Physical Chemistry Chemical Physics最新文献_第8页

Uniaxial Tensile Strain Impact on 1T-NbS2 Monolayers as Cathode Material for Lithium-Sulfur Batteries 单轴拉伸应变对作为锂硫电池阴极材料的 1T-NbS2 单层的影响

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2024-11-12 DOI: 10.1039/d4cp03156c

Shanling Ren, Xiaocong Tan, Xin Huang, zhihong yang, Yunhui Wang

In this work, we report our study on asymmetrical Janus TiSSe monolayers as cathode materials for lithium-sulfur batteries by first-principles calculations, encompassing adsorption, catalytic, and conductive properties. The results indicate that all Lithium Polysulfides (LiPSs) are adsorbed onto the S/Se surface of the TiSSe monolayer with a moderate adsorption energy, effectively suppressing the shuttle effect. The bond formation process were investigated by charge transfer, physical/chemical adsorption and projected crystal orbital Hamiltonian population (pCOHP), which confirmed its occurrence in the early lithiation stage. The Gibbs free energies for the reduction reaction of sulfur on the S/Se surface demonstrate a significant enhancement in the transformation kinetics. Additionally, the low decomposition and diffusion energy barriers for lithium atoms on the S/Se surface of TiSSe monolayer indicate its catalytic potential in facilitating sulfur redox transformation. Furthermore, the TiSSe monolayer exhibits metallic properties prior to and after polysulfide absorption, thereby enhancing electron transport capacity in Li-S batteries. The adsorption, diffusion, and reaction kinetics of TiSSe demonstrate superior performance compared to TiS2 and TiSe2. Therefore, the Janus TiSSe monolayer presents a novel perspective for the selection of battery adsorption materials as a high-performance positive cathode material in Lithium-sulfur batteries.

在这项研究中，我们通过第一性原理计算，对不对称 Janus TiSSe 单层作为锂硫电池阴极材料的吸附、催化和导电特性进行了研究。结果表明，所有多硫化锂（LiPSs）都以适中的吸附能吸附在 TiSSe 单层的 S/Se 表面，有效抑制了穿梭效应。通过电荷转移、物理/化学吸附和投影晶体轨道哈密顿群（pCOHP）对键的形成过程进行了研究，证实其发生在早期锂化阶段。硫在 S/Se 表面发生还原反应的吉布斯自由能表明，转化动力学显著增强。此外，TiSSe 单层 S/Se 表面锂原子的分解和扩散能垒较低，这表明它在促进硫氧化还原转化方面具有催化潜力。此外，TiSSe 单层在吸收多硫化物之前和之后都表现出金属特性，从而提高了锂-S 电池的电子传输能力。与 TiS2 和 TiSe2 相比，TiSSe 的吸附、扩散和反应动力学表现出更优越的性能。因此，Janus TiSSe 单层为选择电池吸附材料作为锂硫电池的高性能正极材料提供了一个新的视角。

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引用次数: 0

Magnetic field enhanced discharge and water activation of atmospheric pressure plasma jet: effect of assistance region and underlying physico-chemical mechanism 大气压等离子体射流的磁场增强放电和水活化：辅助区域的影响和潜在的物理化学机制

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2024-11-12 DOI: 10.1039/d4cp03938f

