Journal of Solid State Chemistry最新文献_第3页

Enabling room-temperature phosphorescence via solvent-mediated crystal packing in 1,8-naphthalimide hybrid perovskites 通过溶剂介导的1,8-萘酰亚胺杂化钙钛矿晶体填充实现室温磷光

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-13 DOI: 10.1016/j.jssc.2026.125828

Dawoon Kim, Jae Ho Lee, In-Chul Hwang, In Chung

We report two new organic-inorganic hybrid perovskite compounds consisting of the one-dimensional (1-D), face-sharing inorganic chain of [PbI₃]_∞^- and charge-compensating ethylammonium-substituted 1,8-naphthalimide (NIEA⁺) cation. The different solvents, polar protic aqueous hydrogen iodide and aprotic N,N-dimethylformamide (DMF), give distinct products of (NIEA)PbI₃ (1) and (NIEA)PbI₃∙DMF (2), respectively, crystallizing in the monoclinic space group P2₁/c. They determine the packing fashion of the organic units in the structure. In 1, the direct π–π interaction dominantly stacks the NIEA⁺ cations along the c-axis. The ammonium groups bond directly to the perovskite inorganic chains to construct the overall structure. In contrast, in 2, the co-crystallized interchain DMF molecules from solvent interrupt such a stacking, giving a distinct structure from 1. They mediate a hydrogen bonding network linking the organic units and [PbI₃]_∞^- inorganic chains. Hirshfeld surface analysis shows that these specific short contacts stabilize the respective structures. The resulting difference in interchain structures causes a substantially increased electronic band gap of 2.83 eV of 2 in comparison with 2.32 eV of 1. Remarkably, only 2 exhibits bright ambient-temperature phosphorescence, originating from the triplet state of the π-conjugated NIEA⁺ cation.

我们报道了两种新的有机-无机杂化钙钛矿化合物，由一维（1- d），面共享无机链[PbI3]∞-和电荷补偿乙基铵取代1,8-萘酰亚胺（NIEA+）阳离子组成。极性质子型水碘化氢和非质子型N，N-二甲基甲酰胺（DMF）在不同溶剂下分别生成（NIEA）PbI3(1)和（NIEA）PbI3∙DMF(2)，在单斜空间群P21/c中结晶。它们决定了结构中有机单元的排列方式。在图1中，直接π -π相互作用主要沿着c轴堆叠NIEA+阳离子。铵基直接与钙钛矿无机链结合，形成整体结构。相反，在2中，来自溶剂的共结晶的链间DMF分子中断了这种堆叠，形成了与1截然不同的结构。它们介导了一个连接有机单元和[PbI3]∞-无机链的氢键网络。Hirshfeld表面分析表明，这些特定的短接触稳定了各自的结构。由此产生的链间结构的差异导致2的电子带隙大大增加，为2.83 eV，而1为2.32 eV。值得注意的是，只有2颗表现出明亮的室温磷光，这是由π共轭的NIEA+阳离子的三重态引起的。

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引用次数: 0

A robust copper(II)-based supramolecular complex with intrinsic proton conductivity: Synthesis, stability, and conducting mechanism 具有本征质子导电性的稳健铜（II）基超分子配合物：合成、稳定性和导电机理

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-12 DOI: 10.1016/j.jssc.2026.125831

