Dalton Transactions最新文献_第3页

Cu-exchanged phosphomolybdic acid induced solvent effect to enhance alkene epoxidation with H2O2 铜交换磷钼酸诱导溶剂效应增强烯烃与H2O2的环氧化反应

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-03 DOI: 10.1039/d5dt02762d

Xiaojing Song, Shuang Liu, Jing Wang, Tingting Wu, Lina Liu, Hao Zhang

Solvent-mediated alkenes epoxidation using H2O2 oxidant is significantly enhanced by a Cu-substituted phosphomolybdic acid anchored on triphenylamine-functionalized porous organic polymers (CuPMA/POPs). The immobilization of CuPMA cluster on POPs supported suppressed the stronger coordinative interactions between Cu ion and PMA cluster, and brings obvious solvent effect. In 1, 4-dioxane, CuPMA/POPs achieves 90% conversion of cyclooctene, and markedly improves epoxide selectivity in styrene oxidation (65.5% vs 36.9% for PMA/POPs). Based on various characterizations, phosphomolybdic acid did not form the active species [PO4MoO(O2)]3-, which typically arise from the interaction PMA-H2O2. Instead, the incorporation of Cu modulates the electronic structure of PMA, facilitating the generation of active peroxo intermediates such as Cu-OOH and Mo-OOH. These species promote oxygen-atom transfer to the C=C bond, thus benefiting for the high epoxides selectivity. Additionally, the hydrogen-bonding network from the solvent effect between by 1,4-dioxane and H2O2 further enhances the reaction efficiency. The catalyst also exhibits excellent recyclability due to strong host-guest interactions, underscoring the synergy between Cu substitution and solvent effects in promoting efficient and stable epoxidation catalysis.

在三苯胺功能化多孔有机聚合物（CuPMA/POPs）上锚定cu取代磷酸，可显著增强H2O2溶剂介导的烯烃环氧化反应。在持久性有机污染物载体上固定pcma簇抑制了Cu离子与pcma簇之间较强的配位相互作用，并带来明显的溶剂效应。在1,4 -二氧六环中，CuPMA/POPs的环烯转化率达到90%，并显著提高了苯乙烯氧化过程中环氧化物的选择性（65.5% vs . PMA/POPs的36.9%）。根据各种表征，磷酸钼酸没有形成活性物质[PO4MoO(O2)]3-，而活性物质通常是由PMA-H2O2相互作用产生的。相反，Cu的加入调节了PMA的电子结构，促进了活性过氧化物中间体的生成，如Cu- ooh和Mo-OOH。这些物质促进氧原子向C=C键转移，从而有利于环氧化物的高选择性。此外，1,4-二氧六烷与H2O2之间的溶剂效应形成的氢键网络进一步提高了反应效率。由于具有很强的主客体相互作用，该催化剂还具有良好的可回收性，强调了Cu取代和溶剂效应之间的协同作用，促进了高效稳定的环氧化催化。

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引用次数: 0

Blue-Light-Driven Aerobic Oxidation via Superoxide Radical-Generating Zinc(II)-Organic Framework Photocatalyst 超氧化物自由基生成锌的蓝光驱动好氧氧化(II)-有机骨架光催化剂

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-03 DOI: 10.1039/d5dt02529j

Jing Zhu, Yumeng Zhang, Juanle Zhang, Junan Ma, Chang-Chun Liu, Xiaoxing Ma

The development of sustainable and efficient photocatalytic systems for aerobic oxidation is a crucial challenge in the field of green chemistry. In this study, we present the rational design and synthesis of a novel zinc(II)-organic framework (Zn-1D) by incorporating anthracene-based photoactive ligands with zinc(II)-oxo clusters. Zn-1D demonstrates significant absorption in the blue-light region (<450 nm), effective charge separation, and the ability to generate superoxide radicals (O2 •-).Structural analysis confirms a crystalline 1D chained structure with hierarchical porosity. Mechanistic investigations reveal a synergistic effect between anthracene-mediated light absorption and zinc(II)-mediated redox reactions. Under blue-light irradiation, Zn-1D exhibits outstanding catalytic performance in aerobic oxidation reactions, such as the thioether oxidation.The microporous channels of the framework stabilize reactive intermediates, preventing overoxidation. Moreover, its excellent chemical and thermal stability allow for five consecutive recycling cycles without loss of activity. This work provides a new model for noble-metal-free photocatalysis by utilizing MOF-confined dual-function sites for blue-light-driven organic transformations, thus promoting the development of sustainable synthetic methods.

