Journal of Solid State Chemistry最新文献

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 : 2026-01-27 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。

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引用次数: 0

Magnetism, orbital splitting and electron–phonon coupling of chalcogenide "11" type iron-based superconductors under high pressure 硫族“11”型铁基超导体在高压下的磁性、轨道分裂和电子-声子耦合

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-27 DOI: 10.1016/j.jssc.2026.125851

Wen-Guang Li , Zheng-Tang Liu , Qi-Jun Liu

Studying the basic physical properties of superconducting materials is an important prerequisite for understanding their superconducting transition mechanism. This article is based on first principles calculations to study the structure, electronic structure, and electron–phonon coupling of FeX (X = S, Se, Te) under high pressure. The calculation results indicate that the crystal structures of FeSe and FeTe undergo abrupt changes under pressure at 7 GPa and 6 GPa, respectively. Structural changes can cause abrupt changes in anion height and magnetism. The electronic structure shows that under the combined action of pressure, planar square field, and tetrahedral field, the energy levels of the five split Fe-d orbitals will rearrange. The analysis of the electron–phonon coupling constant shows that the vibration mode of Fe atoms along the z-direction contributes the most to the electron–phonon coupling of FeS and FeTe, while the vibration mode of Se atoms along the z-direction contributes the most to the electron–phonon coupling (EPC) of FeSe.

研究超导材料的基本物理性质是理解其超导跃迁机理的重要前提。本文基于第一性原理计算，研究了高压下FeX （X = S, Se, Te）的结构、电子结构和电子-声子耦合。计算结果表明，在7 GPa和6 GPa的压力下，FeSe和FeTe的晶体结构发生突变。结构变化会引起阴离子高度和磁性的突变。电子结构表明，在压力、平面方场和四面体场的共同作用下，5个分裂的Fe-d轨道的能级会发生重排。电子-声子耦合常数分析表明，Fe原子沿z方向的振动模式对FeS和FeTe的电子-声子耦合贡献最大，Se原子沿z方向的振动模式对FeSe的电子-声子耦合（EPC）贡献最大。

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引用次数: 0

In-situ construction of amorphous-MgAl2O4/Cu2O heterojunction for enhanced photocatalytic degradation performance 原位构建非晶mgal2o4 /Cu2O异质结增强光催化降解性能

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-26 DOI: 10.1016/j.jssc.2026.125852

Xinwei Zou , Xi'nan Zhang , Fukang Gu , Weiqiang Wang , Yuhui Ma , Xuming Zhang

While heterojunctions are widely used to enhance photocatalysis, the role of amorphous components remains less explored. This work introduces a novel amorphous-MgAl₂O₄/Cu₂O (a-MgAl₂O₄/Cu₂O) heterojunction constructed via a sol-gel combining in-situ chemical precipitation method, where the a-MgAl₂O₄ phase acts as a multifunctional promoter. Its defective nature provides abundant active sites, while the formed interface establishes complex charge transfer pathways. This pathway not only promotes the separation of powerful photogenerated electrons and holes but also preserves their high redox potential. Evidence from UV–vis DRS, XPS, PL, and EIS confirms improved light absorption and accelerated interfacial charge transfer. The optimized composite a-MgAl₂O₄/Cu₂O (0.45:1) demonstrated superior degradation activity against methyl orange under visible light irradiation, outperforming pristine Cu₂O and a-MgAl₂O₄ by a factor of more than 2. Mechanistic studies revealed that ·O₂⁻ radicals and h⁺ are the dominant reactive species, and energy band structure analysis confirmed the proposed Type-II model and charge transfer mechanism within the heterojunction. The findings open a new avenue for leveraging amorphous materials in the precise design of advanced heterojunction photocatalysts.

虽然异质结被广泛用于增强光催化，但非晶组分的作用仍然很少被探索。本文通过溶胶-凝胶结合原位化学沉淀法构建了一种新型的非晶mgal2o4 /Cu2O （a- mgal2o4 /Cu2O）异质结，其中a- mgal2o4相作为多功能启动子。其缺陷性提供了丰富的活性位点，而形成的界面建立了复杂的电荷转移途径。该途径不仅促进了强大的光生电子和空穴的分离，而且保持了它们的高氧化还原电位。来自UV-vis DRS， XPS， PL和EIS的证据证实了光吸收的改善和界面电荷转移的加速。优化后的复合材料a- mgal2o4 /Cu2O（0.45:1）在可见光照射下对甲基橙的降解活性优于原始Cu2O和a- mgal2o4，其降解活性是原始Cu2O和a- mgal2o4的2倍以上。机理研究表明，·O2−自由基和h+是主要的反应物种，能带结构分析证实了异质结内的ii型模型和电荷转移机制。这一发现为利用非晶材料精确设计先进的异质结光催化剂开辟了新的途径。

