化学•材料最新文献

{"title":"Reactive Molecular Dynamics Simulation on the Disintegration of Kapton-POSS Composites during Atomic Oxygen Impact","authors":"Ting-Ting Huang, Hong-Yu Gu, Yu-Zhi Zhang, Liang-Xing Lv, Wen-Zhu Shao","doi":"10.1021/acs.jpcc.4c07192","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07192","url":null,"abstract":"In low Earth orbit (LEO), atomic oxygen (AO) is one of the most prevalent reactive species that affects polymers on spacecraft’s surface, such as Kapton, leading to significant degradation. To enhance the resistance of Kapton against AO-induced degradation, polyhedral oligomeric silsesquioxane (POSS: (SiO1.5)_n) modification has emerged as a promising strategy. However, the underlying mechanisms of this enhancement remain to be elucidated, which is the objective of present study. In this work, we investigate the surface chemistry of various Kapton-POSS composites exposed to AO environments, where n equals 6, 8, 10, and 12, respectively. For simplicity, these POSS structures are referred to as T6, T8, T10, and T12 throughout the text. We employed computational chemical evaluations of both Kapton and Kapton-POSS composites under identical conditions, using the reactive force field (ReaxFF) approach. This method facilitates molecular dynamics (MD) simulations on large-scale systems while allowing for dynamic modeling of chemical reaction processes. Our findings indicate that the resistance of pure Kapton to AO is inferior to that of Kapton-POSS composites, with results corroborating experimental observations. Analysis of mass loss and exfoliation rates among the four composites demonstrates that Kapton-T6 exhibits diminished stability. Moreover, assessments of the spatial distribution and concentration of AO within the material postirradiation reveal that Kapton-T10 is more effective at absorbing the kinetic energy from AO impact. Mechanistic analysis of small molecule product formation revealed the innovative discovery that the POSS structure attracts atomic oxygen (AO) and alters their trajectories, thereby enhancing the anti-AO capability of Kapton. Notably, T6 and T12 demonstrated superior protective performance for Kapton compared to T8 and T10.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"9 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192520","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":"Metal-N4-Functionalized Graphene as Highly Active Catalysts for C–N Bond Formation in Electrochemical Urea Synthesis","authors":"Tsai-Jen Lin, Wei-Sen Chen, Hsien-Chin Li, Chao-Yang Chen, Hansaem Choi, Youngkook Kwon, Mu-Jeng Cheng","doi":"10.1021/acs.jpcc.4c07971","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07971","url":null,"abstract":"Urea is a vital nitrogen-based fertilizer, traditionally produced through energy-intensive processes that consume significant resources and emit substantial CO₂. The electrochemical coreduction of CO₂ and NO₃^–/NO₂^– offers a sustainable alternative, but efficient catalysts are needed to drive this reaction. In this study, density functional theory calculations combined with a constant electrode potential model were employed to investigate the initial C–N bond formation in urea synthesis via the coreduction of CO₂ and NO₃^–. The reaction was driven by a CuN₄ moiety embedded in graphene (<b>gCuN</b>_<b>4</b>), a single-atom catalyst (SAC). Despite the common belief that SACs have a limited ability to facilitate C–N coupling due to the lack of adjacent active sites, our findings show that <b>gCuN</b>_<b>4</b> can efficiently promote this reaction via coupling of surface-bound *N₁ intermediates, generated from NO₃^– reduction, with CO₂ through the Eley–Rideal mechanism. The calculated free energy barriers are near zero at the experimentally relevant potential of <i>U</i> = −1.0 V_SHE. The facile C–N coupling kinetics are retained when Cu is replaced with other first-row transition metals. Surprisingly, the electron dynamics analysis revealed that in most C–N coupling reactions, one of the two electrons forming the C–N bond originates from the graphene support, underscoring its critical role. Additionally, the high reactivity may be due to the use of high-energy electrons from the graphene support and/or nitrogen in the *N₁ intermediates rather than relying on the inert Cu–N bond electrons to form C–N bonds. Strategies to enhance C–N bond formation as well as methods to preserve the highly active single-atom state are discussed. These insights will contribute to the development of efficient and durable catalysts for sustainable urea synthesis.