Physical Chemistry Chemical Physics最新文献

{"title":"Evaluation of the Arrhenius behavior of n-dodecane radical cation (RH●+) reactivity with lanthanide ion-complexed N,N,N’,N’-tetraoctyl diglycolamide (TODGA)","authors":"Maya H. Rogalski, Anh N Dang, Stephen Peter Mezyk","doi":"10.1039/d4cp03633f","DOIUrl":"https://doi.org/10.1039/d4cp03633f","url":null,"abstract":"Temperature-dependent rate constants for the reaction of the n-dodecane radical cation (RH●+) with trivalent lanthanide ion-complexed N,N,N’,N’-tetraoctyl diglycolamide (TODGA) over the range 10-40oC have been determined by electron pulse radiolysis/transient absorption spectroscopy techniques. For the free ligand, an activation energy of Ea = 20.4 ± 0.7 kJ mol-1 and pre-exponential factor of ln(A) = 31.23 ± 0.27 were obtained, corresponding to a room-temperature rate constant of k = (9.94 ± 0.52) x 109 M-1 s-1. The RH●+ reactivity with La(TODGA)3(NO3)3, Nd(TODGA)3(NO3)3, Gd(TODGA)3(NO3)3, Yb(TODGA)3(NO3)3and Lu(TODGA)3(NO3)3 complexes had faster rate constants of k = (5.30 ± 0.51) x 1010, (4.23 ± 0.18) x 1010, (2.44 ± 0.13) x 1010, (1.68 ± 0.03) x 1010, and (9.1 ± 0.7) x 109 M-1 s-1, respectively. The corresponding Arrhenius activation energies determined for three (La, Gd, Lu) lanthanide-TODGA complexes showed consistent values of Ea = 35 ± 2.2, 35.3 ± 2.0, 33.5 ± 3.9 kJ mol-1, respectively. The similar and relatively large barrier energy suggests a common reaction mechanism involving electron abstraction from one of the coordinating nitrate anions, which is consistent for the previously reported decreased degradation of TODGA complexes under radiolytic environments.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"148 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867349","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":"Estimation of PEMFC optimal parameters based on an improved butterfly optimization algorithm","authors":"Zhe Sun, Yan Song, Yijun Du, Zhixin Sun","doi":"10.1039/d4cp03448a","DOIUrl":"https://doi.org/10.1039/d4cp03448a","url":null,"abstract":"This paper introduces a novel butterfly optimization algorithm, called the spiral search and dynamic crossover based butterfly optimization algorithm (SCBO), for parameter estimation in proton exchange membrane fuel cell (PEMFC) models. To enhance the global performance of the butterfly algorithm, a spin-search strategy is incorporated to expand its exploration range, while an adaptive factor is introduced to strike a balance between exploration and exploitation. Additionally, a dynamic crossover operation is integrated to enhance solution diversity, addressing the algorithm's tendency to converge to local optima. Extensive experimentation on benchmark functions in comparison with common optimization algorithms demonstrates that SCBO outperforms others in terms of convergence accuracy and speed. Finally, we employ SCBO for parameter identification in a PEMFC model, showcasing its superior results and its ability to capture the model's dynamics when compared to other algorithms.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"71 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849359","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":"Conformational effects in the identification and quantification of ketohydroperoxides in the oxidation of n-pentane","authors":"Dongyang Li, Deshan Li, Jiabin Huang, Luc-Sy Tran, Guillaume Vanhove, Hans-Heinrich Carstensen, Feng Zhang, Jérémy Bourgalais, Julien Bloino, Frédérique Battin-Leclerc, Majdi Hochlaf, Laurent Nahon, Pilippe Arnoux, Gustavo Adolfo Garcia, Olivier Herbinet","doi":"10.1039/d4cp04184d","DOIUrl":"https://doi.org/10.1039/d4cp04184d","url":null,"abstract":"Stereochemistry plays a key role in both fundamental chemical processes and dynamics of a large set of molecular systems of importance in chemistry, medicine and biology. Predicting the chemical transformations of organic precursors in such environments requires detailed kinetic models based on laboratory data. Reactive intermediates play a critical role in constraining the models but their identification and especially their quantification remain challenging. This work demonstrates, via the study of the gas-phase autoxidation of n-pentane, a typical fuel surrogate, that accounting for spatial orientation is essential for accurate characterization of such intermediates and for their further evolution. Using synchrotron-based photoelectron photoion coincidence spectroscopy and high-level quantum calculations to investigate the electronic structure and ionization dynamics of the main ketohydroperoxide isomer formed during the oxidation of n-pentane, we reveal the multiple thermally