开发可持续、高效的好氧光催化系统是绿色化学领域的一个重要挑战。在这项研究中，我们提出了合理的设计和合成一种新的锌(II)-有机骨架（Zn-1D），将蒽基光活性配体与锌(II)-氧簇结合。Zn-1D在蓝光区（<450 nm）有明显的吸收，有效的电荷分离，以及产生超氧自由基（O2•-）的能力。结构分析证实该晶体为一维链状结构，具有分层孔隙度。机制研究揭示了蒽介导的光吸收和锌（II）介导的氧化还原反应之间的协同效应。在蓝光照射下，Zn-1D在硫醚氧化等有氧氧化反应中表现出优异的催化性能。框架的微孔通道稳定活性中间体，防止过度氧化。此外，其优异的化学和热稳定性允许连续五次循环而不损失活性。本研究为利用mof限制的双功能位点进行蓝光驱动有机转化提供了一种新的无贵金属光催化模式，从而促进了可持续合成方法的发展。

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引用次数: 0

Inter-Ligand Cross-Links Determine Secondary Building Unit Formation in OligoMOFs 配体间交联决定OligoMOFs中二级构建单元的形成

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt03049h

Debobroto Sensharma, Victor Branco B de Sousa, Seth M Cohen

OligoMOFs are a new class of metal-organic frameworks (MOFs) that feature ligands covalently cross-linked into oligomers as intrinsic structural components. Recent studies have demonstrated that the size and flexibility of the tether moieties can result in the formation of oligoMOFs with different isomeric structures via geometrical distortions in the secondary building unit (SBU). In this work, it is demonstrated that tethered dimeric ligands with slightly different carbon chain lengths can direct the formation of oligoMOFs with SBUs of different structure and nuclearity. Specifically, inter-ligand cross links are used as a sensitive probe of the phase landscape of MOFs with the composition [Zn2(R-bdc)2(bpy)] (bdc = 1,4benzenedicarboxylate, bpy = 4,4'-bipyridine), showing that a hexyl tether result in a framework structure identical to MOF-508, based on dinuclear {Zn2} "paddlewheel" SBUs, while heptyl and octyl tethers result in a "honeycomb-like" framework structure based on an infinite rod-like Zn 2+ SBU bridged by carboxylate ligands. These results are the first examples of tether length influencing SBU chemistry in MOFs and help understand the interplay between the MOF lattice and the geometric constraints imposed by inter-ligand cross-links in oligoMOFs.

OligoMOFs是一类新型的金属有机框架（mof），其特征是配体共价交联成低聚物作为其固有结构组分。最近的研究表明，系链基团的大小和柔韧性可以通过次级构建单元（SBU）的几何畸变导致具有不同异构体结构的oligoMOFs的形成。在这项工作中，证明了碳链长度略有不同的系链二聚体可以指导具有不同结构和核的SBUs的oligoMOFs的形成。具体来说，配体间交联被用作[Zn2(R-bdc)2(bpy)] （bdc = 1,4苯二羧酸盐，bpy = 4,4'-联吡啶）组成的mof的相结构的敏感探针，结果表明，基于双核{Zn2}“桨轮”SBUs的己基系链形成了与MOF-508相同的框架结构，而基于羧酸配体桥接的无限棒状Zn2 + SBU的正辛基系链形成了“蜂窝状”框架结构。这些结果是系链长度影响MOF中SBU化学的第一个例子，有助于理解MOF晶格之间的相互作用以及oligomof中配体间交联所施加的几何约束。

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引用次数: 0

The influence of the coordination environment of cobalt(II) ions on the magnetic properties of heterometallic complexes with a {Co2Li2} metal core 钴离子配位环境对{Co2Li2}金属芯异质金属配合物磁性能的影响

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt02560e

Irina K. Rubtsova, Dmitriy S. Yambulatov, Maxim A. Shmelev, Julia K. Voronina, Alexander S. Goloveshkin, Konstantin A. Babeshkin, Nikolay N. Efimov, Anna K. Matiukhina, Stanislav A. Nikolaevskii, Mikhail A. Kiskin, Igor L. Eremenko

