A Novel Banana-Shaped Mixed-Metal Co/Fe Polyoxometalate Cluster.

IF 3 4区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

ChemPlusChem Pub Date : 2024-09-24 DOI:10.1002/cplu.202400473

Javier Quirós-Huerta, José Troya, Miguel Clemente-León, Juan Modesto Clemente-Juan, Eugenio Coronado, Joaquín Soriano-López

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Abstract

The synthesis and characterization of a Co/Fe mixed-metal banana-shaped polyoxometalate with the formula [(Co_2.5Fe_0.5(H₂O)PW₉O₃₄)₂(PW₆O₂₆)]^16- (Co₅Fe) is reported. This transition-metal-substituted polyoxometalate readily assembles from its components in a one-pot reaction and crystallizes in the monoclinic space group P2₁/c. The structure of Co₅Fe can be considered a double sandwich composed by two B-α-{Co_2.5Fe_0.5PW₉O₄₀} Keggin units, in which one coordinatively saturated octahedral metal position is equally occupied by Co(II) and Fe(III) ions with a 50 % of site occupancy. These Keggin units are linked via a hexalacunary Keggin unit {PW₆O₂₆}. Single crystal X-ray diffraction and magnetic measurements support the proposed atom arrangement within the crystal structure. Magnetic measurements of these double trimeric unit {Co_2.5Fe_0.5O₁₃}₂ show a combination of antiferromagnetic interactions, the presence of spin frustration, and the first-order spin-orbit coupling of Co(II) ions. Electrocatalytic water oxidation measurements show that Co₅Fe displays low stability in both homogeneous and heterogeneous conditions. This is evidenced by the constant increase on the catalytic currents over time together with the appearance of polyoxometalate-derived electrode-bound species that can be responsible for the observed catalytic activity.

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一种新颖的香蕉形 Co/Fe 多氧化金属混合簇。

报告了一种 Co/Fe 混合金属香蕉形多氧金属铝酸盐的合成和特性，其化学式为[(Co2.5Fe0.5(H2O)PW9O34)2(PW6O26)]16- (Co5Fe)。这种过渡金属取代的多氧金属铝酸盐很容易在一锅反应中由其组分组装而成，并在单斜空间群 P21/c 中结晶。Co5Fe 的结构可视为由两个 B-α-{Co2.5Fe0.5PW9O40}凯金单元组成的双夹层结构。Keggin单元组成，其中一个配位饱和的八面体金属位置被Co(II)和Fe(III)离子平均占据，占位率为50%。这些 Keggin 单元通过一个六阳离子 Keggin 单元 {PW6O26} 连接在一起。单晶 X 射线衍射和磁性测量结果支持晶体结构中的原子排列。对这些双三聚单元{Co2.5Fe0.5O13}2的磁性测量结果表明，它们结合了反铁磁相互作用、自旋挫折的存在以及 Co（II）离子的一阶自旋轨道耦合。电催化水氧化测量结果表明，Co5Fe 在均相和异相条件下都表现出较低的稳定性。随着时间的推移，催化电流不断增加，同时还出现了多氧金属酸盐衍生的电极结合物种，这些都证明了所观察到的催化活性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ChemPlusChem CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

5.90

自引率

0.00%

发文量

200

审稿时长

1 months

期刊介绍： ChemPlusChem is a peer-reviewed, general chemistry journal that brings readers the very best in multidisciplinary research centering on chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. Fully comprehensive in its scope, ChemPlusChem publishes articles covering new results from at least two different aspects (subfields) of chemistry or one of chemistry and one of another scientific discipline (one chemistry topic plus another one, hence the title ChemPlusChem). All suitable submissions undergo balanced peer review by experts in the field to ensure the highest quality, originality, relevance, significance, and validity.