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引用次数: 0

Iron and nickel vs. cobalt: Precipitation of tris-chelate phenanthroline complexes [ML3][B12Cl12] from the solution 铁、镍与钴：从溶液中析出三螯合菲罗啉配合物[ML3][B12Cl12]

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-26 DOI: 10.1016/j.jssc.2026.125855

Varvara V. Avdeeva, Alexey S. Kubasov, Aleksey V. Golubev, Aleksandr Yu Bykov, Nikolay T. Kuznetsov

The complexation of iron(II)/iron(III), cobalt(II), and nickel(II) with 1,10-phenanthroline (phen) in the presence of the highly chlorinated boron cluster anion [B₁₂Cl₁₂]^2– was investigated. The reactions of FeCl₂ and NiCl₂ with phen (1:3 ratio) readily form the stable tris-chelate complexes [M(phen)₃][B₁₂Cl₁₂] (M = Fe (1), Ni (2)), which were isolated and characterized by X-ray diffraction. In contrast to the reducing behavior of [B_nH_n]^2– anions (n = 10, 12), the [B₁₂Cl₁₂]^2– anion does not reduce iron(III), allowing for the first isolation of a stable iron(III) complex with a polyhedral borane counterion. Specifically, the reaction of FeCl₃ with phen (1:2 ratio) yielded the binuclear μ-oxo complex [Cl(phen)₂FeOFe(phen)₂Cl][B₁₂Cl₁₂] (3). Surprisingly, all attempts to form analogous tris-chelate cobalt(II) complex with [B₁₂Cl₁₂]^2– were unsuccessful, resulting only in the precipitation of known cobalt phenanthroline chlorides or nitrates, while the borate salt remained unreacted. This inertness was confirmed by direct mixing experiments and reactions with cobalt(III) ammine complexes. However, the hydroxyl-functionalized analog, [B₁₂Cl₁₀(OH)₂]^2–, effectively formed the ion-pair complex [Co(phen)₃][B₁₂Cl₁₀(OH)₂] (4). The results highlight a stark difference in the coordinating and crystallizing ability of [B₁₂C₁₂]^2– compared to its well-studied hydride analogs and less chlorinated counterparts, underscoring the critical role of the anion hydrophobicity and specific functionalization in stabilizing metal complexes and their rapid precipitation from the reaction solution.

研究了在高氯化硼簇阴离子[B12Cl12]2 -存在下，铁(II)/铁（III）、钴（II）和镍（II）与1,10-邻菲罗啉（phen）的络合反应。FeCl2和NiCl2与phen（1:3）的反应容易形成稳定的三螯合物[M(phen)3][B12Cl12] (M = Fe (1), Ni(2))，并通过x射线衍射对其进行了分离和表征。与[BnHn]2 -阴离子（n = 10,12）的还原行为相反，[B12Cl12]2 -阴离子不还原铁（III），允许首次分离稳定的铁（III）配合物与多面体硼烷对偶离子。FeCl3与phen（1:2）反应生成双核μ-氧配合物[Cl(phen)2FeOFe(phen)2Cl][B12Cl12](3)。令人惊讶的是，所有试图与[B12Cl12]2 -形成类似的三螯合钴（II）配合物的尝试都是不成功的，只导致已知的邻菲罗啉钴氯化物或硝酸盐的沉淀，而硼酸盐仍未反应。通过直接混合实验和与钴（III）胺配合物的反应证实了这种惰性。然而，羟基功能化的类似物[B12Cl10(OH)2]2 -有效地形成了离子对配合物[Co(phen)3][B12Cl10(OH)2](4)。结果表明[B12C12]2 -的配位和结晶能力与氢化物类似物和较少氯化的类似物相比存在明显差异，强调了阴离子疏水性和特定功能化在稳定金属配合物和从反应溶液中快速沉淀金属配合物中的关键作用。

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引用次数: 0

Synthesis of ZrP–C using MOF-808 as a template and investigation of its fluoride ion adsorption 以MOF-808为模板合成ZrP-C及其对氟离子的吸附研究

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-24 DOI: 10.1016/j.jssc.2026.125850

