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α-Cobalt Hydroxides as 2D Magnets: Tuning Magnetism through Exchange Interactions α-钴氢氧化物作为二维磁体:通过交换相互作用调节磁性
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.jpcc.5c07731
Diego Hunt,Victor Oestreicher,Valeria Ferrari
In this work, we present a microscopic analysis of the magnetic properties of the α-CoII layered hydroxide (LHs) family. Using first-principles molecular dynamics complemented by DFT+U calculations and Monte Carlo simulations, we provide a detailed magnetic characterization of the previously reported hybrid α-CoII LHs ( Chem. Eur. J. 2021, 27, 921−927). By parametrizing Heisenberg-type Hamiltonians, we demonstrate that interlayer magnetic interactions are significantly weaker than intralayer ones and even smaller than the thermal energies involved in typical experiments. This indicates that the magnetic behavior of these systems is primarily governed by intralayer interactions, effectively rendering them two-dimensional magnets. Monte Carlo simulations allow us to estimate the relevant macroscopic magnetic variables, yielding excellent agreement with our previously reported experimental data. Extending the analysis to different coordination ligands, we find that variations in the magnetic properties of α-CoII LHs are mainly driven by local distortions in the tetrahedral Co(II) environment, which directly modulate the superexchange interaction between tetrahedral and octahedral Co(II) ions. For the hybrid α-CoII LHs, these distortions are closely linked to the specific orientation of the organic molecules within the interlayer region, suggesting that a controlled molecular arrangement can be exploited as a form of molecular engineering to tailor the magnetic response of LHs. Our findings support the formulation of a simplified model that captures the essential magnetic physics of these compounds, based on the modulation of intralayer exchange interactions. These insights pave the way toward the design of layered materials with tunable magnetic properties and underscores their potential as adaptable platforms for future spintronics applications.
在这项工作中,我们提出了α-CoII层状氢氧化物(LHs)家族的磁性的微观分析。利用第一性原理分子动力学,辅以DFT+U计算和蒙特卡罗模拟,我们提供了先前报道的杂化α-CoII LHs的详细磁性表征。欧元。[j] .生物工程学报,2016,37(2):921−927。通过参数化海森堡型哈密顿量,我们证明了层间磁相互作用明显弱于层内磁相互作用,甚至小于典型实验中涉及的热能。这表明这些系统的磁性行为主要由层内相互作用控制,有效地使它们成为二维磁体。蒙特卡罗模拟使我们能够估计相关的宏观磁变量,与我们先前报道的实验数据非常一致。将分析扩展到不同配体,我们发现α-CoII LHs的磁性变化主要是由四面体Co(II)环境中的局部畸变驱动的,它直接调节了四面体和八面体Co(II)离子之间的超交换相互作用。对于杂化α-CoII LHs,这些扭曲与层间区域内有机分子的特定取向密切相关,这表明控制分子排列可以作为分子工程的一种形式来定制LHs的磁响应。我们的发现支持了一个简化模型的公式,该模型基于层内交换相互作用的调制,捕捉了这些化合物的基本磁性物理特性。这些见解为设计具有可调磁性的层状材料铺平了道路,并强调了它们作为未来自旋电子学应用的适应性平台的潜力。
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引用次数: 0
Nucleotide-Based White Circularly Polarized Luminescence Materials in Lanthanide Deep Eutectic Solvents 镧系深共晶溶剂中基于核苷酸的白色圆极化发光材料
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.jpcc.5c08455
Xuetao Yan,Lifei Chen,Yuze Ren,Kaixuan Cui,Tianliang Li,Lixing Lin,Zeyu Li,Yingying Chen,Zhenzhen Li,Lingyan Feng
The self-assembly of nucleotides into sophisticated biomolecular architectures offers a powerful platform for developing advanced functional materials. Herein, we exploit the innate chirality and metal-coordination capability of nucleotides to fabricate biomolecular coordination polymers with circularly polarized luminescence (CPL). By integrating nucleotides (AMP, GMP, UMP, CMP) with lanthanide-based deep eutectic solvents (DESs) that serve as both a reactive medium and a source of red and green emission, we successfully constructed nucleotide-lanthanide coordination polymers. These biomolecular complexes not only exhibited characteristic lanthanide emissions but also demonstrated significant CPL activity. Remarkably, a white-light-emitting coordination polymer with white circularly polarized luminescence (W-CPL) was achieved by incorporating blue-emitting carbon dots into the AMP-coordinated system, forming a solvent-free supramolecular assembly. Furthermore, a prototype light-emitting diode (LED) device was fabricated by coating these nucleotide-based complexes onto a UV chip, successfully generating electrically driven polarized visible light. This work underscores the immense potential of nucleotide biomolecules as versatile scaffolds for crafting next-generation polarized optical materials and devices.
