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Tuning aromatic ring polarity in aminoquinoline-based HOFs for enhanced stability and proton conduction 调整氨基喹啉基HOFs的芳香环极性以增强稳定性和质子传导
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-20 DOI: 10.1016/j.jssc.2026.125839
Ke Chen, Zhongxin Wei, Yuke Lin, Jiemin Liu, Chulong Liu, Shengchang Xiang, Zhangjing Zhang
The development of high-performance solid-state proton conductors is crucial for advancing proton exchange membrane fuel cells (PEMFCs), a promising clean energy alternative. While hydrogen-bonded organic frameworks (HOFs) have emerged as potential candidates due to their tunable structures and environmentally friendly processing, their practical application is often limited by poor stability under operational conditions. Herein, we introduce a strategy that utilizes charge-assisted HOFs based on aminoquinoline derivatives with sulfonic acids, specifically focusing on tuning the aromatic ring polarity contrast through isomer selection to precisely control π-π stacking interactions, thereby synergistically enhancing both structural robustness and proton conductivity. Two novel HOFs, HOF-FJU-354 and HOF-FJU-355, were successfully synthesized. Structural analysis confirmed that the aminoquinoline isomer choice effectively dictates the π-π stacking motif and structural organization. This design leads to HOFs that demonstrate exceptional stability, maintaining their crystallinity even under highly corrosive pH conditions. Simultaneously, the frameworks exhibit high proton conductivities, with HOF-FJU-354 reaching a maximum 1.46 × 10−3 S cm−1 at 90 °C and 98 % RH. Activation energy analysis (> 0.4 eV) indicates a vehicle-dominated transport mechanism facilitated by extensive hydrogen-bonding networks and confined water molecules. This study successfully establishes a clear electronic structure-property relationship linking aromatic polarity modulation to performance, providing a strategic pathway for designing stable, high proton conductivity HOF materials.
高性能固体质子导体的开发是推进质子交换膜燃料电池(pemfc)发展的关键。质子交换膜燃料电池是一种前景广阔的清洁能源替代品。虽然氢键有机框架(hof)由于其可调结构和环保加工而成为潜在的候选材料,但其实际应用往往受到操作条件下稳定性差的限制。在此,我们介绍了一种基于氨基喹啉磺酸衍生物的电荷辅助HOFs策略,特别关注通过异构体选择调节芳香环极性对比,以精确控制π-π堆叠相互作用,从而协同提高结构稳健性和质子电导率。成功合成了HOF-FJU-354和HOF-FJU-355两种新型hof。结构分析证实,氨基喹啉异构体的选择有效地决定了π-π堆叠基序和结构组织。这种设计使hof表现出优异的稳定性,即使在高腐蚀性的pH条件下也能保持其结晶度。同时,HOF-FJU-354在90°C和98%相对湿度下的质子电导率最高可达1.46 × 10−3 S cm−1。活化能分析(> 0.4 eV)表明,广泛的氢键网络和封闭的水分子促进了载体主导的运输机制。本研究成功建立了芳香族极性调制与性能之间清晰的电子结构-性能关系,为设计稳定、高质子电导率的HOF材料提供了战略途径。
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引用次数: 0
Novel green synthesis and transformation mechanism of layered double hydroxides from metal hydroxides and light magnesium carbonate 由金属氢氧化物和轻质碳酸镁合成层状双氢氧化物的新型绿色合成及转化机理
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-20 DOI: 10.1016/j.jssc.2026.125843
Yixuan Guo , Qian Zhang , He Zhou , Christine Taviot-Guého , Fabrice Leroux , Yongjun Feng
Green synthesis methods for layered double hydroxides (LDHs) without by-product and water washing has become an important lever in a sustainable development perspective associated to large scale-up for market demand while requiring to revisit the synthesis of LDHs intercalation compounds. Here, MgAl–CO3-LDH with a purity as high as 98.6 % was successfully synthesized via a novel green route using Mg(OH)2, Al(OH)3 and light magnesium carbonate (LMC) as starting materials. The corresponding transformation process was carefully investigated between 170 and 190 °C, and a mechanism was tentatively proposed based on various characterization techniques such as powder X-ray diffractometer (PXRD), X-ray photoelectron spectrometry (XPS), and solid state 27Al nuclear magnetic resonances (NMR). The activation energy for the reaction is calculated as 45.59 kJ mol−1 adopting the Avrami–Erofe'ev equation using Arrhenius formalism. Moreover, the formation process of LDH is found to be divided into four steps: (1) the dissolution of Mg(OH)2; (2) the deposition of Mg2+ and OH onto Al(OH)3 with the bilateral diffusion of Mg2+ and Al3+ in the solid lattice; (3) the self-assembly of Mg(OH)6 and Al(OH)6 Oh building unit blocks to produce MgAl-LDH nuclei, (4) and finally the growth of the LDH nuclei. During the transformation process, one of the key parameters is the temperature since the kinetics of nuclei formation were found to be highly temperature dependent. Undoubtedly, this novel green route associating environment-friendly considerations and low-cost way should promote the mass production of LDHs intercalation compounds.
