Journal of Solid State Chemistry最新文献

Phase transformation of BaAl2Si2O8 through metastable phase-growth in a kaolinite system containing minor impurities 含少量杂质高岭石体系中亚稳相生长的BaAl2Si2O8相变

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-06-01 Epub Date: 2026-02-11 DOI: 10.1016/j.jssc.2026.125888

Shingo Machida , Hajime Okawa , Toshimichi Shibue

Hexacelsian, the metastable phase of BaAl₂Si₂O₈, is composed of stacked tetrahedral aluminosilicate layers; however, practical utilization of this layered structure is hindered by impurity-driven transformation to celsian, the stable phase of BaAl₂Si₂O₈ with a three-dimensional framework crystal structure. In this study, the hexacelsian-to-celsian transformation prepared from kaolinite containing relatively small amounts of by-products was examined by varying a pre-heating step to grow the hexacelsian phase prior to calcination at 1600 °C as the main heating step. X-ray diffraction patterns and solid-state ²⁷Al nuclear magnetic resonance spectra revealed the formation of poorly crystalline and then crystalline hexacelsian, accompanied by small amounts of BaAl₂O₄ and Ba₂SiO₄ originating from the by-products. Although defect signals were not detected by electron spin resonance, the presence of BaAl₂O₄ and Ba₂SiO₄, together with the sharpening and intensity changes of the ²⁷Al signals, were used as qualitative indicators of defect-related factors, which correlate with an accelerated transformation to celsian. Comparisons among specimens with nearly constant crystallinity and surface area confirm this correlation. Comparisons at nearly constant surface area show that increased crystallinity retards the transformation, whereas comparisons at similar crystallinity indicate that surface area still influences the transformation. Therefore, the results indicate that defect-related factors, crystallinity, and surface area dominate the transformation from hexacelsian to celsian, and their individual influences can be qualitatively distinguished through the present comparisons. Thus, this study provides practical guidelines for stabilizing hexacelsian in impurity-bearing raw materials and for exploiting metastable layered aluminosilicates in high-temperature ceramic applications.

六正相是BaAl2Si2O8的亚稳相，由堆叠的四面体铝硅酸盐层组成；然而，这种层状结构的实际利用受到杂质驱动转变为celsian（具有三维框架晶体结构的BaAl2Si2O8的稳定相）的阻碍。在本研究中，从含有相对少量副产物的高岭石制备的六方相到六方相的转变是通过改变预热步骤来生长的，然后在1600°C下作为主要加热步骤进行煅烧。x -射线衍射图和固态27Al核磁共振谱显示，该反应先形成弱晶，再形成六方晶，并伴有少量的BaAl2O4和Ba2SiO4副产品。虽然没有通过电子自旋共振检测到缺陷信号，但BaAl2O4和Ba2SiO4的存在以及27Al信号的锐化和强度变化作为缺陷相关因素的定性指标，与加速向celsian转变有关。在结晶度和表面积几乎恒定的样品之间的比较证实了这种相关性。在接近恒定表面积下的比较表明，结晶度的增加延缓了转变，而在相似结晶度下的比较表明，表面积仍然影响转变。因此，结果表明，缺陷相关因素、结晶度和表面积主导了从六直角向直角的转变，并且通过目前的比较可以定性地区分它们各自的影响。因此，该研究为稳定含杂质原料中的六晶硅以及在高温陶瓷应用中开发亚稳层状硅铝酸盐提供了实用指南。

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引用次数: 0

Three multifunctional coordination polymers based on viologen: photochromic/thermochromic properties, ammonia vapor sensing and applications 三种基于紫紫素的多功能配位聚合物：光致变色/热致变色性能、氨蒸汽传感及其应用

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-05-01 Epub Date: 2026-02-06 DOI: 10.1016/j.jssc.2026.125879

Boyu Shan , Shuqi Zhang , Qi Shi , Yuchen Wang , Yan Chen , Jinghan Zhang , Xin Shi , Yang Zhao , Xinzhu Li , Baili Zhu , Changbin Shao , Shuxin Cui