Xiongfeng Zhou, Bin Chen, Hua Liao, Kun Liu

Magnetic field-assistance holds the promise of becoming a new or complementary approach to enhance the efficiency of atmospheric pressure plasma jet (APPJ), but there is currently a lack of research on the effect of the assistance region between magnetic field and plasma on application of APPJ. Herein, using a 130 mT perpendicular magnetic field to assist APPJ in treating deionized water to prepare plasma activated water (PAW) as a model, we studied the effect of magnetic field-assisted region on the performance of PAW produced by APPJ, and found that introducing a magnetic field could always enhance the performance of the prepared PAW with higher concentrations of H₂O₂, NO₃^-, and NO₂^- and lower concentrations of O₃ and lower pH values, but this enhancement effect was related to the magnetic field-assisted region relative to the APPJ, where the optimized PAW performance was achieved when the magnetic field did not act on the jet tube wall (only assisting plasma plume). To reveal the underlying physico-chemical mechanism behind the differences in the enhanced performance of PAW under different magnetic field-assisted regions, a plasma reaction network involving physical parameters and chemical products was considered. The results showed that the magnetic field-assisted region modulated the equilibrium between the confinement effect and the recombination loss of magnetized electrons, and subsequently altered the reactive species in PAW via plasma reaction network mediated by electron density n_e and electron excitation temperature T_exc which without remarkable changing the discharge intensity, discharge power, plasma plume, and gas temperature T_gas. These insights contribute to understanding the mechanism of magnetic field-assisted region effect on APPJ which provide guidance for optimizing discharge activity and promote the development of applications.

磁场辅助有望成为提高常压等离子体射流（APPJ）效率的一种新方法或补充方法，但目前对磁场和等离子体之间的辅助区域对APPJ应用的影响还缺乏研究。在此，我们以 130 mT 垂直磁场辅助 APPJ 处理去离子水制备等离子活化水（PAW）为模型，研究了磁场辅助区域对 APPJ 制备的 PAW 性能的影响，发现引入磁场始终能提高制备的 PAW 的性能，在 H2O2、但这种增强效果与磁场辅助区有关，而不是 APPJ 区，在 APPJ 区，当磁场不作用于喷射管壁时（仅辅助等离子体羽流），PAW 性能达到最佳。为了揭示不同磁场辅助区域下 PAW 性能增强差异背后的物理化学机制，研究人员考虑了涉及物理参数和化学产物的等离子体反应网络。结果表明，磁场辅助区域调节了禁锢效应和磁化电子重组损耗之间的平衡，并在不显著改变放电强度、放电功率、等离子体羽流和气体温度Tgas的情况下，通过电子密度ne和电子激发温度Texc介导的等离子体反应网络改变了PAW中的活性物种。这些见解有助于理解磁场辅助区域效应对 APPJ 的影响机制，从而为优化放电活动和促进应用开发提供指导。

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引用次数: 0

Annealing approach to form a nanotube from graphdiyne ribbon: A theoretical prediction 从石墨二乙烯带形成纳米管的退火方法：理论预测

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2024-11-12 DOI: 10.1039/d4cp03573a

Bo Song, Kun Cai, Jiao Shi, Qinghua Qin

A precisely controllable heat treatment process is critical for nanofabrication. We developed a two-step method to fabricate a graphdiyne nanotube (GNT) through heat treatment in an argon environment. Initially, we placed a carbon nanotube (CNT) near a rectangular graphdiyne nanoribbon (GNR) to trigger the self-scrolling of the ribbon. Once the ribbon forms a scroll, we increased the ambient temperature to induce the formation of interlayer covalent C-C bonds within the scroll, ultimately resulting in a GNT after system annealing. The self-scrolling process of the GNR, protected by argon gas, is highly sensitive to ambient temperature. Molecular dynamics simulations show that self-scrolling can be controlled by adjusting the gas density and/or ambient temperature. In summary, a controlled heating process starting from an ultralow temperature initiates the self-scrolling of a GNR onto a CNT, followed by the generation of covalent bonds within the GNR at higher temperatures. Since the new covalent bond topology remains stable even after cooling, a stable GNT is obtained. The size of the pores on the GNT shell depends on the number of newly formed bonds. These insights will enhance the fabrication and application of GNTs as nanofilters.