Wanyao Chen , Qi Zhuang , Ping Xiong , Gang Li

Intrinsic proton-conductive supramolecular complexes are promising for proton exchange membrane fuel cells (PEMFCs) due to their structural regularity, tunable non-covalent interactions, and stable proton transport pathways. Herein, a copper(II)-based supramolecular complex, [CuCl(H₅ebidc)]·½(bbe)·CH₃OH (1), was synthesized by employing 2,2′-(1,2-phenylene)bis(1H-imidazole-4,5-dicarboxylic acid) (H₆ebidc) and 1,2-bis(2-benzimidazolyl)ethane (bbe) as mixed ligand. Comprehensive characterization confirms the exceptional stability of 1 in boiling water (24 h), across a broad pH range (1.5–11.5), and up to 234 °C. Alternating current (AC) impedance determinations show that its proton conductivity is strongly dependent on temperature and humidity, achieving 3.31 × 10⁻³ S cm⁻¹ at 100 °C and 98 % relative humidity (RH). Activation energy (E_a) analysis indicates proton transfer follows the Grotthuss mechanism at 98 % RH (E_a = 0.33 eV) and shifts to the vehicular mechanism at 68 % RH (E_a = 0.56 eV). This intrinsic proton transport is enabled by the continuous H-bonding networks formed by carboxyl groups, imidazole N atoms, and guest molecules. This work demonstrates the utility of imidazole carboxylate ligands in constructing stable, high-performance proton-conductive supramolecular complexes, offering a feasible design strategy for PEMFC-oriented materials.

固有质子导电超分子复合物由于其结构的规律性、可调节的非共价相互作用和稳定的质子传输途径，在质子交换膜燃料电池（pemfc）中具有广阔的应用前景。以2,2′-（1,2-苯基）双（1h -咪唑-4,5-二羧酸）（H6ebidc）和1,2-双（2-苯并咪唑）乙烷（bbe）为混合配体，合成了铜（II）基超分子配合物[CuCl(H5ebidc)]·½（bbe）·CH3OH(1)。综合表征证实了1在沸水（24小时）、宽pH范围（1.5-11.5）和高达234°C中的优异稳定性。交流电（AC）阻抗测定表明，其质子电导率与温度和湿度密切相关，在100°C和98%相对湿度（RH）下达到3.31 × 10−3 S cm−1。活化能（Ea）分析表明，在98%相对湿度（Ea = 0.33 eV）下质子转移遵循Grotthuss机制，在68%相对湿度（Ea = 0.56 eV）下质子转移转向载体机制。这种内在质子传递是由羧基、咪唑N原子和客体分子形成的连续氢键网络实现的。这项工作证明了咪唑羧酸配体在构建稳定、高性能质子导电超分子复合物方面的实用性，为面向pemfc的材料提供了一种可行的设计策略。

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引用次数: 0

MOF-derived hierarchical Fe3O4@C cubes for enhanced lithium storage in lithium-ion batteries mof衍生的分层Fe3O4@C立方体，用于增强锂离子电池中的锂存储

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-12 DOI: 10.1016/j.jssc.2026.125832

Beiping Wang , Hui Tian , Shunyan Xiang , Jinfu Ma , Tong Xue , Zhongli Zou , Chunping Hou

Rational design of the microstructure and morphology between Fe₃O₄ and carbon materials can significantly enhance the electrochemical lithium storage performance of composites for lithium-ion batteries (LIBs), enabling excellent rate capability and cycling stability. In this work, Fe₃O₄@N-doped carbon (Fe₃O₄@C) composites were synthesized via carbonization of Fe₂O₃@Fe-MOF precursors, in which Fe₃O₄ submicron cubes are encapsulated by a three-dimensionally networked N-doped amorphous carbon layer to form a hierarchical meso–macroporous architecture. This unique structure effectively buffers the large volume variations during lithiation/delithiation, provides abundant lithium storage active sites, and facilitates fast ion/electron transport. Benefiting from these structural advantages, the Fe₃O₄@C electrode exhibits outstanding electrochemical performance, including a high initial delithiation capacity of 1368.9 mAh/g at 0.1 A/g with a coulombic efficiency of 76.9 %, remarkable rate capability of 570 mAh/g at 5 A/g, and excellent long-term durability with 400 mAh/g retained after 350 cycles at 2 A/g. This study demonstrates a feasible and effective strategy for constructing MOF-derived Fe₃O₄/carbon cubic composites, providing valuable guidance for the development of high-energy-density anode materials for next-generation LIBs.

