Defined metal atom aggregates precisely incorporated into metal–organic frameworks

Kollmannsberger, Kathrin L.; Kronthaler, Laura; Jinschek, Joerg R.; Fischer, Roland A.

doi:10.1039/d1cs00992c

Cited by 37 publications

(33 citation statements)

References 230 publications

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“…Recently, with the prosperous and rapid development of singleatom catalysts (SACs), the exploration of heterogeneous catalysis has been gradually extended to the atomic level (6,(13)(14)(15)(16)(17)(18)(19)(20)(21). Introducing the cation promoters has proved as an effective strategy for activating the relatively inert atoms via effective electronic manipulation, thus realizing the great improvement of the intrinsic activity (22)(23)(24).…”

Section: Introductionmentioning

confidence: 99%

Atomically dispersed Ni activates adjacent Ce sites for enhanced electrocatalytic oxygen evolution activity

Pei

Zhang

et al. 2023

Sci. Adv.

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Manipulating the intrinsic activity of heterogeneous catalysts at the atomic level is an effective strategy to improve the electrocatalytic performances but remains challenging. Here, atomically dispersed Ni anchored on CeO 2 particles entrenched on peanut-shaped hollow nitrogen-doped carbon structures ( a -Ni/CeO 2 @NC) is rationally designed and synthesized. The as-prepared a -Ni/CeO 2 @NC catalyst exhibits substantially boosted intrinsic activity and greatly reduced overpotential for the electrocatalytic oxygen evolution reaction. Experimental and theoretical results demonstrate that the decoration of isolated Ni species over the CeO 2 induces electronic coupling and redistribution, thus resulting in the activation of the adjacent Ce sites around Ni atoms and greatly accelerated oxygen evolution kinetics. This work provides a promising strategy to explore the electronic regulation and intrinsic activity improvement at the atomic level, thereby improving the electrocatalytic activity.

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Section: Introductionmentioning

confidence: 99%

Atomically dispersed Ni activates adjacent Ce sites for enhanced electrocatalytic oxygen evolution activity

Pei

Zhang

et al. 2023

Sci. Adv.

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“…In the search for more efficient photocatalytic systems, doping with metal aggregates (MA, including isolated atoms, quantum dots and nanoparticles) has been proposed as a promising strategy, in particular when copper or iridium MAs were employed, , while platinum and gold MAs seem to be less efficient . However, if doping proves to be efficient, it is crucial to (i) elucidate the precise structure of the MA, (ii) to understand the MA/MOF interface in terms of charge transfer, and (iii) to determine the exact nature of the catalytically active site to expand the methodology . Thus, further research, more likely based on the reticular chemistry principle, is needed to develop novel and versatile MOFs that can overcome these limitations and explore the potential of doping strategies.…”

Section: Discussionmentioning

confidence: 99%

“…In particular, MOF syntheses that are compatible with the stability of preformed MA are still scarce, and thus, further development of soft MOF synthesis routes avoiding harsh conditions are required. Vice versa, if the MA is to be synthesized inside the pores of a MOF, reduction conditions of the MA’s metal precursor are required that do not alter the MOFs structure …”

Section: Discussionmentioning

confidence: 99%

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Metal–Organic Framework Catalysts for Solar Fuels: Light-Driven Conversion of Carbon Dioxide into Formic Acid

Canivet

Wisser

2023

ACS Appl. Energy Mater.

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The direct conversion of carbon dioxide into formic acid as renewable feedstock for chemicals or as fuel using sunlight as the sole energy source would provide a crucial step toward a more sustainable industrialized society. While crucial advances have been made using molecular catalyst, their heterogenization within porous framework can provide additional features, resulting in enhanced efficiency. Thanks to their high affinity toward carbon dioxide and high versatility in composition, Metal−Organic Frameworks (MOFs) already offered appealing opportunities for the design of photocatalysts active in the light-driven carbon dioxide reduction into formic acid. In this Spotlight, we look back on a decade of discovery and understanding in the light-driven MOF-catalyzed formic acid production form carbon dioxide leading to a 1000-fold enhancement in productivity and, moreover, open perspectives for the design of novel porous hybrid photoactive platforms.

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“…Yet, ligand removal often requires harsh conditions and may lead to uncontrolled agglomeration processes. 5,10 Metal−organic frameworks (MOFs) as 3D, crystalline, porous, and tailorable matrixes have proven their ability to scaffold various species ranging from dyes 11 to metal NPs 12,13 to tenth of nanometer-scale enzymes. 14 The embedment of reactive ligand-stabilized clusters into MOFs is known, albeit rarely reported.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into ZIF-8 Encapsulation of Atom-Precise Pt(M) Carbonyl Clusters

et al. 2023

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Precisely designing metal nanoparticles (NPs) is the cornerstone for maximizing their efficiency in applications like catalysis or sensor technology. Metal–organic frameworks (MOFs) with their defined and tunable pore systems provide a confined space to host and stabilize small metal NPs. In this work, the MOF encapsulation of various atom-precise clusters following the bottle-around-ship approach is investigated, providing general insights into the scaffolding mechanism. Eleven carbonyl-stabilized Pt(M) (M = Co, Ni, Fe, and Sn) clusters are employed for the encapsulation in the zeolitic imidazolate framework (ZIF)-8. Infrared and UV/Vis spectroscopy, density functional theory, and ab initio molecular dynamics revealed structure–encapsulation relationship guidelines. Thereby, cluster polarization, size, and composition were found to condition the scaffolding behavior. Encaging of [NBnMe3]2[Co8Pt4C2(CO)24] (Co8Pt4 ) is thus achieved as the first MOF-encapsulated bimetallic carbonyl cluster, Co8Pt4 @ZIF-8, and is fully characterized including X-ray absorption near edge and extended X-ray absorption spectroscopy. ZIF-8 confinement not only promotes property changes, like the T-dependent magnetism, but it also further allows heat-induced ligand-stripping without altering the cluster size, enabling the synthesis of naked, heterometallic, close to atom-precise clusters.

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Defined metal atom aggregates precisely incorporated into metal–organic frameworks

Abstract: Nanosized metal aggregates, including metal nanoparticles and nanoclusters, are often the active species in numerous applications. For maintaining the active form of MAs in use, they need to be anchored and stabilised, preventing agglomeration.

Cited by 37 publications

References 230 publications

Atomically dispersed Ni activates adjacent Ce sites for enhanced electrocatalytic oxygen evolution activity

Atomically dispersed Ni activates adjacent Ce sites for enhanced electrocatalytic oxygen evolution activity

Metal–Organic Framework Catalysts for Solar Fuels: Light-Driven Conversion of Carbon Dioxide into Formic Acid

Mechanistic Insights into ZIF-8 Encapsulation of Atom-Precise Pt(M) Carbonyl Clusters

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