Multifunctional coordination polymers (CPs) with stimulus responses containing viologen have been widely studied and prepared. In this work, based on a novel viologen ligand {H₂BCMBPY·2Cl = 1,1′-bis [(2-carboxybipheny-4-yl)methyl]-4,4′- bipyridinium dichloride}, 1,2,4,5-benzenetetracarboxylic acid (H₄BTEC) and CdCl₂·2.5H₂O/ZnSO₄·7H₂O, three multifunctional CPs were synthesized under solvothermal conditions, named {[Cd₄(BCMBPY)₂(BTEC)₂]·4H₂O}_n (1), {[Zn₂·2(BCMBPY)_1/2·2(BTEC)_1/2]·2H₂O}_n (2a), {[Zn₂(BCMBPY)(BTEC)]·2H₂O}_n (2b). Under irradiation with a Xe lamp, three CPs exhibited distinct color changes: CP 1 turned yellow-green, while 2a and 2b turned blue. Notably, 2b showed high photosensitivity displaying photochromic behavior within 2 s. The discoloration mechanism of three CPs were investigated via time-dependent density functional theory (TDDFT). All three CPs also undergo visible color changes under thermal treatment or ammonia vapor conditions. Furthermore, in studies on inkless erasable printing, QR code anti-counterfeiting and photochromic films, all three CPs demonstrated excellent performance, making them promising candidates for multifunctional stimulus-responsive materials. It was found that the structure and properties of CPs can be tuned by changing the metal center or solvent.

含有紫素刺激反应的多功能配位聚合物（CPs）得到了广泛的研究和制备。本文以一种新的有机配体（H2BCMBPY·2Cl = 1,1′-双[（2-羧基联苯-4-基）甲基]-4,4′-二氯化联吡啶}，1,2,4,5-苯四羧酸（H4BTEC）和CdCl2·2.5H2O/ZnSO4·7H2O）为基础，在溶剂热条件下合成了3种多功能CPs，分别命名为{[Cd4(BCMBPY)2(BTEC)2]·4H2O}n(1)、{[Zn2·2(BCMBPY)1/2·2(BTEC)1/2]·2H2O}n （2a）、{[Zn2(BCMBPY)(BTEC)]·2H2O}n （2b）。在氙灯照射下，3种CPs呈现出明显的颜色变化：CP 1变为黄绿色，2a和2b变为蓝色。值得注意的是，2b具有较高的光敏性，在2 s内表现出光致变色行为。利用时变密度泛函理论（TDDFT）研究了三种CPs的变色机理。这三种CPs在热处理或氨蒸汽条件下也会发生可见的颜色变化。此外，在无墨可擦印刷、二维码防伪和光致变色薄膜的研究中，这三种CPs均表现出优异的性能，成为多功能刺激响应材料的有希望的候选材料。研究发现，通过改变金属中心或溶剂，可以调整CPs的结构和性能。

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引用次数: 0

One-step self-assembly synthesis strategy for hierarchical MoO3/NiMoO4 nanorods: Bifunctional lithium-ion batteries and forensic applications 分层MoO3/NiMoO4纳米棒的一步自组装合成策略：双功能锂离子电池和法医应用

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-05-01 Epub Date: 2026-02-08 DOI: 10.1016/j.jssc.2026.125887