合理设计Fe3O4与碳材料之间的微观结构和形貌，可以显著提高锂离子电池复合材料的电化学储锂性能，使其具有优异的倍率性能和循环稳定性。在这项工作中，通过Fe2O3@Fe-MOF前驱体的碳化合成Fe3O4@N-doped碳（Fe3O4@C）复合材料，其中Fe3O4亚微米立方体被三维网络化的n掺杂无定形碳层包裹，形成层次化的介孔-大孔结构。这种独特的结构有效地缓冲了锂化/去锂化过程中的大体积变化，提供了丰富的锂存储活性位点，并促进了离子/电子的快速传递。得益于这些结构优势，Fe3O4@C电极表现出优异的电化学性能，包括在0.1 a /g下具有1368.9 mAh/g的高初始衰减容量和769%的库仑效率，在5 a /g下具有570 mAh/g的显着倍率容量，以及在2 a /g下循环350次后仍保持400 mAh/g的优异长期耐用性。该研究为构建mof衍生的Fe3O4/碳立方复合材料提供了一种可行有效的策略，为下一代锂离子电池高能量密度负极材料的开发提供了有价值的指导。

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引用次数: 0

Modeling structural, elastic and electronic properties of ternary barium-based low sensitivity energetic perovskite based on DFT 基于DFT的三元钡基低灵敏度能钙钛矿结构、弹性和电子特性建模

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-11 DOI: 10.1016/j.jssc.2026.125829

Feng Gu, Jijun Xiao

As a new energetic material, energetic perovskite has the characteristics of high detonation performance, high thermal stability and low cost, and has a wide application potential in the field of energetic materials, so it is of great significance to study its structure and properties. Based on density functional theory (DFT), the structure, mechanical and electronic properties of a new type of insensitive barium-based energetic perovskite (Hqe)₂(Ba)(ClO₄)₄ (QBP) are introduced in detail. The intensity of coordination bonds is discussed by the method of projected Crystal Orbital Hamilton Population (pCOHP). Furthermore, the intensity of coordination bond is explained by quantitative comparison between Bader charge and electron localization function (ELF). The results of energy band calculation show that QBP compound has indirect band gap, and the valence band is the largest at point D and the conduction band is the smallest at point Γin Brillouin zone. The research results of mechanical properties show that QBP structure is elastic, stable, anisotropic and ductile. For coordination bonds, the stronger the bonding strength, the more stable the crystal geometry and the greater the rigidity of the system. The Hirshfeld surface analysis shows that the hydrogen bonding N/C–H⋯O dominates the intermolecular interaction in QBP crystal and plays an important role in maintaining the stability of crystal structure.

含能钙钛矿作为一种新型含能材料，具有爆轰性能高、热稳定性高、成本低等特点，在含能材料领域具有广泛的应用潜力，因此对其结构和性能的研究具有重要意义。基于密度泛函理论（DFT），详细介绍了一种新型不敏感钡基高能钙钛矿（Hqe）2(Ba)(ClO4)4 （QBP）的结构、力学性能和电子性能。用投影晶体轨道汉密顿居数（pCOHP）的方法讨论了配位键的强度。并用贝德电荷和电子局域化函数（ELF）的定量比较解释了配位键的强度。能带计算结果表明，QBP化合物存在间接带隙，价带在点D处最大，导带在点Γin布里渊区最小。力学性能研究结果表明，QBP结构具有弹性、稳定性、各向异性和延性。对于配位键，成键强度越强，晶体几何结构越稳定，体系刚性越大。Hirshfeld表面分析表明，氢键N/ C-H⋯O在QBP晶体中的分子间相互作用中占主导地位，并在维持晶体结构的稳定性方面发挥重要作用。

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引用次数: 0

Synergetic photo-induced charge carrier dynamics and structural reconstruction for enhancing electrochemical performance of oxygen-vacancy-enriched Bi2O3 anodes 增强富氧Bi2O3阳极电化学性能的协同光诱导载流子动力学和结构重构

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-10 DOI: 10.1016/j.jssc.2026.125809

Jiao Zhang , Suisui Su , Siqi Ying , Daiwei Li , Jia Dong , Shenghua Hu , Cuiqing Zhang , Huihui Gan , Changyuan Hu , Shizheng Zheng

