The Journal of Physical Chemistry C最新文献

{"title":"Room Temperature Dehydrogenation of Gaseous Methanol over Polycrystalline Gold Triggered and Traced by Oxygen K-edge X-rays","authors":"Annette Pietzsch*,&nbsp;Johannes Niskanen,&nbsp;Vinicius Vaz da Cruz,&nbsp;Sebastian Eckert,&nbsp;Mattis Fondell,&nbsp;Raphael M. Jay,&nbsp;Xingye Lu,&nbsp;Daniel McNally,&nbsp;Thorsten Schmitt and Alexander Föhlisch,&nbsp;","doi":"10.1021/acs.jpcc.4c0687010.1021/acs.jpcc.4c06870","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06870https://doi.org/10.1021/acs.jpcc.4c06870","url":null,"abstract":"<p >The room temperature conversion of gaseous methanol to carbon monoxide and hydrogen on a polycrystalline Au film at ambient pressure has been triggered and characterized by oxygen K-edge excitation and vibrationally resolved resonant inelastic X-ray scattering. The rate-limiting first methanol dehydrogenation step is driven by ultrafast O–H dissociation and deprotonation of O K-edge excited CH₃OH. The Au surface further dehydrogenates the CH₃O⁺ photoradical created by X-rays via electron transfer from the Au surface. With vibrationally resolved resonant inelastic X-ray scattering, we trace the CO molecular potential energy surface along the C–O coordinate. The CO bond softens, and the C–O stretch frequency changes from 2250 to 2065 cm^–1 at a CO chemisorption energy of 38–58 kJ/mol. This constitutes weak chemisorption as compared to the transition metals but also stronger bonding than the physisorbed CO species on single-crystal Au surfaces. In liquid methanol, the recombination of the CH₃O⁺ photoradical created by X-rays with protons quenches this conversion.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 5","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":3.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpcc.4c06870","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127659","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":"Exciton Delocalization and Triplet Diffusion in Singlet Fission Materials: A Many-Electron Tight-Binding and Non-Orthogonal CI Study","authors":"Aitor Sánchez-Mansilla, Ionut-Octavian Stan, Ria Broer, Coen de Graaf","doi":"10.1021/acs.jpcc.4c08037","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08037","url":null,"abstract":"A many-electron tight-binding (METB) approach is presented to use the results of nonorthogonal configuration interaction with fragments (NOCI-F) calculations on small ensembles for the study of much larger (or even periodic) systems. The METB approach is validated against NOCI-F for a stack of 15 ethene molecules, small enough to be handled in full by the NOCI-F approach and large enough to extract relevant information from METB treatment. Thereafter, METB is used to show how the singlet fission coupling depends on the degree of delocalization of the singlet excitonic state. Finally, METB is applied to extract the dispersion of some many-electron states in the tetracene crystal. The insight gained from these METB calculations based on NOCI-F parametrization can be used to further study the fundamentals of singlet fission and the subsequent fate of the biexciton.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"36 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055711","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":"Proton Donors Influence Nitrogen Adsorption in Lithium-Mediated Electrochemical Ammonia Synthesis","authors":"Victor Azumah, Lance Kavalsky, Venkatasubramanian Viswanathan","doi":"10.1021/acs.jpcc.4c08138","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08138","url":null,"abstract":"Lithium-mediated electrochemical ammonia synthesis (LiMEAS) has recently shown promise toward efficient electrochemical ammonia production. This process relies on the formation of a lithium nitride film which is subsequently protonated to release ammonia. Designing the electrolyte for this technology requires the selection of a proton donor. In this work, we perform a first-principles analysis to investigate the initial step of nitride formation considering 30 different proton donors (PD). As a baseline, modeling nitrogen on a lithium surface without a PD, we observe that N₂ does not spontaneously dissociate on the lithium surface. However, explicitly introducing a PD into the system results in five unique recurring nitrogen configurations on the lithium slab: (1) embedded, (2) adsorbed, (3) standing, (4) buried, and (5) transferred states. We show that these PD-induced states possess an elongated N–N bond and adsorb more strongly on lithium. Using charge analysis, we show that the charge transferred onto these states strongly correlates with the change in their bond length, a crucial parameter for nitrogen dissociation. These results suggest a more involved role of the PD in the initial stages of nitride formation, and motivate greater consideration for their impact on the LiMEAS pathway.