Self-adjusted reaction pathway enables efficient oxidation of aromatic C-H bonds over zeolite-encaged single-site cobalt catalyst

doi:10.1016/S1872-2067(23)64579-6

Abstract

Abstract:

The selective oxidation of aromatic C-H bonds to high value-added oxygenated products with molecular oxygen remains a key challenge in heterogeneous catalysis. Eligible heterogeneous catalysts are pursued and the reaction mechanism is hotly debated. Herein, we report that zeolite-encaged single-site cobalt ions can efficiently catalyze the model reaction of ethylbenzene aerobic oxidation to acetophenone, outperforming the industrial benchmark catalyst cobalt naphthenate under identical conditions. The self-accelerating phenomenon is observed in the progress of ethylbenzene aerobic oxidation, corresponding to the self-adjusted reaction pathway as revealed by kinetic studies and density functional theory calculations. The formation of reactive O* species on Co sites, resembling the well-known α-O on Fe sites, is identified to be responsible for the self-adjusted reaction pathway of aromatic C-H bond oxidation.

Key words: C-H bonds activation, Heterogeneous catalysis, Co@Y zeolite, Self-accelerating, Reactive O* species

Jian Dang, Weijie Li, Bin Qin, Yuchao Chai, Guangjun Wu, Landong Li. Self-adjusted reaction pathway enables efficient oxidation of aromatic C-H bonds over zeolite-encaged single-site cobalt catalyst[J]. Chinese Journal of Catalysis, 2024, 57: 133-142.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64579-6

https://www.cjcatal.com/EN/Y2024/V57/I2/133

Figures/Tables 5

Fig. 1. Molecular structure of Co@Y and cobalt naphthenate. Co: navy; O: red; Si: yellow; Al: magenta; C: grey; H: white.

Fig. 2. Catalytic performance in EB selective oxidation. EB conversion and product distribution in EB selective oxidation over cobalt naphthenate (a) and Co@Y (b) catalysts. (c) Literature survey of heterogeneous catalysts for EB selective oxidation. Base metal catalysts are shown in circle and noble metal catalysts are shown in square [8??-11,50????????????????-67]. (d) Recycling test of Co@Y catalyst in EB selective oxidation. (one: acetophenone, ol: 1-phenylethanol, acid: benzoic acid, hyde: benzaldehyde). Reaction conditions: 65 μL cobalt naphthenate or 0.17 g Co@Y (both containing ~8.5 mg cobalt), 20 mL EB, 2 mmol biphenyl, 1.5 MPa O2, 383 K.

Fig. 3. Kinetic analyses of relevant steps in EB oxidation. Reaction rates (a) and Arrhenius plots (b) of EB oxidation to ACP over Co@Y catalyst. Reaction rates (c) and Arrhenius plots (d) of 1-phenylethanol oxidation to ACP over Co@Y catalyst. Reaction rates (e) and Arrhenius plots (f) of EB oxidation to ACP in the presence of benzaldehyde over Co@Y catalyst. Reaction conditions: 0.17 g Co@Y, 20 mL EB or 1-phenylethanol, 0 or 20 μL benzaldehyde, 2 mmol biphenyl, 1.5 MPa O2.

Fig. 4. Reaction mechanism of EB oxidation from DFT calculations. Proposed reaction pathways, optimized structures, and the corresponding energy profiles for the formation of PhCOCH3, PhCHOHCH3 and PhCHO over Co@Y zeolite at 0 K.

Fig. 5. Selective oxidation of aromatic C-H bonds. Time-dependent aromatic hydrocarbon conversion and product distribution over Co@Y catalyst. (a) Toluene; (b) propyl benzene; (c) 4-methyl-EB; (d) 1,4-diethyl benzene; (e) 4-methoxy-EB; (f) 4-nitro-EB. Reaction conditions: 0.17 g Co@Y, 20 mL substrate, 2 mmol biphenyl, 1.5 MPa O2. 423 K for toluene and 383 K for others.

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