Progress in Solid State Chemistry最新文献_第2页

Temperature-induced structural phase transitions in inorganic compounds: symmetry and information-entropy analysis 无机化合物中温度诱导的结构相变：对称性和信息熵分析

IF 10.5 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-09-10 DOI: 10.1016/j.progsolidstchem.2025.100547

Sergey V. Krivovichev

The tendency of crystal-structure symmetry increasing under increasing temperature (also known as a ‘Landau rule’) is one of the major empirical observations with regard to the temperature-induced phase transitions. The validity of the rule was investigated by means of the statistical analysis of the 502 temperature-driven phase transitions in inorganic compounds with known crystal-structure information for all polymorphs. The analysis was performed from the viewpoint of symmetry considerations (that is, the analysis in terms of the crystal-system hierarchy, where cubic system is the highest and triclinic is the lowest) and information-entropy calculations. It was revealed that the information-based structural complexity parameters (most importantly, the total information content per reduced unit cell) are more sensitive structural symmetry indicators than the symmetry classification in terms of the crystal-system hierarchy. The information-entropy measures decrease under increasing temperature in more than 77 % of phase transitions under consideration, which corresponds to the overall rise of symmetry under heating (the ‘Landau rule’). In contrast, the simple symmetry analysis confirms the ‘Landau rule’ in 60 % of cases only. The information-based parameters are especially efficient for the cases, when crystal system does not change (most numerous are monoclinic-monoclinic and orthorhombic-orthorhombic transitions). The deviations from the rule of increasing symmetry correspond to: phase transition sequences with intermediate (transitional) structures of high complexity, isosymmetric and reentrant phase transitions, and transitions that involve low-temperature metastable polymorphs. There are some exceptions that cannot be assigned to any of the phase-transition types mentioned above, where symmetry is decreasing under heating. The symmetry breaking results in the decrease in vibrational entropy, which may be considered as a major driving force behind the ‘Landau rule’. However, various phenomena such as formation and breaking of bonds, charge and orbital ordering, stereoactive activity of lone electron pairs, etc., may seriously influence polymorphic transformations under temperature changes.

晶体结构对称性随温度升高而增加的趋势（也称为“朗道规则”）是关于温度诱导相变的主要经验观察之一。通过对已知晶体结构信息的无机化合物中502个温度驱动相变的统计分析，验证了该规律的有效性。分析是从对称考虑的角度进行的（即，根据晶体系统层次结构进行分析，其中立方系统最高，三斜系统最低）和信息熵计算。结果表明，基于信息的结构复杂性参数（最重要的是每个简化的单位胞的总信息量）是比对称分类更敏感的结构对称性指标。在考虑的相变中，超过77%的信息熵测量值随着温度的升高而降低，这对应于加热下对称性的整体上升（“朗道规则”）。相比之下，简单的对称分析只在60%的情况下证实了“朗道规则”。在晶体系统不发生变化的情况下（大多数是单斜-单斜和正交-正交转变），基于信息的参数特别有效。与增加对称性规则的偏离对应于：具有高复杂性的中间（过渡）结构的相变序列，等对称和可重入的相变，以及涉及低温亚稳态多晶的相变。有一些例外不能被分配到上述任何相变类型，其中对称性在加热下下降。对称性破缺导致振动熵的减少，这可能被认为是“朗道规则”背后的主要驱动力。然而，各种现象，如键的形成和断裂、电荷和轨道的排序、孤电子对的立体活性等，都可能严重影响温度变化下的多晶转变。

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引用次数: 0

Plate-like NiCo2O4 integrated with g-C3N4 nanostructures for hybrid supercapacitors and green energy technologies 集成了g-C3N4纳米结构的片状NiCo2O4用于混合超级电容器和绿色能源技术

IF 10.5 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-09-08 DOI: 10.1016/j.progsolidstchem.2025.100546

Ehtisham Umar , Fozia Shaheen , M. Waqas Iqbal , Mohammed T. Alotaibi , Amel Ayari-Akkari , Ali Akremi , Eman Kashita