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"40 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124736","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":"Chemistry Meets Plasmon Polaritons and Cavity Photons: A Perspective from Macroscopic Quantum Electrodynamics","authors":"Liang-Yan Hsu","doi":"10.1021/acs.jpclett.4c03439","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03439","url":null,"abstract":"The interaction between light and molecules under quantum electrodynamics (QED) has long been less emphasized in physical chemistry, as semiclassical theories have dominated due to their relative simplicity. Recent experimental advances in polariton chemistry highlight the need for a theoretical framework that transcends traditional cavity QED and molecular QED models. Macroscopic QED is presented as a unified framework that seamlessly incorporates infinite photonic modes and dielectric environments, enabling applications to systems involving plasmon polaritons and cavity photons. This Perspective demonstrates the applicability of macroscopic QED to chemical phenomena through breakthroughs in molecular fluorescence, resonance energy transfer, and electron transfer. The macroscopic QED framework not only resolves the limitations of classical theories in physical chemistry but also achieves parameter-free predictions of experimental results, bridging quantum optics and material science. By addressing theoretical bottlenecks and unveiling new mechanisms, macroscopic QED establishes itself as an indispensable tool for studying QED effects on chemical systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"25 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124946","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Ketone Synthesis via Cu(I)-Catalyzed Regioselective Coupling of 2-Pyridylthioesters with Grignard Reagents: In Quest of Straightforward Access to Pharmaceuticals","authors":"Masahiko Seki, Shaheen Kasim Mulani, Runlin Yang, Gaurav Shukla, Sandeep Ramesharao Tapkir, Shantanu Nandi, Subarna Jyoti Kalita, Kazushi Mashima","doi":"10.1021/acs.joc.4c02752","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02752","url":null,"abstract":"For commercial production of SGLT2 inhibitors, cryogenic conditions (−78 °C) were required at the key <i>C</i>-glycosidation step, which has restricted their supply to the world market. To address the challenge, reported herein is a new synthetic method based on a new ketone synthesis by means of copper(I)-catalyzed coupling of 2-pyridylthioesters with Grignard reagents. The facile transformation from the ketones to the final APIs was realized under mild conditions due to the use of readily cleavable acetyl protecting groups.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"61 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124951","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tributyl Phosphate Induced Male Reproductive Toxicity in Mice","authors":"Jiayi Wang, Yanfan Cui, Yujie Wang, Yixuan Li, Yuanqiao He, Tao Luo","doi":"10.1021/acs.est.4c10280","DOIUrl":"https://doi.org/10.1021/acs.est.4c10280","url":null,"abstract":"Tributyl phosphate (TBP) is an emerging hazardous material that is ubiquitous in the environment. However, whether TBP affects the male reproductive system remains unknown. In this study, we exposed male ICR mice and mouse spermatocyte GC-2 cells to TBP to explore the male reproductive toxicity of TBP. The results revealed that TBP (50 and 100 mg·kg^–1·day^–1) decreased sperm count and motility, damaged testicular structure, and induced apoptosis in mice after 35 days of oral gavage. TBP (10, 50, and 200 μM) inhibited cell viability, induced apoptosis, and reduced the ratio of BCL2/BAX in GC-2 cells after 24 h of exposure. TBP (50 and 200 μM) triggered the buildup of reactive oxygen species and induced a reduction in the mitochondrial membrane potential within GC-2 cells. In addition, TBP led to gut microbiota dysbiosis and metabolic profile alterations and increased the abundance of Prevotellaceae, which are negatively associated with sperm motility. Furthermore, TBP caused inflammation, induced the infiltration of Th17 cells into the mouse small intestine, and stimulated IL-17A signaling in mouse testes. In conclusion, TBP induced male reproductive toxicity via the gut–testis axis, oxidative stress, and apoptosis, offering fresh perspectives on TBP’s reproductive hazards in male mammals.