Five new heterometallic carboxylate complexes of the composition [Co₂Li₂(A)₆(L)₂] (L = 4-phenylpyridine, A = 2-furoate anion (1); L = 2,2′-bipyridine, A = 2-furoate anion (2), 3,5-di-tert-butylbenzoate anion (3); L = quinoline, A = 3-cyanobenzoate anion (4), 4-cyanobenzoate anion (5)) were synthesized. The structures of all compounds were determined by single-crystal X-ray diffraction. When monodentate N-donor ligands are replaced by chelating 2,2′-bipyridine, the coordination polyhedron of cobalt ions changes from a distorted tetrahedron to a distorted octahedron. Complexes 1–4 are field induced single-molecule magnets. Mechanisms of slow magnetic relaxation are discussed taking into account both experimental data and quantum chemical calculations.

[Co2Li2(A)6(L)2] （L = 4-苯基吡啶，A = 2-糠酸阴离子）组成的五种新型杂金属羧酸配合物L = 2,2′-联吡啶，A = 2-糠酸阴离子(2),3,5-二叔丁基苯甲酸阴离子(3)；合成了L =喹啉，A = 3-三苯甲酸盐阴离子(4)，4-三苯甲酸盐阴离子(5)。所有化合物的结构均通过单晶x射线衍射测定。当单齿n给体被螯合的2,2 ' -联吡啶取代时，钴离子的配位多面体由畸变四面体变为畸变八面体。配合物1-4是场感应单分子磁体。结合实验数据和量子化学计算，讨论了慢磁弛豫的机理。

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引用次数: 0

A multifunctional reconfigurable terahertz chiral metasurface based on VO₂ and graphene. 基于VO2和石墨烯的多功能可重构太赫兹手性超表面。

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d6dt00001k

Hongrun Xu, Zhen Cui

Despite advancements in high integration and miniaturization, terahertz (THz) devices still face challenges such as limited functionality, tunability, and narrow application ranges. To resolve the above concerns, we present a multifunctional reconfigurable THz chiral metasurface based on vanadium dioxide (VO₂) and graphene. This structure exploits VO₂'s phase transition and graphene's electrical tunability, enabling multifunctional responses. The metasurface exhibits a triple-band circular dichroism (CD) response within 1.0-3.5 THz, with peaks at 1.62 THz, 2.89 THz, and 3.19 THz, reaching values of 0.944, 0.83, and 0.88, respectively. Dynamic switching of CD peak numbers is achieved through the synergistic control of VO₂ and graphene. Under linearly polarized light incidence, the metasurface shows a single-band linear dichroism (LD) response in the 4.0-4.2 THz range, with a peak value of 0.9 at 4.093 THz. The intensity of the LD response can be reversibly tuned by adjusting the Fermi level of graphene and the incident polarization angle. Additionally, the metasurface efficiently converts polarization under both x-polarized and left-handed circularly polarized light. This multifunctional metasurface offers new opportunities for THz applications, such as CD supermirrors, intelligent switches, chiral photodetectors, and polarization digital imaging systems.

尽管在高集成度和小型化方面取得了进步，但太赫兹（THz）器件仍然面临着诸如有限的功能、可调性和狭窄的应用范围等挑战。为了解决上述问题，我们提出了一种基于二氧化钒（VO2）和石墨烯的多功能可重构太赫兹手性超表面。这种结构利用了VO2的相变和石墨烯的电可调性，实现了多功能响应。超表面在1.0 ~ 3.5 THz范围内呈现三波段圆二色性（CD）响应，峰值分别在1.62 THz、2.89 THz和3.19 THz处，分别达到0.944、0.83和0.88。通过VO2和石墨烯的协同控制，实现了CD峰数的动态切换。在线偏振光入射下，超表面在4.0 ~ 4.2 THz范围内呈现出单波段线性二色性（LD）响应，在4.093 THz处峰值为0.9。通过调节石墨烯的费米能级和入射偏振角，可以可逆地调节LD响应的强度。此外，超表面在x偏振光和左旋圆偏振光下都能有效地转换极化。这种多功能超表面为太赫兹应用提供了新的机会，如CD超镜、智能开关、手性光电探测器和偏振数字成像系统。