核苷酸自组装成复杂的生物分子结构为开发先进的功能材料提供了一个强大的平台。本研究利用核苷酸固有的手性和金属配位能力,制备了具有圆极化发光(CPL)的生物分子配位聚合物。通过将核苷酸(AMP, GMP, UMP, CMP)与镧系深共晶溶剂(DESs)整合,我们成功构建了核苷酸-镧系配位聚合物。这些生物分子复合物不仅表现出特有的镧系辐射,而且表现出显著的CPL活性。值得一提的是,通过将蓝色碳点加入到amp配位体系中,形成无溶剂的超分子组装体,获得了具有白色圆偏振发光的白光配位聚合物(W-CPL)。此外,通过将这些基于核苷酸的复合物涂覆在UV芯片上,制作了一个发光二极管(LED)器件的原型,成功地产生了电驱动的偏振可见光。这项工作强调了核苷酸生物分子作为制造下一代偏振光学材料和器件的多功能支架的巨大潜力。
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引用次数: 0
Correction to “Photoluminescence Saturation in Quantum-Cutting Yb3+-Doped CsPb(Cl1–xBrx)3 Perovskite Nanocrystals: Implications for Solar Downconversion” 修正“量子切割Yb3+掺杂CsPb(Cl1-xBrx)3钙钛矿纳米晶体的光致发光饱和:对太阳下转换的影响”
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.jpcc.6c00288
Christian S. Erickson,Matthew J. Crane,Tyler J. Milstein,Daniel R. Gamelin
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引用次数: 0
Adsorption and Decomposition of Sarin Simulant DIMP on Reduced and Oxidized TiO2 and Pt/TiO2 沙林模拟剂DIMP在还原氧化TiO2和Pt/TiO2上的吸附与分解
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.jpcc.5c07878
Matthew B. Leonard,Jason K. Navin,Md Raian Yousuf,Ashish Tripathi,Ayman M. Karim,John R. Morris,Thomas P. Pearl,Christopher J. Karwacki
To develop enhanced catalytically active materials for use in protection against toxic chemical exposures, such as chemical warfare agents (CWAs), there needs to be a fundamental understanding of the driving factors for agent decomposition. Within this study, we used in situ infrared absorbance spectroscopy to investigate the role of sample pretreatment in modifying the surfaces of TiO2 and 1% Pt/TiO2 and the subsequent decomposition of the nerve agent simulant diisopropyl methylphosphonate (DIMP). Surface and subsurface defects were generated in both TiO2 and 1% Pt/TiO2 when pretreated in a reducing environment. These defects served as sites for the decomposition of DIMP into acetone, mesityl oxide, and isopropyl alcohol (IPA). Due to the increased defect density on the surface resulting from a strong metal–surface interaction, reduced 1% Pt/TiO2 showed increased DIMP decomposition compared to that of reduced TiO2. Pretreatment of the materials in an oxidizing environment resulted in both TiO2 and 1% Pt/TiO2 having a lower defect density compared with the reduced samples. However, for the oxidized 1% Pt/TiO2, surface-accessible active oxygen species were produced, leading to a more selective degradation of DIMP. This study provides an understanding of the impact of different pretreatments of titania, with and without surface-supported Pt, on DIMP decomposition. This includes capturing the roles defects or active oxygen species formed during pretreatment play in DIMP surface reactivity. These insights will assist in the development of next-generation CWA protection or decontamination materials.
