The Journal of Physical Chemistry C最新文献

{"title":"Predicting Adsorption Energies on MXene Surfaces Using Machine Learning to Enhance Catalyst Design for the Water–Gas Shift Reaction","authors":"Kais Iben Nassar, Tiago L. P. Galvão, José D. Gouveia, José R. B. Gomes","doi":"10.1021/acs.jpcc.4c08353","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08353","url":null,"abstract":"Efficient prediction of gas-phase adsorption energies on MXene surfaces is critical for advancing materials science applications of these materials. This study integrates data from density functional theory calculations, both in-house and from the literature, to train, validate, and test machine learning models for predicting adsorption energies of various species involved in the water–gas shift reaction (WGSR) mechanism (H₂O, CO₂, H₂, CO, O₂, OH, O, H) on MXenes, considering different compositions and surface terminations (O, H, S, F, Cl, among others). Our database comprises 600 data points with diverse structural, electronic, and adsorption properties. We identify key properties influencing adsorption behavior through data preprocessing and feature selection. Five supervised machine learning models were employed: random forest regression (RFR), XGBoost regression (XGB), artificial neural network (ANN), decision tree regression (DTR), and gradient boosting regression (GBR). Each model underwent cross-validation using 80% of the dataset and testing on a 20% hold-out sample. Results demonstrate that RFR and XGB effectively predict adsorption energies of important species in the WGSR, showing a good correlation between actual and predicted values. Feature importance analysis highlights the significance of crucial adsorbate characteristics, such as the number of radical electrons, the molecular weight, and the total number of valence electrons, as well as key MXene features, such as the Bader charges of the transition metal element (M) and of surface terminations (T), and the standard deviation of block, which refers to the measure of the amount of variation or dispersion of properties among elements within a specific block of the periodic table. This study enhances our understanding of MXene-based materials and provides a promising predictive approach for the adsorption behavior, with implications for catalyst design, such as in the WGSR.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"7 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044490","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":"Analysis of Efficiency Roll-Off and Degradation Mechanisms in Nondoped Blue OLEDs Based on Aggregation-Induced Delayed Fluorescence and Achievement of High-Efficiency/Low Roll-Off Blue OLEDs by Insertion Phosphorescence Doping Layer","authors":"Hanlin Li, Wei Liu, Yanfeng Dai, Qian Sun, Xianfeng Qiao, Dezhi Yang, Zujin Zhao, Dongge Ma","doi":"10.1021/acs.jpcc.4c08251","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08251","url":null,"abstract":"A comprehensive understanding of the mechanisms of efficiency roll-off (ERO) and degradation is essential to facilitate the development of high-efficiency/low roll-off and stable organic light-emitting diodes (OLEDs) based on aggregation-induced delayed fluorescence (AIDF). In this study, a design strategy for blue OLEDs based on AIDF molecules is proposed to improve efficiency roll-off and operational lifetime. The exciton dynamics analysis reveals that the excess polarons are the origin of the efficiency roll-off, and the polarons also induce the formation of a quencher, which accelerates the degradation of the nondoped blue OLEDs. The incorporation of a 5 nm blue phosphorescence layer within the nondoped AIDF emission layer results in a notable enhancement in the maximum external quantum efficiency (EQE) of the resulting blue OLEDs, from 21 to 28.7% with low-efficiency roll-off, which is only 5% at a luminance of 1000 cd/m² and the operational lifetime is also enhanced by over 30 times. The phosphorescence layer greatly improves the formation of polarons, thus improving the operation lifetime and efficiency roll-off without sacrificing efficiency. Our results demonstrate the important influence of polarons on device efficiency roll-off and degradation and provide guidance for the design of high-performance and low roll-off blue OLEDs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"9 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050400","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":"Propane Dehydrogenation on Pt Single-Atom and Pt4 and Pt3Sn Single-Cluster Supported on g-C3N4: A Theoretical Study","authors":"Jie Pan, Evgenii Strugovshchikov, Antoni Salóm-Català, Gerard Novell-Leruth, Kamila Kaźmierczak, Daniel Curulla-Ferré, Jorge J. Carbó, Cyril Godard, Josep M. Ricart","doi":"10.1021/acs.jpcc.4c07686","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07686","url":null,"abstract":"Propane