精确可控的热处理过程对于纳米制造至关重要。我们开发了一种在氩气环境中通过热处理制造石墨二炔纳米管（GNT）的两步法。首先，我们将一根碳纳米管（CNT）放置在矩形石墨二炔纳米带（GNR）附近，以引发纳米带的自卷曲。一旦碳带形成卷轴，我们就提高环境温度，促使卷轴内形成层间共价 C-C 键，最终在系统退火后形成 GNT。在氩气的保护下，GNR 的自卷轴过程对环境温度高度敏感。分子动力学模拟显示，自卷积可通过调节气体密度和/或环境温度来控制。总之，从超低温开始的受控加热过程启动了 GNR 在 CNT 上的自卷积，随后在较高温度下在 GNR 内部生成共价键。由于新的共价键拓扑结构在冷却后仍然保持稳定，因此获得了稳定的 GNT。GNT 外壳上孔隙的大小取决于新形成键的数量。这些见解将有助于制造和应用 GNT 作为纳米过滤器。

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引用次数: 0

Correlating Negative Thermal Expansion and Thermal Conductivity in Two-dimensional Carbon-based Materials 二维碳基材料的负热膨胀与热传导相关性

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2024-11-12 DOI: 10.1039/d4cp03776f

Soumya Mondal, Ayan Datta

Negative thermal expansion (NTE) is a fascinating phenomenon where certain materials contract upon heating. The phonon transport properties of two-dimensional carbon-based allotropes are poorly understood in terms of their NTE properties. This work with a specific focus on carbon-based allotropes, explores the underlying mechanisms of the thermal conductivity (TC) and NTE of graphene, haeckelite, pentahexoctite, s-graphene, 6.6.12 and delta Graphynes (Gys). High TC is imperative for efficiently dissipating heat in electronic devices, whereas thermoelectric devices need to be thermally resistive with low TC. Delta-Gy shows highest NTE as well as lowest TC and vice versa is true for graphene. Graphene displays a lower degree of anisotropic TC, while s-graphene exhibits the highest level of anisotropic TC. The behaviour of their TC are understood on the basis of soft-phonon modes, phonon group velocity (vg), phonon lifetime (τ) and mean free path (MFP). The acoustic and optical phonon branches play a key role in determining both TC and NTE of the materials. Out-of-plane buckling of a two-dimensional materials can suppress heat conductivity by increasing the phonon scattering. Buckling is also shown to increase the NTE. A precise control on the pore sizes 5-7 (Haeckelite), 5-6-8 (Pentahexoctite), and 4-8 (s-graphene), 6-12-14 (6.6.12-Gy) and 6-14 (delta-Gy) can make a big impact on their soft unit modes. This investigation not only deepens our understanding of NTE and TC but also highlights the potential of future applications of carbon-based materials with controlled thermal expansion properties in nanotechnology, composites, and beyond.

负热膨胀（NTE）是一种令人着迷的现象，某些材料在加热时会收缩。人们对二维碳基同素异形体的声子传输特性及其负热膨胀特性知之甚少。这项研究特别关注碳基同素异形体，探讨了石墨烯、海泡石、五六方石墨、s-石墨烯、6.6.12 和 delta 石墨（Gys）的热导率（TC）和 NTE 的基本机制。电子设备要有效散热，就必须要有高 TC，而热电设备则需要低 TC 的热阻。δ-Gy显示出最高的NTE和最低的TC，反之亦然。石墨烯的各向异性热电系数较低，而 s 石墨烯的各向异性热电系数最高。我们可以根据软声子模式、声子群速度（vg）、声子寿命（τ）和平均自由路径（MFP）来理解它们的各向同性。声学和光学声子分支在决定材料的 TC 和 NTE 方面起着关键作用。二维材料的平面外屈曲可以通过增加声子散射来抑制热传导。降伏还能增加 NTE。精确控制孔隙尺寸 5-7（海克力石）、5-6-8（五六八石）、4-8（s-石墨烯）、6-12-14（6.6.12-Gy）和 6-14（delta-Gy）可对其软单元模式产生重大影响。这项研究不仅加深了我们对 NTE 和 TC 的理解，还凸显了具有可控热膨胀特性的碳基材料未来在纳米技术、复合材料等领域的应用潜力。