为了开发用于防止有毒化学品暴露的增强催化活性材料,例如化学战剂(CWAs),需要对剂分解的驱动因素有基本的了解。在这项研究中,我们使用原位红外吸收光谱研究了样品预处理在TiO2和1% Pt/TiO2表面改性以及随后神经毒剂模拟物甲基膦酸二异丙酯(DIMP)分解中的作用。在还原环境中预处理后,TiO2和1% Pt/TiO2均产生表面和亚表面缺陷。这些缺陷是DIMP分解成丙酮、二甲酰基氧化物和异丙醇(IPA)的位点。由于金属与表面的强相互作用导致表面缺陷密度增加,与还原后的TiO2相比,还原1%的Pt/TiO2的DIMP分解增加。在氧化环境下对材料进行预处理,与还原后的样品相比,TiO2和1% Pt/TiO2的缺陷密度都较低。然而,对于氧化后的1% Pt/TiO2,产生了表面可接近的活性氧,导致对DIMP的选择性降解。本研究提供了不同预处理的二氧化钛,有和没有表面负载Pt,对DIMP分解的影响的理解。这包括捕获在预处理过程中形成的缺陷或活性氧在DIMP表面反应性中的作用。这些见解将有助于开发下一代CWA保护或净化材料。
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引用次数: 0
Thermodynamics of Transition Metal Electrodeposition in Concentrated Aqueous Electrolytes 过渡金属电沉积在浓水电解质中的热力学
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.jpcc.5c06609
Jing Liu,Thomas M. Webb,Juliana Ortiz-Castillo,Yunan Qin,Tao Gao
Electrodeposition of transition metals (TMs) is important for energy storage and sustainable metal production (such as ironmaking). Although M2+/M redoxes, including Fe2+/Fe, have been investigated in concentrated aqueous electrolytes, thermodynamic measurements and modeling of the equilibrium M2+/M potential considering metal–chloride complexation in highly concentrated electrolytes remain elusive. For the first time, we systematically examine how a concentrated electrolyte affects the thermodynamics of TM electrodeposition by combining experimental, theoretical, and computational methods. Our study revealed that the electrodeposition potentials (Eeq) of a wide range of TMs (Fe, Cr, Co, Ni, Zn) are strongly dependent on the electrolyte concentration. The classical thermodynamic model, the Nernst equation, cannot quantify such concentration dependence due to its neglect of metal–anion complexation, a unique structural feature of concentrated aqueous electrolytes of TM ions due to their strong cation–anion interaction. By examining the energy landscape of the electrodeposition reaction together with the metal–ligand complexation equilibria, we develop a thermodynamic model that predicts the equilibrium electrodeposition potential in concentrated electrolytes. The model is general in structure and can be applied to other aqueous Mn+/M systems when speciation and activity data are available. The model is used for predicting the electrodeposition potential of selected TMs in both supported and unsupported electrolytes, and the prediction agrees very well with experiments. A unified thermodynamic framework for metal deposition is proposed by generalizing our model, which reduces to previously proposed models under limiting conditions and covers electrodeposition from a dilute electrolyte to a molten salt electrolyte. The fundamental and practical implications of the results are discussed, shedding light on future electrolyte engineering for a wide range of electrode reactions and engineering applications.
