Physical Chemistry Chemical Physics最新文献_第2页

Effect of Mg/Al doping at the Co site on the structural and electrochemical performance of LiCoO2 cathode materials Co位Mg/Al掺杂对LiCoO2正极材料结构和电化学性能的影响

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-08 DOI: 10.1039/d5cp00979k

Yubai Li, Zheng Wei, Sumei Wu, Yao Liang, Xiang Liu, Yang Wen, Weiwei Jiang, Tengfei Lu, Yan Cui, Zhihua Zhang

{"title":"Effect of Mg/Al doping at the Co site on the structural and electrochemical performance of LiCoO2 cathode materials","authors":"Yubai Li, Zheng Wei, Sumei Wu, Yao Liang, Xiang Liu, Yang Wen, Weiwei Jiang, Tengfei Lu, Yan Cui, Zhihua Zhang","doi":"10.1039/d5cp00979k","DOIUrl":"https://doi.org/10.1039/d5cp00979k","url":null,"abstract":"LiCoO2, which is one of the earliest commercially available cathode materials for lithium-ion batteries, continues to attract significant research interest owing to its favorable electrochemical properties. However, its practical application is hindered by challenges such as the low Li+ diffusion rate and structural instability during charge–discharge cycles. Al and Mg are the most common dopants used with transition metal-based layered oxides of cathode materials. In this work, Mg/Al was selected for Co site doping, and the influence of doping on the structural stability and electrochemical performance were investigated, with a special focus on lithium ion diffusion behavior. This study was based on the density functional theory and integrated electronic structure (DOS), bond length, migration energy barriers, diffusion coefficients and operating voltage into a unified framework, revealing the synergistic effects of Al/Mg doping. The findings revealed that both Mg and Al doping effectively enhanced the conductivity of LiCoO2. The calculated migration energy barriers of lithium ions along the b axis were reduced to 0.40 eV and 0.42 eV in the Mg- and Al-doped systems, respectively. This simultaneously increased the diffusion rate of Li+ and the operating voltage.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"50 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920450","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}

引用次数: 0

Efficient Fluorescence Emission from Protonated 1,3,4-Oxadiazole Derivatives with Meta Dimethylamino Substitution 间二甲氨基取代的1,3,4-恶二唑质子化衍生物的高效荧光发射

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-08 DOI: 10.1039/d4cp04635h

Yuhan Wang, Weitao Zheng, Binglian Bai, Jungang Cao, Jia-Rui Wu, Haitao Wang, Min Li

{"title":"Efficient Fluorescence Emission from Protonated 1,3,4-Oxadiazole Derivatives with Meta Dimethylamino Substitution","authors":"Yuhan Wang, Weitao Zheng, Binglian Bai, Jungang Cao, Jia-Rui Wu, Haitao Wang, Min Li","doi":"10.1039/d4cp04635h","DOIUrl":"https://doi.org/10.1039/d4cp04635h","url":null,"abstract":"pH-sensing materials are vital in fields such as healthcare, environmental monitoring, and industrial processes, due to their ability to detect and respond to changes in acidity and alkalinity. However, many proton-responsive luminescent materials suffer from fluorescence quenching after protonation, which limits their detection sensitivity. To address this challenge, we have designed and synthesized two donor-acceptor (D-A) type 1,3,4-oxadiazole derivatives (L-mDMAOXDBEN and B mDMAOXDBEN), and their fluorescence and proton-responsive properties were investigated using a combination of experimental techniques and theoretical calculations. Our results show that altering the substitution position of the dimethylamino group on the terminal benzene ring from para to meta significantly enhances intramolecular charge transfer (ICT) properties and leads to highly efficient fluorescence emission from the protonated molecules, with a remarkable quantum yield of 68%. Theoretical studies further reveal that this structural modification increases charge transfer over a slightly longer distance, enhancing ICT properties. Additionally, the widened energy gap between HOMO and LUMO and the strengthened oscillator strength contribute to the observed blue-shift in spectra and the high quantum efficiency. This research offers valuable insights into the relationship between molecular structure and fluorescence behavior, paving the way for the development of more sensitive and effective pH-sensing materials.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"35 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920453","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}

引用次数: 0

Research on the reaction mechanistic and molecular stacking of acid catalyzed naphthalene to prepare mesophase pitch 酸催化萘制备中间相沥青的反应机理及分子堆积研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-08 DOI: 10.1039/d5cp01024a