Bismuth trioxide (Bi₂O₃) has emerged as a compelling anode candidate for aqueous supercapacitors due to its exceptional redox reversibility and ultrahigh theoretical capacitance (1370 F g⁻¹). However, its practical electrochemical performance is hindered by sluggish redox kinetics and structural degradation during cycling. In this work, we present a synergistic strategy that integrates photo-induced charge carrier dynamics and structure-directed reconstruction to systematically overcome these limitations in oxygen-vacancy-enriched Bi₂O₃ anodes. Through a facile solvothermal synthesis oxygen-vacancy-rich Bi₂O₃ nano-flowers are fabricated as model photoactive anode. Under visible-light illumination, electrochemical tests demonstrate a 1.3-fold enhancement in specific capacitance (425 F g⁻¹ at 1 A g⁻¹) compared to traditional performance metrics, alongside remarkable rate capability and long-term stability (115 % capacitance retention after 2000 cycles). The underlying mechanism reveals that photogenerated electron-hole pairs not only reduce electron transfer resistance but also trigger dynamic structural evolution during redox processes, synergistically stabilizing the anode while amplifying its charge storage potential. This work establishes a novel pathway for optimizing photoactive electrode materials by leveraging the interplay between light-responsive charge carrier engineering and adaptive structural reconstruction, offering critical insights for next-generation high-performance supercapacitors.

由于其优异的氧化还原可逆性和超高的理论电容（1370 F g−1），三氧化铋（Bi2O3）已成为水性超级电容器令人信服的阳极候选者。然而，它的实际电化学性能受到缓慢的氧化还原动力学和循环过程中的结构降解的阻碍。在这项工作中，我们提出了一种集成光诱导载流子动力学和结构定向重建的协同策略，以系统地克服富氧Bi2O3阳极的这些限制。通过简单的溶剂热合成，制备了富氧Bi2O3纳米花作为光活性阳极模型。在可见光照明下，电化学测试表明，与传统性能指标相比，比电容（在1 μ g−1时425℉g−1）提高了1.3倍，同时具有显着的倍率能力和长期稳定性（2000次循环后电容保持率为115%）。潜在的机制表明，光产生的电子空穴对不仅降低了电子传递阻力，而且在氧化还原过程中触发了动态结构演变，协同稳定阳极，同时放大了阳极的电荷存储电位。这项工作通过利用光响应电荷载流子工程和自适应结构重建之间的相互作用，为优化光活性电极材料建立了一条新的途径，为下一代高性能超级电容器提供了重要的见解。

{"title":"Synergetic photo-induced charge carrier dynamics and structural reconstruction for enhancing electrochemical performance of oxygen-vacancy-enriched Bi2O3 anodes","authors":"Jiao Zhang , Suisui Su , Siqi Ying , Daiwei Li , Jia Dong , Shenghua Hu , Cuiqing Zhang , Huihui Gan , Changyuan Hu , Shizheng Zheng","doi":"10.1016/j.jssc.2026.125809","DOIUrl":"10.1016/j.jssc.2026.125809","url":null,"abstract":"<div><div>Bismuth trioxide (Bi2O3) has emerged as a compelling anode candidate for aqueous supercapacitors due to its exceptional redox reversibility and ultrahigh theoretical capacitance (1370 F g−1). However, its practical electrochemical performance is hindered by sluggish redox kinetics and structural degradation during cycling. In this work, we present a synergistic strategy that integrates photo-induced charge carrier dynamics and structure-directed reconstruction to systematically overcome these limitations in oxygen-vacancy-enriched Bi2O3 anodes. Through a facile solvothermal synthesis oxygen-vacancy-rich Bi2O3 nano-flowers are fabricated as model photoactive anode. Under visible-light illumination, electrochemical tests demonstrate a 1.3-fold enhancement in specific capacitance (425 F g−1 at 1 A g−1) compared to traditional performance metrics, alongside remarkable rate capability and long-term stability (115 % capacitance retention after 2000 cycles). The underlying mechanism reveals that photogenerated electron-hole pairs not only reduce electron transfer resistance but also trigger dynamic structural evolution during redox processes, synergistically stabilizing the anode while amplifying its charge storage potential. This work establishes a novel pathway for optimizing photoactive electrode materials by leveraging the interplay between light-responsive charge carrier engineering and adaptive structural reconstruction, offering critical insights for next-generation high-performance supercapacitors.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125809"},"PeriodicalIF":3.5,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974208","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