Zuliang Wang , Aotian Gu , Chunhui Gong , Xiqing Xu , Peng Wang , Yi Yang

This work describes the synthesis of a ZrP–C composite adsorbent using MOF-808 as a template via one-step, high-temperature carbonization. The adsorption performance of ZrP–C material toward fluoride ions was investigated as a function of time, solution concentration, temperature, pH, and coexisting anions. After 3 h, the ZrP–C-3 adsorbent achieved saturation in fluoride uptake, demonstrating a final uptake of 37 mg/g at equilibrium. Fit the adsorption process using kinetic and isothermal adsorption models. The study revealed that adsorption was dominated by monolayer chemical adsorption. Adsorption was found to be endothermic, according to thermodynamic studies, with higher temperatures favoring increased uptake. Combined XPS, XRD, and FT-IR studies revealed that ion exchange, surface complexation, and electrostatic interactions jointly governed fluoride removal. For low-concentration fluoride-containing water bodies, typically those with concentrations below 20 mg/L, adding an appropriate amount of adsorbent could effectively reduce the wastewater concentration to meet national standards. These results highlight the strong potential of ZrP–C-3 for practical applications in fluoride removal from wastewater.

本文介绍了以MOF-808为模板，通过一步高温碳化法制备ZrP-C复合吸附剂。考察了ZrP-C材料对氟离子的吸附性能与时间、溶液浓度、温度、pH和共存阴离子的关系。3 h后，ZrP-C-3吸附剂的氟吸收量达到饱和，最终达到37 mg/g的平衡吸收量。采用动力学和等温吸附模型拟合吸附过程。研究表明，吸附以单层化学吸附为主。根据热力学研究，发现吸附是吸热的，较高的温度有利于增加吸收。结合XPS， XRD和FT-IR研究表明，离子交换，表面络合和静电相互作用共同控制氟化物的去除。对于低浓度含氟水体，特别是浓度低于20 mg/L的水体，添加适量的吸附剂可以有效降低废水浓度，达到国家标准。这些结果突出了ZrP-C-3在除氟废水中的实际应用潜力。

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引用次数: 0

Deciphering the trade-off of Co/Mn ratio modulation on electrochemical performance of ultrahigh-nickel cathode materials 解析Co/Mn比调制对超高镍阴极材料电化学性能的影响

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-23 DOI: 10.1016/j.jssc.2026.125848

Hang Chen , Cheng Wei , Jingyuan Guo , Hongyu Yang , Ye Yu , Yang Wu , Lijuan Wang , Yihang Li , Zhimin Li

Ultrahigh-nickel cathode materials (Ni ≥ 0.9) are prime candidates for high power lithium-ion batteries because of their high specific capacity and lower cost compared to high-cobalt cathodes. However, the modulating mechanisms of Co/Mn ratios on electrochemical performance under different cutoff voltages remain elusive. Here, we decouple this relationship by benchmarking three model compositions with distinct Co/Mn ratios: LiNi_0.96Mn_0.04O₂ (Co/Mn = 0), LiNi_0.97Co_0.02Mn_0.01O₂ (Co/Mn = 2), and LiNi_0.94Co_0.05Mn_0.01O₂ (Co/Mn = 5). By employing multi-scale characterization techniques, it is found that the Co/Mn ratio governs both H2/H3 phase-transition reversibility and oxygen-vacancy chemistry under varying cut-off voltages. At 4.3 V, an elevated Co/Mn ratio enhances H2/H3 reversibility, enabling NCM940501 to achieve optimal performance with 212.15 mAh g⁻¹ capacity at 1 C and 92.8 % retention after 100 cycles. Pushing the cut-off to above 4.4 V reverses this trend: lower Co/Mn ratio effectively suppresses H2/H3 phase transition kinetics, endowing NM9604 with superior cyclability. However, the reduced intrinsic oxygen vacancy concentration of NM9604 compromises Li⁺ diffusion kinetics, yielding only 117 mAh g⁻¹ at 10 C, 30 % lower than NCM940501(140 mAh g⁻¹). These findings establish a quantitative link between transition-metal stoichiometry and performance trade-offs, offering a new perspective for the design and modification of high-voltage and high-energy cathodes.