Xi Fan, Qiang Ren, Wenkai Wei

{"title":"Research on the reaction mechanistic and molecular stacking of acid catalyzed naphthalene to prepare mesophase pitch","authors":"Xi Fan, Qiang Ren, Wenkai Wei","doi":"10.1039/d5cp01024a","DOIUrl":"https://doi.org/10.1039/d5cp01024a","url":null,"abstract":"Mesophase pitch (MP) acts as a crucial precursor for the production of high-performance carbon materials. The initial step in MP generation involves the formation of planar condensed polycyclic aromatic hydrocarbon (PAH) macromolecules. This study unveils the catalytic reaction mechanistic giving the production of planar condensed PAH macromolecules through DFT theoretical calculations. Our research delineates that the generation of planar condensed PAH macromolecules entails five key reactions: protonation reaction (PRO), intermolecular electrophilic addition reaction (IEEA), intramolecular electrophilic addition reaction (IAEA), dehydrogenation reaction (DEH), and deprotonation reaction (DEP). The reaction pathway demands substantial energy input and the presence of strong acidic catalyst. Through molecular dynamics simulations, the study compares the stacking of product molecules with varying structures, affirming the role of intramolecular electrophilic addition reaction and dehydrogenation reaction in enhancing molecular planarity and facilitating their orderly arrangement. Molecular interactions are elucidated to unveil the mechanistic behind the formation of stacked graphite-like structures. The research findings not only offer a comprehensive explanation consistent with experimental observations but also mark a significant step in understanding the formation of MP, elucidating the ideal product structure, formation pathway, and the factors influencing orderly molecular stacking. This study, for the first time, comprehensively unveils the reaction mechanistic underpinning MP formation, shedding light on environmentally friendly catalyst development. It establishes crucial guidelines for MP preparation conditions and provides theoretical underpinnings for the production of enhanced-performance MP.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"48 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920455","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}

引用次数: 0

Design of donor-π-acceptor type cyclo[18]carbon derivatives for infrared nonlinear optical materials: A theoretical perspective 红外非线性光学材料中施主-π-受体型环[18]碳衍生物的设计：一个理论视角

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-08 DOI: 10.1039/d5cp00736d

Jingbo Xu, Jiaojiao Wang, Xiaohui Chen, Wenwen Zhao, Xiufen Yan, Zeyu Liu, Tian Lu, Aihua Yuan

{"title":"Design of donor-π-acceptor type cyclo[18]carbon derivatives for infrared nonlinear optical materials: A theoretical perspective","authors":"Jingbo Xu, Jiaojiao Wang, Xiaohui Chen, Wenwen Zhao, Xiufen Yan, Zeyu Liu, Tian Lu, Aihua Yuan","doi":"10.1039/d5cp00736d","DOIUrl":"https://doi.org/10.1039/d5cp00736d","url":null,"abstract":"The geometries, electronic structures, photophysical properties, and optical nonlinearities of four cyclo[18]carbon (C18) derivatives containing hydrogen (-H), amino (-NH2) and/or nitro (-NO2) groups were theoretically explored. The carbon-atom skeleton of molecules with different functional groups do not differ obviously, but their electronic properties are noticeably different. Electronic excitation analysis shows that with the introduction of -NH2 and/or -NO2 groups, the maximum wavelength absorption of derivatives red-shifts slightly, the absorption intensity increases gradually, and the difference in dipole moment between the ground state and the crucial excited state increase sharply, indicating that their first hyperpolarizability increases continuously. The four molecules all have an excellent infrared (IR) transparency in the wavelength range of 800 to 4000 nm. The essence of electronic transition in derivatives mainly concentrated on C18 unit and greater charge separation in NH2-C18-NO2 were elucidated through the charge-transfer spectrum (CTS) analysis, hole-electron analysis, and electrostatic potential (ESP) analysis. Derivative molecules with different combinations of functional groups exhibit markedly different response properties, and the first hyperpolarizability reaches the maximum when -NH2 and -NO2 are introduced simultaneously to form NH2-C18-NO2. The anisotropy and origin of the first hyperpolarizability of four C18 derivatives are revealed by analyzing hyperpolarizability tensor, hyperpolarizability density, and hyperpolarizability decomposition. The comprehensive analysis indicated that donor-π-acceptor (D-π-A) type NH2-C18-NO2 can be considered as potential candidates for novel IR nonlinear optical (NLO) materials.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"119 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920456","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}