The development of nanostructured electrode materials for supercapacitors and green energy applications remains a challenging task, particularly in achieving maximum surface area for optimal electrode-electrolyte interaction. In this study, we synthesize interconnected nanostructured NiCo₂O₄/g-C₃N₄ using a cost-effective hydrothermal method. The NiCo₂O₄/g-C₃N₄ nanocomposite undergoes comprehensive characterization to analyze its structural, morphological, and electrochemical properties using various techniques. Electrodes fabricated from the NiCo₂O₄/g-C₃N₄ material exhibit a high specific capacity (Qs) of 203 C/g. Additionally, the as-fabricated asymmetric supercapacitor (ASC) achieves a remarkable energy density (Ed) of 87.3 Wh/kg and a power density (Pd) of 1038 W/kg at 1.4 A/g, with superior cycling performance, retaining 95.04 % of its capacity after 10,000 cycles. Furthermore, we evaluate the modified NiCo₂O₄/g-C₃N₄ electrodes for their electrocatalytic performance in the oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The results indicate that the NiCo₂O₄/g-C₃N₄ electrode exhibits the best OER performance (overpotential (η) = 287 mV and Tafel slope = 121 mV/dec at 10 mA/cm²) and demonstrates excellent HER activity (η = 336 mV and Tafel slope = 93 mV/dec at −10 mA/cm²) with exceptional cyclic stability. This research highlights the potential of NiCo₂O₄/g-C₃N₄ as a promising material for supercapacitor and green energy technology.

用于超级电容器和绿色能源应用的纳米结构电极材料的开发仍然是一项具有挑战性的任务，特别是在实现最佳电极-电解质相互作用的最大表面积方面。在本研究中，我们采用经济高效的水热法合成了互连的纳米结构NiCo2O4/g-C3N4。采用各种技术对NiCo2O4/g-C3N4纳米复合材料进行了结构、形态和电化学性能的综合表征。NiCo2O4/g- c3n4材料制备的电极具有203 C/g的高比容量（Qs）。此外，所制备的非对称超级电容器（ASC）在1.4 a /g下的能量密度（Ed）为87.3 Wh/kg，功率密度（Pd）为1038 W/kg，具有优异的循环性能，在10,000次循环后仍能保持95.04%的容量。此外，我们还对改性NiCo2O4/g-C3N4电极在析氧反应（OER）和析氢反应（HER）中的电催化性能进行了评价。结果表明，NiCo2O4/g-C3N4电极表现出最佳的OER性能（10 mA/cm2时过电位(η) = 287 mV， Tafel斜率= 121 mV/dec），并表现出优异的HER活性（- 10 mA/cm2时η = 336 mV， Tafel斜率= 93 mV/dec）和优异的循环稳定性。这项研究突出了NiCo2O4/g-C3N4作为超级电容器和绿色能源技术的有前途的材料的潜力。

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引用次数: 0

Insight into Bi-Sb alloys and their chalcogenide compounds for sodium/potassium ion battery (SIB/PIB) anodes 钠/钾离子电池（SIB/PIB）阳极用Bi-Sb合金及其硫系化合物的研究

IF 10.5 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-09-03 DOI: 10.1016/j.progsolidstchem.2025.100545

Defei Li, Ming-Chun Zhao, Tong Yuan, Ke Cui, Fuqin Zhang

Sodium/potassium ion batteries (SIBs/PIBs), emerging as promising alternatives to lithium-ion batteries (LIBs), show great potential in large-scale electrical energy storage systems owing to their abundant reserves, potential cost advantages, and low standard redox potentials. In recent years, Bi-Sb alloys and their chalcogenide compounds (sulfides, selenides, and tellurides) have garnered significant attention due to their unique bimetallic synergistic effects and tunable energy storage mechanisms. This paper reviews the recent progress in Bi-Sb alloys and their chalcogenide compounds as anode materials for SIBs and PIBs. Highlighting the synergistic effects of Bi-Sb systems, the study emphasizes their high theoretical capacity, reduced volume expansion, and enhanced structural stability compared to monometallic counterparts. Key strategies such as nano-structuring (e.g., nanoporous and 2D layered architectures), composite engineering (e.g., carbon-based matrices), and heterostructure design are discussed to address challenges like electrode pulverization. The electrochemical mechanisms, including multi-step alloying and conversion reactions, are analyzed to elucidate performance enhancements in terms of cycling stability, rate capability, and capacity retention. Specifically, the paper examines the structural properties, modification strategies, and performance optimization mechanisms of these materials, and identifies key pathways for their engineering applications, aiming to provide theoretical support and technological references for designing high-capacity anode materials for SIBs/PIBs. Additionally, critical issues, challenges, and prospects for further development are suggested. This work provides critical insights into material design principles and offers pathways for developing next-generation, cost-effective energy storage technologies.