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引用次数: 0

Spectroscopic and electrochemical studies of tin(IV) complexes with noninnocent N₂S₂ and N₂O₂ ligands based on acenaphthene. 基于苊的非无害N2S2和N2O2配合物的光谱和电化学研究。

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt02688a

Liliya D Labutskaya, Varvara A Klok, Irina V Krylova, Pavel G Shangin, Mikhail E Minyaev, Evgeny V Tretyakov, Mikhail A Syroeshkin, Mikhail P Egorov, Elena N Nikolaevskaya

New mononuclear tin(IV) complexes were obtained via condensation of tin oxides (Ph₂SnO and Et₂SnO) with acenaphthene-based bis(thiosemicarbazones). The structure of the complexes was confirmed using ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy, as well as by X-ray diffraction analysis. The electronic and redox properties of complexes 1-5 were studied using UV spectroscopy and cyclic voltammetry (CV). It was shown that the electrochemical reduction of complexes 1-5 is quasi-reversible. Radical anion derivatives of complexes were described using CV and ESR spectroscopy. The second wave of electrochemical reduction of 1-4 is accompanied by further chemical transformations, while the electroreduction of complex 5 leads to the formation of persistent dianion species.

通过锡氧化物（Ph2SnO和Et2SnO）与苊基双硫代氨基脲缩合得到新的单核锡（IV）配合物。配合物的结构通过1H、13C和119Sn核磁共振波谱以及x射线衍射分析得到了证实。利用紫外光谱和循环伏安法（CV）研究了配合物1 ~ 5的电子和氧化还原性质。结果表明，配合物1 ~ 5的电化学还原是准可逆的。利用CV和ESR光谱对配合物的阴离子自由基衍生物进行了描述。1-4的第二波电化学还原伴随着进一步的化学转化，而配合物5的电还原导致了持久的dianion物种的形成。

引用次数: 0

Electrodeposited Polyoxometalate-Cu 2+1 O Hybrid on Copper Foam: Synergistic Electron Transfer for Efficient Nitrate Electroreduction to Ammonia 泡沫铜上电沉积多金属氧酸- cu 2+ O杂化物：协同电子转移对硝酸盐高效电还原制氨的影响

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt03106k

Kaiqun Bai, Xinming Wang, Gang Li, Haijun Pang, Huiyuan Ma

Electrocatalytic nitrate reduction (NO3RR) is a sustainable strategy to address nitrate pollution and replace the energyintensive Haber-Bosch process for ammonia synthesis, but it is hindered by complex multi-electron transfer pathways and severe hydrogen evolution competition. Herein, a hybrid electrocatalyst (Mo7/Cu2+1O/Cu@CF) was successfully fabricated via electrodeposition, integrating [Mo7O24] 6-(noted as Mo7) with Cu2+1O on copper foam (CF). The optimized catalyst exhibits exceptional NO3RR performance in neutral media: at -0.7 V vs. reversible hydrogen electrode (RHE), it achieves a high ammonia yield rate of 7.16 mg h -1 cm -2 and a Faradaic efficiency (FE) of 95.7%, along with outstanding stability over 10 hours of continuous electrolysis. Structural characterizations (XRD, XPS, and TEM) confirm the formation of a hybrid structure with strong electronic coupling at the Mo7/Cu2+1O interface, facilitating efficient interfacial electron transfer. In situ Fouriertransform infrared (FTIR) spectroscopy reveals the reaction pathway as NO3 -→ *NO3 → *NO2 → *NO → *NH2OH → *NH3, while 15 N isotope-labeling experiments verify that NH3 originates exclusively from nitrate. The superior performance stems from the synergistic effect between Mo7 (electron reservoir) and Cu2+1O (active site matrix), which optimizes the electronic structure of active sites and suppresses the hydrogen evolution reaction. This work provides a promising catalyst for sustainable ammonia production and a general design principle for high-performance electrocatalysts via polyoxometalatemetal oxide hybridization.