Physical properties of single crystal NaSmTe2 — A new alkali metal rare-earth telluride with a triangular lattice 单晶NaSmTe2 -一种新型三角形晶格碱金属稀土碲化物的物理性质

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-09 DOI: 10.1016/j.jssc.2026.125826

Jianwei Shao , Mengqing Liu , Mengqin Liu , Jianqi Liu , Xin Zhou , Sheng Li , Hanlin Wu , Wenhui Liu , Zhixiang Shi

The discovery of the triangular lattice spin liquid candidate YbMgGaO

_{4}

has attracted numerous interest in quantum spin liquids (QSLs). Recently, the ARECh

_{2}

(A = alkali metal, RE = rare earth elements, Ch = chalcogen elements) family of materials, featuring triangular lattice geometries and simple structure, has emerged as a new platform for investigating frustrated magnetism including the candidate of QSLs. The majority of investigations on ARECh

_{2}

quantum magnets have focused on oxygen-, sulfur-, and selenium-based chalcogenides (Ch = O/S/Se), and the tellurium-containing analogues remain largely unexplored aspects. Here we successfully synthesized the triangular-lattice compound NaSmTe₂. Electrical transport measurements and UV–vis diffuse reflectance spectroscopy establish the compound as a good insulator. Magnetic measurements reveal pronounced anisotropy. We demonstrate that with the field applied parallel to the

a b

-plane, the magnetization exhibits a broad maximum around 50 K, which originates from crystal electric field (CEF) effects. Both the magnetic susceptibility and specific-heat data show no evidence of long-range magnetic order within the measured temperature range. The low-temperature specific heat data reveal a pronounced Schottky anomaly.

三角晶格自旋液体候选者YbMgGaO4的发现引起了人们对量子自旋液体（QSLs）的极大兴趣。近年来，ARECh2 （A =碱金属，RE =稀土元素，Ch =硫元素）材料族以其三角形晶格几何形状和简单的结构成为研究包括QSLs候选材料在内的受挫磁性的新平台。大多数关于ARECh2量子磁体的研究都集中在氧基、硫基和硒基硫族化合物（Ch = O/S/Se）上，而含碲的类似物在很大程度上仍未被探索。本文成功地合成了三角形晶格化合物NaSmTe2。电输运测量和紫外-可见漫反射光谱证实该化合物是一种良好的绝缘体。磁测量显示明显的各向异性。我们证明了当电场平行于ab平面时，磁化强度在50 K左右表现出较大的最大值，这是由晶体电场（CEF）效应引起的。磁化率和比热数据均显示，在测得的温度范围内不存在长程磁序。低温比热数据显示明显的肖特基异常。

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引用次数: 0

Dual MOF-derived porous carbon composites: Preparation of efficient bifunctional catalysts by pyrolytic protection strategy 双mof衍生多孔碳复合材料：利用热解保护策略制备高效双功能催化剂

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-08 DOI: 10.1016/j.jssc.2026.125810

Jingjing Chen , Yulu Jing , Xiaotong Song , Xiaolong Xu , Changyu Liu , Jianqiu Ruan , Jianbo Jia

Following the "MOF-protected pyrolysis" strategy, a dense carbon shell derived from ZIF tightly encapsulated MIL-53(Fe) during pyrolysis. This approach effectively prevented the high-temperature collapse of MIL-53 pore walls, thereby constructing a robust "MIL-53-carbon skeleton" composite. Furthermore, cetyltrimethylammonium bromide (CTAB) was introduced to regulate ZIF crystal growth and tailor the microporous structure. Ultimately, this process yielded nanoscale dual-MOF hybrid materials, which thus exhibit outstanding activity for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). In alkaline media, its ORR half-wave potential (E_1/2 = 0.926 V) significantly surpasses that of commercial Pt/C (E_1/2 = 0.826 V). For OER, the overpotential required to reach 10 mA cm⁻² (η = 349 mV) is lower than that of RuO₂ (η = 368 mV). The ORR/OER potential gap (ΔE = E_j10 - E_1/2) is only 0.653 V, which is narrower than that of the Pt/C + RuO₂ mixture (m:m = 1:1, ΔE = 0.772 V) under the same conditions. The optimally prepared composite also demonstrated excellent performance in assembled zinc-air batteries, offering a promising strategy for designing efficient bifunctional electrocatalysts.

