Metal–Organic Cages as Porous Photosensitizers for Polyoxometalate Catalysts

IF 7.1 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2026-10-07 DOI:10.1021/acs.chemmater.6c00734

Yuta Sueda,Masaya Yara,Kiyoshi Miyata,Ken Onda,Ryo Ohtani,Benjamin Le Ouay,Masaaki Ohba

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引用次数: 0

Abstract

Abstract Ionic metal–organic cages (MOCs) offer a unique platform to promote the reactivity of their functional counterions by forming “porous functional salts” (PFSs), but the role of MOCs has so far been limited to structuring and porogenic agent without strong coupling of properties. Herein, we report a new PFS, built from the assembly of the stable and noble-metal-free Keggin-type polyoxometalate (POM) SiW12O404– (SiW12) with a cationic Zr-based metal–organic cage (ZrT-NH2). While pristine SiW12 did not present any porosity or light absorption in the visible light region (above 400 nm), the PFS ZrT-NH2/SiW12 presented an appreciable surface area for a POM-based material (SBET(CO2) = 143 m2/g) as well as a photoinduced electron transfer from ZrT-NH2 to SiW12, which then enabled the formation of reactive species from dissolved dioxygen molecules. This combination made the PFS ZrT-NH2/SiW12 highly potent as a photocatalyst for environmental remediation (evaluated with the model pollutant rhodamine B), as porosity led to a pollutant preconcentration and improved accessibility to the SiW12 catalytic centers, while the photosensitizing effect enabled visible light photodegradation without the need for sacrificial reagents. This method of integrating POMs and functional MOCs offers a promising strategy for the development of functional materials with enhanced porosity and activity.

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金属-有机笼作为多金属氧酸盐催化剂的多孔光敏剂

离子金属有机笼（moc）通过形成“多孔功能盐”（pfs）来促进其功能反离子的反应性，为其提供了一个独特的平台，但moc的作用迄今为止仅限于结构和致孔剂，没有很强的性能耦合。在此，我们报道了一种新的PFS，由稳定的无贵金属keggin型多金属氧酸盐（POM） SiW12O404 - (SiW12)与阳离子zr基金属有机笼（ZrT-NH2）组装而成。虽然原始的SiW12在可见光区（400 nm以上）没有任何孔隙或光吸收，但PFS ZrT-NH2/SiW12对于pom基材料来说具有可观的表面积（SBET(CO2) = 143 m2/g），并且从ZrT-NH2到SiW12的光诱导电子转移，从而使溶解的双氧分子能够形成反应物质。这种组合使得PFS ZrT-NH2/SiW12作为一种非常有效的光催化剂用于环境修复（用模型污染物罗丹明B进行评估），因为孔隙导致污染物预浓缩并改善了SiW12催化中心的可及性，而光敏效应使可见光光降解无需牺牲试剂。这种将pom和功能性MOCs相结合的方法为开发具有增强孔隙度和活性的功能材料提供了一种很有前途的策略。

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

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.