无副产物和水洗的层状双氢氧化物(LDHs)绿色合成方法已成为可持续发展的一个重要杠杆,与市场需求的大规模生产有关,同时需要重新审视LDHs插层化合物的合成。本文以Mg(OH)2、Al(OH)3和轻质碳酸镁(LMC)为原料,采用绿色合成方法成功合成了纯度高达98.6%的MgAl-CO3-LDH。通过粉末x射线衍射仪(PXRD)、x射线光电子能谱(XPS)和固态27Al核磁共振(NMR)等多种表征技术,对170 ~ 190℃的相变过程进行了细致的研究,初步提出了相变机理。采用Arrhenius形式的Avrami-Erofe 'ev方程,计算出反应的活化能为45.59 kJ mol−1。LDH的形成过程可分为四个步骤:(1)Mg(OH)2的溶解;(2) Mg2+和Al3+在Al(OH)3上的沉积,同时Mg2+和Al3+在固体晶格中双向扩散;(3) Mg(OH)6和Al(OH)6 OH构建单元块的自组装产生MgAl-LDH核;(4)最后LDH核的生长。在转变过程中,温度是关键参数之一,因为发现核形成动力学高度依赖于温度。毫无疑问,这种结合了环境友好性和低成本的新型绿色路线,将促进LDHs插层化合物的大规模生产。
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引用次数: 0
Hierarchical chemical and microstructural engineering for high thermoelectric performance polycrystalline SnSe, triply incorporated with Na, Ge, and Ta atoms 高热电性能SnSe多晶的分层化学和微观结构工程,三层结合Na, Ge和Ta原子
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-19 DOI: 10.1016/j.jssc.2026.125844
Taeshik Kim , Kwonmin Song , Kwangjoo Kim , Jino Kim , Insub Lee , Hoon Wee , Youngdeog Koh , In Chung
Although polycrystalline SnSe is a promising lead-free thermoelectric material, its performance has remained constrained until recently by low electrical conductivity and unexpectedly higher lattice thermal conductivity compared with single-crystal SnSe. Here, we introduce a hierarchical compositional and structural design strategy that integrates Ge alloying, Na and Ta doping, and a combined post-processing of mechanical ball-milling and H2-reduction purification (BM/H2–R) to address such challenges. Based on the enhanced carrier concentration at ∼1019 cm−3 by Na doping, the Ge substitution at the Sn site slightly decreases hole carrier concentration and suppresses lattice heat transport through mass-fluctuation and strain-field scattering, giving a ZT of ∼1.4 at 800 K. The subsequent Ta doping induces microscale TaSe2 precipitates within the SnSe matrix, facilitating charge carrier transport and introducing additional phonon-scattering centers. The resulting materials exhibit simultaneously increased power factor and decreased thermal conductivity, giving a ZT of ∼1.5 at 800 K. Further microstructural engineering through the BM/H2–R process reduces the particle size of TaSe2 precipitates to a nanoscale and effectively removes surface oxides, markedly suppressing the lattice thermal conductivity, especially at the high temperature regime. The optimized sample exhibits the ultralow lattice thermal conductivity of ∼0.13 W m−1 K−1 and a very high ZT of ∼2.1 at 800 K. These results highlight that simultaneous control of chemical compositions and microstructural hierarchy provides an effective approach to decouple charge and phonon transport, offering a practical pathway for developing high-performance thermoelectric materials.
