerge as promising eco-friendly alternatives to lead-based counterparts, offering excellent thermodynamic stability and environmental compatibility despite lower solar harvesting efficiency. Nonetheless, the dearth of research on tin-based MHPs illustrates the difficulties in their optoelectronic characterization. Herein, we present a computational protocol that integrates <i>ab initio</i> and semiempirical approaches to investigate the electronic, optical, and excitonic properties of the scarcely explored BA₂SnI₄, where BA represents butylammonium. We apply a cost-effective computational framework that combines a maximally localized Wannier function tight-binding (MLWF-TB) method for electronic states with the Bethe–Salpeter equation (BSE) for excitonic properties. To improve the accuracy of the electronic band gap, we employ a relativistic quasi-particle correction (DFT-1/2) within the density functional theory (DFT) framework, which also includes van der Waals corrections and spin–orbit coupling effects. Our findings reveal that replacing Pb with Sn weakens exciton binding, leading to lower exciton binding energies and improved charge extraction efficiency. These results indicate a band gap of 2.0 eV, an exciton ground state energy of 1.85 eV, and an exciton binding energy of 150 meV. The BSE calculations also predict a redshift in absorption, extending the spectral response further into the visible range, compared to the independent particle approximation (IPA). 2D RP BA₂SnI₄ perovskite is a promising photovoltaic material since even in ultrathin films smaller than 0.25 μm, this material can achieve PCE values near 25%, close to the Shockley–Queisser limit. Although Sn-based 2D MHPs present advantageous features, more work is required to resolve manufacturing issues and enhance performance stability.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"134 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087972","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":"The Pore-Branching Channels of Porous Anodic Alumina Formed in an Alkaline Solution of Potassium Phosphate","authors":"Xi Chen,&nbsp;Jiahao Wang,&nbsp;Xinyu Pang,&nbsp;Jiaying Hu,&nbsp;Yi Zhuang,&nbsp;Hao Qiu,&nbsp;Ye Song* and Xufei Zhu*,&nbsp;","doi":"10.1021/acs.jpcc.5c0131210.1021/acs.jpcc.5c01312","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01312https://doi.org/10.1021/acs.jpcc.5c01312","url":null,"abstract":"<p >In this study, the anodizing processes of aluminum in oxalic acid solution (pH ≈0.98) and alkaline aqueous solution (pH ≈12.86) were compared. The channels of porous anodic alumina (PAA) obtained from the two electrolytes were characterized by FESEM. The pore-branching channels of PAA were obtained by anodizing aluminum in an alkaline aqueous solution of potassium phosphate. The pore-branching channels of PAA cannot be clarified by the acidic field-assisted dissolution theory (FADT). In this article, the formation mechanism of PAA under alkaline conditions is explained by the oxide viscous flow model around the oxygen bubble model and electronic current theory. The pore diameter of porous anodic alumina formed in potassium phosphate electrolyte (≈90 nm) is larger than that formed in oxalic acid conditions (≈25 nm) because there are two oxygen bubbles at the large bottom, which is conducive to the formation of pore-branching channels.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 21","pages":"9772–9777 9772–9777"},"PeriodicalIF":3.3,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165964","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":"The Pore-Branching Channels of Porous Anodic Alumina Formed in an Alkaline Solution of Potassium Phosphate","authors":"Xi Chen, Jiahao Wang, Xinyu Pang, Jiaying Hu, Yi Zhuang, Hao Qiu, Ye Song, Xufei Zhu","doi":"10.1021/acs.jpcc.5c01312","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01312","url":null,"abstract":"In this study, the anodizing processes of aluminum in oxalic acid solution (pH ≈0.98) and alkaline aqueous solution (pH ≈12.86) were compared. The channels of porous anodic alumina (PAA) obtained from the two electrolytes were characterized by FESEM. The pore-branching channels of PAA were obtained by anodizing aluminum in an alkaline aqueous solution of potassium phosphate. The pore-branching channels of PAA cannot be clarified by the acidic field-assisted dissolution theory (FADT). In this article, the formation mechanism of PAA under alkaline conditions is explained by the oxide viscous flow model around the oxygen bubble model and electronic current theory. The pore diameter of porous anodic alumina formed in potassium phosphate electrolyte (≈90 nm) is larger than that formed in oxalic acid conditions (≈25 nm) because there are two oxygen bubbles at the large bottom, which is conducive to the formation of pore-branching channels.