引用次数: 0

Understanding the Carbonization-Controlled Microstructure Regulation in Coal-Based Hard Carbon for Strengthen Sodium Storage Performance 炭基硬碳强化储钠性能的碳化控制微观结构调控研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-08 DOI: 10.1039/d5cp00568j

Yu Zhao, Ruyi Zhang, Jian Hao, Xiao Yang, Jianing Chen, Junli Guo, Caixia Chi

{"title":"Understanding the Carbonization-Controlled Microstructure Regulation in Coal-Based Hard Carbon for Strengthen Sodium Storage Performance","authors":"Yu Zhao, Ruyi Zhang, Jian Hao, Xiao Yang, Jianing Chen, Junli Guo, Caixia Chi","doi":"10.1039/d5cp00568j","DOIUrl":"https://doi.org/10.1039/d5cp00568j","url":null,"abstract":"Hard carbon materials have emerged as one of the promising anode materials for sodium-ion batteries (SIBs) due to their abundant resource, low cost, and tunable pore structures. However, the relationship between preparation conditions, material structure, and electrochemical performance remains unclear. In this study, coal-based hard carbon was synthesized via a one-step carbonization method. By characterizing the structure of hard carbons derived from different carbonization temperatures and analyzing their electrochemical performance, we have established the correlation between carbonization temperature, graphite microcrystal structure, and sodium storage behavior. The as-prepared sample at the carbonization temperature of 900 oC showed abundant graphite microcrystal with layer spacing of 0.383 nm, and C=O surface functional groups. It showed a high reversible capacity of 277.7 mAh g-1, a long plateau discharge capacity of 111.76 mAh g-1, and an excellent rate capacity retention of 76% at 1 A g−1. This work offers guidance for production of coal-based hard carbon materials, and provides the possibility of high energy density SIBs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"25 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920347","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}

引用次数: 0

Constructing heterophase structures of α-Cu2V2O7/β-Cu2V2O7 to enhance photovoltaic and photocatalytic properties 构建α-Cu2V2O7/β-Cu2V2O7异相结构，提高其光伏和光催化性能

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-07 DOI: 10.1039/d5cp00244c

Yong Hu, Xiansheng Liu, Jianjun Tian, Chaoyang Kang, Feng Zhang, Erjun Liang, Weifeng Zhang

引用次数: 0

Identifying Key Descriptors in ZrSe2/HfSe2-based Heterostructure and Superlattice for Enhancing Thermoelectric Performance ZrSe2/ hfse2基异质结构和超晶格中关键描述子的识别及热电性能的提高

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-07 DOI: 10.1039/d4cp04837g

Tanu Choudhary, Satarupa Banik, P. M. Jipin, Raju Kumar Biswas

{"title":"Identifying Key Descriptors in ZrSe2/HfSe2-based Heterostructure and Superlattice for Enhancing Thermoelectric Performance","authors":"Tanu Choudhary, Satarupa Banik, P. M. Jipin, Raju Kumar Biswas","doi":"10.1039/d4cp04837g","DOIUrl":"https://doi.org/10.1039/d4cp04837g","url":null,"abstract":"Engineering heterostructure (HS) and superlattice monolayer (SLM) with trigonal symmetry not only provide versatile platforms for exploring material chemistry, it also furnish avenues to thoroughly examine carrier transport mechanisms in achieving high-performance thermoelectric materials. In this context, our study encompasses a comprehensive understanding on structural stability and, especially, the role of interface coupling resulting in thermal transport and thermoelectric properties of ZrSe2/HfSe2 in HS and SLM form. Here, we apply different approaches such as Debye-Callaway, Slack, relaxation time approximation (RTA), iterative methodology to obtain phonon transport coefficients and critically analyse the suitability of these approaches in computing lattice thermal conductivity for HS and SLM. The thermal properties study revealing the appearance of soft optical mode at zone-centre in HS, plays a driving role in controlling the phonon transport by enhancing the three phonon scattering rates especially prominent AAO and AOO scattering processes, while the scattering mechanism is completely non-identical in SLM. Other side, the SLM structure depicts staircase-like two-dimensional (2D) density of states, particularly beneficial to enhance electronic transport and exhibits competitive thermoelectric performance. We also carefully recognise useful descriptors such as phonon group velocity, scattering rates, Grüneisen parameters, phase-space volume, that identify HS and SLM. Overall, our work demonstrates new insights into the materials chemistry perspectives involved in phonon and electronic transport phenomenon for HS & SLM and provides also a broad aspect on interface coupling in assessing carrier transport properties in the field of thermoelectricity.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"25 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915478","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}

