Progress in Solid State Chemistry最新文献_第3页

Original mechanism of transformation from soft metallic (sp2/sp3) C12 to ultra-dense and ultra-hard (sp3) semi-conducting C12: Crystal chemistry and DFT characterizations 软金属（sp2/sp3） C12向超致密超硬（sp3）半导体C12转变的原始机理：晶体化学和DFT表征

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-04-29 DOI: 10.1016/j.progsolidstchem.2025.100521

Samir F. Matar

An original mechanism is proposed for a pressure-induced transformation of orthorhombic C₁₂ from ground state normal pressure (NP) sp²/sp³ allotrope to ultra-dense and ultra-hard high pressure HP sp³ form. Upon volume decrease, the trigonal CC parallel segments characterizing glitter-like tfi topology of NP C₁₂ change to crossing C–C segments with the loss of sp² character accompanied by a large densification with ρ = 3.64 g/cm³, larger than diamond, defining a novel orthorhombic HP C₁₂ with 4⁴T39 topology. The crystal chemistry engineering backed with quantum density functional theory DFT-based calculations let determine the ground state structures and energy derived physical properties. Furthering on that, the E(V) equations of states (EOS) let define the equilibrium NP(E₀,V₀) allotrope at lower energy and higher volume versus HP(E₀,V₀) allotrope at higher energy and smaller volume. A potential pressure induced transformation NP→HP was estimated at ∼100 GPa, reachable with a diamond anvil cell DAC. Both allotropes were found cohesive and mechanically stable with low and large Vickers hardness magnitudes: H_V(tfi C₁₂) = 24 GPa and H_V(4⁴T39 C₁₂) = 90 GPa; the latter being close to diamond hardness (H_V ∼95 GPa). Besides, both allotropes were found dynamically stable with positive phonon frequencies and a spectroscopic signature of CC high frequency bands in tfi C₁₂. The electronic band structures show a metallic behavior for NP tfi C₁₂ and a small band gap for HP 4⁴T39C₁₂ letting assign semiconducting properties. The work is meant to open further the scope of C (sp²)→C (sp³) transformation mechanisms that are fundamental in solid state physics and chemistry.

提出了一种压力诱导正交C12从基态常压（NP） sp2/sp3同素异形体向超致密超硬高压HP sp3形态转变的原始机制。当体积减小时，具有发光样tfi拓扑的三角形CC平行段转变为交叉C-C段，失去sp2特征，并伴随着比金刚石大的ρ = 3.64 g/cm3的大密度，定义了具有44T39拓扑的新型正交型HP C12。以量子密度泛函理论为基础的晶体化学工程计算可以确定基态结构和能量衍生的物理性质。在此基础上，E(V)状态方程（EOS）定义了低能量和高体积下的平衡NP（E0,V0）同素异形体与高能量和小体积下的平衡HP（E0,V0）同素异形体。潜在压力诱导的转化NP→HP估计在~ 100 GPa，用金刚石砧细胞DAC可以达到。两种同素异构体均具有黏合性和机械稳定性，维氏硬度大小分别为：HV(tfi C12) = 24 GPa和HV(44T39 C12) = 90 GPa；后者接近金刚石硬度（HV ~ 95 GPa）。此外，这两种同素异形体在tfi - C12中具有正声子频率和CC高频光谱特征的动态稳定性。电子能带结构显示出NP tfi C12的金属行为和HP 44T39C12的小带隙，使其具有半导体性质。这项工作旨在进一步打开C （sp2）→C （sp3）转化机制的范围，这是固态物理和化学的基础。

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引用次数: 0

Beyond graphene basics: A holistic review of electronic structure, synthesis strategies, properties, and graphene-based electrode materials for supercapacitor applications 超越石墨烯基础：电子结构，合成策略，性能和超级电容器应用的石墨烯基电极材料的全面审查

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-04-16 DOI: 10.1016/j.progsolidstchem.2025.100519