与高钴阴极相比，超高镍阴极材料（Ni≥0.9）具有高比容量和更低成本，是高功率锂离子电池的首选材料。然而，Co/Mn比对不同截止电压下电化学性能的调节机制尚不清楚。在这里，我们通过对具有不同Co/Mn比率的三种模型成分进行基准测试来解耦这种关系：lini0.96 mn0.040 o2 (Co/Mn = 0), lini0.97 co0.02 mn0.010 o2 （Co/Mn = 2）和lini0.94 co0.05 mn0.010 o2 （Co/Mn = 5）。采用多尺度表征技术发现，在不同截止电压下，Co/Mn比影响H2/H3相变的可逆性和氧空位化学性质。在4.3 V电压下，Co/Mn比的提高提高了H2/H3的可逆性，使NCM940501在1℃下具有212.15 mAh g−1的最佳性能，100次循环后的保留率为92.8%。将截止电压提高到4.4 V以上会逆转这一趋势：较低的Co/Mn比有效地抑制了H2/H3相变动力学，使NM9604具有优越的可循环性。然而，降低的NM9604的固有氧空位浓度影响了Li+的扩散动力学，在10℃下仅产生117 mAh g−1，比NCM940501（140 mAh g−1）低30%。这些发现建立了过渡金属化学计量学与性能权衡之间的定量联系，为设计和改进高压高能阴极提供了新的视角。

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引用次数: 0

Structural and magnetic properties of Ce2Co7 single crystal Ce2Co7单晶的结构和磁性能

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-23 DOI: 10.1016/j.jssc.2026.125849

V.V. Govorina , S.N. Mozgovykh , A.M. Bartashevich , V.S. Gaviko , A.S. Ovchinnikov , M.I. Bartashevich , D.S. Neznakhin

Ce₂Co₇ single crystals with the hexagonal Ce₂Ni₇-type structure (space group P6₃/mmc) were obtained and investigated. Single crystal X-ray diffraction confirmed the hexagonal structure, while no evidence of the rhombohedral Gd₂Co₇-type modification was found. This compound exhibits antiferromagnetic behavior at temperatures between 5 and 21 K. Above 21 K, this compound becomes a highly anisotropic ferromagnet with a Curie temperature of 50 K. Magnetic measurements along the c-axis determined the critical field for the antiferromagnetic — ferromagnetic phase transition to have a linear dependence on temperature with a slope of −226 Oe/K. A pronounced magnetic susceptibility anomaly was detected in the temperature range of 50–150 K. However, a scaling analysis commonly used to identify a Griffiths phase revealed no evidence for the presence of such a phase.

制备并研究了具有六方ce2ni7型结构（空间群P63/mmc）的Ce2Co7单晶。单晶x射线衍射证实了其六边形结构，但未发现gd2co7型菱形修饰的证据。该化合物在5 ~ 21 K的温度范围内表现出反铁磁行为。在21 K以上，该化合物成为高度各向异性的铁磁体，居里温度为50 K。沿c轴的磁测量确定了反铁磁-铁磁相变的临界场与温度呈线性关系，斜率为- 226 Oe/K。在50 ~ 150 K温度范围内，检测到明显的磁化率异常。然而，通常用于确定Griffiths阶段的标度分析没有显示出这种阶段存在的证据。

引用次数: 0

Synthesis of a novel functionalized metal-organic framework with N,O-binding sites for efficient adsorption of Pd(Ⅱ) from aqueous solutions 具有N， o结合位点的新型功能化金属-有机骨架的合成，用于从水溶液中高效吸附Pd（Ⅱ）

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-21 DOI: 10.1016/j.jssc.2026.125845

Wen Jiang , Yujie Yang , Xiaonian Liu , Shifeng Miao , Jie Jiang , Xueqin Ran , Chen Yuan , Yunxia Zhang

A novel sorbent, PL-UiO-66, was successfully synthesized by functionalizing NH₂-UiO-66 with ε-polylysine to create N,O-rich binding sites for the selective recovery of Pd(Ⅱ) from aqueous solutions. Systematic screening revealed PL-UiO-66 with a 1:1 mass ratio as the optimal adsorbent after evaluating various MOF substrates. The physicochemical properties of the adsorbent were systematically investigated using XRD, FT-IR, BET, SEM, and XPS. A high adsorption capacity of 206.8 mg/g for Pd(Ⅱ) was achieved by PL-UiO-66 at 323.15 K, with an optimal pH of 2.0, as evidenced by batch adsorption experiments. Kinetics analysis revealed that equilibrium was established within 120 min and followed the pseudo-second-order model. The adsorption isotherm was best fitted by the Langmuir isotherm, suggesting monolayer adsorption. Analysis of the thermodynamic parameters demonstrated that the sorption process is spontaneous and endothermic. In competitive adsorption tests, PL-UiO-66 maintained exceptional preference for Pd(II) even in the presence of multiple interfering metal ions. The adsorbent also demonstrated outstanding reusability, maintaining 85.48 % removal efficiency after 10 regeneration cycles. Mechanistic studies, combining FT-IR and XPS analyses, confirmed that coordination (via N and O atoms from N–H, O–H, and other functional groups) and electrostatic interactions served as critical mechanisms enabling the effective adsorption of Pd(II). This work underscores the significant potential of PL-UiO-66 as a high-performance adsorbent for sustainable palladium recovery.