K.R. Pooja , Manjanna J , C.V. Manjunatha , Y. Venkataramanappa , G. Nagaraju

Hierarchical MoO₃/NiMoO₄ NCs were successfully synthesized via a simple one-step self-assembly hydrothermal method using flaxseed oil as a green fuel and structure-directing agent. Structural characterization confirmed the coexistence of orthorhombic MoO₃ and monoclinic NiMoO₄ phases with strong interfacial coupling, enabling rapid electron transport and enhanced Li⁺ diffusion. When evaluated as an anode material for lithium-ion batteries, the MoO₃/NiMoO₄ electrode delivered an impressive initial discharge capacity of 1450 mAhg⁻¹ at 0.2C, outstanding rate capability (2215 mAhg⁻¹ at 0.1C), and excellent cycling stability with 933 mAhg⁻¹ retained after 500 cycles. These superior electrochemical performances are attributed to the synergistic redox activity, the hierarchical porous nanorod architecture, which effectively accommodates volume variations, and accelerated charge transfer across the heterointerface. Electrochemical impedance spectroscopy further revealed low charge-transfer resistance and improved Li⁺ diffusion kinetics, confirming enhanced interfacial conductivity. Beyond its exceptional energy storage behavior, the material exhibited strong blue-green photoluminescence at 361 nm, which was successfully utilized for latent fingerprint visualization, demonstrating its multifunctional potential. Overall, the MoO₃/NiMoO₄ NCs provide a robust and sustainable platform for next-generation high-performance lithium-ion battery applications.

以亚麻籽油为绿色燃料和结构导向剂，通过简单的一步自组装水热法成功合成了层次化MoO3/NiMoO4纳米材料。结构表征证实了正交相MoO3和单斜相NiMoO4共存，界面耦合强，能够快速传递电子，增强Li+扩散。作为锂离子电池的负极材料，MoO3/NiMoO4电极在0.2C时的初始放电容量为1450 mAhg−1，在0.1C时的倍率容量为2215 mAhg−1，在500次循环后的循环稳定性为933 mAhg−1。这些优异的电化学性能归功于协同氧化还原活性，分层多孔纳米棒结构，有效地适应了体积变化，加速了电荷在异质界面上的转移。电化学阻抗谱进一步揭示了低电荷转移电阻和改善的Li+扩散动力学，证实了界面电导率的增强。除了具有优异的能量存储性能外，该材料在361 nm处表现出强烈的蓝绿色光致发光，成功地用于潜在指纹可视化，显示了其多功能潜力。总体而言，MoO3/NiMoO4 nc为下一代高性能锂离子电池应用提供了一个强大且可持续的平台。

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引用次数: 0

A dual-functional hafnium-amino UiO-66 MOF: Synergistic electrostatic enrichment and in-situ reduction for efficient Cr(VI) detoxification 双功能铪-氨基UiO-66 MOF：协同静电富集和原位还原高效解毒Cr（VI）

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-05-01 Epub Date: 2026-01-20 DOI: 10.1016/j.jssc.2026.125835

Xiaoyi Lin , Sabrina Yanan Jiang , Gang Li

Based on HfCl₄ and 2-amino-terephthalic acid (NH₂–H₂BDC), a hafnium-based metal–organic framework (Hf-UiO-66-NH₂) was solvothermally synthesized in a DMF–H₂O system modulated with acetic acid. The material exhibits excellent performance in removing Cr(VI) from aqueous solution, with a maximum adsorption capacity of 77 mg g⁻¹ and a removal efficiency of 87.72 % in a single-phase system. The Cr(VI) uptake mechanism involves a synergistic process of electrostatic attraction, reduction, and coordination: under acidic conditions, protonated amino groups (–NH₃⁺) attract chromate anions, followed by in situ reduction of Cr(VI) to less toxic Cr(III) by electron-donating moieties (e.g., –OH) within the framework. The resulting Cr(III) species are subsequently immobilized via coordination to amino or other functional groups. This proposed mechanism is consistently supported by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) analyses.

以HfCl4和2-氨基对苯二甲酸（NH2-H2BDC）为原料，在醋酸调制的DMF-H2O体系中溶剂热合成了铪基金属有机骨架（hf - uuo -66- nh2）。该材料在水溶液中表现出优异的去除Cr（VI）的性能，在单相体系中最大吸附量为77 mg g−1，去除效率为87.72%。Cr（VI）的吸收机制涉及静电吸引、还原和配位的协同过程：在酸性条件下，质子化氨基（-NH3 +）吸引铬酸盐阴离子，然后通过框架内的供电子基团（例如-OH）将Cr（VI）原位还原为毒性较小的Cr（III）。得到的Cr（III）随后通过与氨基或其他官能团的配位而固定。这一机制得到了x射线光电子能谱（XPS）和傅里叶变换红外光谱（FTIR）分析的一致支持。