accessible conformers of the chain-branching agent, highlighting how their distinct ionization energies and fragmentation pathways can significantly affect intermediate quantification via photoionization-based probes, a universal in situ method of choice. This research underscores the importance of stereochemistry not only in combustion systems but in any chemical system where a molecular-level understanding is crucial for developing accurate predictive models for both scientific and industrial applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"64 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849360","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":"Unlocking the potential of Ni-rich LiNi0.9Co0.1O2 cathodes: a DFT investigation of performance-limiting factors","authors":"Temitayo Ojuetimi Ikuerowo, Olusegun Tomomewo, Salawu Omotayo Akande","doi":"10.1039/d4cp03475a","DOIUrl":"https://doi.org/10.1039/d4cp03475a","url":null,"abstract":"Ni-rich layered oxides, particularly LiNi<small>_0.9</small>Co<small>_0.1</small>O<small>₂</small>, have garnered significant attention in the realm of high-capacity cathodes for lithium-ion batteries. Despite their promise, their commercialization is hindered by challenges related to structural instability and defect formation. This study utilizes density functional theory (DFT) to unravel the intricate structural, defect formation, and transport properties of LiNi<small>_0.9</small>Co<small>_0.1</small>O<small>₂</small>, thereby providing insights into the performance-limiting factors. Our findings reveal that a 10% cobalt doping while enhancing lithium mobility, is insufficient to significantly mitigate antisite defects and oxygen vacancy formation. These defects are critical in influencing the electrochemical performance and durability of the material. The study further delves into the implications of defect formation on the electrochemical characteristics, emphasizing the need for a higher concentration of cobalt doping to effectively stabilize the Ni-rich cathode. This theoretical investigation contributes to the understanding of defect behaviors in Ni-rich cathodes and paves the way for optimized material design in future high-energy-density battery technologies.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"113 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857942","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":"Nanostructured bismuth ferrite nanoparticles: synthesis, characterization, electrical/magnetic properties and photocatalytic performance","authors":"M. H. Ghozza, Ahmed T. Mosleh, Elbadawy A. Kamoun, Mahmoud Abdel-Aty, M. Alfiras, Mohamed Hafez Ahmed, Shawkat Alkhazaleh, V. Ganesh, H. Y. Zahran, Ibrahim S. Yahia","doi":"10.1039/d4cp04515g","DOIUrl":"https://doi.org/10.1039/d4cp04515g","url":null,"abstract":"Nanostructured bismuth ferrite (BiFeO<small>₃</small>) single-phase nanoparticles with 76.2% crystallinity and 100% perovskite structure were synthesized using a co-precipitation method. The X-ray diffraction pattern confirmed the perovskite structure of BFO, and Rietveld refinement demonstrated the presence of a triclinic structure with the <em>P</em>1 space group. The Scherrer and Williamson–Hall equations were used to calculate the crystallite size (63 and 83 nm, respectively) with a grain size of almost 246 nm and an activation energy of 0.53 eV. The accumulation of free charges at interfaces, which correlate with the sample bulk and the interface between the compound and electrode space-charge polarization, was the reason behind the high values of <em>ε</em>′. As the frequency increased up to 1000 Hz, both dielectric constant <em>ε</em>′ and dielectric loss <em>ε</em>′ fell quickly. In contrast, at high frequencies, the <em>ε</em>′ became more frequency-independent, notably when <em>ε</em>′ increased with a temperature of up to 423 K. The sample exhibited considerable soft ferromagnetic-like activity due to the acquired nanoscale structure that promotes spin coating in the BiFeO<small>₃</small> antiferromagnetic phase. The significant coercivity 2624.5 Oe provides each materials in permanent magnetic and transformers. Photocatalytic activity of the BiFeO<small>₃</small> nanocomposite under UVA-light irradiation was performed using Congo red dye. The maximum photocatalytic degradation efficiency after 200 min for CR was 66%. The exceptional electrical and magnetic characteristics of nanostructured BiFeO<small>₃</small> provide new possibilities for its use in potential technological applications, <em>i.e.</em>, spintronics, data storage microelectronics, and water treatment.