钠/钾离子电池（SIBs/PIBs）作为锂离子电池（LIBs）的潜在替代品，由于其储量丰富、潜在的成本优势和低标准氧化还原电位，在大规模电能存储系统中显示出巨大的潜力。近年来，铋锑合金及其硫族化合物（硫化物、硒化物和碲化物）因其独特的双金属协同效应和可调的储能机制而受到广泛关注。本文综述了近年来铋锑合金及其硫族化合物作为SIBs和PIBs阳极材料的研究进展。该研究强调了Bi-Sb体系的协同效应，与单金属体系相比，它们具有更高的理论容量、更小的体积膨胀和更高的结构稳定性。讨论了纳米结构（如纳米多孔和二维层状结构）、复合材料工程（如碳基矩阵）和异质结构设计等关键策略，以解决电极粉化等挑战。分析了电化学机制，包括多步合金化和转化反应，以阐明在循环稳定性，速率能力和容量保持方面的性能增强。具体而言，本文研究了这些材料的结构特性、改性策略和性能优化机制，并确定了其工程应用的关键途径，旨在为sib / pib高容量阳极材料的设计提供理论支持和技术参考。此外，还提出了关键问题、挑战和进一步发展的前景。这项工作为材料设计原理提供了重要的见解，并为开发下一代具有成本效益的储能技术提供了途径。

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引用次数: 0

Cation substitution enabled electron rearrangement in high-entropy perovskite oxides for enhanced supercapacitor performance 阳离子取代使高熵钙钛矿氧化物中的电子重排增强了超级电容器的性能

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-06-24 DOI: 10.1016/j.progsolidstchem.2025.100536

Xiaoying Hu, Bo Wang, Xiaotong Zhou, Junzhi Li

The controllable synthesis of high-entropy perovskite oxides and the modulation of their electronic structures are crucial for enhancing the electrochemical performance of supercapacitors. However, it remains challenging to regulate the electronic configuration of B-site elements via A-site doping. In this study, we have reconstructed the electron configuration of B-site elements in high-entropy perovskites through Sm doping, and obtained high-entropy perovskite oxides La_1-xSm_x (Mn_0·2Fe_0·2Co_0·2Ni_0·2Cr_0.2)O₃ (LaSmTMO₃−x) with abundant valence states. The fabricated LaSmTMO₃−0.2 exhibits high specific capacitance of 1367.3 F g⁻¹ at 0.5 A g⁻¹. Besides, the asymmetric supercapacitor (ASC) based on LaSmTMO₃−0.2 exhibits an impressive energy density of 41.2 Wh kg⁻¹ at a power density of 400 W kg⁻¹, with a specific capacity retention of 87.1 % after 10000 cycles. The experimental results demonstrate that superior supercapacitor performance can be attributed to electron rearrangement induced by Sm doping, leading to the formation of active metal species with multiple oxidation states. Simultaneously, Sm doping significantly improves structural integrity, electronic conductivity, and ion transfer kinetics. This work emphasizes the importance of A-site regulation of high entropy perovskite oxides for improving electrochemical performance and provides A new direction for the design of perovskite oxides in energy storage and conversion systems.

高熵钙钛矿氧化物的可控合成及其电子结构的调制是提高超级电容器电化学性能的关键。然而，通过掺杂a位来调节b位元素的电子构型仍然具有挑战性。本研究通过Sm掺杂重建了高熵钙钛矿中b位元素的电子构型，得到了价态丰富的高熵钙钛矿氧化物La1-xSmx (Mn0·2Fe0·2Co0·2Ni0·2Cr0.2)O3 （LaSmTMO3−x）。制备的LaSmTMO3−0.2在0.5 A g−1时具有1367.3 F g−1的高比电容。此外，基于LaSmTMO3−0.2的非对称超级电容器（ASC）在功率密度为400 W kg−1时，能量密度为41.2 Wh kg−1，循环10000次后比容量保持率为87.1%。实验结果表明，优异的超级电容器性能可归因于Sm掺杂引起的电子重排，从而形成具有多种氧化态的活性金属。同时，Sm掺杂显著改善了结构完整性、电子导电性和离子转移动力学。本研究强调了高熵钙钛矿氧化物的A位调控对提高电化学性能的重要性，为钙钛矿氧化物在储能和转换系统中的设计提供了新的方向。

