Chemphyschem最新文献

{"title":"Interatomic Interactions and Ion-Transport in a Polyoligomeric Silsesquioxane-Based Multi-Ionic Salt Electrolyte for Lithium-Ion Batteries.","authors":"Shylendran Ardhra, Prabhat Prakash, Rabin Siva Dev, Stephanie L Wunder, Arun Venkatnathan","doi":"10.1002/cphc.202400983","DOIUrl":"10.1002/cphc.202400983","url":null,"abstract":"<p><p>Polyoligomeric silsesquioxane (POSS) tailored with trifluoromethanesulfonylimide-lithium and solvated in tetraglyme (G4) is a potential electrolyte for Li-ion batteries. Using classical MD simulations, at different G4/POSS(-LiNSO₂CF₃)₈ molar ratios, the interactions of Li⁺ ions with the oxygen atoms of G4 and, oxygen/nitrogen sites of the pendant tails, the behaviour of POSS(-^-NSO₂CF₃)₈, and the mobility of species are investigated. The RDFs showed that there exist competing interactions of the O(G4), O(POSS), and N(POSS) sites with Li⁺ ions. The lifetime analysis indicated that Li⁺- - -O(POSS) and Li⁺- - -N(POSS) interactions are longer-lived compared to Li⁺- - -O(G4). The morphological changes of the POSS tails upon interaction with Li⁺ ions were analysed using rotational lifetimes, coiling, and end-to-end distances. The ion-speciation analysis indicated the presence of solvent-separated ion pairs (SSIPs), contact ion pairs (CIPs), and higher-order ion clusters, with SSIPs being the more dominant species at 32/1. The self-diffusion coefficients for the 32/1 system, which showed the least cation-anion interaction, followed the trend: <math> <semantics> <mrow><msub><mi>D</mi> <mrow><mi>G</mi> <mn>4</mn></mrow> </msub> <mo>></mo> <msub><mi>D</mi> <mrow><mi>L</mi> <mi>i</mi> <mo>+</mo></mrow> </msub> <mo>></mo> <msub><mi>D</mi> <mrow><mi>F</mi> <mfenced><mi>P</mi> <mi>O</mi> <mi>S</mi> <mi>S</mi></mfenced> </mrow> </msub> <mo>></mo> <msub><mi>D</mi> <mrow><mi>P</mi> <mi>O</mi> <mi>S</mi> <mi>S</mi></mrow> </msub> </mrow> <annotation>${{D}_{G4}char62 {D}_{Li+}char62 {D}_{Fleft(POSSright)}char62 {D}_{POSS}}$</annotation> </semantics> </math> . The computed cationic transference number (t₊) using the <math> <semantics><msub><mi>D</mi> <mrow><mi>F</mi> <mfenced><mi>P</mi> <mi>O</mi> <mi>S</mi> <mi>S</mi></mfenced> </mrow> </msub> <annotation>${{D}_{Fleft(POSSright)}}$</annotation> </semantics> </math> is consistent with NMR experimental data. The t₊ (and the trends with temperature) computed using the <math> <semantics><msub><mi>D</mi> <mrow><mi>P</mi> <mi>O</mi> <mi>S</mi> <mi>S</mi></mrow> </msub> <annotation>${{D}_{POSS}}$</annotation> </semantics> </math> and ionic conductivities are in good agreement.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400983"},"PeriodicalIF":2.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143499443","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":"Identification of Adsorption Sites for CO₂ in a Series of Rare-Earth and Zr-Based Metal-Organic Frameworks.","authors":"Dylan Tassé, Victor Quezada-Novoa, Christopher Copeman, Ashlee J Howarth, Alain Rochefort","doi":"10.1002/cphc.202401050","DOIUrl":"10.1002/cphc.202401050","url":null,"abstract":"<p><p>The adsorption of <math> <semantics><msub><mi>CO</mi> <mn>2</mn></msub> <annotation>${{rm{CO}}_2 }$</annotation> </semantics> </math> in MOF-808, NU-1000 and a series of rare-earth CU-10 analogues has been studied with first principles DFT and classical Monte-Carlo methods. DFT calculations describe the interaction of <math> <semantics><msub><mi>CO</mi> <mn>2</mn></msub> <annotation>${{rm{CO}}_2 }$</annotation> </semantics> </math> with the different metal-organic frameworks (MOFs) as physisorption, but where we can distinguish several adsorption sites in the vicinity of the metal nodes. Beyond the identification of adsorption sites, the MOFs were synthesized, activated, and characterized to evaluate their experimental <math> <semantics><msub><mi>N</mi> <mn>2</mn></msub> <annotation>${{rm{N}}_2 }$</annotation> </semantics> </math> and <math> <semantics><msub><mi>CO</mi> <mn>2</mn></msub> <annotation>${{rm{CO}}_2 }$</annotation> </semantics> </math> adsorption capacity. Classical Grand Canonical Monte-Carlo (GCMC) simulations for the adsorption of <math> <semantics><msub><mi>CO</mi> <mn>2</mn></msub> <annotation>${{rm{CO}}_2 }$</annotation> </semantics> </math> are in very good agreement with DFT results for identifying the most favored adsorption sites in the MOFs. In contrast, a rather mixed agreement between GCMC simulations and experimental results is found for the estimation of adsorption capacity of several MOFs studied toward <math> <semantics><msub><mi>N</mi> <mn>2</mn></msub> <annotation>${{rm{N}}_2 }$</annotation> </semantics> </math> and <math> <semantics><msub><mi>CO</mi> <mn>2</mn></msub> <annotation>${{rm{CO}}_2 }$</annotation> </semantics> </math> .