A Cu-Doped ZIF-8 metal organic framework as a heterogeneous solid catalyst for aerobic oxidation of benzylic hydrocarbons

Nagarjun, Nagarathinam; Dhakshinamoorthy, Amarajothi

doi:10.1039/c9nj03698a

Cited by 53 publications

(23 citation statements)

References 84 publications

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“…Further, Cu@ZIF-8 was characterized by powder XRD, FT-IR, UV-Visible DRS, SEM methods and the observed results are in line with the reported results. [49,50] Briefly, powder XRD patterns of ZIF-8, Cu@ZIF-8 and CU/ZIF-8 are shown in Figure 1 and they indicate that the structural integrity and crystallinity of ZIF-8 are not altered upon doping/adsorbing with Cu 2 + ions. The facile doping of Cu 2 + ions without affecting crystallinity of ZIF-8 is mainly due to the closer ionic radii between Cu 2 + (0.71 Å) and Zn 2 + (0.74 Å) ions.…”

Section: Resultsmentioning

confidence: 98%

Copper(II)‐Doped ZIF‐8 as a Reusable and Size Selective Heterogeneous Catalyst for the Hydrogenation of Alkenes using Hydrazine Hydrate

2021

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In recent years, synthesis of mixed-metal organic frameworks has received considerable attention due to their superior performance than with mono-metallic metal organic frameworks (MOFs). In the present manuscript, Cu 2 + ions are doped within the framework of ZIF-8 (ZIF: Zeolitic Imidazolate Frameworks) to obtain Cu@ZIF-8 and is characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR), UV-Visible diffuse reflectance spectra (DRS), scanning electron microscope (SEM) and transmission electron microcope (TEM) studies. The reaction conditions are optimized with styrene as a model substrate using Cu@ZIF-8 as a solid catalyst. Heterogeneity of the reaction is confirmed by leaching test and the solid is reusable for three recycles with no diminishing activity. Further, the structural integrity of Cu@ZIF-8 is also retained after hydrogenation of styrene as evidenced by powder X-ray diffraction. The size selective catalysis of Cu@ZIF-8 is demonstrated by comparing the activity of Cu 2 + ions adsorbed over ZIF-8 solid (Cu/ZIF-8) in the hydrogenation of 1-hexene, 1octene, cyclohexene, cyclooctene and t-stilbene. The catalytic results indicate that Cu/ZIF-8 shows superior activity than Cu@ZIF-8 for all these olefins due to the lack of diffusion to access the active sites (Cu 2 + ). In contrast, Cu@ZIF-8 exhibits higher activity for those olefins with lower molecular dimensions (1-hexene, 1-octene) than the pores of ZIF-8 indicating the facile diffusion of these substrates inside the pores ZIF-8 while poor activity is observed with t-stilbene due to its larger molecular dimension than the pore apertures of ZIF-8. These catalytic data clearly establish the size selective hydrogenation of Cu@ZIF-8 due to the effective confinement provided by ZIF-8 framework and the presence of the active sites within the framework. Furthermore, this is the first report showing the size selective hydrogenation of olefins promoted by Cu@ZIF-8 (mixed-metal MOFs) compared to other noble metal nanoparticles (NPs) embedded over MOFs as catalysts.

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Section: Resultsmentioning

confidence: 98%

Copper(II)‐Doped ZIF‐8 as a Reusable and Size Selective Heterogeneous Catalyst for the Hydrogenation of Alkenes using Hydrazine Hydrate

2021

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“…Hence, it can be suggested that the incorporation of cobalt does not alter the topology of the framework structure and the original topology was retained due to: (i) the similarity of the ionic size of cobalt and zinc (Co 2+ 0.79 Å and Zn 2+ 0.74 Å) and (ii) the similarity of coordination number for the Co(II) and Zn(II) ions in this framework structure. 22 Fig. 1(D) presents the N 2 -adsorption isotherms of BE-S and AF-S and the accordingly determined BET surface areas are 1210 and 255 m 2 g À1 respectively.…”

Section: Resultsmentioning

confidence: 99%

Designing bimetallic zeolitic imidazolate frameworks (ZIFs) for aqueous catalysis: Co/Zn-ZIF-8 as a cyclic-durable catalyst for hydrogen peroxide oxidative decomposition of organic dyes in water

et al. 2022

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“…Hitherto, most previous reviews mainly summarized the properties of MOF materials, synthesis strategies, and applications. There are also some applications of MOFs as catalysts, but most of them focus on electrocatalysis, − photocatalysis, − and some oxidation reactions − in liquid or gas phase reactions. However, as far as we know, the application of MOFs as catalysts in hydrogenation reactions has not been systematically summarized.…”

Section: Introductionmentioning

confidence: 99%

Application of Metal–Organic Framework Materials and Derived Porous Carbon Materials in Catalytic Hydrogenation

Shen

et al. 2020

ACS Sustainable Chem. Eng.

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In the past few decades, metal–organic frameworks (MOFs) have gradually become attractive materials in various fields due to their unique properties (adjustable pore size, large specific surface area, highly ordered structure, uniformly distributed metal nodes, good modifiability). MOF-derived porous carbon materials have also attracted great interest in many application fields due to their adjustable chemical and physical properties. The hydrogenation reaction is an important type of reaction in the chemical industry. The catalysts play an important role in the hydrogenation reaction. In recent years, MOFs and derived porous carbon materials have had extensive application in catalytic hydrogenation reactions. Compared with other traditional catalysts, MOFs and derived porous carbon materials have some unique advantages as hydrogenation catalysts, which are described in this review. In addition, we have expounded the rational design of MOF hydrogenation catalysts from the following four aspects: choosing suitable MOFs with coordinated unsaturated metal sites, good stability, and precise control and optimizing the structure of MOF materials and hydrogen storage characteristics of MOF materials. The application of nitrogen-doped carbon materials and MOF-derived porous carbon materials in hydrogenation reactions has also been compared. Moreover, various MOFs and derived porous carbon materials with excellent performance are discussed in detail in various catalytic hydrogenation reactions including olefins, alkynes, alcohols and phenols, aldehydes, carboxylic acids, esters, nitro compounds, and other hydrogenation reactions. Finally, the challenges of MOFs and derived porous carbon materials as hydrogenation catalysts are objectively summarized, and the application and development trends in catalytic hydrogenation reactions are prospected.

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A Cu-Doped ZIF-8 metal organic framework as a heterogeneous solid catalyst for aerobic oxidation of benzylic hydrocarbons

Abstract: Cu(ii) ions doped into ZIF-8 MOFs are shown to activate C–H bonds in benzylic hydrocarbons to their corresponding alcohol/ketone products.

Cited by 53 publications

References 84 publications

Copper(II)‐Doped ZIF‐8 as a Reusable and Size Selective Heterogeneous Catalyst for the Hydrogenation of Alkenes using Hydrazine Hydrate

Copper(II)‐Doped ZIF‐8 as a Reusable and Size Selective Heterogeneous Catalyst for the Hydrogenation of Alkenes using Hydrazine Hydrate

Designing bimetallic zeolitic imidazolate frameworks (ZIFs) for aqueous catalysis: Co/Zn-ZIF-8 as a cyclic-durable catalyst for hydrogen peroxide oxidative decomposition of organic dyes in water

Application of Metal–Organic Framework Materials and Derived Porous Carbon Materials in Catalytic Hydrogenation

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