采用“mof保护热解”策略，由ZIF衍生的致密碳壳在热解过程中紧密包裹MIL-53（Fe）。这种方法有效地防止了MIL-53孔壁的高温坍塌，从而构建了坚固的“MIL-53-碳骨架”复合材料。此外，十六烷基三甲基溴化铵（CTAB）可以调节ZIF晶体生长，调整微孔结构。最终，该工艺制备出了纳米级双mof杂化材料，该材料在氧还原反应（ORR）和析氧反应（OER）中均表现出优异的活性。在碱性介质中，其ORR半波电位（E1/2 = 0.926 V）显著优于商用Pt/C （E1/2 = 0.826 V）。对于OER，达到10 mA cm−2 （η = 349 mV）所需的过电位低于RuO2 （η = 368 mV）。在相同条件下，Pt/C + RuO2混合物（m:m = 1:1， ΔE = 0.772 V）的ORR/OER电位差（ΔE = Ej10 - E1/2）仅为0.653 V。优化后的复合材料在组装锌-空气电池中也表现出优异的性能，为设计高效的双功能电催化剂提供了一种有前途的策略。

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引用次数: 0

Optimal Co substitution enabled enhanced electrocatalytic activity for oxygen evolution reaction in KVO3 优化Co取代可以提高KVO3中析氧反应的电催化活性

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-07 DOI: 10.1016/j.jssc.2026.125818

Poonam Moar , Mange Ram , Krishna Kanta Haldar , Krishnakanta Mondal , Sourabh Barua

Oxygen evolution reaction (OER) is a part of the process of electrochemical (EC) splitting of water, which is a promising technique for the production of renewable hydrogen (H

_{2}

). Oxide perovskites have garnered significant attention as promising materials for OER due to their structural versatility and excellent stability. Doping of 3d transition metals has been an outstanding method to improve the activity of electrocatalysts for water oxidation. Here we report the synthesis of potassium metavanadate (KVO

_{3}

) via a sol–gel technique and the substitution of vanadium with cobalt to different levels with the general formula KV

_{1 - x}

Co

_{x}

O

_{3}

(

x = 0, 0.25, 0.50, 0.75, 1

). Diverse structural and microscopic analyses such as XRD, SEM, XPS, and TEM, confirm the inclusion of Co into the KVO

_{3}

structure. We find that an optimal cobalt (Co) content in KVO

_{3}

serves to increase the electrocatalytic activity for OER, a conclusion supported experimentally and theoretically. Density Functional Theory (DFT) calculations show that the substitution of Co in the pristine structure of KVO

_{3}

leads to a decrease in the band gap, with more Co and oxygen O states approaching the Fermi level.

析氧反应（OER）是水的电化学分解过程的一部分，是一种很有前途的生产可再生氢（H2）的技术。氧化物钙钛矿由于其结构的通用性和优异的稳定性，作为有前途的OER材料而受到了广泛的关注。三维过渡金属的掺杂是提高水氧化电催化剂活性的一种很好的方法。本文报道了用溶胶-凝胶法合成偏氰酸钾（KVO3），并以不同水平的钴取代钒，得到了通式KV1−xCoxO3 （x=0,0.25,0.50,0.75,1）。XRD， SEM， XPS， TEM等多种结构和微观分析证实了Co在KVO3结构中的存在。我们发现KVO3中钴（Co）的最佳含量有助于提高OER的电催化活性，这一结论得到了实验和理论的支持。密度泛函理论（DFT）计算表明，Co在KVO3原始结构中的取代导致带隙减小，有更多的Co和氧O态接近费米能级。