引用次数: 0

Two-Step Insertion/Release of Electrolytic Cations in Redox-Active Hydrogen-Bonding Nanoporous Coordination Crystals 氧化还原活性氢键纳米孔配位晶体中电解阳离子的两步插入/释放

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-07 DOI: 10.1039/d5cp01130b

Makoto Tadokoro, Ryota Nishimura, Hajime Kamebuchi, Fumiya Kobayashi, Jun Miyazaki, Masa-aki Haga

引用次数: 0

Alterations in vibrational spectra of adsorbed water in MIL-101(Cr) and functionalized MIL-101(Cr) using molecular simulations 分子模拟MIL-101（Cr）和功能化MIL-101（Cr）中吸附水的振动谱变化

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-07 DOI: 10.1039/d5cp00878f

Gunjan Auti, Hao Jiang, Jean-Jacques Delaunay, Hirofumi Daiguji

{"title":"Alterations in vibrational spectra of adsorbed water in MIL-101(Cr) and functionalized MIL-101(Cr) using molecular simulations","authors":"Gunjan Auti, Hao Jiang, Jean-Jacques Delaunay, Hirofumi Daiguji","doi":"10.1039/d5cp00878f","DOIUrl":"https://doi.org/10.1039/d5cp00878f","url":null,"abstract":"The vibrational dynamics of adsorbed water, as reflected in its vibrational density of states (VDOS) spectra, differ significantly from those of bulk water. This study employs molecular simulations to explore these modifications in water confined within MIL-101(Cr) and its sulfonic acid-functionalized derivative, MIL-101-SO3H(Cr). Various water models are tested, with systematic adjustments made to identify the one that best replicates the experimental infrared (IR) spectrum. The optimized model is then used to analyze the vibrational properties of adsorbed water. Normal mode analysis (NMA) decomposes the vibrational signal into the underlying normal modes of water molecules, allowing for a detailed examination of water adsorbed at specific framework sites. At low pressures, water molecules preferentially bind to high-affinity sites, such as the unsaturated Cr centers in MIL-101(Cr) and the sulfonic acid hydroxyl (-OH) groups in MIL-101-SO3H(Cr), exhibiting distinct asymmetric stretching modes compared to bulk water. However, as water uptake increases at higher pressures, the VDOS spectra of adsorbed and bulk water begin to converge, signaling the onset of capillary condensation.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"25 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915475","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}

引用次数: 0

Quantum Control of Photoion Circular Dichroism Using Orthogonal Laser Beams 正交激光束对光子圆二色性的量子控制

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-07 DOI: 10.1039/d5cp01127b

Jason Blair Greenwood, Leah Donnelly

{"title":"Quantum Control of Photoion Circular Dichroism Using Orthogonal Laser Beams","authors":"Jason Blair Greenwood, Leah Donnelly","doi":"10.1039/d5cp01127b","DOIUrl":"https://doi.org/10.1039/d5cp01127b","url":null,"abstract":"The circular dichroism manifested in the photoionization yields of the chiral molecule fenchone has been investigated using two laser beams of different wavelengths intersecting at 90 degrees. This allowed different two-colour ionization schemes to be investigated so that the circular dichroism contributions of each step in the multiphoton ionization process could be deduced. The results showed that the circular dichroism generated by a beam at a wavelength of 260 nm could be strongly influenced by the polarization state of a 520 nm beam propagating in a perpendicular direction. The asymmetry in the ion yields was found to change depending on whether the 520 nm beam was left or right circularly polarized, and if it was linear polarized in a direction parallel or perpendicular to the propagation direction of the 260 nm beam. The control exhibited by the direction of the linearly polarized light is attributed to an orientation dependence of the circular dichroism due to selective excitation of the isotropic ensemble by the 520 nm beam. By contrast, when both beams were circularly polarized, the dependence on the polarization direction of the 520 nm pulse is ascribed to either the interference between different ionization pathways or excitation of a chiral vibronic wavepacket in the molecule. These results are the first demonstration of chiroptical quantum control of total ion yields, showing in principle that all-optical enantio-sensitive chemical processing may be possible in the future.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"279 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915625","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}

引用次数: 0