Highly Stereoselective Heterogeneous Diene Polymerization by Co-MFU-4<i>l</i>: A Single-Site Catalyst Prepared by Cation Exchange

Dubey, Romain; Comito, Robert J.; Wu, Zhenwei; Zhang, Guanghui; Rieth, Adam J.; Hendon, Christopher H.; Miller, Jeffrey T.; Dincă, Mircea

doi:10.1021/jacs.7b06841

Cited by 66 publications

(70 citation statements)

References 52 publications

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“…83 In other examples, Co II and V IV analogues of MFU-4l have been reported. 84,85 With a similar ion metathesis approach, Powers has recently shown that a MOF can be used to guide the formation of metastable Pd 2 tetracarboxylate entities. 86 Pd(II) acetate self assembles as a trimer (i.e.…”

Section: General Approaches To Matrix Isolation In Mofsmentioning

confidence: 99%

Isolating reactive metal-based species in Metal–Organic Frameworks – viable strategies and opportunities

et al. 2020

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Section: General Approaches To Matrix Isolation In Mofsmentioning

confidence: 99%

Isolating reactive metal-based species in Metal–Organic Frameworks – viable strategies and opportunities

et al. 2020

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“…Another system of Co‐based SACs within MOFs were studied by Dubey et al [ 85 ] who identified Co SACs supported by MFU‐4 l MOFs (Co‐MFU‐4 l , Figure A) as a catalyst for the highly selective polymerization of 1,3‐butadiene. The Co K‐edge EXAFS fitting for the catalyst contained both Co–N coordination (CN = 3, bond length = 2.02 Å) and Co–Cl coordination (CN = 1, bond length = 2.15 Å).…”

Section: Xas Analysis Of Sacs Supported By Crystalline Porous Materialsmentioning

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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“…Recently, Dincă et al . reported the synthesis of polybutadiene with an extremely high cis selectivity (99.3 %) . However, this result was mainly attributed to the metal centers that acted as a coordination polymerization catalyst with very high performance, and not to an effect of confinement.…”

Section: Polymer Chains At the Single‐nanochannel Scalementioning

confidence: 99%

Polymer in MOF Nanospace: from Controlled Chain Assembly to New Functional Materials

Ouay

Uemura

2018

Israel Journal of Chemistry

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Preparation of composites by inclusion of polymers inside metal-organic frameworks (MOFs) is a very powerful strategy to prepare innovative functional materials. MOF's nanosized pores disrupt polymer chains natural coiling and constrain them in an extended conformation, bringing new properties. At the single nanochannel scale, polymerization reactions are significantly modified due to confinement, and control over the primary structure (sequence, tacticity or branching) can be achieved. Because of confinement and chain extension, physical and chemical properties can also be significantly improved compared to the bulk state. Inclusion is also useful to control organization at a higher scale, for instance for precise polymer positioning or by acting as scaffold for an accessible microporous polymer network. Furthermore, the MOF ordering can be maintained in pure polymer systems even after removal of the host.

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Highly Stereoselective Heterogeneous Diene Polymerization by Co-MFU-4l: A Single-Site Catalyst Prepared by Cation Exchange

Cited by 66 publications

References 52 publications

Isolating reactive metal-based species in Metal–Organic Frameworks – viable strategies and opportunities

Isolating reactive metal-based species in Metal–Organic Frameworks – viable strategies and opportunities

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

Polymer in MOF Nanospace: from Controlled Chain Assembly to New Functional Materials

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