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引用次数: 0

Three d10-MOFs with 5-Aminoisophthalic acid for efficient detection of biomarker 3-nitrotyrosine in serum sample 3个d10- mof - 5-氨基间苯二酸高效检测血清样品中生物标志物3-硝基酪氨酸

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-07 DOI: 10.1016/j.jssc.2026.125819

Yi-Xuan Shi, Qing-Yun Yang, Hui-Cong Kong, Kun Zhang, Rui-Yuan Liu, Jing Ru

3-nitrotyrosine (3-NT) is widely regarded as a biomarker of oxidative stress damage in the human body, and its detection carries great significance for clinical diagnosis and routine disease monitoring. In this work, the solvothermal method was employed to synthesize three d¹⁰-MOFs, named [Cd(AIPA) (BIBP)]_n (AIPA-1), [Cd₂(AIPA)₂ (BIBT)₂]_n (AIPA-2) and [Zn(AIPA) (BPB)_1/2]_n (AIPA-3) (AIPA = 5-Aminoisophthalic acid, BIBP = 4,4′-bi(1H-imidazole-1-yl)-1,1′-biphenyl, BPB = 1,4-bis(pyrid-4-yl)-benzene and BIBT = 4,7-bi(1H-imidazole-1-yl)benzo-[2,1,3] thiadiazole). Structural analysis indicated that AIPA-1-3 all belonged to the monoclinic crystal system, with AIPA-1 in P2₁/c, AIPA-2 in C2, and AIPA-3 in C2/c, respectively. In contrast to the three-dimensional (3D) structure of AIPA-1-2, the 3D architecture of AIPA-3 was mediated by hydrogen bonds (N2–H⋯O3) between its two-dimensional (2D) layers. Additionally, AIPA-1-3 demonstrated reliable chemical and thermal stability. It was noteworthy that AIPA-1-3 showed rapidly and highly selective quenching sensing of the 3-NT, with the limit of detection (LOD) of 0.16 μM, 0.20 μM, and 0.13 μM, respectively. Actual sample experiments revealed that AIPA-1-3 possessed potential practical applicability in serum samples, and exhibited good recovery. Furthermore, the sensing mechanism has also been investigated in detail.

3-硝基酪氨酸（3-NT）被广泛认为是人体氧化应激损伤的生物标志物，其检测对临床诊断和常规疾病监测具有重要意义。本文采用溶剂热法合成了三个d10-MOFs，分别命名为[Cd(AIPA) (BIBP)]n (AIPA-1), [Cd2(AIPA)2 (BIBT)2]n （AIPA-2）和[Zn(AIPA) (BPB)1/2]n (AIPA-3) （AIPA = 5-氨基间苯酸，BIBP = 4,4 ' -双（1h -咪唑-1-基）-1,1 ' -联苯，BPB = 1,4-双（1h -咪唑-1-基）苯和BIBT = 4,7-双（1h -咪唑-1-基）苯-[2,1,3]噻二唑）。结构分析表明，AIPA-1-3均属于单斜晶系，其中AIPA-1位于P21/c， AIPA-2位于C2， AIPA-3位于C2/c。与AIPA-1-2的三维（3D）结构相反，AIPA-3的三维结构是由其二维（2D）层之间的氢键（N2-H⋯O3）介导的。此外，AIPA-1-3表现出可靠的化学和热稳定性。值得注意的是，AIPA-1-3对3-NT表现出快速、高选择性的猝灭感应，检测限（LOD）分别为0.16 μM、0.20 μM和0.13 μM。实际样品实验表明，AIPA-1-3在血清样品中具有潜在的实际适用性，且具有良好的回收率。此外，还对其传感机理进行了详细的研究。