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引用次数: 0

A composite of pineapple leaf-derived porous carbon integrated with ZnCo-MOF for high-performance supercapacitors† 用于高性能超级电容器的菠萝叶多孔碳与 ZnCo-MOF 集成复合材料

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2024-11-12 DOI: 10.1039/D4CP02882A

Xiaoxiao Ma, Yunfan Bai, Shuangli Chen, Zhixian He, Pingping Wu, Yabing Qi and Sijing Zhang

Electrochemical energy storage heavily depends on the activity and stability of electrode materials. However, the direct use of metal–organic frameworks (MOFs) as supercapacitor electrode materials poses challenges due to their low electrical conductivity. In this study, pineapple leaf-derived biochar (PLB) was employed as a carrier for bimetallic ZnCo-MOF, resulting in the composite ZnCo-MOF@PLB-800, synthesized through in situ growth and pyrolysis at 800 °C. The highly porous structure of PLB alleviated the aggregation of ZnCo-MOF particles, thereby enhancing the electron transfer rate and improving the conductivity of the electrode material. Electrochemical testing revealed that ZnCo-MOF@PLB-800 achieved a specific capacitance of 698.5 F g⁻¹ at a current density of 1 A g⁻¹. The assembled asymmetric supercapacitor (ASC) demonstrated excellent specific capacitance and electrochemical stability, delivering a high energy density of 35.85 W h kg⁻¹ at a power density of 350 W kg⁻¹, with robust cycle stability, retaining 90.4% capacitance after 8000 cycles. This work offers an effective integration of bimetallic MOFs with waste biomass-derived porous carbon for electrode materials, supporting both energy storage applications and environmental sustainability.

电化学储能在很大程度上取决于电极材料的活性和稳定性。然而，由于金属有机框架（MOFs）的导电性较低，将其直接用作超级电容器电极材料面临着挑战。本研究采用菠萝叶衍生生物炭（PLB）作为双金属 ZnCo-MOF 的载体，通过 800 °C 原位生长和热解合成了复合 ZnCo-MOF@PLB-800。PLB 的高多孔结构缓解了 ZnCo-MOF 颗粒的聚集，从而提高了电子转移率，改善了电极材料的导电性。电化学测试表明，在电流密度为 1 A g-1 时，ZnCo-MOF@PLB-800 的比电容为 698.5 F g-1。组装后的非对称超级电容器（ASC）表现出了优异的比电容和电化学稳定性，在功率密度为 350 W kg-1 时可提供 35.85 W h kg-1 的高能量密度，并具有强大的循环稳定性，在循环 8000 次后仍能保持 90.4% 的电容。这项研究将双金属 MOFs 与废弃生物质多孔碳有效地整合在电极材料中，既支持了储能应用，又实现了环境的可持续发展。

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引用次数: 0

Extraction mechanism of phenolic compounds by deep eutectic solvents: DFT and molecular dynamics studies 深共晶溶剂萃取酚类化合物的机理：DFT 和分子动力学研究

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2024-11-12 DOI: 10.1039/d4cp03453h

Lan Yi, Jinwen Wang, Jixing Liu, Hao Luo, Xiaoqin Wu, Wen-Ying Li

The mechanism of a deep eutectic solvent consisting of choline chloride and glycerol (ChCl/GLY) for extracting phenolic compounds from coal tar was theoretically studied using density functional theory and molecular dynamics methods. The thermodynamic properties, interaction essence, and molecular dynamics behavior of the extraction system were investigated, as well as the influence of ChCl/GLY on the vibration spectra of phenolic compounds. The results show that the solvation free energy of phenolic compounds in ChCl/GLY is more negative than that in coal tar, leading to the spontaneous transfer of phenolic compounds from coal tar to ChCl/GLY. The electrostatic and dispersion interactions between phenolic compounds and ChCl/GLY have similar significance in the extraction process, with interaction energies ranging from -46 to -53 kJ/mol. The mixing of phenolic compounds with ChCl/GLY has minimal impact on their internal molecular structure, however, it does reduce the diffusion coefficients of each component in ChCl/GLY and shortens the lifetime of hydrogen bonds in both phenolic compounds and ChCl/GLY. The first shell of each phenolic compound is surrounded by 1.15 chloride ions. Following dissolving in ChCl/GLY, the stretching vibration peaks of phenolic compounds, namely the -OH and C-H/-CH3 regions, undergo a shift. The results enhance comprehension of the extraction process of phenolic compounds by DES.

