Confined Pt11+ Water Clusters in a MOF Catalyze the Low‐Temperature Water–Gas Shift Reaction with both CO2 Oxygen Atoms Coming from Water

Rivero‐Crespo, Miguel Ángel; Mon, Marta; Ferrando‐Soria, Jesús; Lopes, Christian Wittee; Boronat, Mercedes; Leyva‐Pérez, Antonio; Corma, Avelino; Hernández‐Garrido, Juan C.; López‐Haro, Miguel; Calvino, José J.; Ramos‐Fernández, Enrique V.; Armentano, Donatella; Pardo, Emilio

doi:10.1002/ange.201810251

Cited by 9 publications

(6 citation statements)

References 32 publications

(50 reference statements)

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“…In a recent work, isolated Pt atoms in aluminum-based porphyrinic MOF can be observed by highresolution STEM, though the structure of the Al-MOF is damaged 89,90 . To reduce the damaging effect from the beam, the measurement can be performed with a cryo-EM sample holder, which has been demonstrated to be effective for high-resolution imaging of MOF structures with atomic resolution 91 .…”

Section: Structural Characterizationsmentioning

confidence: 99%

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Confining isolated atoms and clusters in crystalline porous materials for catalysis

2020

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The recent works on supported isolated metal atoms and metal clusters with a few atoms have reformed our understanding on the structure-reactivity relationship established on conventional nanoparticulate catalysts. One critical issue related to supported subnanometric metal catalysts (including both isolated atoms and clusters) on conventional open-structure carriers is the stability of the metal entities, since they may sinter into large nanoparticles under harsh reaction conditions. By confining the isolated metal atoms or subnanometric metal clusters in crystalline porous materials (such as zeolites and metal-organic frameworks) can improve the stability of these tiny species against sintering into nanoparticles. More importantly, the interaction between the metal species and the porous framework may modulate the geometric and electronic structures of the subnanometric metal species, especially in the cases of metal clusters. Such confinement effect can induce shape-selective catalysis or unique chemoselectivity compared to the counterpart metal entities supported on conventional open-structure solid carriers. In this review, we will discuss the structural features, synthesis methodologies, characterization techniques and catalytic applications of subnanometric species confined in zeolites and metal-organic frameworks, aiming to make critical comparison between confined and un-confined isolated atoms and metal clusters and to give perspectives on the future developments.

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Section: Structural Characterizationsmentioning

confidence: 99%

“…Positively charged Pt 1+ atoms have been introduced and stabilized in the channels of a MOF by a postsynthesis approach 90 . Single-crystal X-ray diffraction reveals that, each Pt 1+ atoms are coordinated with four water molecules, with charge balance from the MOF framework.…”

Section: Water-gas Shift Reactionmentioning

confidence: 99%

Confining isolated atoms and clusters in crystalline porous materials for catalysis

2020

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“…They retain the Pd 2+ cations in specific positions after the insertion process, which allows their homogeneous distribution along the channels, and prevent their agglomeration forming NCs or NPs during the reduction process. Besides, the crystal structure of each phase could be unveiled by SC-XRD given the high crystallinity and robustness [58][59][60][61][62][63][64] of the pristine MOF (Figure 3 and Table S4).…”

Section: D) A) B)mentioning

confidence: 99%

Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids

et al. 2021

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Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use under industrially viable conditions. Here, we show that palladium single atoms are spontaneously formed after dissolving tiny amounts of palladium salts in neat benzyl alcohols, to catalyze their direct aerobic oxidation to benzoic acids without ligands, additives, or solvents. With this result in hand, the gram-scale preparation and stabilization of Pd SACs within the functional channels of a novel methyl-cysteine-based metal−organic framework (MOF) was accomplished, to give a robust and crystalline solid catalyst fully characterized with the help of single-crystal X-ray diffraction (SCXRD). These results illustrate the advantages of metal speciation in ligand-free homogeneous organic reactions and the translation into solid catalysts for potential industrial implementation.Article pubs.acs.org/JACS

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“…The same strategy was used to stabilise Pt1 1+ SACs, 52 within the same anionic MOF used for the growth of Pd4 NCs. In this case, following a two-step PS process -consisting first on the insertion of Pt 2+ cations within MOF channels and second, their in-situ reduction with NaBH4-the gram-scale synthesis of structurally and electronically well-defined Pt1 1+ SACs was achieved (Figure 7a).…”

Section: Atoms Within Mofsmentioning

confidence: 99%

Metal–Organic Frameworks as Chemical Nanoreactors: Synthesis and Stabilization of Catalytically Active Metal Species in Confined Spaces

et al. 2020

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The strategy outlined here has led to unique rewards such as the highly challenging gram-scale preparation of stable and well-defined ligand-free SNMCs, exhibiting outstanding catalytic activities and the preparation of unique SCCs -different to those assembled in solution-with enhanced stabilities, catalytic activities, recyclabilities and selectivities. The results presented in this Accounts are just few recent exponents, but highly encouraging, of the large potential way of MOFs as chemical nano-reactors. More work is needed to found the boundaries and fully understand the chemistry in the confined space. In this sense, mastering the synthetic chemistry of discrete organic molecules and inorganic complexes have basically changed our way of live. Thus, achieving the same degree of control on extended hybrid networks will open new frontiers of knowledge with unforeseen possibilities. We aim to stimulate the interest of researchers working abroad differents fields to fully unleash the host-guest chemistry in MOFs as chemical nanoreactors with exclusive functional species.

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Confined Pt₁¹⁺ Water Clusters in a MOF Catalyze the Low‐Temperature Water–Gas Shift Reaction with both CO₂ Oxygen Atoms Coming from Water

Cited by 9 publications

References 32 publications

Confining isolated atoms and clusters in crystalline porous materials for catalysis

Confining isolated atoms and clusters in crystalline porous materials for catalysis

Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids

Metal–Organic Frameworks as Chemical Nanoreactors: Synthesis and Stabilization of Catalytically Active Metal Species in Confined Spaces

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