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引用次数: 0

Recent advance in preparation, applications and color regulation mechanism of cobalt blue pigment 钴蓝颜料的制备、应用及调色机理研究进展

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-06-07 DOI: 10.1016/j.progsolidstchem.2025.100535

Hao Yang , Bin Mu , Anjie Zhang , Aiqin Wang

Cobalt blue (CoAl₂O₄) pigment is a well-known high-end blue inorganic pigment with a spinel structure, and it is irreplaceable in the blue pigments either inorganic or organic ones due to its strong coloring performance, desirable blue chroma, and excellent chemical stability. Therefore, a series of strategies have been developed for the preparation of CoAl₂O₄ pigment including common solid-phase method, liquid-phase and gas-phase technologies to meet the requirements of different application fields. However, the relevant applications of CoAl₂O₄ pigment are restricted at a certain degree due to the high cost derived from the scarcity of cobalt sources as well as the aggregation of CoAl₂O₄ particles during the high-temperature crystallization process. Interestingly, incorporation of stable inorganic substrates facilitates the decrease in the production cost and the control of the size and blue intensity of CoAl₂O₄ nanoparticles, especially incorporation of natural or waste nonmetallic mineral resources. Therefore, this review provides an overview of the recent advance in the synthesis, relevant applications and color regulation mechanism of CoAl₂O₄ pigment combining with the literatures and our research achievements. It is mainly focused on the synthesis mechanism of different methods, and the relationships between the structures and the application performances, especially the structural composition and color performance of the designed CoAl₂O₄/silicate hybrid pigments. Finally, several suggestions are proposed for the future development trend on CoAl₂O₄ pigment and even other eco-friendly inorganic pigments.

钴蓝（CoAl2O4）颜料是一种知名的尖晶石结构高端蓝色无机颜料，其着色性能强、蓝色色度理想、化学稳定性好，在无机或有机蓝色颜料中都是不可替代的。因此，为了满足不同应用领域的需求，人们开发了一系列的策略来制备CoAl2O4颜料，包括常见的固相法、液相法和气相法。然而，由于钴源稀缺导致的高成本以及高温结晶过程中CoAl2O4颗粒的聚集，在一定程度上限制了其颜料的相关应用。有趣的是，稳定的无机基质的掺入有助于降低生产成本，控制CoAl2O4纳米颗粒的尺寸和蓝色强度，特别是掺入天然或废弃的非金属矿物资源。因此，本文结合文献和本人的研究成果，对近年来CoAl2O4颜料的合成、相关应用及调色机理等方面的研究进展进行综述。重点介绍了不同合成方法的合成机理、结构与应用性能之间的关系，特别是所设计的CoAl2O4/硅酸盐杂化颜料的结构组成和颜色性能。最后，对未来的发展趋势提出了建议，并对其他环保型无机颜料提出了建议。

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引用次数: 0

Quaternary transition metal dichalcogenides (M1-xNxX2(1-y)Y2y) for hydrogen evolution: A review on atomic structure, 3D engineering, and electrocatalytic performance 四元过渡金属二硫族化合物（M1-xNxX2(1-y)Y2y）析氢：原子结构、三维工程和电催化性能综述

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-05-31 DOI: 10.1016/j.progsolidstchem.2025.100532

Rohit Kumar , Rajni Thakur , Sahil Kumar , Shwetharani R , Bhari Mallana Nagaraja , Sunil Mehla , Itika Kainthla

