{"title":"Hydrogen Bond-Mediated Local Structure and Far-Infrared Vibrational Frequencies in Imidazolium-Based Ionic Liquid.","authors":"Panat Nanthanasit, Michael Armstrong, Narupon Chattrapiban, Monchai Jitvisate, Piyarat Nimmanpipug, Sakhorn Rimjaem","doi":"10.1002/cphc.202500093","DOIUrl":"10.1002/cphc.202500093","url":null,"abstract":"<p><p>This study investigates the intermolecular interactions and far-infrared (FIR) vibrational spectra of the ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsul-fonyl)imide ([Emim] <math> <semantics> <mrow><msup><mrow></mrow> <mo>+</mo></msup> </mrow> <annotation>$^{&amp;amp;amp;amp;amp;amp;plus;}$</annotation></semantics> </math> [NTf <math> <semantics> <mrow><msub><mrow></mrow> <mn>2</mn></msub> </mrow> <annotation>$_{2}$</annotation></semantics> </math> ] <math> <semantics> <mrow><msup><mrow></mrow> <mo>-</mo></msup> </mrow> <annotation>$^{-}$</annotation></semantics> </math> ). Density functional theory calculations are used to optimize 24 single ion pair structures, while classical molecular dynamics simulations explore the liquid's cluster structure. The results highlight the role of CH···N, CH···O, and CH···F hydrogen bonding in stabilizing the system. Experimental FIR spectra reveal absorption bands associated with hindered translational modes of cations and anions, as well as intramolecular wagging modes of anions, aligning well with computational predictions. The multiple ion pair structures in the solvent model broaden the calculated peaks of the hindered translational modes and separate the two peaks of the wagging modes for the cis- and trans-anions. These findings provide valuable insights into the interaction of IL, enhancing our understanding of their structure for future applications.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500093"},"PeriodicalIF":2.3,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093025","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}
ChemphyschemPub Date : 2025-05-14DOI: 10.1002/cphc.202500184
Ying-Zhong Ma, Uvinduni I. Premadasa, May Waters, Nitesh Kumar, Benjamin Doughty, Melyse Laud, Yi Liao, Vyacheslav S. Bryantsev
{"title":"Accessing Transient Isomers in the Photoreaction of Metastable-State Photoacid","authors":"Ying-Zhong Ma, Uvinduni I. Premadasa, May Waters, Nitesh Kumar, Benjamin Doughty, Melyse Laud, Yi Liao, Vyacheslav S. Bryantsev","doi":"10.1002/cphc.202500184","DOIUrl":"10.1002/cphc.202500184","url":null,"abstract":"<p>The photoreaction of a metastable-state photoacid (mPAH) generally involves multiple isomers with various connected pathways of photoinduced structural changes during a single reaction cycle. However, only a limited number of isomers have been identified experimentally so far owing to the inherent complexity in combination with the presence of various competing electronic and vibrational processes, as well as the constantly varying interactions between mPAH isomers and solvent molecules. Here, an optical spectroscopic study on a benzimidazole-based mPAH, a novel photoacid using benzimidazole as the structural moiety with the active proton, is reported. Through measurements of linear absorption and steady-state fluorescence in neat solvents and binary mixtures, a pronounced effect of neat water and its binary mixture with glycerol is discovered on the photoreaction of this benzimidazole-mPAH, manifested by the remarkably distinct spectral responses to irradiation from that observed for an organic solution under identical conditions. Measurements of time- and frequency-resolved fluorescence emission further enable to access transient isomers and the associated spectral characteristics from other competing electronic excited-state relaxation processes. Spectral deconvolution analysis and time-dependent density functional theory calculations are applied to separate distinct spectral components and access their potential origin.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 13","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144076296","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}
ChemphyschemPub Date : 2025-05-14DOI: 10.1002/cphc.202500237
Paransa Alimard, Stanley Cazaly, Ioanna Itskou, Hanieh Akbari, Srinivas Gadipelli, Nazila Kamaly, Flurin Eisner, Andreas Kafizas