电催化硝酸还原（NO3RR）是解决硝酸盐污染和取代高能耗的Haber-Bosch合成氨工艺的一种可持续策略，但它受到复杂的多电子转移途径和激烈的析氢竞争的阻碍。本文通过电沉积方法成功制备了一种杂化电催化剂（Mo7/Cu2+ 10o /Cu@CF），将[Mo7O24] 6-（记为Mo7）与Cu2+ 10o集成在泡沫铜（CF）上。优化后的催化剂在中性介质中表现出优异的NO3RR性能：在-0.7 V时，相对于可逆氢电极（RHE），它的氨产率高达7.16 mg h -1 cm -2，法拉第效率（FE）达到95.7%，并且在连续电解10小时内具有出色的稳定性。结构表征（XRD， XPS和TEM）证实了在Mo7/Cu2+ 10界面处形成了具有强电子耦合的杂化结构，促进了高效的界面电子转移。原位傅里叶变换红外（FTIR）光谱分析表明，反应途径为NO3 -→*NO3→*NO2→*NO→*NH2OH→*NH3，而15个N同位素标记实验证实NH3完全来源于硝酸盐。优异的性能源于Mo7（电子库）与Cu2+ 10o（活性位点基质）之间的协同作用，优化了活性位点的电子结构，抑制了析氢反应。这项工作为可持续氨生产提供了一种有前途的催化剂，并通过多金属氧和金属氧杂化提供了高性能电催化剂的一般设计原则。

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引用次数: 0

Boronate esters for the binding and detection of low molecular weight volatile amines 硼酸酯用于结合和检测低分子量挥发性胺

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt02760h

Xiaoning Li, James Boyt, Min Cai, Steven Sloope, Luke T. Lackovic, Mark D. Smith, John J. Lavigne

Conjugated thiophene-based diboronate esters, 1–4, were synthesized to investigate how substituents on catechol alter the Lewis acidity and accessibility to boron, and influence binding interactions with low molecular weight Lewis basic amines. Crystallographic analysis indicated that both boron centres bind analyte and that Lewis base coordination induces deplanarization of the conjugated system. Spectroscopic studies demonstrate that amine binding disrupts conjugation, producing distinct and reproducible optical responses that depend on analyte basicity and structure, with association constants in organic solvent ranging from 10³ to 10⁶ M⁻¹. Quantitative binding analyses indicate strong negative cooperativity between the two boron sites. These results establish design principles for cross-reactive optical sensor arrays capable of differentiating volatile amines relevant to environmental monitoring, food quality assessment, and biomedical diagnostics.

合成了噻吩基共轭二硼酸酯1-4，以研究邻苯二酚上的取代基如何改变刘易斯酸度和对硼的可及性，以及影响与低分子量刘易斯碱胺的结合相互作用。晶体学分析表明，两个硼中心结合分析物，路易斯碱配位引起共轭体系的去平面化。光谱研究表明，胺结合破坏偶联，产生不同的和可重复的光学反应，这取决于分析物的碱度和结构，在有机溶剂中的缔合常数范围为103至106 M−1。定量结合分析表明两个硼位点之间具有很强的负协同性。这些结果建立了能够区分与环境监测、食品质量评估和生物医学诊断相关的挥发性胺的交叉反应性光学传感器阵列的设计原则。

引用次数: 0

Rational design and applications of artificial metalloenzymes based on neuroglobin 基于神经球蛋白的人工金属酶的合理设计与应用

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d6dt00067c

Lijuan Sun, Ying-Wu Lin

The rational design of artificial metalloenzymes enables the expansion of the functionalities of natural metalloenzymes, which has become a research hotspot in biocatalysis. As a member of the globin family, neuroglobin (Ngb) has a stable structure and possesses a tunable intramolecular disulfide bond of Cys46-Cys55, making it an ideal protein scaffold for the rational design of artificial metalloenzymes. This article systematically reviews recent progress in the rational design and applications of artificial metalloenzymes based on Ngb. It highlights strategies such as optimizing the microenvironment in the heme center, substituting key amino acid residues, constructing additional intramolecular disulfide bond, and introducing metal cofactors such as Co-porphyrin, which have successfully endowed Ngb-based artificial metalloenzymes with functions including nitrite reductase, monooxygenase, peroxidase, carbene transferase, hydrogenase, and even carbon monoxide detoxification capabilities. These advances not only deepen the understanding of the structure-function relationships of heme enzymes but also provide new insights in the rational design of artificial metalloenzymes. Artificial metalloenzymes based on Ngb and other protein scaffolds are expected to play significant roles in areas such as green synthesis, biocatalysis, environmental remediation, and biomedicine, etc.