虽然多晶SnSe是一种很有前途的无铅热电材料,但它的性能一直受到限制,直到最近,与单晶SnSe相比,它的电导率低,晶格热导率出乎意料地高。在这里,我们介绍了一种分层的成分和结构设计策略,该策略集成了Ge合金,Na和Ta掺杂,以及机械球磨和h2还原纯化(BM/ H2-R)的联合后处理来解决这些挑战。基于Na掺杂提高了~ 1019 cm−3的载流子浓度,Sn位的Ge取代略微降低了空穴载流子浓度,并通过质量波动和应变场散射抑制了晶格热输运,在800 K时的ZT为~ 1.4。随后的Ta掺杂在SnSe基体中诱导了微尺度的TaSe2沉淀,促进了载流子的输运,并引入了额外的声子散射中心。所得材料同时表现出增加的功率因数和降低的导热性,在800 K时ZT为~ 1.5。通过BM/ H2-R工艺进一步的微观结构工程将TaSe2沉淀的粒度减小到纳米级,并有效地去除表面氧化物,显著抑制晶格导热性,特别是在高温状态下。优化后的样品在800 K时晶格热导率为~ 0.13 W m−1 K−1,ZT高达~ 2.1。这些结果表明,同时控制化学成分和微观结构层次提供了有效的方法来解耦电荷和声子输运,为开发高性能热电材料提供了一条实用的途径。
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引用次数: 0
Synthesis of core-shell three-dimensional porous cobalt –nitrogen doped nano-carbon catalysts for enhanced oxygen reduction in Zinc-Air batteries 锌-空气电池增强氧还原核壳三维多孔钴氮掺杂纳米碳催化剂的合成
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-19 DOI: 10.1016/j.jssc.2026.125841
Qifeng Sun , Jiaxin Zou , Hongbo Liu , Hui Chen
The metal nitrogen-doped carbon catalysts derived from an imidazole zeolite framework have attracted significant attention in the field of oxygen reduction reaction(ORR). In this investigation, a ZIF-67 catalyst is grown epitaxially from a ZIF-8 seed crystal using a simple stirring-resting method, resulting in a ZIF-8@ZIF-67 precursor with a core-shell structure. A Co, N-doped hollow porous carbon catalyst (Co-N-HPC) composed of carbon nanotubes retaining a rhombohedral dodecahedral morphology was obtained through one-step heat treatment. This Co-N-HPC catalyst demonstrates exceptional methanol tolerance and stability, surpassing that of commercial 20 %Pt/C. Remarkably, it achieved a limiting current density of 5.963 mA cm−2, with an onset potential of 1.026 V and a half-wave potential of 0.853 V. When integrated into a rechargeable zinc-air battery, the catalyst enables stable multi-step discharge and reduced polarization. The power density of the battery exceeds that of commercial 20 %Pt/C by approximately 61 %, and it exhibited a cycle charge and discharge time of 248 h.
以咪唑分子筛为骨架的金属氮掺杂碳催化剂在氧还原反应(ORR)领域引起了广泛的关注。在本研究中,采用简单的搅拌-静息法从ZIF-8种子晶体外延生长ZIF-67催化剂,得到具有核-壳结构的ZIF-8@ZIF-67前驱体。通过一步热处理,获得了一种由碳纳米管组成的保持十二面体菱形形貌的Co, n掺杂空心多孔碳催化剂(Co- n - hpc)。这种Co-N-HPC催化剂具有优异的甲醇耐受性和稳定性,超过了20% Pt/C的商用催化剂。其极限电流密度为5.963 mA cm−2,起始电位为1.026 V,半波电位为0.853 V。当集成到一个可充电的锌空气电池,催化剂可以实现稳定的多步放电和减少极化。该电池的功率密度比商用20% Pt/C电池高出约61%,循环充放电时间为248 h。
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引用次数: 0
Correlation between local structure and photoluminescence of Ag ions in luminescent zeolites: An XAFS study 发光沸石中Ag离子的局部结构与光致发光的关系:XAFS研究
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-17 DOI: 10.1016/j.jssc.2026.125836
Haruki Meguro , Junya Narumi , Yushi Suzuki , Takafumi Miyanaga
Local structural changes in Ag-A and Ag–Y zeolites induced by vacuum evacuation and heating were investigated using X-ray absorption fine structure (XAFS). During the evacuation process of Ag-A zeolite, two primary photoluminescence (PL) peaks at 660 nm and 520 nm were observed. The former increased in intensity over the evacuating time, while the latter decreased. Operando XAFS measurements confirmed that the formation of Ag4 clusters during evacuation is responsible for the 660 nm PL. In contrast, the heated Ag–Y zeolite sample, which contains only a small amount of Ag ions and no Ag clusters in its cavities, exhibited PL solely at approximately 500 nm. XAFS analysis revealed a unique local structure around Ag in the heated Ag–Y zeolite. This coordination environment resembles that found in luminescent silver complexes involving ligand-to-metal charge transfer (LMCT), suggesting that the 520 nm luminescence in Ag-A zeolite also originates from LMCT.