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"29 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050312","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":"Exciton Delocalization and Triplet Diffusion in Singlet Fission Materials: A Many-Electron Tight-Binding and Non-Orthogonal CI Study","authors":"Aitor Sánchez-Mansilla,&nbsp;Ionut-Octavian Stan,&nbsp;Ria Broer and Coen de Graaf*,&nbsp;","doi":"10.1021/acs.jpcc.4c0803710.1021/acs.jpcc.4c08037","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08037https://doi.org/10.1021/acs.jpcc.4c08037","url":null,"abstract":"<p >A many-electron tight-binding (METB) approach is presented to use the results of nonorthogonal configuration interaction with fragments (NOCI-F) calculations on small ensembles for the study of much larger (or even periodic) systems. The METB approach is validated against NOCI-F for a stack of 15 ethene molecules, small enough to be handled in full by the NOCI-F approach and large enough to extract relevant information from METB treatment. Thereafter, METB is used to show how the singlet fission coupling depends on the degree of delocalization of the singlet excitonic state. Finally, METB is applied to extract the dispersion of some many-electron states in the tetracene crystal. The insight gained from these METB calculations based on NOCI-F parametrization can be used to further study the fundamentals of singlet fission and the subsequent fate of the biexciton.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 5","pages":"2797–2812 2797–2812"},"PeriodicalIF":3.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127629","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":"Determination of Stable Proton Configurations by Black-Box Optimization Using an Ising Machine","authors":"Jianbo Lin, Tomofumi Tada, Ai Koizumi, Masato Sumita, Koji Tsuda, Ryo Tamura","doi":"10.1021/acs.jpcc.4c07104","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07104","url":null,"abstract":"Stable proton configurations in solid-state materials are a prerequisite for the theoretical microscopic investigation of solid-state proton-conductive materials. However, a large number of initial atomistic configurations should be considered to find stable proton configurations, and relaxation calculations using the density functional theory approach are required for each initial configuration. Consequently, the determination of stable configurations is a difficult and time-consuming task. Furthermore, when the size of the simulation cells or the number of doped atoms increases, the number of initial configurations leads to a combinatorial explosion, rendering the computation infeasible. In this study, black-box optimization was combined with an Ising machine and density functional calculations to perform an efficient search for stable proton configurations. Scandium-doped barium zirconate, a typical high-proton conductive oxide, was selected as the model system. The Ising machine was able to rapidly select the initial atomistic configuration, ultimately leading to stable proton configurations after subsequent relaxation calculations. This optimization strategy should be able to solve various issues related to configuration optimization in solid-state materials, thereby promoting novel scientific discoveries.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"35 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050314","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":"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":"Degeneracy-Broken Toroidal Chain Quasi-Bound States in the Continuum in Photonic Metawires","authors":"Ajay Sah,&nbsp; and ,&nbsp;Seokhyoung Kim*,&nbsp;","doi":"10.1021/acs.jpcc.4c0781710.1021/acs.jpcc.4c07817","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07817https://doi.org/10.1021/acs.jpcc.4c07817","url":null,"abstract":"<p >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.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 5","pages":"2757–2763 2757–2763"},"PeriodicalIF":3.3,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpcc.4c07817","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127207","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":"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":"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,&nbsp;Ryo Toyoshima,&nbsp;Kota Enomoto,&nbsp;Kazuhiko Mase and Hiroshi Kondoh*,&nbsp;","doi":"10.1021/acs.jpcc.4c0665410.1021/acs.jpcc.4c06654","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06654https://doi.org/10.1021/acs.jpcc.4c06654","url":null,"abstract":"<p >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.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 5","pages":"2570–2581 2570–2581"},"PeriodicalIF":3.3,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143126908","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}