采用密度泛函理论和分子动力学方法对氯化胆碱和甘油组成的深共晶溶剂（ChCl/GLY）从煤焦油中萃取酚类化合物的机理进行了理论研究。研究了萃取体系的热力学性质、相互作用本质和分子动力学行为，以及 ChCl/GLY 对酚类化合物振动光谱的影响。结果表明，酚类化合物在 ChCl/GLY 中的溶解自由能比在煤焦油中的溶解自由能更负，导致酚类化合物自发地从煤焦油转移到 ChCl/GLY 中。酚类化合物与 ChCl/GLY 之间的静电作用和分散作用在萃取过程中具有相似的意义，其作用能在 -46 至 -53 kJ/mol 之间。酚类化合物与 ChCl/GLY 的混合对其内部分子结构的影响微乎其微，但却降低了每种成分在 ChCl/GLY 中的扩散系数，缩短了酚类化合物和 ChCl/GLY 中氢键的寿命。每种酚类化合物的第一层外壳都被 1.15 个氯离子包围。在 ChCl/GLY 中溶解后，酚类化合物的伸缩振动峰（即 -OH 和 C-H/-CH3 区域）发生了移动。这些结果加深了人们对 DES 萃取酚类化合物过程的理解。

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引用次数: 0

B92: a complete coating icosahedral B12 core-shell structure B92：完整的涂层二十面体 B12 核壳结构

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2024-11-12 DOI: 10.1039/d4cp03471f

Yi-Sha Chen, Jing-Jing Guo, Peng-Bo Liu, Hui-Yan Zhao, Jing Wang, Ying Liu

Using first-principles calculations, this study unveils a spherically aromatic core-shell B₁₂@B₈₀ structure featuring a B₁₂ icosahedral core, which is the minimum complete coating icosahedral B₁₂ core-shell B_n cluster to date. Detailed orbital and bonding analyses reveal the icosahedral B₁₂ core exhibits prominent superatomic behavior with the electronic configuration of 1S²1P⁶1D¹⁰1F⁸.

通过第一原理计算，本研究揭示了以 B12 二十面体核为特征的球形芳香核壳 B12@B80 结构，这是迄今为止涂层最完整的二十面体 B12 核壳 Bn 簇。详细的轨道和成键分析表明，二十面体 B12 内核具有突出的超原子行为，其电子构型为 1S21P61D101F8。

引用次数: 0

Identifying Winner-Takes-All Emergence in Random Nanowire Networks: an Inverse Problem 识别随机纳米线网络中的 "赢家通吃 "现象：一个逆问题

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2024-11-12 DOI: 10.1039/d4cp03242j