Hydrogen is a clean, efficient, and sustainable alternative to fossil fuels, placing it at the forefront of our energy future. Water electrolysis is more sustainable and eco-friendlier alternative to fossil fuel-based hydrogen production processes. The earth abundance, low cost, high electrocatalytic activities, and stabilities of transition metal dichalcogenides (TMDs) in the hydrogen evolution reaction (HER) set them apart as exceptional electrocatalysts for hydrogen production. Quaternary TMDs have a general formula of M_1-xN_xX_2(1-y)Y_2y, where M and N are transition metals and X and Y are chalcogens. Thus, quaternary TMDs are versatile nanomaterials that exhibit tremendous potential for fine-tuning and optimizing their electrocatalytic performance through composition modulation, as shown by both theoretical and experimental studies. Additionally, additive manufacturing techniques such as 3D printing are emerging as powerful tools for fabricating structurally complex, compositionally tunable TMD-based electrodes with enhanced HER performance. The integration of 3D printing with advanced TMD synthesis methods enables the design of customized electrocatalysts, offering improved charge transport and catalytic activity for sustainable hydrogen production. To delve deeper into the composition-structure-activity relationships that govern the hydrogen evolution performance of quaternary TMDs, this review encapsulates a comprehensive account of the synthesis methods, atomic and electronic structures, properties, and electrocatalytic performance of quaternary TMDs. Furthermore, the unique challenges in using quaternary TMD electrocatalysts and the authors' perspective on their future potential in hydrogen production are elaborated.

氢是一种清洁、高效和可持续的化石燃料替代品，将其置于我们未来能源的最前沿。水电解是比化石燃料制氢工艺更可持续、更环保的替代品。在析氢反应（HER）中，过渡金属二硫族化合物（TMDs）具有丰富的稀土元素、低廉的成本、较高的电催化活性和稳定性，是一种特殊的制氢电催化剂。四元tmd的通式为M1-xNxX2(1-y)Y2y，其中M和N为过渡金属，X和Y为硫元。因此，理论和实验研究表明，四元tmd是一种多功能纳米材料，具有通过组成调制微调和优化其电催化性能的巨大潜力。此外，3D打印等增材制造技术正在成为制造结构复杂、成分可调、具有增强HER性能的tmd电极的强大工具。3D打印与先进的TMD合成方法的集成使定制电催化剂的设计成为可能，为可持续的氢气生产提供改进的电荷传输和催化活性。为了更深入地研究控制四元tmd析氢性能的组成-结构-活性关系，本文综述了四元tmd的合成方法、原子和电子结构、性质和电催化性能。此外，作者还阐述了使用四元TMD电催化剂的独特挑战，并对其在制氢方面的未来潜力进行了展望。

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引用次数: 0

Rare earth doped Zirconia: Structure, physicochemical properties and recent advancements in technological applications 稀土掺杂氧化锆：结构、理化性质及技术应用的最新进展

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-05-29 DOI: 10.1016/j.progsolidstchem.2025.100524

S. Kalaivani, M. Ezhilan, M. Deepa, S. Kannan

Zirconia (ZrO₂) based ceramics have been pivotal in the evolution of materials across various applications. Particularly, rare earth (RE) doped ZrO₂ is of greater interest due to its remarkable thermal stability, mechanical strength, and ionic conductivity, which are primarily influenced by its distinct solid state properties. This review aims to deliver a comprehensive analysis of the structural features induced by RE doping, with a particular emphasis on the phase transitions and stability of the various polymorphs of ZrO₂. The relationship between the ionic size of RE, oxygen vacancies and microstructural behavior is explored in the context of lattice distortion and thermodynamic stabilization. The review highlights the critical role of doping strategies in the varying microstructure and enhancing the performance of ZrO₂ based materials. Emerging applications such as solid oxide fuel cells, thermal barrier coatings, bioceramics and optical devices necessitate a comprehensive understanding of fundamental solid state properties to ensure their effective operation. Additionally, future research directions are suggested to facilitate the development of next generation ZrO₂ based systems, with a focus on enhancing their structural and functional performance.

氧化锆（ZrO2）基陶瓷在各种应用材料的发展中起着关键作用。特别是，稀土（RE）掺杂的ZrO2由于其显著的热稳定性，机械强度和离子电导率而引起了更大的兴趣，这些主要受其独特的固态性质的影响。本文旨在全面分析稀土掺杂引起的ZrO2的结构特征，特别强调了ZrO2各种多晶的相变和稳定性。在晶格畸变和热力学稳定的背景下，探讨了稀土离子大小、氧空位和微观结构行为之间的关系。综述强调了掺杂策略在改变ZrO2基材料的微观结构和提高其性能方面的关键作用。诸如固体氧化物燃料电池、热障涂层、生物陶瓷和光学器件等新兴应用需要全面了解基本的固态特性，以确保其有效运行。展望了未来的研究方向，以促进下一代基于ZrO2的系统的发展，重点是提高其结构和功能性能。