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引用次数: 0

Interface engineering coupled with NiAl-LDH/Ti3C2Tx sacrificial template: Fabrication of 3D flower-like NiO/Al2O3/TiO2 composites and their DMF gas-sensing performances 界面工程耦合NiAl-LDH/Ti3C2Tx牺牲模板：三维花朵状NiO/Al2O3/TiO2复合材料的制备及其DMF气敏性能

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-05-01 Epub Date: 2026-01-27 DOI: 10.1016/j.jssc.2026.125856

Caihong Yuan, Keyue Gong, Xintong Dong, Ying Guo

This paper reports the synthesis of a three-dimensional (3D) flower-like NiO/Al₂O₃/TiO₂ composite for N,N-dimethylformamide (DMF) vapor detection, by calcination of the self-sacrificing NiAl-LDH/Ti₃C₂T_x precursor, which is fabricated via hydrothermal synthesis with monolayer Ti₃C₂T_x MXene as the substrate for LDH growth. Noteworthily, the interface engineering of monolayer Ti₃C₂T_x into the LDH precursor endows the calcined composite oxides with uniform elemental distribution while effectively suppressing nanoparticle aggregation. Further optimization of Ti₃C₂T_x content enables precise control over TiO₂ amount, which not only modulates the morphology of the NiO/Al₂O₃ composite but also tailors its electronic structure. The optimized NiO/Al₂O₃/TiO₂ composite exhibits prominent advantages, including abundant oxygen vacancies, a high specific surface area of 175 m² g⁻¹, and a narrowed band gap. Experimental results demonstrate that the sensitivity of NiO/Al₂O₃/TiO₂ to 100 ppm N, N-dimethylformamide at 245 °C reaches 48.6, which is approximately 3 times as high as that of pure NiO/Al₂O₃. Compared with traditional preparation methods, the as-synthesized composite metal oxide exhibits superior gas-sensing performance. This study provides a new design concept for developing high-performance composite metal oxide gas-sensing materials via precursor interface engineering.

本文报道了一种用于N，N-二甲基甲酰胺（DMF）气相检测的三维（3D）花状NiO/Al2O3/TiO2复合材料，该复合材料采用自牺牲的NiAl-LDH/Ti3C2Tx前驱体，以单层Ti3C2Tx MXene为底物，经水热合成制备而成。值得注意的是，在LDH前驱体中进行了单层Ti3C2Tx的界面工程，使煅烧后的复合氧化物元素分布均匀，同时有效抑制了纳米颗粒的聚集。进一步优化Ti3C2Tx的含量，可以精确控制TiO2的含量，不仅可以调节NiO/Al2O3复合材料的形貌，还可以定制其电子结构。优化后的NiO/Al2O3/TiO2复合材料具有丰富的氧空位、175 m2 g−1的高比表面积和窄带隙等优点。实验结果表明，在245℃下，NiO/Al2O3/TiO2对100 ppm N， N-二甲基甲酰胺的灵敏度达到48.6，约为纯NiO/Al2O3的3倍。与传统的制备方法相比，合成的复合金属氧化物具有优越的气敏性能。本研究为利用前驱体界面工程开发高性能复合金属氧化物气敏材料提供了新的设计思路。