电沉积过渡金属(TMs)对能量储存和可持续金属生产(如炼铁)具有重要意义。虽然M2+/M氧化还原,包括Fe2+/Fe,已经在浓水电解质中进行了研究,但考虑到高浓度电解质中金属-氯络合的平衡M2+/M电位的热力学测量和建模仍然难以捉摸。本文首次通过实验、理论和计算相结合的方法,系统地研究了浓电解质对TM电沉积热力学的影响。我们的研究表明,广泛的TMs (Fe, Cr, Co, Ni, Zn)的电沉积电位(Eeq)强烈依赖于电解质浓度。经典热力学模型,即能斯特方程,由于忽略了金属-阴离子络合作用,无法量化这种浓度依赖性。金属-阴离子络合作用是TM离子的浓水电解质的独特结构特征,因为它们具有强的正离子-阴离子相互作用。通过考察电沉积反应的能量格局以及金属配体络合平衡,我们建立了一个热力学模型来预测浓电解质中的平衡电沉积电位。该模型在结构上是通用的,当有形态和活性数据可用时,可以应用于其他水性Mn+/M体系。用该模型预测了所选TMs在有负载和无负载电解质中的电沉积电位,预测结果与实验结果吻合较好。通过推广我们的模型,提出了一个统一的金属沉积热力学框架,该模型在限制条件下简化为先前提出的模型,并涵盖了从稀电解质到熔盐电解质的电沉积。讨论了这些结果的基础和实际意义,为未来的电解质工程提供了广泛的电极反应和工程应用。
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引用次数: 0
The Effects of Iron and Manganese Doping on the Carbonation of Brucite [Mg(OH)2] 铁锰掺杂对水镁石[Mg(OH)2]碳酸化的影响
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.jpcc.5c06987
Dong Youn Chung,Juliane Weber,Lawrence M. Anovitz,Barbara R. Evans,Ke Yuan,Sai Adapa,Matthew G. Boebinger,Michael A. McGuire,Raphaël P. Hermann,George Yumnam,Joanne E. Stubbs,Peter J. Eng,Peter J. Heaney,Andrew G. Stack
Brucite [Mg(OH)2] is a promising sorbent for carbon dioxide removal (CDR) due to its availability and low calcination temperatures. However, natural and synthetic brucites tend to contain metal impurities, such as iron or manganese, and how these impurities affect the interfacial chemical reactivity is uncertain. Here, the impact of low concentrations of iron and manganese impurities on the carbonation efficiency of Mg(OH)2 was examined. Mg(OH)2 with small amounts (1–5 mol %) of Fe and Mn was synthesized. The increasing substitution of Fe into Mg(OH)2 was accompanied by the oxidation of Fe. The phase transformation sequence during the carbonation was found to be brucite [Mg(OH)2] → amorphous magnesium carbonate (MgCO3·nH2O) → nesquehonite (MgCO3·3H2O), regardless of impurity concentration. Both the Fe- and Mn-doped Mg(OH)2 samples were more reactive than endmember Mg(OH)2, possibly due to their higher surface areas and lower stabilities. During carbonation, 3 mol % Fe- and Mn-doped Mg(OH)2 showed the highest reactivity. The variance in reactivity for Mn-doped Mg(OH)2 was less than that of Fe-doped Mg(OH)2. These results suggest that natural or industrial waste Mg(OH)2 with less than 5 mol % Fe and Mn impurities may be targeted as more effective CDR sorbents than endmember Mg(OH)2.