利用ε-聚赖氨酸对NH2-UiO-66进行功能化，制备了一种新型吸附剂PL-UiO-66，该吸附剂可选择性地从水溶液中回收Pd（Ⅱ）。通过对各种MOF基质的评价，系统筛选结果表明，质量比为1:1的PL-UiO-66是最佳吸附剂。采用XRD、FT-IR、BET、SEM、XPS对吸附剂的理化性质进行了系统的研究。批量吸附实验表明，在323.15 K条件下，PL-UiO-66对Pd（Ⅱ）的吸附量为206.8 mg/g，最佳pH为2.0。动力学分析表明，反应在120 min内达到平衡，符合准二阶模型。吸附等温线最符合Langmuir等温线，表明吸附为单层吸附。热力学参数分析表明，吸附过程是自发的吸热过程。在竞争吸附测试中，即使存在多种干扰金属离子，PL-UiO-66也保持对Pd（II）的特殊偏好。该吸附剂具有良好的可重复使用性，在10次再生循环后，吸附剂的去除率仍保持在85.48%。结合FT-IR和XPS分析的机理研究证实，配位（通过N - h、O - h和其他官能团的N和O原子）和静电相互作用是有效吸附Pd（II）的关键机制。这项工作强调了PL-UiO-66作为可持续回收钯的高性能吸附剂的巨大潜力。

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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 : 2026-01-20 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

Coupled redox and ion-exchange dynamics in [Ru(bpy)3]-Intercalated layered MnO2 [Ru(bpy)3]-插层MnO2的耦合氧化还原和离子交换动力学

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2026-01-20 DOI: 10.1016/j.jssc.2026.125838

Kazuaki Tomono, Rion Yamaguchi, Soma Kataoka, Ryota Sugawara, Ryo Sasaki

Layered manganese dioxide (MnO₂) films intercalated with tris(2,2′-bipyridine)ruthenium(II) ([Ru(bpy)₃]²⁺) complexes were electrodeposited under potential control, enabling the selective formation of double-layered (D-type) and single-layered (S-type) intercalation structures. Upon immersion in water, D-type films underwent a controlled structural contraction to form an SD-type single-layer structure while partially retaining the Ru complexes. Comprehensive structural and spectroscopic analyses (XRD, Raman, FT-IR, UV–vis, EDS) revealed that Na⁺ ion exchange was strongly suppressed in the SD-type, whereas direct ion exchange occurred readily in the D-type. In contrast, S-type films exhibited intrinsic structural stability with minimal Ru leaching. Electrochemical measurements (CV, EIS) demonstrated that residual [Ru(bpy)₃] in the SD-type acted as a redox mediator, significantly lowering the charge-transfer resistance and enhancing pseudocapacitance, whereas S-type films promoted ion diffusion through their open layered framework. After 50 charge–discharge cycles, specific capacitances of 268 and 234 F g⁻¹ were obtained for SD- and S-type films, respectively, exceeding that of Na@MnO₂. This work provides direct evidence for redox–ion exchange coupling in layered MnO₂ and presents a rational strategy to tune interlayer structure and interfacial charge-transfer kinetics through controlled intercalation of redox-active metal complexes.

在电位控制下，电沉积了三（2,2′-联吡啶）钌（II）（[Ru(bpy)3]2+）配合物的层状二氧化锰（MnO2）膜，可以选择性地形成双层（d型）和单层（s型）的插层结构。浸入水中后，d型薄膜经过可控的结构收缩形成sd型单层结构，同时部分保留Ru配合物。综合结构和光谱分析（XRD, Raman, FT-IR, UV-vis， EDS）表明，在sd型中Na+离子交换被强烈抑制，而在d型中则容易发生直接离子交换。相比之下，s型薄膜表现出固有的结构稳定性，且Ru浸出量最小。电化学测量（CV， EIS）表明，sd型薄膜中的残留[Ru(bpy)3]充当氧化还原介质，显著降低电荷转移电阻并增强赝电容，而s型薄膜则通过其开放的层状框架促进离子扩散。经过50次充放电循环后，SD型和s型薄膜的比电容分别达到268和234 F g−1，超过Na@MnO2。这项工作为层状二氧化锰中氧化还原-离子交换耦合提供了直接证据，并提出了通过控制氧化还原活性金属配合物的嵌入来调整层间结构和界面电荷转移动力学的合理策略。

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引用次数: 0