Effective and Selective Catalysts for Cinnamaldehyde Hydrogenation: Hydrophobic Hybrids of Metal–Organic Frameworks, Metal Nanoparticles, and Micro‐ and Mesoporous Polymers

Kuo, Yu‐An; Song, Tianqun; Wang, Dawei; Zhang, Xiaotao; Gao, Xiang; Zou, Ye; Dong, Huanli; Tang, Zhiyong; Hu, Wenping

doi:10.1002/anie.201801289

Cited by 140 publications

(87 citation statements)

References 33 publications

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“…Furthermore, the energy‐dispersive X‐ray spectroscopy (EDS) mapping analysis of Pt void @MOF(Y) showed that the Zn, Ni, and Pt elements in Pt void @MOF(Y) are homogeneously distributed on the Echinoidea‐like structure (Figure E). Thus, the spatial distribution of incorporated Pt NPs in/on the MOF can be controlled by their addition sequence …”

Section: Methodsmentioning

confidence: 99%

Rational Localization of Metal Nanoparticles in Yolk–Shell MOFs for Enhancing Catalytic Performance in Selective Hydrogenation of Cinnamaldehyde

et al. 2019

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Supported metal nanoparticle (MNP) catalysts are of interest in heterogeneous catalysis because of their fascinating catalytic behavior,inresponse to challenges in the fine-chemicals industry. [1] However, the leaching/agglomeration of MNPs that usually occurs resultsi nadiminishment of their catalytic activity over time owing to the weak anchorage on supports. On the other hand, strong immobilization of supported stabilizers aroundM NPs could prohibit the catalytic activity of surface metal atoms. [2] Recently,e ncapsulating MNPs in porous materials such as zeolites, activated carbon,a nd metal-organic frameworks (MOFs) by means of appropriate anchorage has been regarded as as ustainable strategy to improve catalytic activity and facilitate catalyst recovery. [3] Moreover,t he porous structures can not only serve as templates for synthesizing monodisperse MNPs, but also provideawell-definedm icroenvironmentt hat can controlt he selectivity of catalytic reactions on the encapsulated MNPs and avoid the leaching of MNPs. [4] For example, Jiang and co-workersr eported Pt@MIL-125/Au as ah igh-performance photocatalystf or water splitting. [4h] Tang and co-workers synthesized sandwich MIL-101@Pt@MIL-101 for hydrogenation of a,b-unsaturated aldehydest ou nsaturated alcohols. [4i] Astruca nd co-workers preparedt ransition metal NPs/ ZIF-8 composites for H 2 generation on hydrolysis of ammoniaborane. [4j] To date, in porous-material-supported MNPs for heterogeneous catalysis, the MNPs either decorate the outer surfaceo r are completely incorporated within the porous materials. [5] In the former case, the MNPs immobilized on the outer surface have high surface energya nd tend to migrate and aggregate into larger particles;t his leads to loss of catalytic activity during continuous reactions. In addition, the weak metal-support interaction is also unfavorable for stability and selectivity. [6] In the latter case, the inner porouss pace can ensure uniform dispersion of incorporated MNPs with high stability and catalytic selectivity. [7] However, the criticalb ottleneck is the slow diffusion rate when the reactants pass through the long path in the support to access active sites of MNPs.T he slow diffusion would result in poor reactionefficiencyifthe rate-limiting step is diffusion of the reactant to the active sites or diffusion of product out of the catalyst. Clearly,t he spatial distribution of MNPs in the porousm aterials brings about at rade-off between the reaction efficiency and selectivity. [8] The selectiveh ydrogenationo fa,b-unsaturated aldehydes (C=Ov ersus C=C) to produce unsaturated alcohols is an essential step in the preparation of various fine chemicals, but achieving high selectivity to the unsaturated alcohols at high conversion is challenging. [9] The use of heterogeneousc atalysts is ap otential way to achieve both atom-efficient and environmentally friendly chemical procedures.I nt his work, cinnamaldehyde( CAL), as ar epresentative a,b-unsaturateda ldehyde, was chosen as am odel substrate...