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引用次数: 0

Integration of non-Ti3C2 MXene with carbon-based materials for energy storage devices: Recent advancements and future aspects 非ti3c2 MXene与碳基材料集成用于储能设备：最新进展和未来展望

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-05-24 DOI: 10.1016/j.progsolidstchem.2025.100523

Iftikhar Hussain , Karanpal Singh , Avinash C. Mendhe , Mohammad R. Thalji , Soumen Mandal , Ijaz Ali , Ahmed F.M. EL-Mahdy , P. Rosaiah , Muhammad Kashif Aslam , Tensangmu Lama Tamang , Kaili Zhang

MXenes find practical use in electrochemical systems, particularly in energy storage devices like supercapacitors and batteries. Notably, Ti₃C₂ MXene has been extensively studied, but also non-Ti₃C₂ MXene materials have shown promising properties in energy storage applications. Non-Ti₃C₂ MXenes, when combined with carbonaceous materials like activated carbon, carbon nanotubes, graphene, etc. exhibit superior specific capacitance, excellent rate capability, and higher electrical conductivity, making them attractive for supercapacitors and batteries. Herein, the incorporation of non-Ti₃C₂ MXenes with various carbon materials in energy storage systems has been discussed, showing potential for enhancing the overall electrochemical performance. Strategies to enhance the interaction between non-Ti₃C₂ MXenes and carbon materials have been summarized to tackle challenges and capitalize on opportunities for more efficient and sustainable energy storage technologies.

MXenes在电化学系统中有实际应用，特别是在超级电容器和电池等能量存储设备中。值得注意的是，Ti3C2 MXene已经得到了广泛的研究，但非Ti3C2 MXene材料在储能应用中也显示出了很好的性能。当非ti3c2 MXenes与活性炭、碳纳米管、石墨烯等碳质材料结合时，表现出优异的比电容、优异的倍率能力和更高的导电性，使其成为超级电容器和电池的理想材料。本文讨论了非ti3c2 MXenes与各种碳材料在储能系统中的结合，显示出提高整体电化学性能的潜力。本文总结了增强非ti3c2 MXenes与碳材料之间相互作用的策略，以应对挑战并利用更高效和可持续的储能技术的机遇。

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引用次数: 0

Study on novel blue-purple high-NIR reflectance pigments and acrylic coatings based on Ca2Zn1-xMxSi2O7 (M = Mn and Ni) 基于Ca2Zn1-xMxSi2O7 （M = Mn和Ni）的新型蓝紫色高近红外反射颜料及丙烯酸涂料的研究

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry

Pub Date : 2025-05-23 DOI: 10.1016/j.progsolidstchem.2025.100522

Zhiwei Wang , Yinan Shen , Liangsheng Tian , Suwit Suthirakun , Wongsathorn Kaewraung , Qi Menghang , Hang Zhao , Xin Xin , Ruoxiu Xiao , Peng Jiang , Qu Li , Tingting Lu

The coating optimized with high near-infrared reflectance pigments can effectively reduce the energy consumption for heating and cooling in buildings, thereby alleviating the pressure on global energy consumption. Using a high-temperature solid-state method, blue-violet pigments with high near-infrared reflectance, Ca₂Zn_1-xM_xSi₂O₇ (M = Mn, 0 ≤ x ≤ 0.4 and Ni, 0 ≤ x ≤ 0.2) solid solutions, were synthesized for the first time, with a maximum solar reflectance of 82.67%. Using XPS analysis, it was determined that the oxidation state of Ni in the pigment is +2, while Mn exists in mixed oxidation states of +2 and +3. UV-VIS-NIR spectroscopy analysis indicates that the blue-violet color of the pigment originates from the d-d transitions of the transition metal ions. As the doping concentration increases, the near-infrared reflectance of the pigment decreases. The DFT calculations have also confirmed that the color of pigments originates from transition metal ions. The as-synthesized pigments were incorporated into acrylic to create colored coatings. Improving the near-infrared solar reflectance of the acrylic coating. The excellent high near-infrared solar reflectance and coating property optimization make the synthesized pigment a potential energy-saving coating.