水镁石[Mg(OH)2]是一种很有前途的二氧化碳脱除吸附剂,因为它的可用性和较低的煅烧温度。然而,天然和合成的水镁石往往含有金属杂质,如铁或锰,这些杂质如何影响界面化学反应性是不确定的。本文考察了低浓度铁和锰杂质对Mg(OH)2碳化效率的影响。合成了含有少量(1-5摩尔%)铁和锰的Mg(OH)2。铁在Mg(OH)2中取代的增加伴随着铁的氧化。碳化过程中的相变顺序为水镁石[Mg(OH)2]→无定形碳酸镁(MgCO3·nH2O)→无定形碳酸镁(MgCO3·3H2O),与杂质浓度无关。Fe和mn掺杂的Mg(OH)2样品都比端元Mg(OH)2反应性更强,可能是由于它们的比表面积更大而稳定性更低。在碳化过程中,3mol % Fe和mn掺杂的Mg(OH)2表现出最高的反应活性。mn掺杂Mg(OH)2的反应性变化小于fe掺杂Mg(OH)2。这些结果表明,天然或工业废水中Fe和Mn杂质低于5 mol %的Mg(OH)2可能是比端分子Mg(OH)2更有效的CDR吸附剂。
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引用次数: 0
A Self-Assembled Covalently Linked Porphyrin as a High-Density Reaction Center 作为高密度反应中心的自组装共价连接卟啉
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-01 DOI: 10.1021/acs.jpcc.5c07706
Chiranjeevulu Kashi,Bhaskar Chilukuri,Ursula Mazur,K. W. Hipps
Metal porphyrins find wide use in catalysis, photoelectronics, sensing, and other applications. The application of covalently linked porphyrins is a new area that deserves attention. The driving forces are the desire for a high density of single metal ions on a surface, the potential to design in both electronic and steric intramolecular cooperativity, and chemical tunability. One method for creating surfaces with a high density of covalently linked porphyrins, self-assembly from fluid solution, is almost unexplored. In this study we give a detailed analysis of the self-assembled monolayer formed from an alkyne linked porphyrin dimer, 1,4-Bis{[5,10,15,20-tetra(n-hexyl)porphyrinato]zinc(II)}butadiyne, that forms well-ordered structures upon adsorption on highly oriented pyrolytic graphite (HOPG) from 1,2,4-trichlorobenzene. The adlayer is studied by scanning tunneling microscopy (STM) and by density functional theory (DFT). By combining experiment with computation, the detailed structure of the adlayer is determined. It is found that it has a higher density of single metal atoms (0.66 sites/nm2) than adlayers of well-known dimeric porphyrins or monomeric zinc octaethylporphyrin. DFT is key to understanding the alkane chain disposition and its possible role in cooperativity.
金属卟啉广泛应用于催化、光电子、传感等领域。共价连接卟啉的应用是一个值得关注的新领域。驱动力是对表面上单个金属离子高密度的渴望,在电子和空间分子内协同性设计的潜力,以及化学可调性。一种制造具有高密度共价连接卟啉的表面的方法,即从流体溶液中自组装,几乎没有被探索过。在本研究中,我们详细分析了由炔连接卟啉二聚体1,4-二{[5,10,15,20-四(正己基)卟啉]锌(II)}丁二炔形成的自组装单层,该单层在高取向热解石墨(HOPG)上吸附1,2,4-三氯苯后形成有序结构。利用扫描隧道显微镜(STM)和密度泛函理论(DFT)对其进行了研究。通过实验与计算相结合的方法,确定了层的详细结构。结果表明,它具有较高的单金属原子密度(0.66个位点/nm2),比众所周知的二聚体卟啉或单聚辛乙基锌卟啉的镀层要高。DFT是理解烷烃链分布及其在协同作用中可能起的作用的关键。
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引用次数: 0
Unlocking Thermal Flexibility in Ni-Based Fluorinated Square-Pillared MOFs: Insights into Pore Transitions and Node-Linker Dynamics 解锁ni基氟化方柱mof的热灵活性:对孔隙转变和节点链接器动力学的见解
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-01 DOI: 10.1021/acs.jpcc.5c07920
Silda Peters,Renjith S. Pillai,Tumpa Sadhukhan
The thermally responsive behavior of metal–organic frameworks offer a pathway to materials capable of adapting their internal architecture to external stimuli. In this study, we elucidate how fluorinated AlF5 pillars, together with linker-dependent internal motions, govern the distinctive thermoresponsive behavior of ALFFIVE-Ni frameworks. Using molecular simulations, we examine the temperature-induced structural evolution across three linkers of increasing rigidity and length and show that linker tilting, mediated through node–linker dynamics, drives the transformation from large-pore (lp) to narrow-pore (np) states. The magnitude and onset of this transition are finely tuned by linker chemistry, while all systems display pronounced negative thermal expansion arising from coordinated internal vibrations. Water interactions further modulate this response by stabilizing the framework under humid conditions and partially suppressing thermal contraction. By clarifying the microscopic mechanisms underlying flexibility in fluorinated MOFs, this work provides a foundation for designing thermally adaptive materials with tailored pore behavior, structural responsiveness, and application-specific performance.