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"21 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144067275","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":"Engineering the Structure and Optical Properties of Gold Nanostars with Microfluidics","authors":"Sruthy Sanjeev Ambady, Rahaf Mihyar, Rui Zhang, Mattia Tiboni, Alessio Pricci, Sven Thoröe-Boveleth, Luca Casettari, Fabian Kiessling, Josbert M. Metselaar, Twan Lammers, Roger M. Pallares","doi":"10.1021/acs.jpcc.5c02395","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c02395","url":null,"abstract":"Gold nanostars (AuNS) are anisotropic gold nanoparticles with structure-tunable optical properties. Most synthetic protocols rely on multistep procedures and on the use of cytotoxic and/or strongly bound chemicals, which can hamper AuNS applications. While the synthesis of AuNS with HEPES overcomes these limitations by using a biocompatible buffer that acts as both a shape-directing and a reducing agent, the resulting nanoparticles are highly heterogeneous and polydisperse. In this paper, we use a microfluidic chip to manipulate the morphology and optical properties of AuNS, while significantly improving their monodispersity. Notably, by adjusting microfluidic parameters, including viscosity of the organic phase, flow rate ratio, and buffer-to-gold ratio, this protocol can manipulate the growth mechanism of the nanoparticles, switching between seedless and seed-mediated-like growth, and it does so without the need to add a presynthesized seed. Such control is not possible with one-pot bench synthesis. Our results provide new opportunities to tailor the growth and formation of gold nanoparticles while significantly improving their monodispersity.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"29 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144067276","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":"Engineering the Structure and Optical Properties of Gold Nanostars with Microfluidics","authors":"Sruthy Sanjeev Ambady,&nbsp;Rahaf Mihyar,&nbsp;Rui Zhang,&nbsp;Mattia Tiboni,&nbsp;Alessio Pricci,&nbsp;Sven Thoröe-Boveleth,&nbsp;Luca Casettari,&nbsp;Fabian Kiessling,&nbsp;Josbert M. Metselaar,&nbsp;Twan Lammers and Roger M. Pallares*,&nbsp;","doi":"10.1021/acs.jpcc.5c0239510.1021/acs.jpcc.5c02395","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c02395https://doi.org/10.1021/acs.jpcc.5c02395","url":null,"abstract":"<p >Gold nanostars (AuNS) are anisotropic gold nanoparticles with structure-tunable optical properties. Most synthetic protocols rely on multistep procedures and on the use of cytotoxic and/or strongly bound chemicals, which can hamper AuNS applications. While the synthesis of AuNS with HEPES overcomes these limitations by using a biocompatible buffer that acts as both a shape-directing and a reducing agent, the resulting nanoparticles are highly heterogeneous and polydisperse. In this paper, we use a microfluidic chip to manipulate the morphology and optical properties of AuNS, while significantly improving their monodispersity. Notably, by adjusting microfluidic parameters, including viscosity of the organic phase, flow rate ratio, and buffer-to-gold ratio, this protocol can manipulate the growth mechanism of the nanoparticles, switching between seedless and seed-mediated-like growth, and it does so without the need to add a presynthesized seed. Such control is not possible with one-pot bench synthesis. Our results provide new opportunities to tailor the growth and formation of gold nanoparticles while significantly improving their monodispersity.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 21","pages":"9819–9828 9819–9828"},"PeriodicalIF":3.3,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165963","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":"Thermal and Structural Characterization of PS/ZnO Nanocomposites: Effects of ZnO Concentration on Dispersion, Thermal Stability, and Degradation Kinetics","authors":"A. Rahimli*,&nbsp;A. Huseynova,&nbsp;E. Gasimov and M. Jafarov,&nbsp;","doi":"10.1021/acs.jpcc.5c0130310.1021/acs.jpcc.5c01303","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01303https://doi.org/10.1021/acs.jpcc.5c01303","url":null,"abstract":"<p >This study investigates the thermal and structural properties of polystyrene PS/ZnO nanocomposites with varying zinc oxide (ZnO) concentrations (1, 5, and 10%) using TEM, AFM, X-ray diffraction (XRD), Raman spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and thermal kinetic analysis. TEM images reveal well-dispersed ZnO nanoparticles with sizes ranging from 5 to 20 nm, indicating a good compatibility between ZnO and PS. AFM analysis shows surface roughness variations with the height distribution ranging from 80 to 100 nm, aligning with the observed ZnO dispersion. XRD patterns confirm ZnO incorporation, with characteristic peaks at 31.71, 34.53, 36.26°, and others becoming more prominent with higher ZnO content. Thermal analysis reveals a clear dependence of peak temperature (<i>T</i>_p) on heating rate, with a notable increase in <i>T</i>_p from 430.5 to 457.6 °C as the heating rate increases from 20 to 30 °C/min. The Kissinger method shows activation energy values ranging from 59.16 to 55.77 kJ/mol, indicating stable thermal degradation, while the Arrhenius method yields slightly lower activation energies ranging from 37.85 to 39.84 kJ/mol, reflecting the material’s sensitivity to heating rate changes. Overall, the PS/ZnO nanocomposites exhibit enhanced thermal stability, showing potential for applications requiring high thermal resistance.