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"23 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849363","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":"Controlling anomalous Hall conductivity using antiferromagnetic configurations in GdPtBi","authors":"Fiqhri Heda Murdaka, Yusuf Wicaksono, Edi Suprayoga, Abdul-Muizz Pradipto, Bambang Prijamboedi, Isao Watanabe, Agustinus Agung Nugroho","doi":"10.1039/d4cp03836c","DOIUrl":"https://doi.org/10.1039/d4cp03836c","url":null,"abstract":"The magnetic, electronic, and topological properties of GdPtBi were systematically investigated using first-principles density functional theory (DFT) calculations. Various magnetic configurations were examined, including ferromagnetic (FM) and antiferromagnetic (AFM) states, with particular focus on AFM states where the Gd magnetic moments align either parallel (AFM<small>_∥</small>) or perpendicular (AFM<small>_⊥</small>) to the [111] crystal direction. For AFM<small>_⊥</small>, the in-plane angles φ were varied at φ = 0°, 15°, 30° (denoted as AFM<small>_⊥,φ=0°</small>, AFM<small>_⊥,φ=15°</small>, and AFM<small>_⊥,φ=30°</small>, respectively). The ground-state magnetic structure of GdPtBi was validated through dipolar magnetic field calculations at the muon sites, corroborating the internal magnetic fields observed in muon spin relaxation (μSR) experiments. The results indicate that the AFM<small>_⊥,φ=30°</small> configuration aligns with the μSR-measured internal field. The DFT-calculated band structure and Berry curvature reveal AFM<small>_⊥</small> belongs to triple-point semimetals (TPSMs) where the triple-point nodes positioned along the <em>Z</em>-Γ-<em>Z</em> and <em>F</em>-Γ-<em>F</em> paths with their energies shifting as the spin-orbit coupling strength varies with φ. Notably, this shift in triple-point energy corresponds to a significant change in the anomalous Hall conductivity (AHC, (σ<small>_<em>xy</em></small>)), with a difference of 75.06 Ω<small>^-1</small>cm<small>^-1</small> at the Fermi energy between AFM<small>_⊥,φ=0°</small> and AFM<small>_⊥,φ=30°</small>. These findings highlight the potential for controlling the AHC through precise manipulation of the AFM structure.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"45 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849365","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":"What Comes Next: The Fate of Germa, Stanna, and Plumba-closo-Dodecaborate Based Electrolytes in Calcium Ion Batteries","authors":"Mohmmad Faizan, Ravinder Pawar","doi":"10.1039/d4cp04670f","DOIUrl":"https://doi.org/10.1039/d4cp04670f","url":null,"abstract":"Recent investigations on plumba- and stanna-closo-bornae-based electrolytes for alkali metal-ion batteries have demonstrated improved ionic conductivities at elevated temperatures. However, the potential of germa, stanna, and plumba borane in divalent ion batteries is uncertain. To address this knowledge gap, a theoretical approach has been adopted to explore the potential of Ge-, Sn-, and Pb-based borane anions as electrolytes for CIBs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"22 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849358","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":"Z-type heterojunction degradation of tetracycline by 2D g-C3N4 with 3D oxygen vacancy Bi2WO6","authors":"Xiao Kang, Xiangyan Li, Abulikemu Abulizi, Mihiriguli Abulimiti, Nuerla Ailijiang, Anwar Mamat","doi":"10.1039/d4cp02969k","DOIUrl":"https://doi.org/10.1039/d4cp02969k","url":null,"abstract":"Photocatalytic degradation is a promising strategy for environmental remediation. Graphitic carbon nitride (g-C3N4) is the most extensively reported metal-free, Hierarchical flower-shaped Bi2WO6 particles were obtained using a simple hydrothermal method, with petals of flower-like Bi2WO6 with oxygen vacancies (Bi2WO6 OVs) with controlled content successfully decorated on g-C3N4 nanosheets. A novel Z-scheme 2D/3D heterojunction photocatalyst, g-C3N4/Bi2WO6 OVs, was successfully prepared, with its composition and structure studied using a series of material characterization techniques. Compared to single g-C3N4 and Bi2WO6 OVs, the g-C3N4/Bi2WO6 OVs exhibited improved photocatalytic activity for the degradation of tetracycline, with a degradation rate of more than 90%. Moreover, electron paramagnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and Mott–Schottky measurements suggest that a Z-scheme heterojunction formed between the g-C3N4 nanosheets and Bi2WO6 OVs floral forms and that the photoinduced electrons in Bi2WO6 OVs bind to holes in g-C3N4, thus enhancing the extraction and utilization of carriers under photoexcitation. Hence, this study presents an effective method for constructing 2D/3D heterojunctions for solar fuel conversion and photocatalytic water treatment.