The Journal of Physical Chemistry C最新文献

{"title":"Spontaneous Structural Reconstructions and Properties of Ultrathin Triangular ZnSe Nanoplatelets","authors":"Alexander I. Lebedev","doi":"10.1021/acs.jpcc.4c08561","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08561","url":null,"abstract":"Two-dimensional (2D) materials have revolutionized all areas of development of high-performance electronic devices. In particular, the unique electronic and optical properties of II–VI semiconductor nanoplatelets have been found to be very promising for optoelectronics. However, not all properties of this intriguing class of materials are yet known. A new, previously unknown hexagonal 2D structure of ZnSe nanoplatelets whose energy is lower than the energies of all previously studied systems is found from first-principles calculations. This structure appears as a result of spontaneous reconstruction of the wurtzite structure and differs from it by the stacking order of the bulk and near-surface Zn atomic layers. The phonon spectrum, electronic structure, and band gap of the obtained nanoplatelets are calculated. The phonon spectra of the nanoplatelets are in complete agreement with the spectra observed in experiment and differ strongly from the vibrational spectra of ZnSe nanoclusters. The adsorption of ZnCl₂ and <span>l</span>-cysteine molecules on the surface of the nanoplatelets is studied and is shown to be accompanied by yet another spontaneous reconstruction of the hexagonal structure into a tetragonal one and a new rearrangement of Zn atoms in the near-surface layers. Calculations of the natural optical activity of nanoplatelets covered with <span>l</span>-cysteine reveal an increase in the specific (calculated per chiral molecule) optical activity, which is especially strong for the Janus structures, as compared to the free <span>l</span>-cysteine molecule.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"49 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745218","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":"Ag Nanoparticles-Decorated 2D WSe2 as Highly Sensitive Surface-Enhanced Raman Spectroscopy Substrates for Nitrofurantoin Detection","authors":"Jiancheng Feng, Kunle Li, Xinkuo Zhang, Yalong Li, Yinyin Wang, Yibin Yang, Xing Feng, Jiancai Xue, Yunwei Sheng, Yu Zhao","doi":"10.1021/acs.jpcc.5c00583","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00583","url":null,"abstract":"Nitrofurantoin, a derivative of nitrofuran, has been banned due to its carcinogenic potential, necessitating sensitive detection methods to monitor its illegal use and facilitate the clinical diagnosis of associated conditions. In this study, a composite structure of silver nanoparticles (AgNPs) on tungsten diselenide (WSe₂) sheets was developed for the detection of nitrofurantoin using surface-enhanced Raman spectroscopy (SERS). AgNPs prepared via mechanical exfoliation were selectively distributed on the surface of two-dimensional (2D) transition-metal dichalcogenides, resulting in enhanced SERS performance for molecular detection. The AgNPs/WSe₂ substrate demonstrated a detection limit (LOD) for rhodamine 6G molecules as low as 10^–10 M, outperforming previously reported Au/WSe₂ composite structures. Notably, the AgNPs/WSe₂ substrate achieved an LOD of 10^–9 M for nitrofurantoin, surpassing other SERS detection methods reported to date. Furthermore, the substrate can quantitatively detect nitrofurantoin in milk solutions with an LOD of 10^–6 M, demonstrating its potential in practical application. Its remarkable Raman enhancement effect may come from the synergistic effect of electromagnetic mechanism enhancement of AgNPs and chemical mechanism enhancement of 2D WSe₂. The excellent uniformity and stability of the AgNPs/WSe₂ composite make it a promising candidate for sensitive and reproducible SERS-based molecular detection.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"23 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758062","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":"High-Performance Sr and Mg Co-Doped LaAlO3 Proton Conducting Electrolyte for Semiconductor Ion Fuel Cells","authors":"Jiangyu Yu, Yingbo Zhang, Decai Zhu, Wenliang Fan, Nan Wang, Yaohui Niu, Jiali Zhou, Chengjun Zhu","doi":"10.1021/acs.jpcc.5c00591","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00591","url":null,"abstract":"A major challenge for semiconductor ion fuel cells (SIFCs) is to design an electrolyte with proton transport properties so that it can maintain high ionic conductivity within relatively low temperatures. Herein, we develop a Sr and Mg codoped LaAlO₃ electrolyte that facilitates efficient conduction of protons and oxygen ions by enriching oxygen vacancies and reducing the activation