Fábio Rangel Duarte, shardul mukim, Mauro Ferreira, Claudia Gomes da Rocha

Random nanowire networks (NWNs) are interconnects that enable the integration of nanoscopic building blocks (the nanowires) in a disorganized fashion, enabling the study of complex emergent phenomena in nanomaterials and built-in fault-tolerant processing functionalities; the latter can lead to advances in large-scale electronic devices that can be fabricated with no particular array/grid high-precision pattern. However, when various nanowires are assembled to form an intricate network, their individual features are somehow lost in the complex NWN frame, in line with the complexity hallmark “the whole diﬀers from the sum of the parts”. Individual nanowire materials and geometrical features can only be inferred indirectly by attempting to extract information about their initial conditions from a response function measurement. In this work, we present a mathematical framework that enables inference of the intrinsic properties of highly complex/intricate systems such as random NWNs in which information about their individual parts cannot be easily accessed due to their network formation and dynamical conductance behaviour falling in the category of memristive systems. Our method, named misﬁt minimization, is rooted in nonlinear regression supervised learning approaches in which we ﬁnd the optimum parameters that minimize a cost function deﬁned as the square least error between conductance evolution curves taken for a target NWN system and multiple conﬁgurational NWN samples composing the training set. The optimized parameters are features referent to the target NWN system’s initial conditions obtained in an inverse fashion: from the response output function, we extract information about the target system’s initial conditions. Accessing the nanowire individual features in a NWN frame, as our methodology allows, enables us to predict the conduction mechanisms of the NWN subjected to a current input source; these can be via a “winner takes all” energy-eﬃcient scheme using a single conduction pathway composed of multiple nanowires connected in series or via multiple parallel conduction pathways. Predicting the conduction mechanism of complex and dynamical systems such as memristive NWNs is critical for their use in next-generation memory and brain-inspired technologies since their memory capability relies on the creation of such pathways activated and consolidated by the input current signal.

随机纳米线网络（NWN）是一种能够将纳米构件（纳米线）以无序的方式集成在一起的互连器件，可用于研究纳米材料中的复杂突发现象，并具有内置容错处理功能；后者可推动大规模电子器件的发展，这些器件可在没有特定阵列/网格高精度模式的情况下制造。然而，当各种纳米线组装成错综复杂的网络时，它们各自的特征会在复杂的纳米线网络框架中消失，这符合 "整体与部分之和不同 "的复杂性特征。只有尝试从响应函数测量中提取有关其初始条件的信息，才能间接推断出单个纳米线材料和几何特征。在这项工作中，我们提出了一个数学框架，可以推断随机纳米线等高度复杂/错综复杂系统的内在特性，由于它们的网络形成和动态传导行为属于记忆系统的范畴，因此不容易获取其单个部分的信息。我们的方法被命名为误差最小化，它植根于非线性回归监督学习方法，在这种方法中，我们找到最优参数，使成本函数最小化，该成本函数被定义为目标 NWN 系统的电导演化曲线与构成训练集的多个概括性 NWN 样本之间的平方最小误差。优化参数是以反向方式获得的与目标 NWN 系统初始条件相关的特征：我们从响应输出函数中提取目标系统初始条件的信息。在我们的方法论允许的情况下，通过访问氮化网络框架中的纳米线单个特征，我们可以预测氮化网络在电流输入源作用下的传导机制；这些机制可以是通过 "赢家通吃 "的节能方案，使用由多个串联纳米线组成的单个传导通路，也可以是通过多个并联传导通路。预测复杂动态系统（如记忆性 NWN）的传导机制对于它们在下一代记忆和脑启发技术中的应用至关重要，因为它们的记忆能力依赖于创建由输入电流信号激活和巩固的此类通路。

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引用次数: 0

Structure and dynamics of aqueous VOSO4 solutions in conventional flow through cell design: a molecular dynamics simulation study† 传统流动池设计中 VOSO4 水溶液的结构和动力学：分子动力学模拟研究

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2024-11-12 DOI: 10.1039/D4CP02934H

Anwesa Karmakar

A theoretical model has been proposed to study the structure and dynamics of aqueous vanadyl sulfate (VOSO₄) solution used in the conventional flow (CF) through cell design operating under varying thermodynamic conditions. Classical molecular dynamics simulations have been carried out for aqueous solutions of vanadyl sulfate (VOSO₄) and sulfuric acid (H₂SO₄) at two different concentrations and temperatures considering the temperature dependent degree of dissociation of sulfuric acid. The MD trajectories are used to study the equilibrium structural, dynamical properties such as viscosity, diffusivity and surface tension of the aqueous solution of vanadyl sulfate (VOSO₄). According to the new model, the cation–cation and cation–anion interaction should be low in order to have a good current density in the conventional flow through cell design and further explains the importance of considering mass transport when designing high energy density redox flow batteries. The model is further validated by calculating the viscosity of each system, individual diffusion coefficient of each ion and by comparing them with the experimental data wherever they are available.