利用x射线吸收精细结构(XAFS)研究了真空抽吸和加热对Ag-A和Ag-Y沸石局部结构的影响。在Ag-A沸石的抽吸过程中,在660 nm和520 nm处观察到两个初级光致发光峰。前者的强度随疏散时间的延长而增加,后者的强度随疏散时间的延长而减少。Operando XAFS测量证实,在疏散过程中形成的Ag4团簇是导致660nm PL的原因。相比之下,加热后的Ag - y沸石样品仅含有少量Ag离子,其空腔中没有Ag团簇,仅在约500nm处表现出PL。XAFS分析显示,在加热后的Ag - y沸石中,Ag周围存在独特的局部结构。这种配位环境类似于发光银配合物中涉及配体到金属电荷转移(LMCT)的配位环境,表明Ag-A沸石中的520 nm发光也来源于LMCT。
{"title":"Correlation between local structure and photoluminescence of Ag ions in luminescent zeolites: An XAFS study","authors":"Haruki Meguro ,&nbsp;Junya Narumi ,&nbsp;Yushi Suzuki ,&nbsp;Takafumi Miyanaga","doi":"10.1016/j.jssc.2026.125836","DOIUrl":"10.1016/j.jssc.2026.125836","url":null,"abstract":"<div><div>Local structural changes in Ag-A and Ag–Y zeolites induced by vacuum evacuation and heating were investigated using X-ray absorption fine structure (XAFS). During the evacuation process of Ag-A zeolite, two primary photoluminescence (PL) peaks at 660 nm and 520 nm were observed. The former increased in intensity over the evacuating time, while the latter decreased. Operando XAFS measurements confirmed that the formation of Ag<sub>4</sub> clusters during evacuation is responsible for the 660 nm PL. In contrast, the heated Ag–Y zeolite sample, which contains only a small amount of Ag ions and no Ag clusters in its cavities, exhibited PL solely at approximately 500 nm. XAFS analysis revealed a unique local structure around Ag in the heated Ag–Y zeolite. This coordination environment resembles that found in luminescent silver complexes involving ligand-to-metal charge transfer (LMCT), suggesting that the 520 nm luminescence in Ag-A zeolite also originates from LMCT.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125836"},"PeriodicalIF":3.5,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035076","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
Structures of ternary rare-earth germanides α-CeIrGe2, β-CeIrGe2, Yb4Ir7Ge6, and Yb5Ir4Ge10 稀土锗化合物α-CeIrGe2、β-CeIrGe2、Yb4Ir7Ge6和Yb5Ir4Ge10的结构
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-16 DOI: 10.1016/j.jssc.2026.125837
Dundappa Mumbaraddi , Arthur Mar
Crystal growth of ternary rare-earth iridium germanides RE–Ir–Ge (RE = Ce, Yb) was investigated in indium flux. These experiments resulted in the formation of two polymorphs of CeIrGe2, termed α and β, as well as Yb4Ir7Ge6 and Yb5Ir4Ge10. Single-crystal X-ray diffraction analysis revealed that α-CeIrGe2 adopts the CeNiSi2-type structure (orthorhombic, Cmcm, a = 4.3312(16) Å, b = 17.101(6) Å, c = 4.3803(16) Å, Z = 4) containing zigzag chains of Ge atoms, whereas β-CeIrGe2 adopts the YIrGe2-type structure (orthorhombic, Immm, a = 4.3842(7) Å, b = 8.8960(14) Å, c = 16.258(3) Å, Z = 8) containing dumbbells of Ge atoms. The structure of Yb4Ir7Ge6 was determined at 296 and 193 K, and confirmed to be the U4Re7Si6-type. Yb5Ir4Ge10 adopts the Sc5Co4Si10-type structure (tetragonal, P4/mbm, a = 12.8799(6) Å, c = 4.2797(2) Å, Z = 2) containing squares and dumbbells of Ge atoms; the structure contracts anisotropically, faster along a than c, upon cooling to 100 K.