Sachin Kumar Yadav, Anil Kumar, Neeraj Mehta

This review presents a comprehensive analysis of graphene-based electrode materials for supercapacitor application, focusing on electronic structure, synthesis strategies, and key attributes. The remarkable 2D-structure of graphene, characterized by sp² hybridized carbon atoms, confers exceptional electronic mobility (100000 cm²V⁻¹s⁻¹), large specific surface area (2600 m²g^-1), and mechanical flexibility (2.4 ± 0.4 TPa), making it an ideal contender for next-generation energy storage devices. We have discussed various synthesis strategies, including CVD, mechanical exfoliation, and chemical reduction, emphasizing their impact on the electrochemical performance of graphene electrodes. The integration of graphene with other nanomaterials, such as metal oxides, TMDs, conducting polymers, and MXenes, is explored to enhance the specific capacitance, cycle stability, and energy density of supercapacitor electrode materials. This review also covers the tunable electronic properties of graphene, addressing charge transport, ion diffusion, and electrochemical performance, which are critical for efficient supercapacitor design. Graphene-based electrodes' flexibility and mechanical stability are examined, highlighting their role in wearable and portable electronic applications. Challenges such as large-scale production, electrode degradation, and cost-effectiveness are also discussed, offering potential solutions through innovative synthesis routes and composite material design. This review provides a holistic perspective on the current advancement of graphene-based electrode materials for supercapacitor applications.

本文综述了石墨烯基超级电容器电极材料的电子结构、合成策略和关键特性。石墨烯以sp2杂化碳原子为特征，具有卓越的电子迁移率（100,000 cm2V−1s−1），大比表面积（2600 m2g-1）和机械灵活性（2.4±0.4 TPa），使其成为下一代储能设备的理想竞争者。我们讨论了各种合成策略，包括CVD、机械剥离和化学还原，强调了它们对石墨烯电极电化学性能的影响。石墨烯与其他纳米材料，如金属氧化物、tmd、导电聚合物和MXenes的集成，以提高超级电容器电极材料的比电容、循环稳定性和能量密度。本综述还涵盖了石墨烯的可调谐电子特性，解决电荷传输，离子扩散和电化学性能，这是高效超级电容器设计的关键。研究了石墨烯基电极的灵活性和机械稳定性，强调了它们在可穿戴和便携式电子应用中的作用。还讨论了大规模生产、电极降解和成本效益等挑战，并通过创新合成路线和复合材料设计提供了潜在的解决方案。本文综述了石墨烯基超级电容器电极材料的研究进展。

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引用次数: 0

Elucidating interfacial behaviors of Li-ion argyrodites through μ-cavity electrode analysis 用μ腔电极分析阐明锂离子银柱石的界面行为

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-04-09 DOI: 10.1016/j.progsolidstchem.2025.100518

Orynbassar Mukhan , Yuvaraj Subramanian , Sharon Mugobera , Sung-Soo Kim , Kwang-Sun Ryu

In the current scenario, All-Solid-State Batteries (ASSBs) are one of the inevitable energy storage systems due to their high energy density and safety aspects. Nonetheless, they have some limitations in their implementation for high performance solid-state lithium batteries. Notably, the reactions at the electrode and electrolyte interface, which negatively affects the Li-ion transport. From this perspective, we prepared the renowned high ionic conductive solid electrolytes (Li₆PS₅Cl, Li_6.2P_0.8Si_0.2S₅Cl_0.5Br_0.5, Li_5.3PS_4.3Cl_1.7 and Li_5.3PS_4.3ClBr_0.7) using a ball milling process subsequent to calcination at appropriate temperatures. The prepared electrolytes exhibited ionic conductivity values of 4.5, 5.3, 9.0 and 15.9 mS cm⁻¹, respectively. Importantly, the electrode and electrolyte interface processes are examined through microcavity electrode system using our prepared electrolyte and LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523) cathode. In this case, a single particle confined in a micro cavity electrode system, NCM523-Li_6.2P_0.8Si_0.2S₅Cl_0.5Br_0.5 exhibits the highest initial discharge capacity value of 5.27 nAh, and an even higher initial Coulombic efficiency of 87.9 % surpassing other micro electrode systems. This and the electrochemical kinetic parameters evaluated through the Tafel plot analysis confirm that Si substitution minimizes chemical side reactions at the interface. The electrochemical kinetic parameters reveal that Li_6.2P_0.8Si_0.2S₅Cl_0.5Br_0.5 electrolyte has high exchange current, low charge transfer resistance and high lithium diffusion coefficient values. This proves that a favorable interface was formed between the NCM523 and the SE, thereby resulting in high rate of lithium-ion exchange between the NCM523 and the SE. The comparative study confirms the electrochemical kinetics improved by the bromine and silicon incorporation in the Li-argyrodite structure and offers flexible Li-ion pathways for better electrochemical performances.

