Synthetic strategies to incorporate Ru-terpyridyl water oxidation catalysts into MOFs: direct synthesis <i>vs.</i> post-synthetic approach

Liseev, Timofey; Howe, Andrew; Hoque, Asmaul; Gimbert‐Suriñach, Carolina; Llobet, Antoni; Ott, Sascha

doi:10.1039/d0dt01890b

Cited by 7 publications

(7 citation statements)

References 49 publications

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“…Liseev at al. 293 postsynthetically introduced a ditopic linker of this type (with 4-carboxylpyridine ligands) into a UiO-type MOF with ethynyldibenzoic acid linkers. The resulting mixed linker MOF was, however, a rather poor OER catalyst.…”

Section: Chemicalmentioning

confidence: 99%

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

et al. 2023

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The modularity and synthetic flexibility of metal–organic frameworks (MOFs) have provoked analogies with enzymes, and even the term MOFzymes has been coined. In this review, we focus on molecular catalysis of energy relevance in MOFs, more specifically water oxidation, oxygen and carbon dioxide reduction, as well as hydrogen evolution in context of the MOF–enzyme analogy. Similar to enzymes, catalyst encapsulation in MOFs leads to structural stabilization under turnover conditions, while catalyst motifs that are synthetically out of reach in a homogeneous solution phase may be attainable as secondary building units in MOFs. Exploring the unique synthetic possibilities in MOFs, specific groups in the second and third coordination sphere around the catalytic active site have been incorporated to facilitate catalysis. A key difference between enzymes and MOFs is the fact that active site concentrations in the latter are often considerably higher, leading to charge and mass transport limitations in MOFs that are more severe than those in enzymes. High catalyst concentrations also put a limit on the distance between catalysts, and thus the available space for higher coordination sphere engineering. As transport is important for MOF-borne catalysis, a system perspective is chosen to highlight concepts that address the issue. A detailed section on transport and light-driven reactivity sets the stage for a concise review of the currently available literature on utilizing principles from Nature and system design for the preparation of catalytic MOF-based materials.

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Section: Chemicalmentioning

confidence: 99%

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

et al. 2023

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“…[26][27][28]30,31 So far, various molecular photosensitizers and catalysts have been integrated into MOFs as functionalorganic linkers through the routine synthetic strategies of the mixed-ligand multivariate approach, post-synthetic exchange and sequent post-synthetic metalation (Fig. 2A), 5,29,[31][32][33][34] such as Ru and Ir-based molecular photosensitizers, 33,[35][36][37][38] Ru-based water oxidation catalysts, [39][40][41] Pt-based H 2 evolution catalysts, 33,42 and Mn, Re and Ir-based CO 2 reductive catalysts, 36,43 etc. In these cases, molecular catalysts are installed into Fig.…”

Section: The Design Classification and Synthesis Of The Heterogenous ...mentioning

confidence: 99%

Impacts of host–guest assembly on the photophysical and photocatalytic properties of heterogenized molecular photosensitizer and catalysts

Shi

et al. 2023

J. Mater. Chem. A

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“…Coordination polymers (CPs) are composed of transition-metal ions as connectors and multidentate ligands as linkers, which have attracted growing attention with respect to both academic research and many potential practical applications. These CP materials have not only the functions of metal complexes and organic linkers but also those determined by their well-defined one-, two-, and three-dimensional (3D) supramolecular, nanoscale, and porous structures. − The porous CPs are also called metal–organic frameworks (MOFs) that have been largely developed recently, which can be prepared by template and solvothermal synthesis. − The well-defined crystal structure of MOFs as produced provides a convenient route for the structural analysis as well as the investigation of their physicochemical properties and practical applications. In addition, a bottom-up interfacial molecular assembly technique can be used to design and construct the CPs and surface MOFs at the molecular level, especially at the air–liquid interfaces and on the solid surfaces and by the traditional Langmuir–Blodgett (LB) method and layer-by layer (LBL) assembly techniques. − …”

