Heterogeneous Amorphous Cu–MOF‐74 Catalyst for C‐N Coupling Reaction

Ma, Peilong; Meng, Fei; Wang, Nan; Zhang, Jie; Xie, Jianwei; Dai, Bin

doi:10.1002/slct.201802837

Cited by 18 publications

(16 citation statements)

References 74 publications

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“…Moreover, Pt/MOF-BTC sample was tested by XRD (Figure S5) after reaction. The used Pt/MOF-BTC catalyst may be transformed into amorphous structure, which was consistent with previous study [55]. However, the presence of amorphous structure does not affect the performance of the catalyst (Figure 7a).…”

Section: Catalyst Performancesupporting

confidence: 91%

Excellent Catalytic Performance of Ce–MOF with Abundant Oxygen Vacancies Supported Noble Metal Pt in the Oxidation of Toluene

Liu

Chen²,

Chen

et al. 2022

Catalysts

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Metal organic framework (MOF) is a type of porous organic material. In this work, three catalysts loaded with noble metal Pt were prepared by NaBH4 reduction method with three different morphologies of Ce–MOF as carriers. Their physicochemical properties were characterized by XRD, Raman, FTIR, N2 adsorption, SEM, XPS, and TGA. The catalytic performances of different catalysts were evaluated via toluene oxidation and CO2 selectivity. Rod–shaped Pt/MOF–BTC exhibited best catalytic performance compared to Pt/MOF–808 and Pt/UiO–66, its T50 and T90 were 140 °C and 149 °C, respectively. After deducting the effect of specific surface, Pt/MOF–BTC still had the lowest apparent activation energy (62.8 kJ·mol−1), which is due to the abundant atomic Pt and oxygen vacancy content on its surface. After the reaction, the structure of Pt/MOF–BTC may become amorphous according to XRD results. Furthermore, the presence of amorphous structure had no effect on the catalytic activity of the catalyst. In the stability test of Pt/MOF–BTC to toluene oxidation, both toluene conversion and CO2 selectivity remained at 100%, and remained stable for 11 h. Moreover, Pt/MOF–BTC also had better resistance to high weight hourly space velocity (WHSV) or water resistance. The catalyst maintained high catalytic activity for 3 times reusability. This study provides valuable experience for the future work of MOF in the field of VOC catalytic oxidation.

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Section: Catalyst Performancesupporting

confidence: 91%

Excellent Catalytic Performance of Ce–MOF with Abundant Oxygen Vacancies Supported Noble Metal Pt in the Oxidation of Toluene

Liu

Chen²,

Chen

et al. 2022

Catalysts

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“…Koner et al designed an efficient heterogeneous catalyst for C–N cross-coupling reactions by anchoring a Cu(II) Schiff-base moiety into a porous isoreticular metal–organic framework (IRMOF-3) through a post-synthetic modification method . Furthermore, the use of MOFs for direct application in coupling reactions is evident from the growing number of reports. , In addition, MOF-derived porous carbon nanocrystals (NCs) have also been reported to have outstanding performance toward Ullmann-type C–N cross-coupling reactions . The lack of substrate tolerance is a common drawback in MOF catalyzed cross-coupling reactions as only aromatic and alicyclic heterocycles are employed for coupling towards carbon heteroatom bond formation.…”

Section: Introductionmentioning

confidence: 99%

Multifunctional Catalysis by a One-Dimensional Copper(II) Metal Organic Framework Containing Pre-existing Coordinatively Unsaturated Sites: Intermolecular C–N, C–O, and C–S Cross-Coupling; Stereoselective Intramolecular C–N Coupling; and Aziridination Reactions

et al. 2022

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The coordinatively unsaturated sites (CUS) are vital in metal-centered catalysis. Metal–organic frameworks (MOFs) provide a unique opportunity to generate and stabilize CUS due to their robust structure. Generally, the generation of CUS in MOFs needs prior activation under heat and high vacuum to remove labile molecules occupying the catalytic sites. Herein, we report a solvothermal synthesis of a ready-to-use copper MOF containing accessible pre-existing CUS that does not need activation. The single crystal X-ray diffraction structure reveals a square planar Cu(II) center with two N-methylimidazoles (Mim) and one benzenedicarboxylic acid (BDC) with the formula unit [CuII(BDC)(Mim)2] n (Cu-1D) forming an infinite one-dimensional (1D) chain along the c axis. The 1D chains are stabilized by noncovalent π–π, CH···π, and H-bonding interaction to give 2D (sheet-like) and 3D networks in the solid state. The quantification of non-covalent interaction is studied by Hirshfeld surface analysis, and the formation of a higher architecture in the solid state is confirmed by SEM analysis. The reported Cu-1D MOF acts as a solid heterogeneous catalyst and exhibits efficient catalytic activity in intermolecular and intramolecular cross-coupling reactions. Intermolecular C-heteroatom cross-coupling of a variety of N-heterocycles, aliphatic, aromatic, alicyclic amines and amides (C–N), phenols (C–O), and thiols (C–S) with aryl halides (halide = I, Br) was achieved with 70 to 95% yield, better than the state-of-the-art Cu-based homogenous system. The C–N coupling catalytic cycle is initiated by the in situ reduction of Cu(II) by KOH/DMSO to Cu(I) species. Subsequently, Cu(I) undergoes oxidative addition followed by reductive elimination to form a cross-coupled product. High stereoselectivity was found for the intramolecular C–N coupling reaction to give tetrahydroquinoxalines with an enantiomeric excess (ee) of more than 99%. For a broader application, Cu-1D was applied as the catalyst for the synthesis of a library of aziridines that gives yields of up to 99% with more than 93% recyclability for each cycle.

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“…[4][5][6] Most recently, some aMOF-based catalysts were disclosed to have unique catalytic ability in some reactions, such as oxidation, esterification and crosscoupling reaction. [7][8][9] Over the past decade, significant progress in the precise control of the synthesis of porphyrin MOFs has been achieved, and their structures and catalytic performances can be adjusted for specific applications. [10][11][12] Among all porphyrin linkers, tetrakis(4-carboxyphenyl)porphyrin (tcpp) is one of the most well-studied linkers in the synthesis of MOFs (Fig.…”

Section: Introductionmentioning

confidence: 99%

“…4–6 Most recently, some aMOF-based catalysts were disclosed to have unique catalytic ability in some reactions, such as oxidation, esterification and cross-coupling reaction. 7–9…”

Section: Introductionmentioning

confidence: 99%

Amorphous zirconium metal–organic frameworks assembled from mixed porphyrins as solvent-free catalysts for Knoevenagel condensation

et al. 2022

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Heterogeneous Amorphous Cu–MOF‐74 Catalyst for C‐N Coupling Reaction

Cited by 18 publications

References 74 publications

Excellent Catalytic Performance of Ce–MOF with Abundant Oxygen Vacancies Supported Noble Metal Pt in the Oxidation of Toluene

Excellent Catalytic Performance of Ce–MOF with Abundant Oxygen Vacancies Supported Noble Metal Pt in the Oxidation of Toluene

Multifunctional Catalysis by a One-Dimensional Copper(II) Metal Organic Framework Containing Pre-existing Coordinatively Unsaturated Sites: Intermolecular C–N, C–O, and C–S Cross-Coupling; Stereoselective Intramolecular C–N Coupling; and Aziridination Reactions

Amorphous zirconium metal–organic frameworks assembled from mixed porphyrins as solvent-free catalysts for Knoevenagel condensation

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