</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401050"},"PeriodicalIF":2.3,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143490985","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 Sites in Ga-Ni Supported Catalytically Active Liquid Metal Solutions (SCALMS) for Selective Ethylene Oligomerization.","authors":"Alexander Søgaard, Tzung-En Hsieh, Julien Steffen, Simon Carl, Mingjian Wu, Yousuf R Ramzi, Sven Maisel, Johannes Will, Anna Efimenko, Mihaela Gorgoi, Regan G Wilks, Johannes Frisch, Nicola Taccardi, Marco Haumann, Erdmann Spiecker, Andreas Görling, Marcus Bär, Peter Wasserscheid","doi":"10.1002/cphc.202400651","DOIUrl":"10.1002/cphc.202400651","url":null,"abstract":"<p><p>Supported catalytically active liquid metal solutions (SCALMS) are materials composed of a liquid metal alloy deposited on a porous support. Due to the dynamic properties of the liquid metal alloy, these systems are suggested to form single atom sites, resulting in unique catalytic properties. Ga-Ni SCALMS were successfully applied to ethylene oligomerization, yielding catalysts that were stable up to 120 h time on stream. A workflow based on synchrotron-based X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) as well as density function theory (DFT) and ab initio molecular dynamics (AIMD) simulations was applied to investigate the nature of the active species in these materials. The combination of XPS with DFT calculations indeed indicates the presence of isolated single Ni atoms on the liquid metal surface, while TEM measurements show high dynamics in the liquid metal with intermetallic phase dissolution and transformation. Furthermore, DFT/AIMD methods allowed for rationalizing the role of hydrogen pretreatment in enriching the Ni atom at the surface of the liquid metal alloy.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400651"},"PeriodicalIF":2.3,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143490991","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-Pressure Stability and Electronic Properties of Sodium-Rich Nitrides: Insights from First-Principles Calculations.","authors":"Qiuyue Li, Qiuping Yang, Shuai Han, Fei Li, Yansun Yao, Guochun Yang","doi":"10.1002/cphc.202401150","DOIUrl":"10.1002/cphc.202401150","url":null,"abstract":"<p><p>Using first-principles structure search calculations, we investigated the phase stability of sodium-nitrogen (Na-N) compounds under high pressure. Our study reveals that increasing pressure promotes the formation of Na-rich nitrides, leading to the prediction of three previously unreported stoichiometries: Na₂N, Na₅N, and Na₈N. Notably, the electride Na₅N undergoes a pressure-induced structural transition from a P6/mmm to a P6₃/mmc phase. This transformation is characterized by spatial reorientation and redistribution of interstitial anionic electrons (IAEs). In the P6₃/mmc phase, IAEs adopt a zero-dimensional, triangular-like configuration, whereas in the low-pressure P6/mmm phase, they form an interconnected, graphene-like network. With increasing pressure, P6₃/mmc phase undergoes a transition from metallic to semiconducting behavior due to the increased interaction between sodium and IAEs. Additionally, C2/m Na₈N, featuring triangular- and ship-like IAEs, is predicted to exhibit superconductivity. Our findings provide new insights into the behavior and stability of Na-rich nitrides under high-pressure conditions.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401150"},"PeriodicalIF":2.3,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143490983","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":"Substituent Effect of Superhalogens on the Metallodrug IMeAuCl: A DFT Study.","authors":"Xin Cheng, Bin Liu, Jing-Hua Chen, Wei-Ming Sun","doi":"10.1002/cphc.202401124","DOIUrl":"10.1002/cphc.202401124","url":null,"abstract":"<p><p>Halogens are usually involved in numerous anticancer drugs and play an important role in anticancer activity. Taking the IMeAuCl, a potent anticancer drug as an example, the substituent effect of superhalogens X@B₁₂N₁₂ (X=F, Cl, and Br) on the structures, electronic properties, and chemical reactivity with biomolecular targets of this metallodrug has been investigated. Substituting X@B₁₂N₁₂ for the Cl atom of IMeAuCl results in polar covalent bonds between Au and N atoms in the resulting Au-X (X=F, Cl, and Br) derivatives. The introduction of superhalogens enhances the polarity and solubility of Au-X, which enables them to directly react with biological target molecules without undergoing hydrolysis. In particular, it is found that the higher electron affinity (EA) of X@B₁₂N₁₂ results in the lower energy barrier of the reaction between Au-X and target molecules, which maybe benefit its high biological activity. With regard to this, another complex Au-BF₄ with better anticancer activity has been also designed by replacing the Cl atom of IMeAuCl with BF₄, a well-known superhalogen with higher EA value than X@B₁₂N₁₂. Thus, this study provides a new strategy to improve the antitumor activity of halogen-containing drugs from a theoretical point of view.