{"title":"Interface engineering coupled with NiAl-LDH/Ti3C2Tx sacrificial template: Fabrication of 3D flower-like NiO/Al2O3/TiO2 composites and their DMF gas-sensing performances","authors":"Caihong Yuan, Keyue Gong, Xintong Dong, Ying Guo","doi":"10.1016/j.jssc.2026.125856","DOIUrl":"10.1016/j.jssc.2026.125856","url":null,"abstract":"<div><div>This paper reports the synthesis of a three-dimensional (3D) flower-like NiO/Al2O3/TiO2 composite for N,N-dimethylformamide (DMF) vapor detection, by calcination of the self-sacrificing NiAl-LDH/Ti3C2Tx precursor, which is fabricated via hydrothermal synthesis with monolayer Ti3C2Tx MXene as the substrate for LDH growth. Noteworthily, the interface engineering of monolayer Ti3C2Tx into the LDH precursor endows the calcined composite oxides with uniform elemental distribution while effectively suppressing nanoparticle aggregation. Further optimization of Ti3C2Tx content enables precise control over TiO2 amount, which not only modulates the morphology of the NiO/Al2O3 composite but also tailors its electronic structure. The optimized NiO/Al2O3/TiO2 composite exhibits prominent advantages, including abundant oxygen vacancies, a high specific surface area of 175 m2 g−1, and a narrowed band gap. Experimental results demonstrate that the sensitivity of NiO/Al2O3/TiO2 to 100 ppm N, N-dimethylformamide at 245 °C reaches 48.6, which is approximately 3 times as high as that of pure NiO/Al2O3. Compared with traditional preparation methods, the as-synthesized composite metal oxide exhibits superior gas-sensing performance. This study provides a new design concept for developing high-performance composite metal oxide gas-sensing materials via precursor interface engineering.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"357 ","pages":"Article 125856"},"PeriodicalIF":3.5,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075880","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis, crystal structure and high-temperature investigation of new Dion-Jacobson type titanoniobates 新型Dion-Jacobson型钛酸盐的合成、晶体结构及高温研究

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-05-01 Epub Date: 2026-02-05 DOI: 10.1016/j.jssc.2026.125846

O.V. Krasheninnikova, M.S. Lomakin, I.S. Sorokin, E.V. Suleimanov, V.A. Oloventsova, D.N. Titaev

New Dion–Jacobson type layered titanoniobates RbEu₂Ti₂NbO₁₀, RbSm₂Ti₂NbO₁₀ and their proton-exchanged analogues HEu₂Ti₂NbO₁₀·0.68H₂O and HSm₂Ti₂NbO₁₀·0.73H₂O were synthesized for the first time. Rb-containing phases were obtained by high-temperature solid-state reactions, while protonated derivatives were produced through ion exchange in hydrochloric acid solution. Phase and chemical purity were verified by XRD, EDX and TGA. The crystal structures of RbEu₂Ti₂NbO₁₀ and RbSm₂Ti₂NbO₁₀ were refined in the tetragonal P4/mmm space group, confirming the characteristic Dion–Jacobson arrangement with strong Ti/Nb B-site ordering. Polyhedral analysis revealed that decreasing lanthanide ionic radius leads to enhanced distortions of the [LnO₁₂] and outer [(Ti/Nb)O₆] octahedra, while the central [TiO₆] units remain nearly undistorted. Thermal behavior was examined using DTA/TGA and high-temperature XRD. Rb-containing phases are stable up to 1273 K, whereas protonated forms are metastable and undergo sequential dehydration and deprotonation accompanied by partial collapse of the layered framework. Optical diffuse-reflectance spectroscopy showed direct band gaps of 3.41–3.62 eV. Band-edge potentials indicate that all compounds are active under UV irradiation and are capable of generating superoxide radicals, suggesting their suitability for photocatalytic oxidation processes.

首次合成了新型Dion-Jacobson型层状钛酸盐RbEu2Ti2NbO10、RbSm2Ti2NbO10及其质子交换类似物HEu2Ti2NbO10·0.68H2O和HSm2Ti2NbO10·0.73H2O。通过高温固相反应得到含rb相，在盐酸溶液中通过离子交换得到质子化衍生物。通过XRD、EDX和TGA对样品进行了物相和化学纯度的验证。RbEu2Ti2NbO10和RbSm2Ti2NbO10的晶体结构在P4/mmm空间群中细化，证实了具有强Ti/Nb b位有序的Dion-Jacobson排布特征。多面体分析表明，镧系离子半径的减小导致[LnO12]和外围[(Ti/Nb)O6]八面体的畸变增强，而中心[TiO6]单元几乎保持不变。采用DTA/TGA和高温XRD对其热行为进行了表征。含rb相在1273 K时是稳定的，而质子化形式则是亚稳的，并经历连续的脱水和去质子化，同时伴有层状框架的部分坍塌。光学漫反射光谱显示直接带隙为3.41 ~ 3.62 eV。带边电位表明，所有化合物在紫外线照射下都具有活性，并且能够产生超氧自由基，表明它们适合于光催化氧化过程。