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"123 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124473","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Forced dynamic operation of propylene selective oxidation to acrolein on bismuth-molybdate structured catalysts","authors":"Mohammad Moniruzzaman ,&nbsp;Lars C. Grabow ,&nbsp;Michael P. Harold","doi":"10.1016/j.apcata.2024.120034","DOIUrl":"10.1016/j.apcata.2024.120034","url":null,"abstract":"<div><div>Forced dynamic operation (FDO) of selective oxidation of propylene to acrolein is evaluated on a structured alumina foam coated with a mixed metal oxide catalyst (bismuth molybdate-based). Reactor experiments examine feed composition modulation as a strategy to increase the yield of acrolein. At lower temperatures, separating the oxidant (O₂) and reductant (C₃H₆) enhances propylene conversion and acrolein selectivity. Variation in the reaction-regeneration switching amplitude and frequency gives a 40 % higher cycle-averaged acrolein yield compared to steady-state operation (SSO) for the same overall feed composition. The results suggest that FDO maintains a higher concentration of selective oxygen species during the propylene feed, while pre-oxidation of the catalyst maximizes the amount of selective oxygen species, leading to increased acrolein yield at the beginning of the reaction cycle. Experiments at lower temperature for both commercial promoted and in-house, unpromoted catalysts reveal both catalysts are most active and selective at their highest oxidation states.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120034"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135251","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Proton-Transfer-Coupled Spin Transitions in Mononuclear Iron(II) Compounds: Interplay of Intra- and Intercenter Interactions","authors":"Sophia I. Klokishner, Oleg S. Reu","doi":"10.1021/acs.jpcc.4c07925","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07925","url":null,"abstract":"Recently, a new trend in the field of spin transitions has been reported that is represented by iron(II) molecular compounds exhibiting proton-transfer-coupled spin-transition behavior. The present paper focuses on the elucidation of the origin of this type of transitions, and explanation on this basis of the observed behavior of the [Fe(HL-Cl)₂](AsF₆)₂ compound proved to be the first exhibiting such a type of behavior. Since the proton lies on the nitrogen of the hydrazone or pyridine moiety in the ligand in the ⁵T₂ and ¹A₁ states of the Fe(II) ion, respectively, the developed model takes into account the proton transfer between its two positions. The cooperativity in the model is assured by electron-deformational and intermolecular dipole–dipole interactions because the spin transition is accompanied by an appreciable elongation of the iron–nitrogen bonds and redistribution of the proton density inside the complex. The parameters of interactions involved are estimated with the aid of structural data and through density functional theory (DFT) calculations. The problem of interacting molecules is solved within the mean field approximation. The suggested model captures the main features of the phenomenon and provides quite a good description of the temperature dependence of the χ<i>T</i> product and Mössbauer spectra of the [Fe(HL-Cl)₂](AsF₆)₂ compound.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"29 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192521","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":"Different Inactivation Mechanisms of Staphylococcus aureus and Escherichia coli in Water by Reactive Oxygen and Nitrogen Species Generated from an Argon Plasma Jet","authors":"Junghyun Lim, Seungil Park, Seungmin Ryu, Sanghoo Park, Min Sik Kim","doi":"10.1021/acs.est.4c10363","DOIUrl":"https://doi.org/10.1021/acs.est.4c10363","url":null,"abstract":"The atmospheric pressure plasma jet (APPJ) is a promising technology for inactivating waterborne pathogens by generating diverse reactive species under ambient conditions. However, uncertainties regarding the bacterial