在当前情况下，全固态电池（assb）因其高能量密度和安全性而成为不可避免的储能系统之一。尽管如此，它们在实现高性能固态锂电池方面仍有一些局限性。值得注意的是，电极和电解质界面的反应对锂离子的输运产生了负面影响。从这个角度来看，我们在适当的温度下煅烧后采用球磨工艺制备了著名的高离子导电性固体电解质（Li6PS5Cl, Li6.2P0.8Si0.2S5Cl0.5Br0.5, Li5.3PS4.3Cl1.7和Li5.3PS4.3ClBr0.7）。制备的电解质离子电导率分别为4.5、5.3、9.0和15.9 mS cm−1。重要的是，利用制备的电解质和LiNi0.5Co0.2Mn0.3O2 （NCM523）阴极，通过微腔电极系统研究了电极和电解质的界面过程。在这种情况下，单个粒子被限制在微腔电极体系中，NCM523-Li6.2P0.8Si0.2S5Cl0.5Br0.5显示出最高的初始放电容量值5.27 nAh，并且比其他微电极体系具有更高的初始库仑效率（87.9%）。这与通过Tafel图分析评估的电化学动力学参数证实，Si取代最小化了界面上的化学副反应。电化学动力学参数表明，Li6.2P0.8Si0.2S5Cl0.5Br0.5电解质具有大的交换电流、低的电荷转移电阻和高的锂扩散系数值。这证明NCM523与SE之间形成了良好的界面，从而导致NCM523与SE之间的锂离子交换率高。通过对比研究，证实了溴和硅的掺入改善了锂银石结构的电化学动力学，并提供了柔性的锂离子通路以获得更好的电化学性能。

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引用次数: 0

Boosting photoluminescence of Ba5P6O20:Dy3+ phosphor through facile alkali charge compensation 通过易碱电荷补偿增强Ba5P6O20:Dy3+荧光粉的光致发光

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-02-24 DOI: 10.1016/j.progsolidstchem.2025.100517

Yiting Huang , Xiaoyang Zhao , Zibo Huang , Jingkai Quan , Youwen Tang , Chenyang Jia , Jianguo Jia , Jintao Xie , Yanqiong Shen , Jing Zhu

Trivalent dysprosium (Dy³⁺)-activated inorganic phosphors have become fascinating due to tunable yellow/white light emission. Nevertheless, the challenge for solid-state lighting utilization is achieving highly luminous efficiency and thermostability of Dy³⁺. In this study, a new Ba₅P₆O₂₀ (BPO) phosphor is developed via replacing Ba²⁺ with Dy³⁺. The luminescence behaviors in response to the occupancy sites and content of Dy³⁺ activators are thoroughly investigated. Subsequently, to enhance comprehensive luminescence performances, alkali metal ions are co-doped based on charge compensation strategy. Especially, the K⁺ compensation can induce that the luminous efficiency and intensity are increased by around 4 and 2 times, separately. Meanwhile, the high thermal quenching resistance and chromaticity shifting resistance for Dy³⁺ emissions are achieved. Finally, the optimized BPO:5%Dy³⁺,5%K⁺ sample is employed to obtain a satisfactory solid-state white lighting source.

三价镝（Dy3+）激活的无机荧光粉由于其可调谐的黄光/白光发射而受到人们的关注。然而，固态照明应用的挑战是实现高发光效率和热稳定性的Dy3+。本研究通过用Dy3+取代Ba2+，制备了一种新的Ba5P6O20 （BPO）荧光粉。研究了Dy3+激活剂的占据位置和含量对发光行为的影响。随后，基于电荷补偿策略，对碱金属离子进行共掺杂，以提高综合发光性能。其中，K+补偿可使发光效率提高约4倍，发光强度提高约2倍。同时，该材料具有较高的耐热猝灭性和耐色度漂移性。最后，采用优化后的BPO:5%Dy3+，5%K+样品获得了满意的固态白光光源。

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引用次数: 0

Yttrium iron garnets: Phase study and synthesis methods 钇铁石榴石：物相研究及合成方法

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-01-06 DOI: 10.1016/j.progsolidstchem.2024.100507