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引用次数: 0

Controlled synthesis of close-packed ternary sulfides heterojunction based on ZIF-8@In-TCPP and enhanced photocatalytic hydrogen evolution 基于ZIF-8@In-TCPP和增强光催化析氢的紧密排列三元硫化物异质结的受控合成

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-05-01 Epub Date: 2026-01-30 DOI: 10.1016/j.jssc.2026.125857

Fuyuan Yang, Zhongqiao Sun, Hao Meng, Yide Han, Wenhao Li, Xia Zhang

Metal organic frameworks (MOFs), being as a sacrificial precursor were used to synthesize composite semiconductors, that is found with the superiorities in designing the special architecture, including high-disperse metal nodes, hierarchical porous structure and close-packed heterojunction. In this study, lamellar In-TCPP was employed to incorporate ZIF-8 to fabricate a MOF@MOF architecture (ZIF-8@In-TCPP), which was then subjected to a thioacetamide (TAA)-assisted sulfidation process, yielding a ternary sulfide composed of ZnS, ZnIn₂S₄ (ZIS), and In₂S₃, denoted as Z@In-t (where t represents the controlled sulfidation duration). The sulfidation time was varied from 6 h to 36 h to optimize the final hetero structure and the photocatalytic activity of Z@In-t. Compared to original ZIF-8@In-TCPP, the bandgap of Z@In-12 is narrowed till 2.34 eV, showing hierarchically porous nanosheet structure with tightly interconnected interface junction. Irradiated with visible light (λ ≥ 420 nm), the Z@In-12 demonstrates the best photocatalytic hydrogen evolution rate of 4449.79 μmol g⁻¹ h⁻¹, while no precious metal co-catalysts were added. This photocatalytic rate markedly exceeds the values by the single In-TCPP and binary ZIF-8@In-TCPP, and also surpasses most of previously reported values by MOF-derived sulfides. The electrochemical analyses, including transient photocurrent-time (I-t) curves, electrochemical impedance spectroscopy (EIS), and electron paramagnetic resonance (EPR) spectroscopy were used to clarify the enhance photocatalytic mechanism. This work enriches the researches related to MOF-derived multiple sulfides, and designing the MOFs precursors in the improved visible light photocatalytic hydrogen production.

金属有机骨架（MOFs）作为一种牺牲前驱体用于合成复合半导体，在设计高分散金属节点、分层多孔结构和密密的异质结等特殊结构方面具有优势。在本研究中，采用层状In- tcpp将ZIF-8加入到制造MOF@MOF结构（ZIF-8@In-TCPP）中，然后进行硫乙酰胺（TAA）辅助硫化过程，得到由ZnS， ZnIn2S4 （ZIS）和In2S3组成的三元硫化物，表示为Z@In-t（其中t表示受控硫化持续时间）。硫化时间为6 ~ 36 h，以优化Z@In-t的最终异质结构和光催化活性。与原来的ZIF-8@In-TCPP相比，Z@In-12的带隙缩小到2.34 eV，呈现出层次化的多孔纳米片结构，界面结紧密相连。在可见光（λ≥420 nm）下，Z@In-12的最佳光催化析氢速率为4449.79 μmol g−1 h−1，未添加贵金属助催化剂。这一光催化速率明显超过了单一In-TCPP和二元ZIF-8@In-TCPP的值，也超过了之前报道的mof衍生硫化物的大多数值。利用瞬态光电流-时间（I-t）曲线、电化学阻抗谱（EIS）和电子顺磁共振（EPR）谱等电化学分析方法阐明了增强光催化的机理。本工作丰富了mof衍生的多硫化物的相关研究，并设计了mof前驱体用于改进的可见光催化制氢。

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引用次数: 0

Millimeter-sized Ba5Nb4O15 single crystals: Growth, structural characterization, and specific heat 毫米尺寸Ba5Nb4O15单晶：生长、结构表征和比热