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401124"},"PeriodicalIF":2.3,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143482260","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":"NMR Insights into Pore Architecture and Li⁺ Accessibility for Optimized Energy Density in Li-O₂ Batteries.","authors":"Santiago Agustín Maldonado-Ochoa, Sofía Raviolo, Fernando Cometto, Guillermina Leticia Luque, Fabián Vaca Chávez","doi":"10.1002/cphc.202400938","DOIUrl":"10.1002/cphc.202400938","url":null,"abstract":"<p><p>Lithium-oxygen batteries have gained prominence in recent years due to their potential advantages over conventional lithium-ion batteries, including higher energy density, cost-effectiveness and environmental sustainability. To fully exploit these advantages, it is essential to understand the interplay between porous carbon electrode materials and electrolytes in these devices. This study presents a nuclear magnetic resonance investigation of the confined LiTFSI (lithium bis(trifluoromethanesulfonyl)imide) - TEGDME (tetraethylene glycol dimethyl ether) electrolyte within carbonaceous materials with different pore sizes. Three carbon materials (microporous, mesoporous, and hierarchical) were synthesized from the same precursor to ensure equivalent surface chemistry, which was verified by X-ray photoelectron spectroscopy. The dynamics and distribution of solvent and Li ions in the different pores were studied by <math> <semantics><msup><mrow></mrow> <mn>1</mn></msup> <annotation>${^1 }$</annotation> </semantics> </math> H and <math> <semantics><msup><mrow></mrow> <mn>7</mn></msup> <annotation>${^7 }$</annotation> </semantics> </math> Li, 1D and 2D exchange, NMR spectroscopy. It was found that the accessibility of Li <math> <semantics><msup><mrow></mrow> <mo>+</mo></msup> <annotation>${^+ }$</annotation> </semantics> </math> within the pores of the carbonaceous material depends not only on their size but also on their size distribution. The knowledge gained from this study can contribute to the design of the appropriate pore size distribution, which could optimize the electrolyte utilization and consequently increase the energy density of lithium-oxygen batteries.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400938"},"PeriodicalIF":2.3,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143490988","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":"Car-Parrinello Molecular Dynamics Elucidate Atomic Nitrogen Reactivity Under Nanoflask (C₇₀) Confinement Conditions.","authors":"Núbia Maria Nunes Rodrigues, Rodrigo A Lemos Silva, Daniel F Scalabrini Machado, Heibbe C B de Oliveira, Luciano Ribeiro","doi":"10.1002/cphc.202400755","DOIUrl":"10.1002/cphc.202400755","url":null,"abstract":"<p><p>We performed an ab initio molecular dynamics study with a nitrogen atom in the 1/2 spin state, which corresponds to an excited electronic state, in contrast to the ground state with 3/2 spin state. This N atom was encapsulated with an H₂ molecule in a C70 fullerene, as a \"nanoflask\" for experimentation. This approach was initially proposed by Morinaka and colleagues (Angew. Chem. Int. Ed. 2017, 56, 6488-6491), where they demonstrated, using spectroscopy, that the N(⁴S) atom, does not react with the H₂ molecule. By analyzing the trajectory from Car-Parrinello molecular dynamics simulations and performing Density Functional Theory, Quantum Theory of Atoms in Molecules, Reduced Density Gradient and Interaction Region Indicator calculations, we successfully reproduced the experiment observations, examining the interaction between the N atom and the H₂ molecule encapsulated within the fullerene C₇₀.