energy of ion conduction. The optimized electrolyte shows a low activation energy of 0.31 eV and demonstrates remarkably elevated ionic conductivity at low temperatures, e.g., 0.1994 S cm^–1 at 550 °C. This is attributed to the significant increase in oxygen vacancies, which has been verified by XPS technology. Meanwhile, the Sr and Mg codoped LaAlO₃ electrolyte exhibits remarkable proton transport properties, confirmed by proton filtration experiments, which provide further evidence for the improvement of the electrolyte ionic conductivity. As a result, the fuel cell with an optimized LaAlO₃ electrolyte delivers an impressive peak power density of 977 mW·cm^–2 with an open circuit voltage (OCV) of 1.126 V at 550 °C. Particularly, compared with the fuel cell with a pure LaAlO₃ electrolyte, the peak power density is increased by 38.4%. The dual-ion doping strategy provides crucial insight into the further development of high ionic conductivity electrolytes for SIFCs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"58 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758064","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":"Active Microfluidic Mixing Using Photoacoustic Laser Streaming from Gold-Implanted Optical Fibers and Glass Beads","authors":"Tian Tong, Paththini Kuttige S. Nonis, Chengzhen Qin, Feng Lin, Elizabet Rosas, Di Chen, Wei-Kan Chu, Jiming Bao","doi":"10.1021/acs.jpcc.4c08786","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08786","url":null,"abstract":"Efficient microfluidic mixing remains a significant challenge due to the difficulty of generating advection and turbulence, especially as many applications demand reduced sample and reagent consumption for improved efficiency and lower costs. In this work, we introduce a new active mixing method─photoacoustic laser streaming (PALS)─which uses laser pulses to produce fluid jets. PALS integrates photoacoustic effects with acoustic streaming, transforming metal-coated surfaces into fluidic pumps without moving mechanical parts. To demonstrate the concept, we fabricated a fiber-based PALS pump by implanting gold (Au) onto the facet of an optical fiber. The fiber tip was immersed in liquids to perform mixing in a microplate (50 μL volume), achieving complete mixing in 3 min compared to hours required for diffusion alone. Additionally, we utilized Au-coated glass microbeads as PALS stirrers. Upon light excitation, the beads not only generated jets from their surfaces but were also recoiled by the jets, creating enhanced turbulence and more efficient mixing. While this method was demonstrated in a microplate, we anticipate even greater effectiveness in microfluidic channels, where traditional mixing techniques face significant limitations.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"15 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745163","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":"Intercalation and Interface Engineering of Layered MnO2 Cathodes toward High-Performance Aqueous Zinc-Ion Batteries","authors":"Shixue Zhong, Yan Xin, Li’e Mo, Bijiao He, Fang Zhang, Chen Zhao, Linhua Hu, Huajun Tian","doi":"10.1021/acs.jpcc.5c01408","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01408","url":null,"abstract":"Manganese-based layered compounds offer promising cathode materials for aqueous zinc-ion batteries (AZIBs) due to their high safety, low cost, and environmental friendliness. However, their sluggish reaction kinetics, poor conductivity, and irreversible manganese dissolution result in severe capacity fading. Herein, a simple two-step method is successfully proposed to intercalate Ba²⁺ ions into layered manganese oxide (Ba-MnO₂), which were utilized as cathode materials for AZIBs. Ba²⁺ ions have been innovatively introduced into the MnO₂ cathode, generating abundant oxygen vacancies. Notably, the incorporated Ba²⁺ spontaneously forms an in situ BaSO₄ layer during charging, which functions as a protective cathode electrolyte interface. These improvements promote the conductivity and ion diffusion of MnO₂, enabling a reversible MnO₂/Mn²⁺ deposition/dissolution reaction. The Zn//Ba-MnO₂ full battery delivers a high capacity of 355 mA h g^–1 at 0.3 C and maintains an ultrastable cycling stability of over 1200 cycles even at 3 C. This work provides an innovative strategy and a profound understanding of designing high-performance cathodes for AZIBs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"72 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737223","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 Insights into the Thermocatalytic Cracking of Ammonia-Hydrogen Blends on Fe(110). 