Metal–Organic Framework Nodes Support Single-Site Nickel(II) Hydride Catalysts for the Hydrogenolysis of Aryl Ethers

Song, Yang; Li, Zhe; Ji, Pengfei; Kaufmann, Michael; Feng, Xuanyu; Chen, Justin S.; Wang, Cheng; Lin, Wenbin

doi:10.1021/acscatal.8b04611

Cited by 72 publications

(59 citation statements)

References 50 publications

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“… 27 − 29 Metal–organic frameworks (MOFs), as emerging coordination polymers with well-defined structure, uniform channel structures, and high surface area, are promising supports to fabricate single-site catalysts. 30 − 33 The single-metal sites can be deliberately anchored on well-defined positions of MOFs by postsynthetic modification, making them have uniform distribution throughout the MOFs’ support. Also, the high density of single-metal sites can be obtained through choosing suitable ligands for active metal anchoring, which is hard to achieve on traditional supports.…”

Section: Resultsmentioning

confidence: 99%

Constructing Well-Defined and Robust Th-MOF-Supported Single-Site Copper for Production and Storage of Ammonia from Electroreduction of Nitrate

et al. 2021

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A combined technique of production and storage of ammonia (NH 3 ) from electroreduction of nitrate (NO 3 – ) through one material is highly desirable but remains a huge challenge. Herein, we proposed a proof-of-concept strategy for combined NH 3 production and storage from electroreduction of NO 3 – through elaborately designing a single-site Cu II -bipyridine-based thorium metal–organic framework (Cu@Th-BPYDC). Noticeably, the single Cu II site, anchored by a solid–liquid postsynthetic metalation within Th-BPYDC, shows a novel square coordination structure, as determined by the single-crystal X-ray diffraction. This strongly implies its enormous potential as an open metal site and consequently enables excellent performance in electroreduction of NO 3 – for NH 3 production, giving 92.5% Faradaic efficiency and 225.3 μmol h –1 cm –2 yield. Impressively, we can further use Cu@Th-BPYDC material to effectively capture the previously produced NH 3 from electroreduction of NO 3 – , affording an uptake up to 20.55 mmol g –1 at 298 K at 1 bar. The results in this work will outline a new direction toward the combined technique for advanced electrocatalysis such as gas production plus storage/or separation.

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Section: Resultsmentioning

confidence: 99%

Constructing Well-Defined and Robust Th-MOF-Supported Single-Site Copper for Production and Storage of Ammonia from Electroreduction of Nitrate

et al. 2021

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“…When a hydrogenation reaction comprises several elementary steps to various products, the control of the hydrogenation to the desired product will be a challenge. Single-site Ni(II) hydride species confined in a Ti-MOF have been reported for the hydrogenolysis of model lignocellulose compounds 158 . In the case of benzyl phenyl ether, only toluene and cyclohexanol can be obtained under mild conditions (140 o C, 1 bar of H2).…”

Section: Hydrogenation Reactionsmentioning

confidence: 99%

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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“…Lin et al further used XAS to systematically investigate the structure of Co SACs supported by various MOF supports. [54,[86][87][88][89] One example is the Co single atoms introduced into UiO-MOFs. [89] The coordination environments of Co were analyzed using Co K-edge XAS ( Figure 10D,E); the major peaks observed in the region between 1 and 2 Å provided evidence for the existence of single-atom sites.…”

Section: Structural Characterizationmentioning

confidence: 99%

“…Figure 5D shows another example where metal nodes in the MOFs are used to stabilize SACs. [ 54 ] In this case, single nickel sites coordinated by Ti 8 clusters are formed in MOFs and used as catalysts in the aryl ethers hydrogenolysis reaction.…”

Section: Introductionmentioning

confidence: 99%

Single‐Atom Catalysts Supported by Crystalline Porous Materials: Views from the Inside

et al. 2020

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Reducing the size of nanoparticle catalysts is one desirable method that can improve their catalytic activity. Single-atom catalysts (SACs) represent the smallest possible size a catalyst can achieve with maximum atomic efficiency. [6] Moreover, recent studies have shown that the use of single-atom catalytic sites, rather than ensembles of atoms, is crucial in many catalytic reactions. [7] Without proper protection, however, single-atom sites in these catalysts are not stable since they tend to aggregate and form larger particles. [8-10] To solve this problem, many different protecting supports have been developed such as polymers and porous organic cages. [11,12] Crystalline porous materials, such as zeolites and metal-organic frameworks (MOFs), have been widely used to stabilize small metal species in catalytic reactions due to the controllable size, shape, and dimensions of their pores and channels. [13-15] Therefore, they are highly desirable in supporting SACs. [13] Despite the promising aspects of zeolite and MOF-supported SACs, their characterization remains challenging due to the single-atomic nature of their bonding environments; atomic-level resolution is needed for the structural characterization of these catalysts. X-ray absorption spectroscopy (XAS) is a powerful tool in studying the structure and properties of atoms in their coordination environments with subatomic resolution, [16,17] and thus is considered particularly suitable for the study of SACs. [16,17] In this contribution, a comprehensive review of representative works on zeolite-and MOF-protected SACs will be presented from the XAS perspective. The subatomic resolution (0.01 Å level) of synchrotron-based XAS technique allows for views from "inside" the SACs regarding their structure, electronic properties, and catalytic activities. The processed data from extended X-ray absorption fine structure (EXAFS) will be shown as a powerful tool to probe the atomic structure of SACs in zeolites and MOFs. Through the standard fitting analysis of EXAFS, together with the assistance of advanced analysis tools, detailed information concerning the local structure of SACs can be obtained. Additionally, it will be demonstrated that the X-ray absorption near-edge structure (XANES) can provide insight into the unique electronic properties of SACs. Furthermore, in situ/operando XAS techniques, coupled with state-of-the-art Single-atom catalysts (SACs) have recently emerged as an exciting system in heterogeneous catalysis showing outstanding performance in many catalytic reactions. Single-atom catalytic sites alone are not stable and thus require stabilization from substrates. Crystalline porous materials such as zeolites and metal-organic frameworks (MOFs) are excellent substrates for SACs, offering high stability with the potential to further enhance their performance due to synergistic effects. This review features recent work on the structure, electronic, and catalytic properties of zeolite and MOF-protected SACs, offering atomic-scale views from the "insid...

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Metal–Organic Framework Nodes Support Single-Site Nickel(II) Hydride Catalysts for the Hydrogenolysis of Aryl Ethers

Cited by 72 publications

References 50 publications

Constructing Well-Defined and Robust Th-MOF-Supported Single-Site Copper for Production and Storage of Ammonia from Electroreduction of Nitrate

Constructing Well-Defined and Robust Th-MOF-Supported Single-Site Copper for Production and Storage of Ammonia from Electroreduction of Nitrate

Confining isolated atoms and clusters in crystalline porous materials for catalysis

Single‐Atom Catalysts Supported by Crystalline Porous Materials: Views from the Inside

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