{"title":"Exploring the Influence of Carbonaceous Material on the Photocatalytic Performance of the Composites Containing Bi-BiOBr and P25 TiO<sub>2</sub> for NO<sub>x</sub> Remediation.","authors":"Paransa Alimard, Stanley Cazaly, Ioanna Itskou, Hanieh Akbari, Srinivas Gadipelli, Nazila Kamaly, Flurin Eisner, Andreas Kafizas","doi":"10.1002/cphc.202500237","DOIUrl":"10.1002/cphc.202500237","url":null,"abstract":"<p><p>The Bi-BiOBr-P25 TiO<sub>2</sub> composite material exhibits high and synergistic improvements in the photocatalytic activity for nitrogen oxides (NO<sub>x </sub> = NO + NO<sub>2</sub>) removal. Herein, the influence of adding carbonaceous material to this composite, namely graphene (G), graphene oxide (GO), carbon nanotubes (CNT), and buckminsterfullerene (F) is explored; all at 1 wt%. Samples are synthesised using a one-pot solvothermal method. The structural and morphological properties, composition, and photocatalytic performance of all samples are examined using scanning electron microscopy, carbon-hydrogen-nitrogen elemental analysis, high-resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, ultraviolet-visible (UV-vis) spectroscopy, X-ray photoelectron spectroscopy, N<sub>2</sub> sorption at 77 K, photoluminescence spectroscopy, diffuse reflectance transient absorption spectroscopy), and photocatalytic testing against NO<sub>x</sub> gas in accordance with ISO protocol (22197-1:2016). Among the studied carbonaceous composites, the composite including GO shows the highest performance toward NO<sub>x</sub> remediation. For reactions in NO gas, it shows a combined higher NO<sub>x</sub> removal rate (21.9%) than its parent materials P25 (8.7%), Bi-BiOBr (6.5%), and GO (0%). For reactions in NO<sub>2</sub> gas, it shows a higher NO<sub>x</sub> removal rate (≈15%) than its parent materials P25 (≈10%), Bi-BiOBr (≈5%), and GO (0%).</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500237"},"PeriodicalIF":2.3,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144076297","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 Investigation of a High-Chern-Number Quantum Anomalous Hall Insulator Mn<sub>2</sub>Bi<sub>2</sub>O<sub>6</sub> and Its BN-Coupled Multilayer Heterostructures.","authors":"Jiaming Hu, Jingshen Yan, Kaixuan Chen, Shu-Shen Lyu","doi":"10.1002/cphc.202500161","DOIUrl":"10.1002/cphc.202500161","url":null,"abstract":"<p><p>In modern condensed matter physics, the quantum anomalous Hall effect (QAHE), an important manifestation of topological quantum states, has attracted much attention due to its ability to exhibit the quantum Hall effect without the need for an external magnetic field. In this study, the discovery of a new high-Chern-number quantum anomalous Hall insulator, Mn<sub>2</sub>Bi<sub>2</sub>O<sub>6</sub> is reported. Utilizing first-principles calculations based on density functional theory (DFT), its electronic and topological properties are systematically investigated. The results reveal that monolayer Mn<sub>2</sub>Bi<sub>2</sub>O<sub>6</sub> possesses a remarkable energy gap of 110 meV and a Chern number of 3, corresponding to three intrinsic conductive edge channels. The material exhibits both strong robustness and stability upon applied strain. Moreover, by stacking double layers with a boron nitride (BN) insulating layer, a heterostructure system with a larger bandgap (117.4 meV) and an increased Chern number of 6 can be realized. When substituting the upper layer's oxygen atoms with tellurium atoms, it forms a Janus structure, accompanied by a transition of Chern number from 3 to 1. This work not only introduces new candidates for expanding the class of QAHE materials but also establishes a new platform for applications in low-power electronic devices and topological quantum computing.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500161"},"PeriodicalIF":2.3,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143983808","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}
ChemphyschemPub Date : 2025-05-14DOI: 10.1002/cphc.202500087
Stefan Charon, Niloofar Zarrabi, Jatan K. Sharma, Paul A. Karr, Francis D’Souza, Prashanth K. Poddutoori
{"title":"Temperature Tunable Optical Properties of Tetraheptylaluminum(III) Porphyrin Toward Molecular Thermometer","authors":"Stefan Charon, Niloofar Zarrabi, Jatan K. Sharma, Paul A. Karr, Francis D’Souza, Prashanth K. Poddutoori","doi":"10.1002/cphc.202500087","DOIUrl":"10.1002/cphc.202500087","url":null,"abstract":"<p>Amphiphilic aluminum(III) porphyrin (AlC7P) has been designed, and its aggregation-induced photophysics has been reported. The <i>meso</i>-positions of the aluminum(III) porphyrin are functionalized with a heptyl chain (C7), while the central porphyrin features an axial OH group on the Al center. The hydrophilic (<span></span>OH) and hydrophobic (C7) properties combined with the Lewis acid (Al center) and Lewis base (<span></span>OH group) functionality to facilitate the formation of aggregation through self-assembly. Spectroscopic studies indicate that aggregation can be modulated by solvent and temperature; it is more pronounced in long-chain hydrocarbon solvents, such as hexanes and <i>n</i>-heptane, and is favored at lower temperatures. At low temperature conditions, the aggregated molecules manifest low fluorescence yields, whereas at higher temperatures, the self-assembly breaks down to exhibit high fluorescence yields. This temperature-dependent aggregation-induced photophysical behavior observed in hexanes makes this porphyrin ideal for a luminescent molecular thermometer.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 13","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202500087","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143973942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemphyschemPub Date : 2025-05-12DOI: 10.1002/cphc.202401158