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400755"},"PeriodicalIF":2.3,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143482258","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":"Navigating Antibiotic Resistance in Gram-Negative Bacteria: Current Challenges and Emerging Therapeutic Strategies.","authors":"Reshma Kumari, Ishu Saraogi","doi":"10.1002/cphc.202401057","DOIUrl":"https://doi.org/10.1002/cphc.202401057","url":null,"abstract":"<p><p>The rapid rise of antibiotic resistance poses a severe global health crisis, necessitating new approaches to counter this growing threat. The problem is exacerbated in Gram-negative bacterial pathogens as many antibiotics are unable to enter these cells owing to their unique additional outer membrane barrier. In this review, we discuss the challenges of targeting Gram-negative bacteria, including the complexity of the outer membrane, as well as the presence of efflux pumps and β-lactamases that contribute to resistance. We also review solutions proposed to facilitate the entry and accumulation of antibiotics in Gram-negative bacteria. These involve using existing antibiotics in combination with other inhibitors to attack the bacterial cell synergistically. We also highlight approaches to target Gram-negative pathogens via novel modes of action, providing new strategies to tackle antibiotic resistance.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401057"},"PeriodicalIF":2.3,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143457039","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":"Two-Dimentional Conductive Metal-Organic Frameworks: Promising Materials for Advanced Energy Storage.","authors":"Guang Zhang, Long Chen","doi":"10.1002/cphc.202400769","DOIUrl":"10.1002/cphc.202400769","url":null,"abstract":"<p><p>With the rapid development of science and technology and for a sustainable future, the main energy resources in the world are transitioning from fossil fuels to renewable electricity which is conceived to play a predominant role in the future. Therefore, it is essential to develop high-performance energy-storage devices such as supercapacitors and rechargeable batteries, and even though they are commercialized, intense research efforts are still devoted to further improving the device performance, e. g. energy density, safety, durability, and charging rate. Therefore, exploring new advanced materials for better devices is a promising approach. Recently, the emerging two-dimensional conductive metal-organic frameworks (2D c-MOFs) with their inherent electrical conductivities and porosity, rich redox active sites, and tailor-made architectures and functions have attracted considerable attention among the energy-storage community. The initial research results revealed that 2D c-MOFs are promising electrode materials for advanced energy storage.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400769"},"PeriodicalIF":2.3,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439999","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":"Exploring the Potential of Quantum Dot-Sensitized Solar Cells: Innovation and Insights.","authors":"Jyoti Singh, Rakhi Thareja, Pragati Malik","doi":"10.1002/cphc.202400800","DOIUrl":"10.1002/cphc.202400800","url":null,"abstract":"<p><p>Photovoltaic technologies have garnered significant attention towards generating renewable and clean energy from solar power. Quantum-dot-sensitized solar cells represent a promising third-generation photovoltaic technology that offers alternatives to conventional silicon-based solar cells due to their unique properties, their favourable optoelectronic properties for photovoltaic applications including simplified manufacturing, lower processing temperatures, enhanced flexibility, semi-transparent design, and a theoretical efficiency up to 44 %. The unique characteristic of tailoring the size and composition of quantum dots makes them valuable absorber materials capable of efficiently harnessing a broader range of the solar spectrum. The potential of quantum dot-sensitized solar cells to revolutionize the field of photovoltaic technology is a cause for optimism. However, the major limitation of the overall power conversion efficiency lies in their inability to absorb ultraviolet and near-infrared. Therefore, a photovoltaic technology that can effectively harness the entire solar spectrum becomes imperative. This review discusses the synthesis and light conversion mechanisms of these solar cells. Additionally, it offers an overview of the various advancements made in quantum dot-sensitized solar cells for enhancement in the efficiency of energy conversion. It focuses on the light-absorbing materials used, their efficiency, and the advantages and drawbacks of quantum dot solar cell technology.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400800"},"PeriodicalIF":2.3,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143448335","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}