Section: Introductionmentioning

confidence: 99%

Interfacial Self-Assembly of Organized Ultrathin Films of Tripodal Metal-Terpyridyl Coordination Polymers as Luminophores and Heterogeneous Catalysts for Photocatalytic CO₂ Reduction

Liu

Shen

et al. 2023

Langmuir

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Metal-directed interfacial self-assembly of well-defined coordination polymer (CP) ultrathin films can control the metal complex arrangement and distribution at the molecular level, providing a convenient route for the design and fabrication of novel opto-electrical devices and heterogeneous catalysts. Here, we report the assembly of two series of CP multilayers with the transition-metal ions of Fe2+, Co2+, Zn2+ and Tb3+ as connectors and tripodal terpyridyl ligands of 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)tris(1-(4-([2,2′:6′,2″-terpyridin]-4′-yl)benzyl)pyridin-1-ium) (TerPyTa) and 4,4′,4″-(benzene-1,3,5-triyl)tris(1-(4-([2,2′:6′,2″-terpyridin]-4′-yl)benzyl)pyridin-1-ium) (TerPyBen) as linkers at the air–water interface. The as-prepared Langmuir–Blodgett (LB) films display strong luminescence, with the emission wavelength and relative intensity dependent on both the metal ions and linkers; among them, the Zn-TerPyTa and Zn-TerPyBen CPs give off the strongest luminescent emission centered at about 370 nm with an emission lifetime of approximately 0.2–0.3 ns. The Tb-TerPyTa CPs can give off emission at approximately 490, 546, 586, and 622 nm, attributed to the 5D4 to 7F3–6 electron transitions of typical Tb3+ ions. Finally, these CP LB films can act as efficient heterogeneous photocatalysts for the CO2 reduction to selectively produce CO. The catalytic efficiency can be optimized by adjusting the experimental conditions (light sensitizer, electron donor, and water content) and CP composition (metal ion and ligand) with an excellent yield of up to 248.1 mmol g–1. In particular, it is revealed that, under the same conditions, the catalytic efficiency of the Fe-TerPyTa CP LB film is nearly 2 to 3 orders of magnitude higher than that of the other metalated complexes investigated in the homogeneous system. UV–vis spectroscopy and cyclic voltammetry studies demonstrated that the dual active sites of Fe-terpyridine and TerPyTa units contribute to the enhanced catalytic activity. This work provides an effective method to introduce the earth-abundant metal complexes into CP films to construct efficient noble-metal-free photocatalysts for the CO2 reduction.

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Synthetic strategies to incorporate Ru-terpyridyl water oxidation catalysts into MOFs: direct synthesis vs. post-synthetic approach

Abstract: Incorporating molecular catalysts into metal-organic frameworks (MOFs) is a promising strategy for improving their catalytic longevity and recyclability. In this article, we investigate and compare synthetic routes for the incorporation...

Cited by 7 publications

References 49 publications

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

Impacts of host–guest assembly on the photophysical and photocatalytic properties of heterogenized molecular photosensitizer and catalysts

Interfacial Self-Assembly of Organized Ultrathin Films of Tripodal Metal-Terpyridyl Coordination Polymers as Luminophores and Heterogeneous Catalysts for Photocatalytic CO₂ Reduction

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Synthetic strategies to incorporate Ru-terpyridyl water oxidation catalysts into MOFs: direct synthesis vs. post-synthetic approach

Abstract: Incorporating molecular catalysts into metal-organic frameworks (MOFs) is a promising strategy for improving their catalytic longevity and recyclability. In this article, we investigate and compare synthetic routes for the incorporation...

Cited by 7 publications

References 49 publications

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

Impacts of host–guest assembly on the photophysical and photocatalytic properties of heterogenized molecular photosensitizer and catalysts

Interfacial Self-Assembly of Organized Ultrathin Films of Tripodal Metal-Terpyridyl Coordination Polymers as Luminophores and Heterogeneous Catalysts for Photocatalytic CO2 Reduction

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Product

Resources

About

Interfacial Self-Assembly of Organized Ultrathin Films of Tripodal Metal-Terpyridyl Coordination Polymers as Luminophores and Heterogeneous Catalysts for Photocatalytic CO₂ Reduction