The Journal of Physical Chemistry C最新文献

{"title":"Adsorption of H on the ZnO(0001) Surface and d0 Magnetism: An Ab Initio Study","authors":"Odin Vázquez-Robaina, Arles Víctor Gil Rebaza, Alejandra Fabiana Cabrera, Claudia Elena Rodríguez Torres","doi":"10.1021/acs.jpcc.4c05207","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05207","url":null,"abstract":"Ab initio total energy calculations were performed to study the adsorption of atomic hydrogen on the polar surface of Zn–ZnO(0001) for different degrees of surface coverage. The most stable configuration was calculated as a function of the distance between H and the surface. The present results show that the manifest ferromagnetism depends on purely surface interactions. It involves charge transfer from the H-1s level to the Zn-4s level, leading to a magnetic moment of 1.0 μ_<i>B</i> for full H surface coverage in the supercell. The magnetic interaction between H atoms is ferromagnetic. In addition, for a fully hydrogenated ZnO monolayer with zinc vacancies (V_Zn) or hydrogen-passivated zinc vacancies (V_Zn–H), a transition from a nonmagnetic semiconductor to a magnetic half-metal semiconductor has been achieved. Both configurations exhibit a surface magnetic moment of 2.0 μ_B, which is twice that obtained for the case without the vacancy. These theoretical calculations agree with our previously published experimental results, where it was observed that hydrogen is incorporated into the ZnO structure and acts as a surface donor.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"26 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832944","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":"Laser-Induced Circular Charge Migration in Endohedral Fullerenes in the Presence of Ionization","authors":"Leonardo Biancorosso, Emanuele Coccia, Jean Christophe Tremblay","doi":"10.1021/acs.jpcc.4c06331","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06331","url":null,"abstract":"In this study, we explore the behavior of endohedral fullerenes and examine how different doping species influence the ultrafast photoinduced electronic dynamics. We analyzed a reference fullerene (C₆₀) and two endohedral fullerenes with Cl^– and Mg atoms inside the cage using electronic dynamics calculations. By applying circularly polarized light, we observed the transfer of angular momentum from the light to the electron density in these systems. The optical properties and specific excitations were determined through quantum chemical calculations, which formed the basis of our analysis. In the C₆₀ reference system, excitation led to a significant rotation of the electron density and the formation of a large rotating dipole. For the Mg@C60 system, the electron density changes were mostly localized around the Mg atom, resulting in a smaller induced dipole but more localized excitations. In the Cl^–@C₆₀ system, minimal angular momentum transfer was observed with an isotropic distribution of charges due to the charge-transfer nature of the excitations. The distinct behaviors observed in these systems highlight the diverse phenomena that can arise and represent a significant step toward developing novel molecular devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"87 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832945","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":"Elucidating the Impact of Doping and Strain on the Electrochemical Oxidation of Ammonia over β-M@NiOOH(0001) (M = Fe, Co, and Cu): A Comprehensive Theoretical Investigation","authors":"Jingwen Zhou, Jin Suk Chung, Sung Gu Kang","doi":"10.1021/acs.jpcc.4c06524","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06524","url":null,"abstract":"Designing effective Pt-free catalysts and understanding their mechanism of the electrochemical ammonia oxidation reaction (AOR) are critical for hydrogen production. In this study, we theoretically investigated the AOR mechanism underlying N₂ formation over the β-NiOOH(0001) and β-M@NiOOH(0001) (M = Fe, Co, and Cu) surfaces to explore the roles of doping and strain on the AOR. The enhancement in the β-NiOOH(0001) catalyst activity observed with the doping effect was essentially attributed to the upshifted ε_d, which strengthened the key intermediate <i>E</i>_ads(NH₂). The strain effect enabled high activity in catalysts by enhancing <i>E</i>_ads(NH₂) through increased amounts of electron transfer from the strain-applied surface to adsorbed NH₂, and all potential-determining steps were NH₃* deprotonation on the catalysts. In addition, an analysis of nitrogen-containing products indicated that compressive strain-applied <i>β-</i>NiOOH(0001) surfaces with high catalytic activity and N₂ selectivity can be superior to those of Pt-free AOR catalysts. The relation between the limiting potential and <i>E</i>_ads(NH₂) exhibited a volcano curve.