金属有机框架的热响应行为为能够适应外部刺激的内部结构的材料提供了一条途径。在这项研究中,我们阐明了如何氟化的AlF5柱,连同连接体相关的内部运动,控制ALFFIVE-Ni框架的独特热响应行为。通过分子模拟,我们研究了温度诱导的三种刚性和长度增加的连接体的结构演变,并表明通过节点-连接体动力学介导的连接体倾斜驱动了从大孔(lp)到窄孔(np)状态的转变。这种转变的幅度和开始是由连接剂化学精细调节的,而所有系统都表现出由协调的内部振动引起的明显的负热膨胀。水的相互作用通过在潮湿条件下稳定框架和部分抑制热收缩来进一步调节这种反应。通过阐明氟化mof柔韧性的微观机制,本研究为设计具有定制孔隙行为、结构响应性和特定应用性能的热适应性材料提供了基础。
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引用次数: 0
Tuning Far-Red Luminescence Properties of KAlSi2O6:Cr3+ Phosphors via Partial Cation Substitution 通过部分阳离子取代调整KAlSi2O6:Cr3+荧光粉的远红发光性能
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-01 DOI: 10.1021/acs.jpcc.5c07727
Panpan Li,Huanping Wang,Ruoshan Lei,Denghao Li,Youjie Hua,Shiqing Xu
Far-red phosphors are critically important for advancing plant growth lighting. In this work, a novel far-red phosphor, KAlSi2O6:Cr3+, was synthesized and optimized. The material crystallizes in a tetragonal structure with space group I41/a. It exhibits two excitation bands at 428 nm (4A2 → 4T1) and 571 nm (4A2 → 4T2) and emits a dominant peak at 710 nm (R-line) with a weak shoulder at 730 nm (N2-line). XRD Rietveld refinement results reveal that the doped Cr3+ and Rb+ preferentially occupy K+ sites, while Ga3+ substitutes for Al3+ sites. Raman and XPS analyses show that these dopants induce lattice distortion, suppress high-frequency phonons, and slightly alter the electron cloud distribution of Cr3+ ions. Notably, Ga3+-Rb+ codoping shifts the main emission to 695 nm and markedly improves thermal stability (I423 K/I303 K increases from 46.01% to 66.52%). By leveraging the spectral overlap with phytochrome PFR absorption, pc-LED devices were fabricated. Pc-LEDs based on the Ga3+-doped or Ga3+–Rb+ codoped phosphors not only promote mint growth but also enable clear imaging in night-vision scenarios, demonstrating strong potential for dual-functional lighting.