研究了稀土锗化铱(RE = Ce, Yb)在铟助熔剂中的晶体生长。这些实验结果形成了两个CeIrGe2的多态性,称为α和β,以及Yb4Ir7Ge6和Yb5Ir4Ge10。单晶x射线衍射分析表明,α-CeIrGe2为含Ge原子之形链的cenisi2型结构(正交,Cmcm, a = 4.3312(16) Å, b = 17.101(6) Å, c = 4.3803(16) Å, Z = 4),而β-CeIrGe2为含Ge原子哑哑形链的yirge2型结构(正交,Immm, a = 4.3842(7) Å, b = 8.8960(14) Å, c = 16.258(3) Å, Z = 8)。在296和193 K时测定了Yb4Ir7Ge6的结构,确定为u4re7si6型。Yb5Ir4Ge10采用sc5co4si10型结构(四边形,P4/mbm, a = 12.8799(6) Å, c = 4.2797(2) Å, Z = 2),包含Ge原子的正方形和哑哑形;在冷却至100k时,结构沿a方向的各向异性收缩比沿c方向的收缩快。
{"title":"Structures of ternary rare-earth germanides α-CeIrGe2, β-CeIrGe2, Yb4Ir7Ge6, and Yb5Ir4Ge10","authors":"Dundappa Mumbaraddi ,&nbsp;Arthur Mar","doi":"10.1016/j.jssc.2026.125837","DOIUrl":"10.1016/j.jssc.2026.125837","url":null,"abstract":"<div><div>Crystal growth of ternary rare-earth iridium germanides <em>RE</em>–Ir–Ge (<em>RE</em> = Ce, Yb) was investigated in indium flux. These experiments resulted in the formation of two polymorphs of CeIrGe<sub>2</sub>, termed <em>α</em> and <em>β</em>, as well as Yb<sub>4</sub>Ir<sub>7</sub>Ge<sub>6</sub> and Yb<sub>5</sub>Ir<sub>4</sub>Ge<sub>10</sub>. Single-crystal X-ray diffraction analysis revealed that <em>α</em>-CeIrGe<sub>2</sub> adopts the CeNiSi<sub>2</sub>-type structure (orthorhombic, <em>Cmcm</em>, <em>a</em> = 4.3312(16) Å, <em>b</em> = 17.101(6) Å, <em>c</em> = 4.3803(16) Å, <em>Z</em> = 4) containing zigzag chains of Ge atoms, whereas <em>β</em>-CeIrGe<sub>2</sub> adopts the YIrGe<sub>2</sub>-type structure (orthorhombic, <em>Immm</em>, <em>a</em> = 4.3842(7) Å, <em>b</em> = 8.8960(14) Å, <em>c</em> = 16.258(3) Å, <em>Z</em> = 8) containing dumbbells of Ge atoms. The structure of Yb<sub>4</sub>Ir<sub>7</sub>Ge<sub>6</sub> was determined at 296 and 193 K, and confirmed to be the U<sub>4</sub>Re<sub>7</sub>Si<sub>6</sub>-type. Yb<sub>5</sub>Ir<sub>4</sub>Ge<sub>10</sub> adopts the Sc<sub>5</sub>Co<sub>4</sub>Si<sub>10</sub>-type structure (tetragonal, <em>P</em>4/<em>mbm</em>, <em>a</em> = 12.8799(6) Å, <em>c</em> = 4.2797(2) Å, <em>Z</em> = 2) containing squares and dumbbells of Ge atoms; the structure contracts anisotropically, faster along <em>a</em> than <em>c</em>, upon cooling to 100 K.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125837"},"PeriodicalIF":3.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035075","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
Effect of nitrogen incorporation on the phase structure, thermal behaviour and structural properties of apatite wollastonite (AW) bioactive ceramics 氮掺入对磷灰石硅灰石(AW)生物活性陶瓷相结构、热行为和结构性能的影响
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-15 DOI: 10.1016/j.jssc.2026.125833
Erhan İbrahimoğlu , Fatih Çalışkan , Zafer Tatlı , Stuart Hampshire
In this research, a powder mixture of SiO2–P2O5–CaO–CaF2–MgO–Al2O3 compound was prepared, and the melt-quenching process was employed to obtain apatite wollastonite (AW) bioactive glasses. The mixture was melted in an alumina crucible at a temperature exceeding 1500 °C for 1 h under both ambient and protective nitrogen (N2) atmosphere conditions. By using a melt-quenching method, the melted glass was cooled over a critical cooling rate into a graphite crucible. The prepared sample in N2 condition (G2) and ambient condition (G1) glasses were investigated in terms of chemical content (XRD, EDS and FTIR), microstructure (FESEM), physical (density) and mechanical properties (hardness and indentation fracture toughness). The protective atmosphere (N2) caused a meaningful increase in the indentation fracture toughness (IFT), from 1.54 to 1.72 MPa m1/2, 12 %, while the hardness of glasses was slightly increased from 5.98 to 6.00 GPa by the N2 condition. The findings demonstrate that nitrogen not only contributes to the structural organisation but also plays a critical role in driving the thermodynamic stability and microstructural evolution of the system, significantly influencing the specific phase transformation occurring from β-wollastonite to pseudowollastonite and the thermal behaviour in glass-ceramic systems. This could be considered a critical parameter for future material design and functional applications.