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"27 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849364","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":"Single-atom transition metal supported on B-doped g-C3N4 monolayer for electrochemical nitrogen reduction","authors":"Huadou Chai, Weiguang Chen, Yi Li, Mingyu Zhao, Jinlei Shi, Yanan Tang, Xianqi Dai","doi":"10.1039/d4cp03247k","DOIUrl":"https://doi.org/10.1039/d4cp03247k","url":null,"abstract":"Electrochemical reduction of the naturally abundant nitrogen (N2) under ambient conditions is a promising way of ammonia (NH3) synthesis, while the development of a highly active, stable and low-cost catalyst is a challenge for it. Herein, the N2 reduction reaction of TM@g-BC3N4 in electrochemical nitrogen reduction has been systematically investigated by density functional theory (DFT) calculation and compared with that of TM@g-C3N4. It was found that TM atoms are more stable anchored to g-BC3N4 than g-C3N4. The adsorption free energy of N2 molecule on Fe@g-BC3N4 has the greatest change compared with that on Fe@g-C3N4, decreasing by 1.08 eV. The spin charge density around the Fe atom in Fe@g-BC3N4 increases significantly compared with that in Fe@g-C3N4, and the total magnetic moment of the system increases by 3.26 μB. The limiting potential (-0.57 V) of Fe@g-BC3N4 in nitrogen reduction is decreased by 0.06 V compared with that of Fe@g-C3N4 (-0.63 V), and the desorption free energy of ammonia molecules decreases from 1.72 eV to 0.46 eV. Fe atom has higher catalytic activity, ammonia molecule is easier to desorption, nitrogen reduction performance is better. This provides an important reference for the application of g-C3N4-based single atom catalyst in the field of nitrogen reduction.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"102 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841727","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":"Study of the pH effects on water-oil-illite interfaces by molecular dynamics","authors":"Anderson Arboleda-Lamus, Leonardo Muñoz-Rugeles, Jorge M. del Campo, Nicolas Santos-Santos, Enrique Mejía","doi":"10.1039/d4cp03985h","DOIUrl":"https://doi.org/10.1039/d4cp03985h","url":null,"abstract":"Illite mineral is present in shale rocks and its wettability behavior is relevant for the oil and gas industry. In this work, the pH effects on the affinity between the (001) and (010) crystallographic planes of illite K2(Si7Al)(Al3Mg)O20(OH)4 and direct and inverse emulsions were studied by molecular dynamics simulations. To develop the simulations, the atomistic model of illite was constructed following the Löwenstein’s rule. The oily phase was modeled by heptane, toluene, and mixtures of heptane/heptanoic acid, heptane/heptanoate, heptane/hexylamine and heptane/hexylammonium. For the heptane/heptanoate and heptane/hexylammonium mixtures, Na+ and Cl- ions were used to neutralize the excess electrical charge of the droplets, respectively. The affinity of the mineral surface to the oil models was estimated by the contact angle for systems where it was possible; whereas, for systems where the droplets did not adhere to the mineral, a methodology based on the height of the droplet on the surface was proposed. The results show that in general, in the case of the inverse emulsions, water has a high affinity for both illite surfaces and its contact angle is below to 45º regardless to pH. However, the heptane/heptanoic acid inverse emulsions on the edge surface were the exception to that behavior, i.e., the contact angles calculated for the water droplets reveled mixed wettability because of the hydrogen bonds between the carboxylic functional groups (pH &lt;&lt; 4.4) and the surface silanols and alumminols. On the other hand, oil droplets suspended in water did not adhere to the illite surfaces and contact angles were not measurable; nevertheless, the heptane/heptanoic acid droplets (pH &lt;&lt; 4.4) showed heights around 2 and 4 Å above the basal and edge surfaces, respectively. This behavior was due to the hydrogen bonds formed between the carboxylic functional groups and the water molecules located on the mineral surfaces. Finally, the heptane/heptanoate (pH &gt;&gt; 4.4) and heptane/hexylammonium (pH &lt;&lt; 10.64) droplets were localized at distances over 8 Å from the surface, presumably due to a charge repulsion effect between the mineral surface and the surface of the droplets.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"256 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841723","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}