远红色荧光粉对促进植物生长照明至关重要。本文合成并优化了一种新型远红荧光粉——KAlSi2O6:Cr3+。该材料结晶为具有空间群I41/a的四方结构。在428 nm (4A2→4T1)和571 nm (4A2→4T2)处有两个激发带,在710 nm处有一个优势峰(r线),在730 nm处有一个弱肩峰(n2线)。XRD Rietveld细化结果表明,掺杂的Cr3+和Rb+优先占据K+位,而Ga3+取代了Al3+位。拉曼和XPS分析表明,这些掺杂剂诱导晶格畸变,抑制高频声子,并轻微改变Cr3+离子的电子云分布。值得注意的是,Ga3+-Rb+共掺杂将主发射峰移至695 nm,显著提高了热稳定性(I423 K/I303 K从46.01%提高到66.52%)。利用光敏色素PFR吸收的光谱重叠,制备了pc-LED器件。基于Ga3+掺杂或Ga3+ -Rb +共掺杂荧光粉的pc - led不仅可以促进薄荷生长,还可以在夜视场景中实现清晰的成像,显示出双功能照明的强大潜力。
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引用次数: 0
Complex Impedance Formalism for Probing Dehydration, Dehydroxylation, and Rehydroxylation Dynamics of UiO-66-Based Metal–Organic Frameworks 探测uio -66基金属-有机骨架脱水、去羟基化和再羟基化动力学的复杂阻抗形式
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-01 DOI: 10.1021/acs.jpcc.5c08228
Tosapol Maluangnont,Kanokwan Chaithaweep,Saichon Sriphan,Parinya Meejaiyen,Wipark Anutrasakda,Pawnprapa Pitakjakpipop,Naratip Vittayakorn
It is known that the UiO-66 metal–organic framework (MOF) undergoes dehydration of physisorbed water and dehydroxylation of the zirconium clusters from RT to ∼300 °C, while the porous structure remains intact. These two processes are typically studied by thermogravimetric analysis and its derivative method (TGA/DTG), as well as differential scanning calorimetry (DSC). Here, we probe the same phenomena using temperature-dependent complex impedance spectroscopy. Peaks observed in the AC conductivity and in the real and imaginary parts of the dielectric permittivity (σAC, ε′, and ε″) are due to thermally accelerated proton (Grotthuss) hopping competing with the loss of proton carriers during guest removal and dehydroxylation up to 350 °C. Meanwhile, peaks in the loss tangent (tan δ) and phase shift (Θ) identify the temperature at which dielectric-to-heat conversion is maximized. Additionally, peaks in the imaginary part of the impedance (−Z″) and in the real part of the electric modulus (M′) mark the temperature at which the material exhibits its highest insulating character. The MOFs examined include UiO-66 with the 1,4-benzenedicarboxylate linker and UiO-66-Py with the 2,5-pyridinedicarboxylate linker, the latter further modified through trifluoroacetic acid modulation, 1-bromopropane functionalization, and optional intermediate heat treatment. Impedance measurements under cooling reveal composition-dependent rehydroxylation behavior, with the conductivity recovery as early as at 250 °C in some Py-based derivatives vs flat response in pristine UiO-66. Overall, our work provides a comprehensive analysis of several complex electrical quantities and their physical interpretation, offering complementary insights into the dehydration, dehydroxylation, and rehydroxylation dynamics of UiO-66-based MOFs.
已知UiO-66金属有机骨架(MOF)经历了物理吸附水的脱水和锆团簇的脱羟基作用,从RT到~ 300℃,而多孔结构保持完整。这两个过程通常通过热重分析及其衍生方法(TGA/DTG)和差示扫描量热法(DSC)来研究。在这里,我们使用温度相关的复阻抗谱来探测相同的现象。在交流电导率和介电常数的实部和虚部(σAC, ε′和ε″)中观察到的峰值是由于热加速的质子(Grotthuss)跳变与在客体去除和去羟基化过程中质子载流子的损失相竞争造成的。同时,损耗正切(tan δ)和相移(Θ)的峰值确定了介电-热转换最大化的温度。此外,阻抗虚部(−Z″)和电模量实部(M’)的峰值标志着材料表现出最高绝缘特性的温度。测试的MOFs包括带有1,4-苯二羧酸酯连接剂的UiO-66和带有2,5-吡啶二羧酸酯连接剂的UiO-66- py,后者通过三氟乙酸调制、1-溴丙烷功能化和可选的中间热处理进一步改性。冷却下的阻抗测量揭示了组分依赖的再羟基化行为,在一些基于py的衍生物中,电导率早在250°C时就恢复了,而在原始的UiO-66中则是平坦的。总的来说,我们的工作提供了几个复杂的电量及其物理解释的综合分析,为uio -66基mof的脱水、去羟基化和再羟基化动力学提供了补充的见解。
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引用次数: 0
期刊
The Journal of Physical Chemistry C
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