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"22 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832947","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":"Dynamical Disorder in the Mesophase Ferroelectric HdabcoClO4: A Machine-Learned Force Field Study","authors":"Elin Dypvik Sødahl, Jesús Carrete, Georg K. H. Madsen, Kristian Berland","doi":"10.1021/acs.jpcc.4c06615","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06615","url":null,"abstract":"Hybrid molecular ferroelectrics with orientationally disordered mesophases offer significant promise as lead-free alternatives to traditional inorganic ferroelectrics owing to properties such as room temperature ferroelectricity, low-energy synthesis, malleability, and potential for multiaxial polarization. The ferroelectric molecular salt HdabcoClO₄ is of particular interest due to its ultrafast ferroelectric room-temperature switching. However, so far, there is limited understanding of the nature of dynamical disorder arising in these compounds. Here, we employ the neural network NeuralIL to train a machine-learned force field (MLFF) with training data generated using density functional theory. The resulting MLFF-MD simulations exhibit phase transitions and thermal expansion in line with earlier reported experimental results, for both a low-temperature phase transition coinciding with the orientational disorder of ClO₄^– and the onset of rotation of both Hdabco⁺ and ClO₄^– in a high-temperature phase transition. We also find proton transfer even in the low-temperature phase, which increases with temperature and leads to associated proton disorder as well as the onset of disorder in the direction of the hydrogen-bonded chains.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"30 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841888","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":"Ligand Triplet Energy Transfer from Perylene Diimide Derivatives to PbS Quantum Dots in Solution","authors":"Shengxian Hou, Zhenyu Geng, Jing Yang, Yongyao Li, Shuping Zhuo, Shuhai Chen, Yishi Wu, Chuan Li, Hongtao Lin","doi":"10.1021/acs.jpcc.4c07489","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07489","url":null,"abstract":"A novel strategy has been devised to regulate the rate of triplet energy transfer by manipulating the energy level difference between the organic singlet fission donors and inorganic acceptors. The triplet energy donor PBI-OMe and acceptor PbS quantum dots are interconnected through carboxyl groups, resulting in varying degrees of orbital coupling between quantum dots of different energy levels and the donor. This is achieved through energy level diagrams and triplet energy transfer rates. The TET rate constants of PBI-OMe 0.91, PBI-OMe 1.29, and PBI-OMe 1.45 with different band gaps calculated are 2.63 × 10⁹, 6.59 × 10⁹, and 7.97 × 10⁹ s^–1 by time-resolved absorption spectroscopy, respectively. We confirmed that the TET rate from PBI-OMe to PbS QDs is limited by the degree of orbital coupling between PBI-OMe and PbS QDs, and that within a certain band gap range, samples with higher band gaps have better orbital coupling and achieve faster TET rates. Our work provides a straightforward and controllable platform to investigate the interfacial energy transfer process between SF materials and inorganic semiconductors, offering a new way to design molecule–nanocrystal combinations with high photovoltaic conversion efficiency and potential applications in other optoelectronic fields.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"30 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832950","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":"Topological Hall Effect in Bi/Cr2Te3 Heterostructure Thin Films","authors":"Zijun Yan, Wenyu Hu, Liang Zhou, Xinru Han, Jie Jiang, Hangyu Yin, Yang Qiu, Hongtao He, Shu Ping Lau, Gan Wang","doi":"10.1021/acs.jpcc.4c06440","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06440","url":null,"abstract":"The topological Hall effect (THE) due to the spatially varying magnetizations appears as humps and dips near the coercive field in the Hall resistance curves. It is possible that magnetic skyrmions might be applied to next-generation data storage devices. Previous calculations predicted that the combination of Cr₂Te₃ thin film with strong perpendicular anisotropy (PMA) and Bi with strong spin–orbit coupling (SOC) could induce Dzyaloshinskii–Moriya interaction (DMI) and magnetic skyrmions. THE has been observed in Cr₂Te₃ thin films with Bi bilayer nanosheets intercalated. However, the distribution of inserted Bi nanosheets was random, therefore, locating and studying the interface between Bi and Cr₂Te₃ layers is difficult. The growth scheme of Bi on the Cr₂Te₃ surface is still blank. In this work, Bi/Cr₂Te₃ heterostructure thin films were fabricated by molecular beam epitaxy (MBE). The Bi (1 1 0) surface was grown on the Cr₂Te₃ (0 0 0 1) layer in islands from cross-sectional and plane-view scanning transmission electron microscopy (STEM) observation. THE signals were observed in the Bi/Cr₂Te₃ heterostructure thin films below 130 K. The two-component anomalous Hall effect (AHE) that might induce similar hump and dip signals near the coercive field was excluded by the minor loop method.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"4 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832992","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":"Solvent Vapor Annealing of CsPbI3 Nanocrystal Superlattices Followed by In Situ X-ray Scattering","authors":"Yangning Zhang, Cherrelle J. Thomas, Hyun Gyung Kim, Jungchul Noh, Thana Shuga Aldeen, Allison J. Segapeli, Detlef-M. Smilgies, Brian A. Korgel","doi":"10.1021/acs.jpcc.4c06965","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06965","url":null,"abstract":"Tetragonal superlattices of orientationally ordered, cube-shaped, perovskite CsPbI₃ nanocrystals were annealed with hexane vapor and characterized with <i>in situ</i> grazing incidence small- and wide-angle X-ray scattering (GISAXS/GIWAXS). The superlattice expands in all directions and periodic order is retained in the <i>c</i>-direction orthogonal to the substrate, while in-plane orientational order is eventually lost. The tetragonal superlattice structure with orientational nanocrystal order is recovered after removing the solvent vapor. The perovskite crystal structure of the CsPbI₃ nanocrystals remains unaffected throughout the solvent vapor annealing process.