Jiayi Xu, Prajay Patel, Chang Yan, Cong Liu
{"title":"Understanding the active site structures and achieving catalytic activity tuning of atomically dispersed FeN4 sites for oxygen reduction reaction.","authors":"Jiayi Xu, Prajay Patel, Chang Yan, Cong Liu","doi":"10.1002/cphc.202401158","DOIUrl":"https://doi.org/10.1002/cphc.202401158","url":null,"abstract":"<p><p>Atomically dispersed Fe-N-C catalysts with high oxygen reduction reaction (ORR) activity have attracted great attention since the last decade. Due to its comparable ORR activity and low material cost, it is a promising platinum-group metal (PGM) free catalyst that can replace the commercialized Pt/C materials; furthermore, it can facilitate the efficiency of the fuel cell technologies and mitigate our dependence on fossil fuels. Great advancements have been made to experimentally optimize the synthesis approach of the Fe-N-C catalysts, enhance the ORR activity, and improve the catalyst stability. Similarly, recent theoretical studies also provide enriched understanding of the active site structures, properties, and reaction mechanisms. In this review, discussions are made upon utilizing combined experimental and computational spectroscopy to reveal the active site structures, employing mechanistic studies to investigate reaction thermodynamics and kinetics, as well as developing scaling relationships to assist the design and development of future PGM free catalyst materials. Furthermore, recent advances in studying Fe-N-C catalysts utilizing electrified surface and explicit solvation models are discussed. Not only can these aspects improve the accuracy of theoretical simulation and predictions but also deepen the understanding of the catalyst properties and reaction mechanisms under the effect of surface charges and solvent molecules.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401158"},"PeriodicalIF":2.3,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980606","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}
ChemphyschemPub Date : 2025-05-12DOI: 10.1002/cphc.202500054
Huibo Qiao, Chenxi He, Jin Zhang, Zhiheng Zhao, Junhong Tao, Wanqi Ying, Baoshu Chen, Ning Dang, Tianbao Zhao
{"title":"Realizing Improved Sodium-Ion Storage for Anthracite-Derived Hard Carbon Anode by Activation-Surface Modification Strategy.","authors":"Huibo Qiao, Chenxi He, Jin Zhang, Zhiheng Zhao, Junhong Tao, Wanqi Ying, Baoshu Chen, Ning Dang, Tianbao Zhao","doi":"10.1002/cphc.202500054","DOIUrl":"10.1002/cphc.202500054","url":null,"abstract":"<p><p>Anthracite offers several advantages, including a high carbon content, a well-developed aromatic structure, and low cost, making it a cost-effective precursor for hard carbon anodes in sodium-ion batteries. However, its higher impurity levels and fewer surface defects limit its broader applications. Herein, an activation and surface modification strategy is proposed to address its shortcomings, specifically low sodium storage-ion capacity and low initial Coulombic efficiency (ICE). ZnCl<sub>2</sub> is used as an activator to introduce numerous pores into the structure of hard carbon, thereby increasing the sodium-ion storage sites. Furthermore, soft carbon pitch is applied to refine the oversized pore structure in hard carbon, improving its ICE. As a result, the modified hard carbon achieves a reversible capacity of 240 mAh g<sup>-1</sup> and an ICE of 82.52% at a discharge rate of 0.1C. The PCAC-1200 also demonstrates good cycle stability with 76.2% retention after 100 cycles. Besides, it still has a capacity of 101.2 mAh g<sup>-1</sup> at a high magnification of 5C. The anthracite hard carbon anode prepared by activation-surface modification strategy is believed to show good application prospects in the field of sodium-ion energy storage.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500054"},"PeriodicalIF":2.3,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143981181","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}
ChemphyschemPub Date : 2025-05-12DOI: 10.1002/cphc.202401089
Blagoj Achevski, Ljupcho Pejov