N. Askarzadeh, H. Shokrollahi

Due to the rapid progress in the development of communication systems, magnetic ceramics-including spinels, hexaferrites, and garnets-have become increasingly attractive for use in various electronic and optoelectronic devices, particularly in the microwave range. Among the different types of ferrites, garnets generally exhibit higher electrical resistivity, lower dielectric losses, softer magnetic behavior, higher Curie points, and narrower ferromagnetic resonance linewidth. These properties make garnets suitable for spintronic technology, electro-optical applications, and the microwave/GHz domain, including devices such as phase shifters, circulators, and isolators. This important class of ferrimagnetic materials is found in two different compositional forms: unsubstituted garnets, or yttrium iron garnets (Y₃Fe₅O₁₂, YIG), and substituted garnets (R_xY_3-xM_yFe_5-yO₁₂). In addition to changes in chemical composition through doping and/or substitution of elements, other factors that can affect the performance of garnets include synthesis methods and heat treatment. Given the recent interest in nanotechnology, various shapes—including nanoparticles, thin films, nanorods, and nanotubes—have been considered alongside the bulk structure, either as composites or in uncombined forms, to develop materials for specific applications. This paper aims to provide an overview of the crystal structure, phase study, and various synthetic methods of garnets concerning their magnetic and structural behaviors.

由于通信系统的快速发展，磁性陶瓷-包括尖晶石，六铁体和石榴石-在各种电子和光电子器件中，特别是在微波范围内的应用越来越有吸引力。在不同类型的铁氧体中，石榴石通常具有较高的电阻率，较低的介电损耗，较软的磁性行为，较高的居里点和较窄的铁磁共振线宽。这些特性使石榴石适用于自旋电子技术、电光应用和微波/GHz域，包括移相器、环行器和隔离器等设备。这类重要的铁磁性材料有两种不同的组成形式：未取代石榴石或钇铁石榴石（Y3Fe5O12, yg）和取代石榴石（RxY3-xMyFe5-yO12）。除了通过掺杂和/或取代元素而改变化学成分外，影响石榴石性能的其他因素还包括合成方法和热处理。考虑到最近对纳米技术的兴趣，各种形状——包括纳米颗粒、薄膜、纳米棒和纳米管——已经被考虑作为复合材料或非组合形式，以开发用于特定应用的材料。本文综述了石榴石的晶体结构、物相研究以及各种合成方法对其磁性和结构行为的影响。

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引用次数: 0

Progress and outlook of ferroelectric/non-ferroelectric polar glass-ceramics for multi-catalytic applications 多催化铁电/非铁电极性微晶玻璃的研究进展与展望

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2024-11-12 DOI: 10.1016/j.progsolidstchem.2024.100497

Chirag Porwal , Gurpreet Singh , Moolchand Sharma , Vishal Singh Chauhan , Rahul Vaish

Glass-ceramics have been long recognized for their capability to offer shared characteristics of both glassy as well as crystalline phases. By controlling volume fraction of crystalline phase dispersed in glassy matrix, the properties of glass-ceramics can be tuned for variety of applications such as dental implants, heat-resistant cooking ware, missiles nozzle cones, etc. A specific family of glass-ceramics that consists of ferroelectric/non-ferroelectric polar crystallites offers second-harmonic generation, pyroelectric, piezoelectric, and ferroelectric properties for actuators, sensors, non-linear optical devices, and lasers applications, that were traditionally not possible in glassy materials. Fabrication, crystallization behavior, and electrical properties of such glass-ceramics have been extensively studied in the last decade and widely reviewed in multiple documents in the literature. Recently, the presence of ferroelectric/non-ferroelectric polar crystallites in glasses unveils the new environmental applications of glass-ceramics using photocatalysis, piezocatalysis, and tribocatalysis processes stimulated by light, mechanical, and frictional energy, respectively. Ferroelectric/non-ferroelectric polar glass-ceramics for multi-catalysis is relatively a new and emerging area, that have potential to provide solution for real-environmental problems such as water-pollution. Thus, this review provides a comprehensive overview of multi-catalytic nature of ferroelectric/non-ferroelectric polar glass-ceramics. It discusses the underlying catalytic mechanisms and unveils the performance of these glass-ceramics in environmental applications. It highlights the advantages and challenges of ferroelectric/non-ferroelectric polar glass-ceramics as photo/piezo/tribocatalysts. This review will motivate glass researchers to work in the area of environmental applications of glass-ceramics using catalytic processes.