dehydrogenation (PDH) is one of the most widely used processes to produce propylene. Platinum is an effective catalyst for PDH. However, metallic Pt facilitates deep dehydrogenation and coke formation. In contrast, small subnanoparticles and, at the limit, single-atom catalysts have shown high reactivity, prevent coke formation, and are much cheaper. Graphitic carbon nitride (g-C₃N₄) has been used as a support for several catalytic and electrocatalytic processes. In this work, three Pt-based catalysts, single-atom (Pt₁), single-cluster (Pt₄), and bimetallic Pt₃Sn anchored on the heptazine units of g-C₃N₄ were modeled using the density functional theory approach in conjunction with microkinetic analysis. Ab initio molecular dynamics has also been used to ensure the stability of the systems. All three systems showed good activity for PDH. However, we have shown that the conversion is only satisfactory at high temperatures, according to the thermodynamic and kinetic requirements, due to the high cost of propene desorption. On the other hand, the energy barriers for the deep dehydrogenation side reaction remain similar as the temperature increases. Substituting a Pt atom by Sn in Pt₄ to give a bimetallic subnanometric Pt₃Sn cluster facilitates propene desorption and inhibits deep dehydrogenation and subsequent coke formation.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"120 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044485","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":"Unraveling the Role of F-Type Color Centers on the Optical and Electrical Properties of Al2W3O12 Nanoparticles with Different Content of Oxygen Vacancies","authors":"Jessica Gil-Londoño, Marco Cremona, Klaus Krambrock, André Linhares Rossi, Raquel Pires Gonçalves, Arthur R. J. Barreto, Lanna Isabely Morais Sinimbu, Munique Eva Paiva de Araújo, Lidija Mančić, Alexandre Mello, Bojan A. Marinkovic","doi":"10.1021/acs.jpcc.4c06098","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06098","url":null,"abstract":"Identification and tuning of defects in nanomaterials are critical to the advancement of emerging technologies. In this work, F-type color centers in Al₂W₃O₁₂ nanopowders, formed via extrinsic oxygen vacancies, were comprehensively studied for the first time. By correlating photoluminescence (PL), electron paramagnetic resonance (EPR), and diffuse reflectance spectroscopy (DRS), the types of F color centers were identified, unraveling their influence on the optical and electrical properties of Al₂W₃O₁₂ nanopowders. EPR coupled with X-ray photoelectron spectroscopy (XPS) demonstrated that the formation of F-type color centers in Al₂W₃O₁₂ nanopowders is mainly generated by an electronic charge compensation process. Our experimental findings highlighted that the increased concentration of F and F⁺ color centers, present in the heat-treated Al₂W₃O₁₂ nanopowders under inert and reducing atmospheres, contributed to enhanced visible light sensitivity and higher electrical conductivity due to the introduction of intermediate energy levels within the band gap by the F-type color centers, the contribution of free electrons from the formation of F⁺ color centers, and the excitation of trapped electrons in the F⁺ and F color centers to the conduction band. These findings provide new insights into the creation and tuning of F-type color centers in nanomaterials, potentially enabling applications in advanced technological devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"47 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050292","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 Calculation of Lithium and Sodium Ion Diffusion in Crystalline Silicon Suboxide for Next-Generation Battery Anodes","authors":"Ali Lashani Zand, Maryam Kookhaee, Maryam Soleimani, Forough Shobeyrian, Amin Niksirat, Zeinab Sanaee, Mahdi Pourfath","doi":"10.1021/acs.jpcc.4c07141","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07141","url":null,"abstract":"Silicon suboxides (SiO_<i>x</i>, <i>x</i> &lt; 2) are emerging as promising anode materials for lithium-ion and sodium-based batteries, especially when their oxygen content is minimized. These materials offer significant potential for advancing energy storage technologies by enabling various novel phases through electrochemical-induced solid-state amorphization and crystallization. This study utilizes first-principles simulations to investigate the structural evolution at lithiated and sodiated SiO₂@Si surfaces, focusing on different crystalline orientations (SiO₂@Si(110), (100), and (111)). Our results reveal that lithiation and sodiation processes are more favorable on the SiO₂@Si(110) surface compared to the other orientations. Additionally, the ion transfer rate for Li⁺ increased from 7.62 × 10^–5 to 2.14 × 10^–4 cm²/s. These findings provide valuable insights into ion behavior at the atomistic level and suggest design principles for optimizing electrode materials by elucidating the mechanisms of partial oxide Si alloy formation across various anode architectures.