inactivation mechanisms persist due to varying findings in prior research. This study aimed to clarify the inactivation mechanisms of two representative bacteria, <i>Staphylococcus aureus</i> (<i>S. aureus</i>, Gram-positive) and <i>Escherichia coli</i> (<i>E. coli</i>, Gram-negative), using an argon-based APPJ (Ar-APPJ) system in a controlled medium, primarily deionized water. We identified several reactive oxygen and nitrogen species (RONS), including hydrogen peroxide, peroxynitrous acid/peroxynitrite (ONOOH/ONOO^–), hydroxyl radical (^•OH), and hydroperoxyl radical/superoxide radical, and evaluated their roles in bacterial inactivation. Inactivation experiments and quantification of suspected RONS revealed that ONOOH was the primary lethal agent for <i>S. aureus</i>, while ^•OH predominantly inactivated <i>E. coli</i>. Assessment of cell membrane integrity and intracellular RONS levels showed that <i>E. coli</i>, with its thinner cell wall, was more vulnerable to surface damage caused by ^•OH. In contrast, for <i>S. aureus</i>, with its thicker cell wall, intracellular attack by penetrated ONOOH, being significantly more diffusive than ^•OH, was more effective, as ^•OH alone could not induce sufficient surface damage. These findings advance our understanding of bacterial inactivation by the Ar-APPJ and provide valuable insights for designing effective water disinfection strategies utilizing this technology.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"9 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Catalytic reforming of biomass pyrolysis gas over Ni catalysts: Alumina, spent fluid catalytic cracking catalyst and char as supports","authors":"Ching Wei Low ,&nbsp;Andrei Veksha ,&nbsp;Rupendra Aryal ,&nbsp;Wei Ping Chan ,&nbsp;Grzegorz Lisak","doi":"10.1016/j.apcata.2024.120074","DOIUrl":"10.1016/j.apcata.2024.120074","url":null,"abstract":"<div><div>The potential replaceability of a Ni catalyst supported on commercial α-Al₂O₃ (Ni/Al₂O₃) by Ni on biomass-derived char (Ni/Char), and Ni on spent fluid catalytic cracking catalyst (Ni/FCC) for steam reforming of biomass pyrolysis gas was investigated (14 h at 850°C, steam/carbon ratio = 5). The catalysts reformed 60–80 % of C₂-C₅ hydrocarbons, producing 2.7–4.1 mg min⁻¹ of H₂. The reforming activity of Ni/Al₂O₃ and Ni/FCC was higher compared to Ni/Char, indicating the beneficial role of metal oxide supports. The use of Al₂O₃ and FCC resulted in a lower thermo-oxidative stability of coke formed on Ni/Al₂O₃ and Ni/FCC compared to Ni/Char. Furthermore, the deposited Ni showed higher stability towards oxidation by steam into NiO in case of Al₂O₃ and FCC compared to char. According to reforming activity, H₂ production rate, coking, and Ni oxidation of the catalysts, FCC has better prospects as an alternative support in a reforming catalyst than char.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120074"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nickel promoter effect in rhenium catalysts for valorization of bio-oil model molecules","authors":"N. Mora ,&nbsp;E. Blanco ,&nbsp;J. Seguel ,&nbsp;J.N.Díaz de León ,&nbsp;N. Escalona","doi":"10.1016/j.apcata.2024.120033","DOIUrl":"10.1016/j.apcata.2024.120033","url":null,"abstract":"<div><div>In the present work, the promoter effect of nickel over rhenium-supported catalysts was studied for the valorization of bio-oil model compounds. The catalysts were characterized by X-ray diffraction, N₂ adsorption isotherms at −196 °C, temperature programmed reduction, NH₃-temperature programmed desorption, CO chemisorption, and X-ray photoelectron spectroscopy. The catalytic performance was evaluated in a batch reactor at 350 °C and 50 bar of H₂. The characterization results show that two phenomena occur with the inclusion of Ni through post-impregnation: A higher exposure of rhenium phases and formation of ReC and metallic Re at higher Ni contents and an electronic transfer from Ni to Re. The catalysts were evaluated for the hydrodeoxygenation reaction (HDO) of guaiacol used as a bio-oil model compound. The most active catalysts were the Re-Ni(3 %)/AC and Re-Ni(5 %)/AC samples. Cyclohexanol and cyclohexane were the main products obtained from the hydrogenation of phenol promoted by the reduced rhenium species.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120033"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}