本研究制备了SiO2-P2O5-CaO-CaF2-MgO-Al2O3复合物的粉末混合物,并采用熔融淬火工艺制备了磷灰石硅灰石(apatite wollastonite, AW)生物活性玻璃。在环境和保护氮气(N2)气氛下,将混合物在温度超过1500℃的氧化铝坩埚中熔化1小时。采用熔融淬火法,将熔融玻璃以临界冷却速率冷却到石墨坩埚中。对制备的样品在N2条件(G2)和环境条件(G1)下的化学含量(XRD、EDS和FTIR)、微观结构(FESEM)、物理(密度)和力学性能(硬度和压痕断裂韧性)进行了研究。保护气氛(N2)使压痕断裂韧性(IFT)从1.54提高到1.72 MPa m1/2,提高了12%,而玻璃的硬度则从5.98提高到6.00 GPa。研究结果表明,氮不仅有助于结构组织,而且在驱动系统的热力学稳定性和微观结构演化中起着关键作用,显著影响从β-硅灰石到伪硅灰石的特定相变和玻璃陶瓷系统的热行为。这可以被认为是未来材料设计和功能应用的关键参数。
{"title":"Effect of nitrogen incorporation on the phase structure, thermal behaviour and structural properties of apatite wollastonite (AW) bioactive ceramics","authors":"Erhan İbrahimoğlu ,&nbsp;Fatih Çalışkan ,&nbsp;Zafer Tatlı ,&nbsp;Stuart Hampshire","doi":"10.1016/j.jssc.2026.125833","DOIUrl":"10.1016/j.jssc.2026.125833","url":null,"abstract":"<div><div>In this research, a powder mixture of SiO<sub>2</sub>–P<sub>2</sub>O<sub>5</sub>–CaO–CaF<sub>2</sub>–MgO–Al<sub>2</sub>O<sub>3</sub> compound was prepared, and the melt-quenching process was employed to obtain apatite wollastonite (AW) bioactive glasses. The mixture was melted in an alumina crucible at a temperature exceeding 1500 °C for 1 h under both ambient and protective nitrogen (N<sub>2</sub>) atmosphere conditions. By using a melt-quenching method, the melted glass was cooled over a critical cooling rate into a graphite crucible. The prepared sample in N<sub>2</sub> condition (G2) and ambient condition (G1) glasses were investigated in terms of chemical content (XRD, EDS and FTIR), microstructure (FESEM), physical (density) and mechanical properties (hardness and indentation fracture toughness). The protective atmosphere (N<sub>2</sub>) caused a meaningful increase in the indentation fracture toughness (IFT), from 1.54 to 1.72 MPa m<sup>1/2</sup>, 12 %, while the hardness of glasses was slightly increased from 5.98 to 6.00 GPa by the N<sub>2</sub> condition. The findings demonstrate that nitrogen not only contributes to the structural organisation but also plays a critical role in driving the thermodynamic stability and microstructural evolution of the system, significantly influencing the specific phase transformation occurring from β-wollastonite to pseudowollastonite and the thermal behaviour in glass-ceramic systems. This could be considered a critical parameter for future material design and functional applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125833"},"PeriodicalIF":3.5,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035077","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
Ferroelectric properties influenced by the formation of oxygen vacancy layers within PbTiO3 multilayer thin films 氧空位层形成对PbTiO3多层薄膜铁电性能的影响
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-14 DOI: 10.1016/j.jssc.2026.125827
Eunmi Lee , Jong Yeog Son
The imprint phenomenon, in which the ferroelectric hysteresis loop of ferroelectric thin films moves in one direction, is caused by an internal electric field generated by an imbalance of internal charges. This internal electric field formed in the ferroelectric thin films can be generated from the imbalance of defects caused by using two different electrodes or heat treatment. In this study, we investigated the imprinted ferroelectric hysteresis loops occurring in PbTiO3 (PTO) multilayer thin films composed of oxygen-deficient PbTiO3-δ (DPTO) layers combined with PTO thin films. To form PTO multilayer thin films on Nb-doped SrTiO3 substrates by a pulsed laser deposition method, a normal PTO layer and an oxygen-deficient DPTO layer were mixed and deposited where the oxygen-deficient DPTO layer was deposited by a PbTiO3-δ target. PTO capacitors with configurations of PTO/DPTO and DPTO/PTO exhibited implanted ferroelectric hysteretic loops moving left and right, respectively. In particular, the PTO capacitor of the DPTO/PTO/DPTO structure exhibited imprinted ferroelectric hysteresis loops spreading in both directions. The results provide an opportunity for free control of the imprint direction of the PTO multilayer films by controlling the position of the oxygen-vacancy DPTO layer applying ferroelectric hysteresis loops.