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"7 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044446","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":"Temperature Dependence of Photocatalytic Water Splitting under Visible Light Irradiation over Ir- and Sb-Codoped SrTiO3:Al","authors":"Erika Kikuchi, Nobuhiro Saito, Yuichi Yamaguchi, Akihiko Kudo","doi":"10.1021/acs.jpcc.4c07699","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07699","url":null,"abstract":"Temperature dependence of photocatalytic water splitting over CrO_<i>x</i>/Rh and CoOOH cocatalyst-coloaded SrTiO₃:Al codoped with Ir and Sb single-particulate photocatalysts (CrO_<i>x</i>/Rh/SrTiO₃:Ir,Sb,Al/CoOOH) under visible light irradiation was investigated. When the reaction temperature was increased from 280 to 340 K, the activity became low, and degradation became significant. Moreover, the activity was partially revived with lowering reaction temperature from 340 to 290 K. These results suggest that reversible and irreversible negative factors worked with rising reaction temperature. The temperature dependence was caused by the working of the negative factors such as the irreversible degradation of photocatalyst · cocatalyst and the reversible increase of recombination probability of photogenerated carriers more than the positive factor such as increasing the rate of surface reaction. X-ray photoelectron spectra revealed that detachment and/or aggregation of CoOOH loaded on SrTiO₃:Ir,Sb,Al brought the irreversible degradation of the photocatalyst material at 340 K. In contrast to it, the change of a CrO_<i>x</i> shell in the CrO_<i>x</i>/Rh cocatalyst was not observed, suggesting that the reverse reactions to form water from evolved H₂ and O₂ and to reduce O₂ were not enhanced even though reaction temperature was risen. On the other hand, the photoluminescence intensity of Eu³⁺ as a guest doped to SrTiO₃:Ir,Sb,Al as a host due to band gap excitation of SrTiO₃ became low with rising reaction temperature, suggesting that the recombination probability as a nonradiative deactivation of photogenerated carriers in the host of SrTiO₃ increased. Therefore, it was suggested that the negative factors such as degradation of a CoOOH cocatalyst and increasing recombination probability of photogenerated carriers caused the decrease of the photocatalytic water-splitting activity of CrO_<i>x</i>/Rh/SrTiO₃:Ir,Sb,Al/CoOOH.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"63 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044486","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":"Interface-Sensitive Soft X-ray Absorption Spectroscopy by Electron/Ion-Yield Methods and Its Application to Solid–Liquid Interfaces for SrTiO3 and CoOOH","authors":"Zi Wang, Ryo Toyoshima, Kota Enomoto, Kazuhiko Mase, Hiroshi Kondoh","doi":"10.1021/acs.jpcc.4c06654","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06654","url":null,"abstract":"The understanding of solid–liquid interfaces is crucial for numerous chemical processes, although it presents significant challenges. We employed soft X-ray absorption spectroscopy (sXAS) in electron and ion detection modes to explore various interfaces. It was observed that the electron yield mode provides interface-sensitive results, while the ion yield mode captures ionic currents from the surface to the bulk liquid, which results in bulk sensitivity. Interestingly, differences in the currents in the ion mode for the two electrodes replicate the interface sensitivity. We applied these interface-sensitive modes to strontium titanate (SrTiO₃) and cobalt oxyhydroxide (CoOOH) systems to characterize structures of interface water and chemical states of the solid surfaces. Notably, surface cobalt atoms in CoOOH exhibit a high spin state when interacting with liquid water, which is a sharp contrast to its low spin state in a vacuum. The interface water on the SrTiO₃ surface displayed an ice-like structure. These findings provide insights into the sensitivities of different sXAS detection modes, which enhance our understanding of dynamic behaviors at the liquid–solid interfaces under various conditions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"9 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044445","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":"Defect Segregation, Water Layering, and Proton Transfer at Zirconium Oxynitride/Water Interface Examined Using Neural Network Potential","authors":"Akitaka Nakanishi, Shusuke Kasamatsu, Jun Haruyama, Osamu