我们提出了一个理论模型，用于研究在不同热力学条件下运行的传统流动（CF）直通电池设计中使用的硫酸钒水溶液（VOSO4）的结构和动力学。考虑到硫酸的解离程度与温度有关，我们对两种不同浓度和温度下的硫酸钒（VOSO4）和硫酸（H2SO4）水溶液进行了经典分子动力学模拟。利用 MD 轨迹研究了硫酸钒水溶液（VOSO4）的平衡结构和动力学特性，如粘度、扩散性和表面张力。根据新模型，阳离子与阳离子和阳离子与阴离子之间的相互作用应该较低，以便在传统的流过式电池设计中获得良好的电流密度，并进一步解释了在设计高能量密度氧化还原液流电池时考虑质量传输的重要性。通过计算每个系统的粘度和每个离子的扩散系数，并将其与现有的实验数据进行比较，进一步验证了该模型。

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引用次数: 0

The local atomic distribution in tetragonal PZT 四方 PZT 中的局部原子分布

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2024-11-11 DOI: 10.1039/d4cp03354j

Jun-Yu Niu, zengzhe Xi, Chong Li

Expanding on the comprehensive research conducted by previous scholars. Herein, to elucidate the intrinsic piezoelectricity of tetragonal Pb(Zr1-xTix)O3 (PZT), we focus on the local atomic distribution which was neglected for a long time, through the supercell approach based on colour symmetry. Density functional theory (DFT) was employed to perform first-principles calculations on the electronic, phononic structures and piezoelectricity, of various tetragonal PZT supercells. Building upon the evaluation of piezoelectric properties of 22 distinct distributions, classical Monte Carlo methods were utilized to explore the statistical macroscopic properties at the morphotropic phase boundary (MPB). The results reveal that at x=0.5 and x=0.55, the d33 reached 957pm/V and 893pm/V, respectively. The analysis of phonon vibration modes exposed significant disparity between different colour symmetries. The supercells of lower symmetry contain B-site atoms in asymmetric positions, and they exhibit softer vibrational frequencies in phonon spectrum. This soft phonon vibration modes resulting from colour symmetry breaking are unprecedented. The weakening and reorientation of the covalent bonds between O2p and d orbit was found in electronic structures. The free energy flattening in the polarization rotation path is the origin of the high piezoelectricity of this type of supercell. The analysis of the electronic structure is consistent with the experimental observations. Finally, colour symmetry proved to be an effective and accurate way to describe the local atomic distribution in supercells. It will also bring new perspectives to understanding the structure of domain walls and phase boundaries etc.

在前辈学者的综合研究基础上。在此，为了阐明四方 Pb（Zr1-xTix）O3（PZT）的内在压电性，我们通过基于颜色对称的超胞方法，重点研究了长期以来被忽视的局部原子分布。我们采用密度泛函理论（DFT）对各种四方 PZT 超电池的电子、声波结构和压电性进行了第一原理计算。在对 22 种不同分布的压电特性进行评估的基础上，利用经典蒙特卡罗方法探索了形态相边界 (MPB) 的宏观统计特性。结果显示，在 x=0.5 和 x=0.55 时，d33 分别达到 957pm/V 和 893pm/V。声子振动模式的分析表明，不同颜色对称性之间存在显著差异。对称性较低的超级晶胞含有位置不对称的 B 位原子，在声子谱中表现出较软的振动频率。这种因颜色对称性破坏而产生的软声子振动模式是前所未有的。在电子结构中发现了 O2p 和 d 轨道之间共价键的减弱和重新定向。极化旋转路径上的自由能扁平化是这类超级电池具有高压电性的原因。电子结构分析与实验观察结果一致。最后，颜色对称被证明是描述超级电池中局部原子分布的一种有效而准确的方法。它还将为理解畴壁和相界等结构带来新的视角。

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引用次数: 0