2. Kinetics","authors":"J. Mark P. Martirez, Sophia Kurdziel, Emily A. Carter","doi":"10.1021/acs.jpcc.4c07303","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07303","url":null,"abstract":"Ammonia (NH₃) is an energy-rich molecule that is routinely synthesized from nitrogen (N₂) and hydrogen (H₂). NH₃’s more favorable physical properties compared to H₂ suggests it may offer a way to more conveniently store, transport, and, when needed, extract H₂ via thermal decomposition. However, the high kinetic barrier and endoergicity to decompose to H₂ and N₂ require high temperatures. The standard reaction free energy indicates nearly 100% thermodynamic conversion to the diatomic molecules only at ∼673 K and higher. However, even at these temperatures, a catalyst, e.g., iron (Fe), is needed for favorable kinetic conversion. Here, we explore via density functional theory the kinetics of NH₃ decomposition on the most stable facet of body-centered cubic Fe, namely, (110), under typical high-temperature and finite-pressure operando conditions. We predict coverage-dependent energetics of elementary surface reactions, often neglected in atomic-scale modeling. From these models, we find the recombinative desorption of adsorbed N as N₂ is rate-determining at 573.15–773.15 K and even at an extreme case of 1173.15 K. From microkinetic modeling, we find that the steady-state turnover frequencies (TOFs) for N₂ and H₂ generation rates (<i>r</i>_H₂) depend exponentially on temperature. The catalyst achieves a steady-state TOF of 36.4 s^–1 and an <i>r</i>_H₂ of 0.107 μmol cm^–2 s^–1 for a feed of 1.8 bar NH₃ with 0.2 bar H₂ at 1173.15 K. However, at 773.15 K, with the same feed composition and velocity, the steady-state TOF and <i>r</i>_H₂ decrease to 0.14 s^–1 and 4.10 × 10^–4 μmol cm^–2 s^–1, respectively, as the process is significantly hindered by slow N₂ desorption. Although at first glance counterintuitive, our simulations suggest that surface modifications that reduce Fe’s reactivity toward NH<i>_<i>x</i></i> species should enhance its overall NH₃ decomposition activity.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"23 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745167","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":"Probabilistic Features of Photocatalytic CO2 Conversion","authors":"Zhonghui Zhu, Yimin Xuan, Xianglei Liu, Ying Zhang, Jin Wang, Qibin Zhu","doi":"10.1021/acs.jpcc.4c08747","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08747","url":null,"abstract":"Photocatalytic CO₂ conversion involves stochastic events comprising interactions of incident photons, charge carriers, and surface molecules. However, the probabilistic features of photocatalytic processes remain unclear. Herein, a probabilistic framework is proposed to analyze the random characteristics of photocatalytic CO₂ conversion by coupling charge carrier random behaviors with surface reaction kinetics. The probabilistic mechanism of the Gibbs energy change Δ<i>G</i> = −<i>nFE</i> is elucidated in photocatalytic CO₂ conversion. Parameter correlation analysis shows that the surface electron density is primarily influenced by the light intensity and active site density. Crucially, a criterion for screening optimal cocatalysts of various photocatalysts─including oxides, sulfides, titanates, and nitrides─is established by optimizing the potential difference between the photocatalyst and cocatalyst. Moreover, regulation strategies are suggested to minimize irreversible losses in light absorption, carrier transport, and surface reactions for photocatalysts. The experimental results validate the universality of the method, further clarifying that the cause of the limited number of electron transfers in the reaction is the mismatch between the reactant supply and carrier transfer probabilities. This work establishes a probabilistic approach to analyzing the stochastic energy losses in photocatalytic CO₂ reduction, providing guidance for efficient catalyst design and optimization.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"103 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745221","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":"Vacancy-Dependent Diffusion Mechanism in Oxygen-Defective SrFeO3 Perovskite Materials: First-Principles Density Functional Theory and Experimental Approach","authors":"Hari P. Paudel, Shree Ram Acharya, Eric J. Popczun, Jonathan W. Lekse, Yuhua Duan","doi":"10.1021/acs.jpcc.4c08288","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08288","url":null,"abstract":"Understanding oxygen diffusion at the atomic scale in SrFeO_3−δ perovskites is crucial for developing oxygen storage materials with optimal performance. Such materials are required to have high stability, corrosion resistance, and acceptable oxygen storage capacity at moderate operating temperatures and pressures. Here, we