玻璃陶瓷长期以来一直被认为具有玻璃相和结晶相的共同特性。通过控制分散在玻璃基体中的晶相的体积分数，可以调整微晶玻璃的性能，用于各种应用，如牙科植入物、耐热炊具、导弹喷嘴锥等。由铁电/非铁电极性晶体组成的特定玻璃陶瓷家族为致动器、传感器、非线性光学器件和激光应用提供了二次谐波产生、热释电、压电和铁电特性，这些特性传统上在玻璃材料中是不可能的。近十年来，人们对这种微晶玻璃的制备、结晶行为和电学性能进行了广泛的研究，并在多篇文献中进行了广泛的综述。最近，铁电/非铁电极性晶体在玻璃中的存在揭示了玻璃陶瓷的新环境应用，分别使用光催化、压电催化和摩擦催化过程，分别受到光、机械和摩擦能的刺激。用于多重催化的铁电/非铁电极性微晶玻璃是一个相对较新的新兴领域，具有解决水污染等实际环境问题的潜力。因此，本文综述了铁电/非铁电极性微晶玻璃的多催化性质。讨论了潜在的催化机制，并揭示了这些微晶玻璃在环境应用中的性能。强调了铁电/非铁电极性微晶玻璃作为光/压电/摩擦催化剂的优势和挑战。本文综述将激励玻璃研究人员在催化工艺的环境应用领域开展工作。

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引用次数: 0

Boosting the phosphorus uptake of La2(CO3)3·8H2O based adsorbents via sodium addition: Relationship between crystal structure and adsorption capacity 通过添加钠提高基于 La2(CO3)3-8H2O 的吸附剂对磷的吸收：晶体结构与吸附容量之间的关系

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2024-11-12 DOI: 10.1016/j.progsolidstchem.2024.100496

Zuo-Bei Wang , Xin Ye , Jie Yang , Yong-Hui Zhang , Zi-Ang Nan , Yi-Fan Wang , You-Gui Huang , Wei Wang

Excess phosphate contents in water bodies triggers eutrophication, which posts significant challenges to the aquatic ecosystem. Lanthanum-carbonate based adsorbents exhibit excellent phosphate binding properties for remediating eutrophication. However, they suffer from significant adsorption-capacity loss (>85 %) at high pH. Little has been done on understanding this behavior for improving the phosphorus adsorption of lanthanum-carbonate adsorbents in alkaline environments (e.g. eutrophic water bodies). Here, we discover that La₂(CO₃)₃·8H₂O, when produced by a conversion reaction from NaLa(CO₃)₂·xH₂O, exhibits high phosphate adsorption capacity in a wide pH window. Under alkaline conditions (e.g. pH = 10), its adsorption capacity decreases by only 8 % compared to the value under neutral pH. By isolating three different lanthanum-carbonate based compounds and analyzing their molecular structures, we find that the trace amount of Na⁺ residual in our La₂(CO₃)₃·8H₂O alters the chemical environment surrounding the La³⁺ ions, which may significantly boost the phosphate uptake at high pH. Our results provide molecular insights for further tuning the material structure of phosphate adsorbents to achieve robust performances.

水体中磷酸盐含量过高会引发富营养化，给水生生态系统带来巨大挑战。以碳酸镧为基础的吸附剂具有出色的磷酸盐结合特性，可用于解决富营养化问题。然而，在 pH 值较高时，它们的吸附容量会明显下降（85%）。为了改善碳酸镧吸附剂在碱性环境（如富营养化水体）中对磷的吸附，人们对这种行为的了解还很少。在这里，我们发现，由 NaLa(CO3)2-xH2O 通过转化反应生成的 La2(CO3)3-8H2O 在较宽的 pH 值范围内具有较高的磷酸盐吸附能力。在碱性条件下（如 pH = 10），其吸附能力仅比中性 pH 值低 8%。通过分离三种不同的碳酸镧化合物并分析其分子结构，我们发现 La2(CO3)3-8H2O 中残留的微量 Na+ 改变了 La3+ 离子周围的化学环境，这可能会显著提高高 pH 值下的磷酸盐吸收能力。我们的研究结果为进一步调整磷酸盐吸附剂的材料结构以实现强大性能提供了分子见解。