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"60 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832948","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":"CO2 Poisoning of CNx Catalysts for the Oxygen Reduction Reaction","authors":"Aishwarya Rao, Vance Gustin, Jonathan Hightower, Seval Gunduz, Dishari Basu, Yehia Khalifa, Anant Sohale, Anne C. Co, Aravind Asthagiri, Umit S. Ozkan","doi":"10.1021/acs.jpcc.4c07363","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07363","url":null,"abstract":"CN_<i>x</i> catalysts show promising activity and stability for the oxygen reduction reaction (ORR) under acidic conditions, but the nature of the active site is still under debate. ORR on CN_<i>x</i> has been found to be resistant to common poisons such as CO, H₂S, and CN. In this study, we demonstrate that bubbling CO₂ in the electrolyte can lead to the partial poisoning of CN_<i>x</i> for ORR activity. Cyclic voltammetry (CV) experiments show a partial decrease in the ORR activity for CN_<i>x</i> catalysts after bubbling CO₂ through a 0.1 M HClO₄ electrolyte. The relative stability of CO₂-derived species (CO₂*, H₂CO₃*, HCO₃*, and CO₃*) on 13 CN_<i>x</i> site models at 1.0 V-RHE was examined using density functional theory (DFT). The calculations predict that HCO₃ is favored adjacent to the N species on several CN_<i>x</i> site models and CO₃ is favored on pyrrolic sites. Difference spectra of the N 1s from near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) of the ex-situ poisoned CN_<i>x</i> and pristine CN_<i>x</i> shows a shift in binding energies of N species that qualitatively match the DFT N 1s binding energy shifts due to HCO₃/CO₃ on the CN_<i>x</i> site models. DFT predicts that these HCO₃ surface species can block and delay the initial step of the ORR on several CN_<i>x</i> sites.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"26 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832691","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":"Rapid and Energy-Saving Synthesis of MnCo2O4/MWCNT Nanocomposites for High-Energy-Density Asymmetric Supercapacitors","authors":"Shivam Kumar Mittal, Sandeep Saini, Udeshwari Jamwal, Deepak Yadav, Deepanshu Kaneria, Kanhaiya Lal Yadav","doi":"10.1021/acs.jpcc.4c05938","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05938","url":null,"abstract":"Recent advancements in materials science have resulted in impressive electrode materials; however, their practical implementation is often limited by complex and resource-intensive synthesis processes including high-temperature requirements, long synthesis times, and low yield. To advance the field of energy storage, it is crucial to develop synthesis methods that minimize both energy and time consumption. In this study, we employed a low-temperature, time-efficient, and cost-effective synthesis technique for fabricating high-performance electrode materials. Herein, a MnCo₂O₄/multiwalled carbon nanotube (MWCNT) (MCOC) nanocomposite is synthesized via a low-temperature coprecipitation approach. The effect of MWCNTs on the electrochemical properties of the nanocomposites has been studied. The synthesized MCOC1 sample (0.99MnCo₂O₄ + 0.01MWCNT) demonstrated enhanced electrochemical characteristics, exhibiting a specific capacitance of 540 Fg^–¹ at 0.5 Ag^–¹ and good cyclic stability with 87.91% capacitance retention over 5000 cycles at 8 Ag^–¹, attributed to its higher surface area (113 m²/g) and mesoporous pore size distribution. An asymmetric supercapacitor was constructed by using MCOC1 as the cathode and activated carbon as the anode, demonstrating the highest specific energy density and power density of 58 and 21 kW kg^–1, respectively. The device also exhibited 80.5% capacitance retention and a Coulombic efficiency of 97.82% over 5000 cycles at 3 Ag^–¹ in a PVA/KOH gel electrolyte. Notably, when two devices were connected in series, they successfully powered three green LEDs for over 4 min each. The facile low-temperature synthesis and excellent electrochemical properties of the synthesized MnCo₂O₄/MWCNT nanocomposites make them promising candidates for high-performance supercapacitors.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"53 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841887","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":"Plexcitons in Bowtie Nanocavities–Quantum Dots Systems Studied by Electron Energy Loss Spectroscopy","authors":"Rongyue Yao, Shihang Zhao, Yuan Zhang, Changlin Zheng, Luxia Wang","doi":"10.1021/acs.jpcc.4c02606","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c02606","url":null,"abstract":"As hybrid excitations formed by strongly coupled plasmons and excitons, plexcitons are conventionally investigated by far-field scattering, absorption, or photoluminescence spectroscopy. Stimulated by the recently improved energy resolution, near-field electron energy loss spectroscopy (EELS) is gradually explored to reveal more insights into the plexciton phenomena with unprecedented spatial and energy resolution. In the current study, we study the plexcitons in silver bowtie nanocavities–semiconductor quantum dots (QDs) systems with EELS by numerical simulation and compare them theoretically with the far-field technique to illustrate the advantages of EELS, i.e., subnanometer resolution and dark plasmons. The insights gained might guide further theoretical and experimental studies of the strong coupling.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"88 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833050","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}