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-05-01 Epub Date: 2026-02-03 DOI: 10.1016/j.jssc.2026.125880

Yao Zhou , Xin Zhang , Wenjun Chu , Xinyu Yin , Lulu Tang , Han-Shu Xu

We report the growth of high-quality, millimeter-sized Ba₅Nb₄O₁₅ single crystals using a flux method, with the largest crystals reaching dimensions of 3 × 1.5 × 0.3 mm³. X-ray diffraction (XRD) analyses confirms that Ba₅Nb₄O₁₅ crystallizes in the hexagonal perovskite-related structure with space group

P \overline{3} m 1

, and that the naturally exposed facets correspond to the (00l) plane. Importantly, the temperature-dependent specific heat is well described by the Debye–Einstein phonon model, yielding a Debye temperature (

Θ_{D}

) of 165 K and an average phonon velocity (

v_{p}

) of 1343.9 m/s. Moreover, no anomaly indicative of a structural phase transition is observed in the entire measurement range of 2–220 K.

我们报道了使用通量法生长高质量的毫米级Ba5Nb4O15单晶，最大的晶体尺寸达到3 × 1.5 × 0.3 mm3。x射线衍射（XRD）分析证实，Ba5Nb4O15在空间群P3 - m1的六方钙钛矿相关结构中结晶，自然暴露的面对应于（00l）面。重要的是，德拜-爱因斯坦声子模型很好地描述了与温度相关的比热，得出德拜温度（ΘD）为165 K，平均声子速度（vp）为1343.9 m/s。此外，在2 ~ 220 K的整个测量范围内未观察到结构相变的异常。

引用次数: 0

Effect of nickel on structural, thermal and electrical properties bismuth niobate/tantalate pyrochlore 镍对铌酸铋/钽酸盐焦绿盐结构、热学和电学性能的影响

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-05-01 Epub Date: 2026-02-06 DOI: 10.1016/j.jssc.2026.125876

N.A. Zhuk , N.A. Sekushin , M.G. Krzhizhanovskaya , D.V. Sivkov , K.A. Badanina

The crystal structure, thermal and electrical properties of nickel-containing pyrochlore of the Bi₂NiNb₂O₉ composition are studied. The disordered crystalline structure of pyrochlore (sp. gr. Fd-3m, a = 10.53784 Å, Z = 4) is refined by the Rietveld method based on X-ray powder diffraction (XRD) data. In contrast to the loose, porous tantalum pyrochlore (grain size of 0.5-2.0 μm), the microstructure of the niobium ceramics is grainless and low-porous. Niobium pyrochlore has a structure of disordered pyrochlore, in which the bismuth atoms are displaced to the 96g position, and the oxygen atoms are distributed over 48f and 8a with incomplete occupancy. Nickel cations are distributed over the bismuth and niobium positions. The tolerance of the octahedral tantalum sublattice to nickel cations is higher and its capacity with respect to Ni(II) is 5.3% higher than that of the niobium sublattice. At the same time, the vacancy of the bismuth sublattice is 22% compared to 18% for niobium pyrochlore. The thermal expansion of the cell is studied by high-temperature X-ray diffraction in the temperature range of 30-1200 °C. The thermal expansion coefficient (TEC) is higher than for tantalum pyrochlore (from 3.8 × 10⁻⁶ to 7.0 × 10⁻⁶ °C⁻¹ at 30–750 °C), monotonically increases from 5.12 × 10⁻⁶ °С⁻¹ (30°С) to 7.73 × 10⁻⁶ °С⁻¹ (750°С). The mechanism of thermal destruction of pyrochlores Bi₂NiNb₂O₉ and Bi₂NiTa₂O₉ is similar and consists in the formation of isostructural intermediate compounds NiNb₂O₆/NiTa₂O₆ and the proximity of the thermal dissociation temperature of pyrochlores 1110/1080°С, which is associated with volatility and removal of bismuth(III) oxide at high temperature. The dielectric characteristics of niobium pyrochlore are significantly better than for tantalum-containing pyrochlore of similar composition. Bi₂NiNb₂O₉ is characterized by a high activation energy of 1.43 eV; high frequency-independent dielectric permittivity of ∼144 (up to 300°С) and a dielectric loss tangent of ∼0.002 at 1 MHz. Ion transport was not detected. The investigated ceramics can be used in the multilayer ceramic capacitor creation.