铁电薄膜的铁电滞回线向一个方向移动的压印现象是由内部电荷不平衡产生的内部电场引起的。这种在铁电薄膜中形成的内部电场可以由使用两种不同电极或热处理引起的缺陷不平衡产生。在本研究中,我们研究了由缺氧PbTiO3-δ (DPTO)层与PTO薄膜结合而成的PbTiO3 (PTO)多层薄膜中出现的印迹铁电磁滞回线。采用脉冲激光沉积法在铌掺杂SrTiO3衬底上制备PTO多层薄膜,将正常PTO层与缺氧DPTO层混合沉积,其中缺氧DPTO层由PbTiO3-δ靶沉积。PTO/DPTO和DPTO/PTO结构的PTO电容器分别表现出向左和向右移动的植入铁电滞后环。特别是,DPTO/PTO/DPTO结构的PTO电容器呈现出双向扩展的印迹铁电磁滞回。研究结果为利用铁电磁滞回线控制氧空位DPTO层的位置来自由控制PTO多层膜的压印方向提供了机会。
{"title":"Ferroelectric properties influenced by the formation of oxygen vacancy layers within PbTiO3 multilayer thin films","authors":"Eunmi Lee ,&nbsp;Jong Yeog Son","doi":"10.1016/j.jssc.2026.125827","DOIUrl":"10.1016/j.jssc.2026.125827","url":null,"abstract":"<div><div>The imprint phenomenon, in which the ferroelectric hysteresis loop of ferroelectric thin films moves in one direction, is caused by an internal electric field generated by an imbalance of internal charges. This internal electric field formed in the ferroelectric thin films can be generated from the imbalance of defects caused by using two different electrodes or heat treatment. In this study, we investigated the imprinted ferroelectric hysteresis loops occurring in PbTiO<sub>3</sub> (PTO) multilayer thin films composed of oxygen-deficient PbTiO<sub>3-δ</sub> (DPTO) layers combined with PTO thin films. To form PTO multilayer thin films on Nb-doped SrTiO<sub>3</sub> substrates by a pulsed laser deposition method, a normal PTO layer and an oxygen-deficient DPTO layer were mixed and deposited where the oxygen-deficient DPTO layer was deposited by a PbTiO<sub>3-δ</sub> target. PTO capacitors with configurations of PTO/DPTO and DPTO/PTO exhibited implanted ferroelectric hysteretic loops moving left and right, respectively. In particular, the PTO capacitor of the DPTO/PTO/DPTO structure exhibited imprinted ferroelectric hysteresis loops spreading in both directions. The results provide an opportunity for free control of the imprint direction of the PTO multilayer films by controlling the position of the oxygen-vacancy DPTO layer applying ferroelectric hysteresis loops.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125827"},"PeriodicalIF":3.5,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035073","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, structure, and magnetic properties of a new vanadium tellurite AgV2TeO7 新型碲酸钒AgV2TeO7的合成、结构和磁性能
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-14 DOI: 10.1016/j.jssc.2026.125834
Tianyu Zhu , Donger Cheng , Wenbin Wei , Fuxi Zhou , Pengfei Zhou , Guang Wang , Junrong Zhang , Xiao Wang , Erxi Feng
Spin-1/2 dimerized quantum magnets offer an ideal platform for exploring novel quantum states and phase transitions, hosting singlet-triplet excitations as elementary magnetic excitations. In this work, we report the hydrothermal synthesis of a V4+-based dimer compound, AgV2TeO7. Its crystal structure features dimers composed of edge-sharing VO6 octahedra, which are effectively isolated by non-magnetic [VTeO7] chains. Magnetic measurements show that this compound exhibits short-range magnetic order below ∼55 K, with no magnetic long-range order down to 2 K, and the intrinsic susceptibility approaches zero at low temperature, a signature of the spin dimer state with gap around 78 K.