{"title":"Three d10-MOFs with 5-Aminoisophthalic acid for efficient detection of biomarker 3-nitrotyrosine in serum sample","authors":"Yi-Xuan Shi, Qing-Yun Yang, Hui-Cong Kong, Kun Zhang, Rui-Yuan Liu, Jing Ru","doi":"10.1016/j.jssc.2026.125819","DOIUrl":"10.1016/j.jssc.2026.125819","url":null,"abstract":"<div><div>3-nitrotyrosine (3-NT) is widely regarded as a biomarker of oxidative stress damage in the human body, and its detection carries great significance for clinical diagnosis and routine disease monitoring. In this work, the solvothermal method was employed to synthesize three d10-MOFs, named [Cd(AIPA) (BIBP)]n (AIPA-1), [Cd2(AIPA)2 (BIBT)2]n (AIPA-2) and [Zn(AIPA) (BPB)1/2]n (AIPA-3) (AIPA = 5-Aminoisophthalic acid, BIBP = 4,4′-bi(1H-imidazole-1-yl)-1,1′-biphenyl, BPB = 1,4-bis(pyrid-4-yl)-benzene and BIBT = 4,7-bi(1H-imidazole-1-yl)benzo-[2,1,3] thiadiazole). Structural analysis indicated that AIPA-1-3 all belonged to the monoclinic crystal system, with AIPA-1 in P21/c, AIPA-2 in C2, and AIPA-3 in C2/c, respectively. In contrast to the three-dimensional (3D) structure of AIPA-1-2, the 3D architecture of AIPA-3 was mediated by hydrogen bonds (N2–H⋯O3) between its two-dimensional (2D) layers. Additionally, AIPA-1-3 demonstrated reliable chemical and thermal stability. It was noteworthy that AIPA-1-3 showed rapidly and highly selective quenching sensing of the 3-NT, with the limit of detection (LOD) of 0.16 μM, 0.20 μM, and 0.13 μM, respectively. Actual sample experiments revealed that AIPA-1-3 possessed potential practical applicability in serum samples, and exhibited good recovery. Furthermore, the sensing mechanism has also been investigated in detail.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125819"},"PeriodicalIF":3.5,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974204","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

Amino-functionalized silica covalently anchored monovacant phosphomolybdic acid catalytic oxidation of iodide ions 氨基官能化二氧化硅共价锚定单空磷酸钼酸催化氧化碘离子

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-07 DOI: 10.1016/j.jssc.2026.125820

Ziyue Xia, Jun Guo, Honghong Dou, Guoqiang Chen, Kui An, Yulu Peng

A novel heterogeneous catalyst, PMo₁₁/NH₂–SiO₂, was synthesized by using (triethoxysilyl)-propyl isocyanate as an organic linker. Polyoxometalate [PMo₁₁O₃₉]^7- (PMo₁₁) was covalently immobilized on the surface of amino-functionalized silica (NH₂–SiO₂) via urea bond (–NH–C(=O)–NH-). The catalyst was characterized by FT-IR, ²⁹Si MAS NMR, and XPS, which confirmed the formation of a stable covalent interface between the PMo₁₁ clusters and the silica support. The catalytic performance was evaluated in the hydrogen peroxide-mediated oxidation of iodide ions under optimized conditions (c(I⁻) = 2.5 × 10⁻³ M, c(H₂O₂) = 2.0 × 10⁻³ M, pH = 2.0, T = 55 °C). The reaction reached completion within 68 s, achieving an iodine generation rate of 1.83 × 10⁻⁵ mol L⁻¹ s⁻¹. Furthermore, the catalyst maintained exceptional stability, retaining 99.67 % of its initial activity after 28 consecutive reaction cycles.

以（三乙氧基硅基）异氰酸丙酯为有机连接剂，合成了一种新型非均相催化剂PMo11/ NH2-SiO2。通过尿素键（- nhh - c (=O) - nhh -）将多金属氧酸盐[PMo11O39]7- (PMo11)共价固定在氨基功能化二氧化硅（NH2-SiO2）表面。通过FT-IR、29Si MAS NMR和XPS对催化剂进行了表征，证实了PMo11簇与二氧化硅载体之间形成了稳定的共价界面。在最佳条件(c（I−)= 2.5 × 10−3 M, c(H2O2) = 2.0 × 10−3 M, pH = 2.0, T = 55℃）下，考察了过氧化氢催化氧化碘离子的催化性能。反应在68 s内完成，碘的生成速率为1.83 × 10−5 mol L−1 s−1。此外，该催化剂在连续28个反应周期后仍保持了99.67%的初始活性。

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