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引用次数: 0

Investigation of Sr-substituted Ba1-xSrx(Zn1/3Nb2/3)O3 complex perovskites: Structural, electrical and electrochemical properties 研究锶取代的 Ba1-xSrx(Zn1/3Nb2/3)O3 复合包晶：结构、电学和电化学特性

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2024-11-09 DOI: 10.1016/j.progsolidstchem.2024.100495

Y. Feng , K.B. Tan , S.K. Chang , Y. Sulaiman , H.N. Lim , M. Lu , Y. Wang

Herein we report the structural, dielectric and electrochemical properties of Ba_1-xSr_x(Zn_1/3Nb_2/3)O₃ (BSZN, 0 ≤ x ≤ 1) solid solution synthesised by solid-state reaction. A complete substitutional solid solution was obtained, wherein the BSZN cubic perovskites of the space group of Pm

\overline{3}

m were obtained at x ≤ 0.6 while the pseudo-cubic phases were discernible at x > 0.6. The nano-sized crystallites, as determined by both Scherrer and Williamson-Hall analyses, supported the claim of large polyhedral grains of 0.1–0.3 μm by FE-SEM. Both ε′ and tan δ were found to vary consistently with increasing dopant concentration, except for an anomalous observation for the composition, x = 0.6 with the lowest tan δ of 0.0783 and the highest ε′ of 27.5. Such phenomenon could be attributed to the combined effects of larger grain size, higher relative density and stronger polarisation per molar volume. The impedance analysis revealed that these BSZN perovskites were of the negative temperature coefficient of resistance (NTCR) type. The combined plots of imaginary modulus (M″) and impedance (Z″) against frequency showed the short-range movement of localised charge carriers, suggesting a non-Debye-type relaxation process.

在此，我们报告了通过固态反应合成的 Ba1-xSrx(Zn1/3Nb2/3)O3（BSZN，0 ≤ x ≤ 1）固溶体的结构、介电和电化学特性。在 x ≤ 0.6 时，获得了空间群为 Pm 3‾m 的 BSZN 立方包晶，而在 x > 0.6 时，则可以看到假立方相。通过舍勒分析和威廉森-霍尔分析确定的纳米级结晶支持了通过 FE-SEM 确定的 0.1-0.3 μm 大多面体晶粒的说法。随着掺杂剂浓度的增加，ε′和tan δ都发生了一致的变化，除了成分 x = 0.6 的异常观察，其最低的 tan δ为 0.0783，最高的ε′为 27.5。这种现象可归因于较大的晶粒尺寸、较高的相对密度和单位摩尔体积较强极化的综合影响。阻抗分析表明，这些 BSZN 包晶属于负温度系数电阻（NTCR）类型。假想模量（M″）和阻抗（Z″）与频率的组合图显示了局部电荷载流子的短程运动，表明这是一种非德拜型弛豫过程。

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引用次数: 0

New solid solutions with the R-type hexaferrite structure, BaFe4-xMxM’2O11 (M = In, Sc; M’ = Ti, Sn) 具有 R 型六铁氧体结构 BaFe4-xMxM'2O11 (M = In, Sc; M' = Ti, Sn) 的新固溶体

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2024-11-08 DOI: 10.1016/j.progsolidstchem.2024.100494

Yu-An Huang , Jun Li , Arthur P. Ramirez , M.A. Subramanian

Hexaferrites are a family of complex iron oxides with hexagonal structures. Novel compositions with the R-type hexaferrite structure, BaFe_4-xM_xM’₂O₁₁ (M = In, Sc; M’ = Ti, Sn; x = 0.0–1.8), are synthesized and characterized. Structural analyses using powder neutron diffraction reveal that trivalent iron cations are distributed among all the available M sites (octahedral and trigonal bipyramidal sites), with site preference varying with the composition. Ferrimagnetic behavior is observed for all the compounds, and the observed magnetic hysteresis loop indicates that the compounds are soft magnets. The color of the new solid solution can be tuned from dark reddish brown to reddish-orange and yellowish-orange as In or Sc substitutions increase. The origin of colors in these ferrite-based solid solutions results from the combination of ligand-to-metal charge transfer and electron-pair transitions across the face-shared octahedra, as seen in the hematite (Fe₂O₃). Reducing Fe content in the parent compound improves the diffuse reflectance in the near-infrared range, suggesting potential applications as cool pigments.