used first-principles density functional theory and thermogravimetric analysis to study the vacancy-dependent oxygen diffusion in oxygen-deficient SrFeO_3−δ (δ = 0, 0.065, 0.125, 0.25, 0.5) perovskites. The electronic structures, including the partial- and spin-resolved density of states, for different SrFeO_3−δ phases were calculated and compared with available experimental and theoretical results. By mapping the migration pathways, we investigated diffusion mechanisms and calculated the energy barriers for oxygen diffusion in cubic, orthorhombic, and brownmillerite phases of SrFeO_3−δ perovskites. Using the calculated energy barriers, we deduced the diffusion time scales and diffusion coefficients within SrFeO_3−δ. A diffusion coefficient on the order of 10^–8 m²/s was obtained for SrFeO_2.875. We experimentally investigated the roles of temperature and oxygen partial pressures on the redox kinetics and deduced the kinetics rate and diffusion density, which agreed well with the calculated values for the density of diffusing oxygen vacancy in the lattice. Our results showed that the energy barrier tends to reduce at higher oxygen concentrations. Our results serve as an important guideline for designing oxygen storage materials with optimal redox kinetics.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"8 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745220","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":"Facile Ball-Milling Synthesis of Carbon-Coated Layered K-Birnessite for High-Rate and Long-Term Potassium-Ion Batteries","authors":"Bingxian Li, Xinhai Wang, Tinghong Gao, Wensheng Yang, Qinyan Jian, Jiarui Liu, Lishan He, Zhenhua Wu, Yunjun Ruan","doi":"10.1021/acs.jpcc.5c00253","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00253","url":null,"abstract":"Layered manganese oxide cathode materials have been widely employed in energy storage systems because of their high energy density and low cost. However, manganese-based cathodes for potassium-ion batteries face significant challenges, including large volume changes during K⁺ intercalation/deintercalation processes, severe capacity loss, and sluggish K⁺ transport kinetics. Herein, the K_0.28MnO₂·0.29H₂O (KMO) precursor, synthesized via a solid-state reaction, was ball-milled with Ketjen black to form the KMO@C0.2 composite. The carbon coating layer prevents direct contact between KMO and the electrolyte, effectively mitigating the Jahn–Teller effect of Mn and ensuring the structural integrity of the cathode during rapid and stable K⁺ intercalation/deintercalation processes. Density functional theory (DFT) calculations confirm that the carbon layer enhances the material’s electronic conductivity, reduces the electrochemical reaction resistance, and significantly improves the sample’s rate capability. The KMO@C0.2 cathode delivers an initial discharge capacity of 137.9 mAh g^–1 at 20 mA g^–1, a rate capability of 77.2 mAh g^–1 at 500 mA g^–1, and retains 81% of its capacity after 300 cycles. These findings regarding the surface protection layer structure provide valuable insights for advancing manganese-based layered cathodes with enhanced interfacial stability for potassium-ion batteries.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"36 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737221","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":"Machine Learning Lattice Parameters of M2AX Phases","authors":"Cesare Roncaglia, Fábio Lopes, Nick Goossens, Michael Stuer, Daniele Passerone","doi":"10.1021/acs.jpcc.4c08730","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08730","url":null,"abstract":"MAX phases, with a general composition of M_<i>n</i>+1AX_<i>n</i>, are layered materials with hexagonal symmetry that have increasingly captivated a lot of attention because of their unique way of combining ceramic and metallic properties into a homogeneous bulk material. We developed a machine learning approach to predict the lattice parameters a and c of M₂AX phases. This approach consists of training an ensemble model on a data set collecting all experimentally synthesized M₂AX phases’ lattice parameters. Our approach combines a data augmentation scheme with state-of-the-art regression models and hyperparameter optimization tools. We tested our model on newly synthesized compositionally complex high-entropy M₂AX phases with positive results. Finally, we also show that our machine learning predictions of lattice parameters are useful as initial values for variable-cell relaxations of M₂AX structures with the density functional theory.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"58 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745170","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}