研究了Bi2NiNb2O9含镍焦绿石的晶体结构、热学和电学性能。基于x射线粉末衍射（XRD）数据，采用Rietveld方法对焦绿石（sp. gr. Fd-3m, a = 10.53784 Å， Z = 4）的无序晶体结构进行了细化。与松散多孔的焦绿钽（晶粒尺寸为0.5 ~ 2.0 μm）相比，铌陶瓷的微观结构是无晶粒和低孔的。铌焦绿石具有无序焦绿石结构，其中铋原子位移到96g位置，氧原子分布在48f和8a上，不完全占据。镍离子分布在铋和铌的位置上。八面体钽亚晶格对镍离子的容忍度更高，其对Ni（II）的容量比铌亚晶格高5.3%。同时，铋亚晶格的空位率为22%，而焦绿铌的空位率为18%。用高温x射线衍射研究了电池在30 ~ 1200℃温度范围内的热膨胀。热膨胀系数（TEC）高于焦绿钽（在30 - 750℃时从3.8 × 10−6到7.0 × 10−6°C−1），从5.12 × 10−6°С−1（30°С）单调增加到7.73 × 10−6°С−1（750°С）。烧绿石Bi2NiNb2O9和Bi2NiTa2O9的热破坏机理相似，主要表现为形成了等结构中间化合物NiNb2O6/NiTa2O6，且烧绿石的热解离温度接近1110/1080°С，这与高温下氧化铋（III）的挥发性和脱除有关。铌焦绿石的介电特性明显优于类似成分的含钽焦绿石。Bi2NiNb2O9具有较高的活化能（1.43 eV）；与频率无关的介电常数为~ 144（高达300°С），在1 MHz时介电损耗正切为~ 0.002。未检测到离子输运。所研究的陶瓷可用于制作多层陶瓷电容器。

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引用次数: 0

Enhanced photocatalytic hydrogen evolution by N atoms doping in pyrene-based one-dimensional covalent organic frameworks (1D-COFs) 芘基一维共价有机骨架（1D-COFs）中N原子掺杂增强光催化析氢

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-05-01 Epub Date: 2026-02-04 DOI: 10.1016/j.jssc.2026.125881

Changyu Qin , Xuxin Fan , Yao Yang , Shuang Zhang , Yang Xiong , Xianglin Yu , Junbo Li

Photocatalytic hydrogen production relies on efficient photocatalysts. Nowadays, metal-free catalysts have become a research hotspot, especially covalent organic frameworks (COFs) based catalysts. The introduction of nitrogen atoms into COFs could alter the electronic structure, increase catalytic sites, and enhance photocatalytic performance. In this work, nitrogen atoms were introduced into pyrene-based 1D-COF, the as-prepared 1N–COF exhibits optimal photocatalytic hydrogen production performance of 10.57 mmol g⁻¹ h⁻¹. Photoelectrical property tests verified that the 1N–COF has good charge transfer ability and slower electron-hole recombination rate compared with 0N–COF. Additionally, DFT calculations revealed that the introduction of nitrogen atoms increased catalytic sites and reduced H adsorption free energy.

光催化制氢依赖于高效的光催化剂。目前，无金属催化剂已成为研究热点，特别是基于共价有机框架（COFs）的催化剂。引入氮原子可以改变COFs的电子结构，增加催化位点，提高光催化性能。本研究将氮原子引入芘基1D-COF中，制备的1N-COF光催化产氢性能最佳，为10.57 mmol g−1 h−1。光电性能测试表明，与0N-COF相比，1N-COF具有良好的电荷转移能力和较慢的电子-空穴复合速率。此外，DFT计算表明，氮原子的引入增加了催化位点，降低了H的吸附自由能。

引用次数: 0