六铁氧体是一种具有六角形结构的复杂铁氧化物。本文合成并表征了具有 R 型六铁氧体结构的新型成分 BaFe4-xMxM'2O11（M = In、Sc；M' = Ti、Sn；x = 0.0-1.8）。利用粉末中子衍射进行的结构分析表明，三价铁阳离子分布在所有可用的 M 位点（八面体和三叉双锥位点）上，位点偏好随成分而变化。所有化合物都具有铁磁性，观察到的磁滞回线表明这些化合物是软磁体。随着 In 或 Sc 取代度的增加，新固溶体的颜色可从深红棕色调整为橘红色和橘黄色。这些铁基固溶体的颜色来源于配体到金属的电荷转移和面共八面体上的电子对跃迁，赤铁矿（Fe2O3）中就有这种现象。降低母体化合物中的铁含量可提高近红外范围的漫反射率，这表明它们有可能被用作冷颜料。

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引用次数: 0

Novel Mn5+-activated Ba2TiO4 phosphor emitting in the second near-infrared biological window 新型 Mn5+ 激活的 Ba2TiO4 荧光粉在第二近红外生物窗口发光

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2024-11-07 DOI: 10.1016/j.progsolidstchem.2024.100493

Hang Zhao , Xin Xin , Liangsheng Tian , Theeranun Siritanon , Suwit Suthirakun , Wongsathorn Kaewraung , Menghang Qi , Ruoxiu Xiao , Jingyi Ren , Peng Jiang

In recent years, second near-infrared window emitting phosphors have gained widespread research interest due to their excellent tissue penetration and high imaging accuracy. In this work, a new type of Ba₂Ti_1-xMn_xO_4+x/2 (0.02 ≤ x ≤ 0.10) phosphors were successfully prepared by high-temperature solid-phase method and their potential in luminescence thermometry is evaluated. PL and PLE spectral analysis prove that the optimal Mn doping concentration is x = 0.03. The as-synthesized phosphors exhibit a broad excitation band of 550–1000 nm and a narrow emission band of 1170–1220 nm. The electronic structures of the original Ba₂TiO₄ and Mn-doped Ba₂TiO₄ were calculated and analyzed using the DFT + U method, which facilitates a better understanding of the impact of Mn doping on the luminescent properties of Ba₂TiO₄. The luminescence decay lifetime is measured to be 101.44 μs at room temperature, which is a giant enhancement compared to conventional nanosecond lifetime phosphor, indicating a progress in imaging accuracy. In addition, the as-synthesized phosphors maintain over 75 % of the maximum luminescence intensity within the physiological temperature range. The potential applications in luminescence temperature measurement were also analyzed by the LIR ratio method, and the relative sensitivity could reach 2.31 %K⁻¹ at 283 K, which is a relatively high value in the second near-infrared window. Therefore, the as-synthesized Ba₂Ti_1-xMn_xO_4+x/2 (0.02 ≤ x ≤ 0.10) phosphors demonstrate great potential in NIR applications such as biological imaging and luminescent thermometry.

近年来，第二种近红外窗口发射荧光粉因其出色的组织穿透性和高成像精度而获得了广泛的研究兴趣。本研究采用高温固相法成功制备了一种新型 Ba2Ti1-xMnxO4+x/2 （0.02 ≤ x ≤ 0.10）荧光粉，并评估了其在发光测温中的应用潜力。PL 和 PLE 光谱分析证明，最佳锰掺杂浓度为 x = 0.03。合成的荧光粉显示出 550-1000 纳米的宽激发带和 1170-1220 纳米的窄发射带。利用 DFT + U 方法计算并分析了原始 Ba2TiO4 和掺杂锰的 Ba2TiO4 的电子结构，从而更好地理解了掺杂锰对 Ba2TiO4 发光特性的影响。室温下测得的发光衰减寿命为 101.44 μs，与传统的纳秒寿命荧光粉相比有了大幅提高，这表明成像精度有了进步。此外，合成的荧光粉在生理温度范围内能保持 75% 以上的最大发光强度。我们还利用 LIR 比值法分析了发光温度测量的潜在应用，在 283 K 时，相对灵敏度可达 2.31 %K-1，这在第二近红外窗口中是一个相对较高的值。因此，合成的 Ba2Ti1-xMnxO4+x/2 （0.02 ≤ x ≤ 0.10）荧光粉在生物成像和发光测温等近红外应用领域具有很大的潜力。

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