Sugino","doi":"10.1021/acs.jpcc.4c05857","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05857","url":null,"abstract":"Zr oxides and oxynitrides are promising candidates to replace precious metal cathodes in polymer electrolyte fuel cells. Oxygen reduction reaction activity in this class of materials has been correlated with the amount of oxygen vacancies, but a microscopic understanding of this correlation is still lacking. To address this, we simulate a defective Zr₇O₈N₄/H₂O interface model and compare it with a pristine ZrO₂/H₂O interface model. First, ab initio replica exchange Monte Carlo sampling was performed to determine defect segregation at the surface in the oxynitride slab model, then molecular dynamics accelerated by neural network potentials was used to obtain 1000 independent trajectories of 500 ps-dynamics to attain sufficient statistical accuracy of the solid/liquid interface structure. The presence of oxygen vacancies on the surface was found to clearly modify the local adsorption structure: water molecules were found to adsorb preferentially on Zr atoms surrounding oxygen vacancies, but not on the oxygen vacancies themselves. The fact that oxygen vacancy sites are free from poisoning by water molecules may explain the activity enhancement in defective systems. The layering of water molecules was also modified considerably, which should influence the proton and O₂ transport near the interfaces which is another parameter that determines the overall activity. Differences in the details of proton transfer on the defective and pristine surfaces are also discussed.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"206 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050291","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":"Tuning Topologically Nontrivial States in the BHT-Ni Metal–Organic Framework","authors":"Nafiseh Falsafi, Saeed H. Abedinpour, Fariba Nazari, Francesc Illas","doi":"10.1021/acs.jpcc.4c06013","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06013","url":null,"abstract":"Using first-principles calculations, we have demonstrated the creation of multiple quantum states in the experimentally accessible metal–organic framework BHT-Ni. Specifically, quantum spin Hall and quantum anomalous Hall states are induced by two- and four-electron doping, respectively. Geometrical symmetry breaking is also investigated in cis- and trans-like structures. For a low electron doping concentration of two electrons per unit cell, the Fermi energy shifts to a nontrivial band gap between the Dirac bands, predicting a quantized spin Hall conductivity. Subsequently at a high electron doping concentration, an anomalous Hall conductivity with a quantized value is observed. In addition, for a centrosymmetric (trans-like) structure, it preserves the quantum spin Hall state and quantized spin Hall conductivity. In contrast, in the noncentrosymmetric (cis-like) structure, the breaking of space inversion symmetry leads to the emergence of the valley Hall effect and the disappearance of spin Hall conductivity.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"10 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055718","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":"Degeneracy-Broken Toroidal Chain Quasi-Bound States in the Continuum in Photonic Metawires","authors":"Ajay Sah, Seokhyoung Kim","doi":"10.1021/acs.jpcc.4c07817","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07817","url":null,"abstract":"Optical metawires (MWs) refer to dielectric nanowires with periodic modulation of the <i>effective</i> refractive index, which exhibit unusual meta-photonic properties such as optical bound states in the continuum (BICs). Despite recent advances in the experimental observations of MW BICs, the fundamental understanding of their nature and polarization response still remains limited. In this work, we present degeneracy-broken toroidal chain <i>quasi</i>-BICs in a dielectric MW, which manifest as Fano resonances with drastically disparate line widths under transverse magnetic (TM) and electric (TE) polarizations. We show that the different mirror symmetries of the two toroidal chain modes determine the disparate polarization response. Using temporal coupled-mode theory (TCMT), we also demonstrate that an excessively large excitation strength of the TM mode prevents it from becoming a true BIC, whereas the excitation of the TE mode remains sufficiently small to satisfy the BIC condition through additional geometric tuning. Finally, we show that in-plane polarization rotation effectively controls the azimuthal orientation of the BIC-enhanced electric fields around the MW, enabling nearly 800% absorption modulation of MW-coupled low-dimensional devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"22 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044487","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}