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 21","pages":"9892–9902 9892–9902"},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165924","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":"Harmonizing Adsorption and Diffusion in Active Learning Campaigns of Gas Separations in a MOF","authors":"Etinosa Osaro,&nbsp;Matthew LaCapra and Yamil J. Colón*,&nbsp;","doi":"10.1021/acs.jpcc.5c0092210.1021/acs.jpcc.5c00922","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00922https://doi.org/10.1021/acs.jpcc.5c00922","url":null,"abstract":"<p >This study establishes an active learning (AL) framework designed to enhance the prediction of selectivity in the metal–organic framework (MOF) CuBTC by addressing the adsorption and diffusion mechanisms essential for gas separation applications. Traditional methods of predicting gas selectivity across broad pressure, temperature, and composition (PTX) conditions face considerable computational demands, particularly when simulating both adsorption and diffusion in porous materials. We tackled this challenge by integrating Gaussian Process (GP) models with grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations, applying AL to iteratively select data points exclusively based on the highest model uncertainty (emphasizing exploration), and others schemes, to systematically improve prediction accuracy across diverse conditions. We evaluated several AL strategies tailored to two distinct molecular-level phenomena involved in gas separations: adsorption and diffusion. Specifically, adsorption-based selectivity prediction methods employed AL to preferentially select data points characterized by high uncertainty in adsorption predictions. In contrast, diffusion-based selectivity prediction methods directed AL toward regions exhibiting high uncertainty in diffusion predictions. These approaches included direct prediction of selectivity as well as propagation-based methods, where selectivity uncertainty was calculated from individual component uncertainties in adsorption or diffusion predictions. The culmination of this exploration is an end-to-end (E2E) framework that integrates adsorption and diffusion modeling within a single AL-driven data-labeling process. In this framework, uncertainty in either adsorption or diffusion predictions guides data selection, enabling more precise model training across adsorption and diffusion. Results indicate that the diffusion-focused E2E scheme yields the highest predictive accuracy and a more efficient process. This approach minimizes redundant sampling and improves the efficiency of data acquisition across adsorption and diffusion models.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 21","pages":"9877–9891 9877–9891"},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165847","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":"Correction to “Energies of Formation Reactions Measured for Adsorbates on Late Transition Metal Surfaces”","authors":"Trent L. Silbaugh,&nbsp; and ,&nbsp;Charles T. Campbell*,&nbsp;","doi":"10.1021/acs.jpcc.5c0294410.1021/acs.jpcc.5c02944","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c02944https://doi.org/10.1021/acs.jpcc.5c02944","url":null,"abstract":"","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 21","pages":"9969 9969"},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165853","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":"Correction to “Energies of Formation Reactions Measured for Adsorbates on Late Transition Metal Surfaces”","authors":"Trent L. Silbaugh, Charles T. Campbell","doi":"10.1021/acs.jpcc.5c02944","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c02944","url":null,"abstract":"The two changes listed below should be made on these two entries in Table 1, Table 2 and Table S1. Reaction 56: The coverage here is listed as 1/3. That is not correct. It should be changed to 1/5. Reaction 76: The adsorbed product “═CH–CH₃/Pt(111)” is incorrect as written. That should be changed to “≡C–CH₃/Pt(111)”. Corrected Supporting Information is published with this Correction. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.5c02944. Lists of enthalpies and energies of reactions used to calculate average values reported in Table 1 and enthalpies of formation and heat capacities of gas-phase species used in making Table 2 from the data in Table 1 (PDF) Correction to “Energies\u0000of Formation Reactions\u0000Measured for Adsorbates on Late Transition Metal Surfaces” <span> 2 </span><span> views </span> <span> 0 </span><span> shares </span> <span> 0 </span><span> downloads </span> Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144067278","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}