人工金属酶的合理设计使天然金属酶的功能得以拓展，已成为生物催化领域的研究热点。神经球蛋白（neuroglobin, Ngb）作为珠蛋白家族的一员，具有稳定的结构，具有可调节的Cys46-Cys55分子内二硫键，是合理设计人工金属酶的理想蛋白支架。本文系统地综述了近年来基于Ngb的人工金属酶的合理设计和应用研究进展。重点介绍了优化血红素中心微环境、替换关键氨基酸残基、构建分子内二硫键、引入co -卟啉等金属辅因子等策略，成功赋予了基于ngb的人工金属酶亚硝酸盐还原酶、单加氧酶、过氧化物酶、碳转移酶、氢化酶甚至一氧化碳解毒能力。这些进展不仅加深了对血红素酶结构-功能关系的认识，而且为人工金属酶的合理设计提供了新的见解。基于Ngb等蛋白质支架的人工金属酶有望在绿色合成、生物催化、环境修复、生物医学等领域发挥重要作用。

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引用次数: 0

Investigations of Co(II) to Co(III) oxidation mechanisms at Fe3-δO4 nanoparticle surface Fe3-δO4纳米颗粒表面Co（II）到Co（III）氧化机理的研究

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt03034j

Laura Fablet, Mathieu Pédrot, Fadi Choueikani, Anthony Beauvois, Thomas Stephant, Valérie Briois, Rémi Marsac

Understanding and predicting the interaction mechanisms between Co and spinel iron oxides (Fe3-δO4; including magnetite, maghemite and their solid solutions) is of major interest in both the environmental and industrial contexts. While the surface complexation of Co2+, its polymerization and the surface precipitation of Fe3-δO4@CoO have been well been documented, the oxidation of Co2+ to Co3+ and interaction mechanisms between Co3+ and Fe3-δO4 nanoparticles in the presence of O2 have attracted less attention. In this study, experimental and modeling results, combined with XAS and XMCD analyses at the L2,3-edges, as well as TEM and XRD analysis, allowed the differentiation of several Co-species according to the Co concentration, at pH 8 under atmospheric O2. At the lowest Co concentrations investigated, Co2+ prevailed as surface complexes, incorporated into Fe3-δO4 nanoparticles, or as Co(OH)2-like surface precipitates. Increasing Co concentration lead to the formation of an additional Co3O4-like phase on the surface of Fe3-δO4 nanoparticles. Quick-XAS measurements at the Co K-edge allowed to follow the kinetics of Co sorption and oxidation on Fe3-δO4 nanoparticles, supporting the equilibrium observations. These results provide a more detailed understanding of Co sorption mechanisms onto Fe3-δO4 nanoparticles under oxic conditions, which offers an environmentally friendly route for the synthesis alternative of Co-doped Fe3-δO4 nanoparticles. In addition, this allows to understand the potential interaction between Co and Fe3-δO4 nanoparticles in environmental systems.

了解和预测Co与尖晶石氧化铁（Fe3-δO4，包括磁铁矿、磁铁矿及其固溶体）之间的相互作用机制在环境和工业背景下都具有重要意义。虽然Co2+的表面络合，其聚合和Fe3-δO4@CoO的表面沉淀已经得到了很好的记录，但在O2存在下Co2+氧化成Co3+以及Co3+与Fe3-δ o4纳米颗粒之间的相互作用机制却很少受到关注。在本研究中，结合实验和建模结果，结合L2、3边的XAS和XMCD分析，以及TEM和XRD分析，在大气O2下pH为8时，可以根据Co浓度区分几种Co-species。在最低Co浓度下，Co +以表面配合物的形式存在，结合到Fe3-δO4纳米颗粒中，或以Co(OH)2样表面沉淀的形式存在。Co浓度的增加导致Fe3-δO4纳米颗粒表面形成额外的co3o4样相。在Co - k边缘的快速xas测量允许跟踪Co在Fe3-δO4纳米颗粒上的吸附和氧化动力学，支持平衡观察。这些结果为在氧化条件下Co在Fe3-δO4纳米颗粒上的吸附机理提供了更详细的了解，为合成可替代的共掺杂Fe3-δO4纳米颗粒提供了一条环保途径。此外，这也有助于了解环境系统中Co和Fe3-δO4纳米颗粒之间的潜在相互作用。

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引用次数: 0