{"title":"Understanding the Infrared Multiple Photon Dissociation Spectra of Hydrogen-Tagged Protonated Betaine: Vibrational Confinement Counteracts the Hydrogen Bonding Induced OH Stretching Frequency Downshift.","authors":"Blagoj Achevski, Ljupcho Pejov","doi":"10.1002/cphc.202401089","DOIUrl":"10.1002/cphc.202401089","url":null,"abstract":"<p><p>Finite-temperature vibrational spectra of protonated betaine and its noncovalently bonded clusters with molecular hydrogen are modeled using Lagrangian dynamics with the atom-centered density matrix propagation (ADMP) scheme. The focus is put on the OH stretching mode, which serves as a primary indicator of the type and strength of the noncovalent intermolecular interactions. The computed anharmonic OH stretching vibrational frequency shifts in the case of protonated betaine upon tagging with H<sub>2</sub> at the OH group site at 40 K are in quantitative agreement with the experimental infrared multiple photon dissociation data. The shifts computed from simulations at 4 K contain only the harmonic contributions. It is found that this is a consequence of vibrational confinement of the OH oscillator caused by the H<sub>2</sub> tagger, which remains close to the vibrating atoms throughout the simulation and counteracts the frequency redshift induced by the weak hydrogen bonding interaction. Changes in the OH stretching potential, along with a small but observable confinement relaxation at 40 K leads to OH stretching frequency downshift as compared to 4 K. Application of the two-trace 2D correlation analysis of the computed vibrational density of states spectra enables a clear distinction between bands of different origin to be made.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2401089"},"PeriodicalIF":2.3,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143967032","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":"Planar Patterning Design and Energy Storage Performance Comparison of Laser-Induced Graphene Flexible Supercapacitors.","authors":"Qi Xiong, Jiaheng Xu, Huiting Li, Jianghai Li, Lin Li, Jinyu Wu, Xianqing Liang, Wenzheng Zhou, Peilin Qing, Zhiqiang Lan, Guangxu Li, Haifu Huang","doi":"10.1002/cphc.202500145","DOIUrl":"10.1002/cphc.202500145","url":null,"abstract":"<p><p>Laser-induced graphene (LIG) has gained significant attention due to its efficient and rapid production, and ability to create patterned electrodes. However, the operating voltage of LIG supercapacitor (LIG SC) unit devices is relatively low, and the different patterning LIG SC devices show different performances. Additionally, the size of the laser power also has a significant impact on the performance of the device. Herein, the energy storage performance of LIG SC devices in a variety of patterns and at different laser powers is investigated. The LIG SC device based on the interdigital pattern shows the best performance compared with the spiral pattern, mirror circular pattern, and concentric circular pattern LIG devices. When the laser power is 2.75 W, the area-specific capacitance of the interdigital LIG SCs is up to 10.78 mF cm<sup>-</sup> <sup>2</sup> at 0.2 mA cm<sup>-</sup> <sup>2</sup>, with a wide operating voltage (1.8 V) and a maximum energy density of 4.85 μWh cm<sup>-</sup> <sup>2</sup>. Additionally, it maintained 84.1% of its capacitance after 8000 charge-discharge cycles and achieved an area-specific capacitance of 8.33 mF cm<sup>-</sup> <sup>2</sup> when bent at an angle of 60°. This digital interpattern LIG device etched by a laser power of 2.75 W can provide important insights into the development of planar flexible supercapacitors.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500145"},"PeriodicalIF":2.3,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143983117","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 Structures of Substituted Adamantyl Esters and Ethers Using Rotational Spectroscopy and Computations.","authors":"Nataša Burić, Donatella Loru, Jasna Alić, Marina Šekutor, Melanie Schnell, Pablo Pinacho","doi":"10.1002/cphc.202500035","DOIUrl":"10.1002/cphc.202500035","url":null,"abstract":"<p><p>Adamantane derivatives are promising candidates in the design of new materials with unique properties. In this study, the molecular structure of a series of adamantyl esters and ethers with an increasing substituent size using broadband rotational spectroscopy is investigated. The experimental structure for three of the compounds using different methods to compare them with theoretical bond distances and angles is determined. The influence on oxygen functional group variation as well as the increasing size of the second alkyl substituent on the adopted gas-phase structure is assessed. This study advances previous work on similar systems to shine more light on the molecular features of adamantyl covalent assemblies with oxygen atoms.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500035"},"PeriodicalIF":2.3,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143983232","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}