采用高近红外反射率颜料优化的涂料，可以有效降低建筑的供暖和制冷能耗，从而缓解全球能源消耗压力。采用高温固相法首次合成了具有高近红外反射率的蓝紫色颜料Ca2Zn1-xMxSi2O7 （M = Mn, 0≤x≤0.4,Ni, 0≤x≤0.2）固溶体，最大太阳反射率为82.67%。通过XPS分析，确定了Ni在颜料中的氧化态为+2，Mn以+2 +3的混合氧化态存在。紫外-可见-近红外光谱分析表明，颜料的蓝紫色源于过渡金属离子的d-d跃迁。随着掺杂浓度的增加，颜料的近红外反射率降低。DFT计算也证实了颜料的颜色来源于过渡金属离子。合成的颜料被掺入丙烯酸制成彩色涂料。提高丙烯酸涂料的近红外太阳反射率。优异的高近红外太阳反射率和涂层性能优化使合成的颜料成为一种有潜力的节能涂料。

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引用次数: 0

Atomically dispersed Pt and Pt clusters on CeO2 supports for H2 production via low-temperature water-gas shift reaction 在CeO2载体上原子分散的Pt和Pt团簇通过低温水气转换反应制氢

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.2025.100520

Liping Du, Aishu Li, Song Hu, Sheng Su, Yi Wang, Long Jiang, Jun Xu, Kai Xu, Jun Xiang

Water-gas shift (WGS) reaction plays a crucial role in the steam reforming of carbon-based fuels for hydrogen production. Pt-CeO₂ catalysts have attracted significant attention due to their excellent low-temperature activity, and optimizing the catalytic system performance is essential for reducing energy consumption. In this study, we investigated the impact of metal dispersion differences on the catalytic activity of CeO₂-supported clusters and atomically dispersed Pt catalysts from the perspectives of oxygen vacancies and metal-support interactions. The results indicated that the adsorption capacity of CO on the catalyst surface was significantly influenced by the oxidation state and aggregation of Pt, with atomically dispersed Pt⁰ exhibiting a stronger affinity for CO. The metal-support interaction was evident in the formation of Pt-O-Ce composite bonds resulting from the incorporation of Pt ions into the CeO₂ lattice, which enhanced Pt accessibility on the CeO₂ surface. All samples demonstrated outstanding catalytic performance, achieving CO conversion exceeding 70 % and H₂ yield surpassing 150 mL g⁻¹ at low temperatures. The IMP-Pt characterized by an elevated oxygen vacancy concentrations (OVC) of 3.99 × 10²¹ cm⁻³, arising from partially reduced Ce³⁺ in unsaturated coordination states, exhibited a ∼10 % decline in CO conversion and a ∼20 °C increase in T₅₀. Undercoordinated Pt clusters led to strong CO binding and high CO vibration frequencies, while the presence of Pt^δ+ weakened CO adsorption but promoted carbonation reactions. The superior lattice oxygen mobility and dynamic oxygen storage capacity of atomically dispersed Pt-CeO₂ catalysts resulted in faster calculated reaction rates on exposed Pt atoms and higher turnover frequencies.

水气转换反应在碳基燃料的蒸汽重整制氢过程中起着至关重要的作用。Pt-CeO2催化剂因其优异的低温活性而备受关注，优化催化体系性能对降低能耗至关重要。在这项研究中，我们从氧空位和金属-载体相互作用的角度研究了金属分散差异对ceo2负载簇和原子分散Pt催化剂催化活性的影响。结果表明，Pt的氧化态和聚集对CO在催化剂表面的吸附能力有显著影响，原子分散的Pt0对CO具有更强的亲和力。由于Pt离子进入CeO2晶格，形成Pt- o - ce复合键，从而增强了Pt在CeO2表面的可及性，金属-载体相互作用明显。所有样品均表现出优异的催化性能，在低温下CO转化率超过70%，H2产率超过150 mL g - 1。由于Ce3+在不饱和配位态的部分还原，IMP-Pt的氧空位浓度（OVC）提高了3.99 × 1021 cm−3，CO转化率下降了~ 10%，T50升高了~ 20°C。Ptδ+的存在削弱了CO的吸附，但促进了碳化反应的发生。原子分散Pt- ceo2催化剂优越的晶格氧迁移率和动态氧存储能力使得暴露Pt原子的计算反应速率更快，周转频率更高。

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