Synthetic Access to Atomically Dispersed Metals in Metal–Organic Frameworks via a Combined Atomic-Layer-Deposition-in-MOF and Metal-Exchange Approach

Klet, Rachel C.; Wang, Yichen; Fernandez, Laura E.; Truhlar, Donald G.; Hupp, Joseph T.; Farha, Omar K.

doi:10.1021/acs.chemmater.5b04887

Cited by 90 publications

(96 citation statements)

References 16 publications

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“…The interaction between Ni sub and the surrounding C atoms resulted in the excellent HER activity (η onset = 50 mV) and stability (loss of 10% activity after 120 h at 150 mV). Klet et al presented a combined atomic layer deposition in metal–organic frameworks and metal exchange (AIM‐ME) method to prepare dispersed metal atoms into the mesoporous MOF, NU‐1000 . After a metal‐exchange procedure of Zn‐AIM intermediates prepared by AIM method, single atoms Cu, Co, or Ni presented porous materials were finally obtained.…”

Section: Functionalization Strategies For Synthesis and Catalysis Ofmentioning

confidence: 99%

Functionalization of Hollow Nanomaterials for Catalytic Applications: Nanoreactor Construction

et al. 2018

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Hollow nanomaterials have attracted a broad interest in multidisciplinary research due to their unique structure and preeminent properties. Owing to the high specific surface area, well-defined active site, delimited void space, and tunable mass transfer rate, hollow nanostructures can serve as excellent catalysts, supports, and reactors for a variety of catalytic applications, including photocatalysis, electrocatalysis, heterogeneous catalysis, homogeneous catalysis, etc. Based on state-of-the-art synthetic methods and characterization techniques, researchers focus on the purposeful functionalization of hollow nanomaterials for catalytic mechanism studies and intricate catalytic reactions. Herein, an overview of current reports with respect to the catalysis of functionalized hollow nanomaterials is given, and they are classified into five types of versatile strategies with a top-down perspective, including textual and composition modification, encapsulation, multishelled construction, anchored single atomic site, and surface molecular engineering. In the detailed case studies, the design and construction of hierarchical hollow catalysts are discussed. Moreover, since hollow structure offers more than two types of spatial-delimited sites, complicated catalytic reactions are elaborated. In summary, functionalized hollow nanomaterials provide an ideal model for the rational design and development of efficient catalysts.

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Section: Functionalization Strategies For Synthesis and Catalysis Ofmentioning

confidence: 99%

Functionalization of Hollow Nanomaterials for Catalytic Applications: Nanoreactor Construction

et al. 2018

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“…NU‐1000‐Zn, formed by AIM of NU‐1000, was later synthesised and found to contain 4 Zn atoms per Zr 6 node, whilst DFT (density functional theory) calculations were used to precisely predict the location of the Zn atoms at the Zr 6 cluster. NU‐1000‐Zn was then transmetalated, allowing the Zn atoms to be postsynthetically exchanged (with varying successes observed) for Cu, Co and Ni which were unable to be prepared directly from solution phase reactions …”

Section: Postsynthetic Cluster Modificationmentioning

confidence: 99%

Postsynthetic Modification of Zirconium Metal‐Organic Frameworks

2016

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Metal-organic frameworks (MOFs) have been in the spotlight for a number of years due to their chemical and topological versatility. As MOF research has progressed, highly functionalised materials have become desirable for specific applications, and in many cases the limitations of direct synthesis have been realised. This has resulted in the search for alternative synthetic routes, with postsynthetic modification (PSM), a term used to collectively describe the functionalisation of pre-synthesised MOFs whilst maintaining their desired characteristics, becoming a topic of interest. Advances in the scope of reactions performed are reported regularly; however reactions requiring

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“…In our current work, we targeted cobalt as the deposited metal ions on NU-1000 since nanosized spinel Co 3 O 4 have been shown to catalyze the propane ODH process under gentle reaction conditions. 30 Two deposition techniques were used to anchor Co(II) ions to NU-1000: solvothermal deposition in a MOF (SIM), 31 , 32 and atomic layer deposition in a MOF (AIM). 33 , 34 We demonstrate that both materials, namely, Co-SIM+NU-1000 and Co-AIM+NU-1000, are active for propane ODH catalysis at temperatures as low as 200 °C, in contrast to the commonly used 300–500 °C required for supported VO x catalysts.…”

Section: Introductionmentioning

confidence: 99%

Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature

et al. 2016

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Zr-based metal–organic frameworks (MOFs) have been shown to be excellent catalyst supports in heterogeneous catalysis due to their exceptional stability. Additionally, their crystalline nature affords the opportunity for molecular level characterization of both the support and the catalytically active site, facilitating mechanistic investigations of the catalytic process. We describe herein the installation of Co(II) ions to the Zr6 nodes of the mesoporous MOF, NU-1000, via two distinct routes, namely, solvothermal deposition in a MOF (SIM) and atomic layer deposition in a MOF (AIM), denoted as Co-SIM+NU-1000 and Co-AIM+NU-1000, respectively. The location of the deposited Co species in the two materials is determined via difference envelope density (DED) analysis. Upon activation in a flow of O2 at 230 °C, both materials catalyze the oxidative dehydrogenation (ODH) of propane to propene under mild conditions. Catalytic activity as well as propene selectivity of these two catalysts, however, is different under the same experimental conditions due to differences in the Co species generated in these two materials upon activation as observed by in situ X-ray absorption spectroscopy. A potential reaction mechanism for the propane ODH process catalyzed by Co-SIM+NU-1000 is proposed, yielding a low activation energy barrier which is in accord with the observed catalytic activity at low temperature.

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Synthetic Access to Atomically Dispersed Metals in Metal–Organic Frameworks via a Combined Atomic-Layer-Deposition-in-MOF and Metal-Exchange Approach

Cited by 90 publications

References 16 publications

Functionalization of Hollow Nanomaterials for Catalytic Applications: Nanoreactor Construction

Functionalization of Hollow Nanomaterials for Catalytic Applications: Nanoreactor Construction

Postsynthetic Modification of Zirconium Metal‐Organic Frameworks

Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature

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