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Section: Methodsmentioning

confidence: 99%

Rational Localization of Metal Nanoparticles in Yolk–Shell MOFs for Enhancing Catalytic Performance in Selective Hydrogenation of Cinnamaldehyde

et al. 2019

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“…Among numerous reported studies on MOFs as catalysts, some works have demonstrated the high catalytic performance of hydrophobic MOFs . In particular, due to their hydrophobic nature, some hydrophobic MOFs showed a selective catalytic activity for certain specific substrates.…”

Section: Potential Applicationsmentioning

confidence: 99%

Hydrophobic Metal–Organic Frameworks: Assessment, Construction, and Diverse Applications

et al. 2020

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Tens of thousands of metal–organic frameworks (MOFs) have been developed in the past two decades, and only ≈100 of them have been demonstrated as porous and hydrophobic. These hydrophobic MOFs feature not only a rich structural variety, highly crystalline frameworks, and uniform micropores, but also a low affinity toward water and superior hydrolytic stability, which make them promising adsorbents for diverse applications, including humid CO2 capture, alcohol/water separation, pollutant removal from air or water, substrate‐selective catalysis, energy storage, anticorrosion, and self‐cleaning. Herein, the recent research advancements in hydrophobic MOFs are presented. The existing techniques for qualitatively or quantitatively assessing the hydrophobicity of MOFs are first introduced. The reported experimental methods for the preparation of hydrophobic MOFs are then categorized. The concept that hydrophobic MOFs normally synthesized from predesigned organic ligands can also be prepared by the postsynthetic modification of the internal pore surface and/or external crystal surface of hydrophilic or less hydrophobic MOFs is highlighted. Finally, an overview of the recent studies on hydrophobic MOFs for various applications is provided and suggests the high versatility of this unique class of materials for practical use as either adsorbents or nanomaterials.

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“…Then, in 2018, Hu et al. cleverly constructed a new FeP‐CMP@Pt@MIL‐101 (Cr) composite (FeP=iron(III) porphyrin and CMP=conjugated micro‐ and mesoporous polymer) (Figure ) . After, the synthesis of the NP@MOF core–shell structure, the composite was capped with the hydrophobic porous polymer that contained iron porphyrins.…”

Section: Metal Nanoparticle@mof Compositesmentioning

confidence: 99%

“… (A) Synthetic route of FeP‐CMP@Pt@ MIL‐101 and the water contact angle measurements of MIL‐101 (A‐a), FeP‐CMP@Pt@ MIL‐101 (A‐b). (B) Selective hydrogenation of cinnamaldehyde (cinnamyl alcohol inside the red rectangle is the desired product; molecules inside the blue rectangles are other possible byproducts) …”

Section: Metal Nanoparticle@mof Compositesmentioning

confidence: 99%

Recent Advances of MOFs and MOF‐Derived Materials in Thermally Driven Organic Transformations

Yang

Bulut

et al. 2018

Chemistry A European J

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Owing to the almost boundless structural tunability, MOF and MOF-derived catalysts have recently exhibited structures of higher complexity, and hence, have demonstrated activity in a wide array of organic transformations. These reactions have a broad range of important applications ranging from pharmaceuticals to agriculture. Given the increasing number of publications in the area, this Minireview is focused on the most recent advancements in thermally driven organic transformations using both MOFs, nanoparticle@MOF (NP@MOF) composites, and several classes of MOF-derived materials. The most recent advancements made in materials design and the utility of these materials in a broad range of reactions are discussed.

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Effective and Selective Catalysts for Cinnamaldehyde Hydrogenation: Hydrophobic Hybrids of Metal–Organic Frameworks, Metal Nanoparticles, and Micro‐ and Mesoporous Polymers

Cited by 140 publications

References 33 publications

Rational Localization of Metal Nanoparticles in Yolk–Shell MOFs for Enhancing Catalytic Performance in Selective Hydrogenation of Cinnamaldehyde

Rational Localization of Metal Nanoparticles in Yolk–Shell MOFs for Enhancing Catalytic Performance in Selective Hydrogenation of Cinnamaldehyde

Hydrophobic Metal–Organic Frameworks: Assessment, Construction, and Diverse Applications

Recent Advances of MOFs and MOF‐Derived Materials in Thermally Driven Organic Transformations

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