自旋1/2二聚体量子磁体提供了一个理想的平台,用于探索新的量子态和相变,承载单重态-三重态激发作为基本磁激发。本文报道了一种基于V4+的二聚体化合物AgV2TeO7的水热合成。它的晶体结构是由共享边的VO6八面体组成的二聚体,它们被非磁性的[VTeO7]链有效地隔离。磁性测量表明,该化合物在~ 55 K以下表现出短程磁序,在2 K以下没有磁长程磁序,在低温下的本征磁化率接近于零,这是自旋二聚体状态的一个特征,其间隙在78 K左右。
{"title":"Synthesis, structure, and magnetic properties of a new vanadium tellurite AgV2TeO7","authors":"Tianyu Zhu ,&nbsp;Donger Cheng ,&nbsp;Wenbin Wei ,&nbsp;Fuxi Zhou ,&nbsp;Pengfei Zhou ,&nbsp;Guang Wang ,&nbsp;Junrong Zhang ,&nbsp;Xiao Wang ,&nbsp;Erxi Feng","doi":"10.1016/j.jssc.2026.125834","DOIUrl":"10.1016/j.jssc.2026.125834","url":null,"abstract":"<div><div>Spin-1/2 dimerized quantum magnets offer an ideal platform for exploring novel quantum states and phase transitions, hosting singlet-triplet excitations as elementary magnetic excitations. In this work, we report the hydrothermal synthesis of a V<sup>4+</sup>-based dimer compound, AgV<sub>2</sub>TeO<sub>7</sub>. Its crystal structure features dimers composed of edge-sharing VO<sub>6</sub> octahedra, which are effectively isolated by non-magnetic [VTeO<sub>7</sub>] chains. Magnetic measurements show that this compound exhibits short-range magnetic order below ∼55 K, with no magnetic long-range order down to 2 K, and the intrinsic susceptibility approaches zero at low temperature, a signature of the spin dimer state with gap around 78 K.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125834"},"PeriodicalIF":3.5,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035035","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
Growth, discovery and characterization of single crystalline Eu0.8 Pt6Al16.4 Eu0.8 Pt6Al16.4单晶的生长、发现与表征
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-01-13 DOI: 10.1016/j.jssc.2026.125830
Juan Schmidt , Oliver Janka , Jutta Kösters , Sergey L. Bud’ko , Paul C. Canfield
We report the discovery of a ternary compound, Eu0.8Pt6Al16.4. We determine its chemical and structural characteristics based on energy-dispersive X-ray spectroscopy as well as both powder and single-crystal X-ray diffraction, demonstrating that it crystallizes in a hexagonal structure type EuPt6Al17 with no reported structural analog. The temperature- and field-dependent magnetization, and temperature-dependent resistance measurements, reveal that the Eu2+ magnetic moments order antiferromagnetically below 2.8 K.
我们报道了一个三元化合物Eu0.8Pt6Al16.4的发现。我们根据能量色散x射线光谱以及粉末和单晶x射线衍射确定了它的化学和结构特征,表明它结晶为六方结构类型的EuPt6Al17,没有报道过类似的结构。温度和场相关磁化强度以及温度相关电阻测量表明,Eu2+磁矩在2.8 K以下呈反铁磁序。
{"title":"Growth, discovery and characterization of single crystalline Eu0.8 Pt6Al16.4","authors":"Juan Schmidt ,&nbsp;Oliver Janka ,&nbsp;Jutta Kösters ,&nbsp;Sergey L. Bud’ko ,&nbsp;Paul C. Canfield","doi":"10.1016/j.jssc.2026.125830","DOIUrl":"10.1016/j.jssc.2026.125830","url":null,"abstract":"<div><div>We report the discovery of a ternary compound, Eu<sub>0.8</sub>Pt<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span>Al<sub>16.4</sub>. We determine its chemical and structural characteristics based on energy-dispersive X-ray spectroscopy as well as both powder and single-crystal X-ray diffraction, demonstrating that it crystallizes in a hexagonal structure type EuPt<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span>Al<sub>17</sub> with no reported structural analog. The temperature- and field-dependent magnetization, and temperature-dependent resistance measurements, reveal that the Eu<span><math><msup><mrow></mrow><mrow><mn>2</mn><mo>+</mo></mrow></msup></math></span> magnetic moments order antiferromagnetically below 2.8 K.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125830"},"PeriodicalIF":3.5,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974209","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
期刊
Journal of Solid State Chemistry
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