Reaction kinetics and phase behavior in the chemoselective hydrogenation of 3-nitrostyrene over Co-N-C single-atom catalyst in compressed CO2

doi:10.1016/S1872-2067(20)63785-8

Abstract

Abstract:

Single-atom catalysts (SACs) have demonstrated excellent performances in chemoselective hydrogenation reactions. However, the employment of precious metals and/or organic solvents compromises their sustainability. Herein, we for the first time report the chemoselective hydrogenation of 3-nitrostyrene over noble-metal-free Co-N-C SAC in green solvent — compressed CO₂. An interesting inverted V-curve relation is observed between the catalytic activity and CO₂ pressure, where the conversion of 3-nitrostyrene reaches the maximum of 100% at 5.0 MPa CO₂ (total pressure of 8.1 MPa). Meanwhile, the selectivities to 3-vinylaniline at all pressures remain high (> 99%). Phase behavior studies reveal that, in sharp contrast with the single phase which is formed at total pressure above 10.8 MPa, bi-phase composed of CO₂/H₂ gas-rich phase and CO₂-expanded substrate liquid phase forms at total pressure of 8.1 MPa, which dramatically changes the reaction kinetics of the catalytic system. The reaction order with respect to H₂ pressure decreases from ~0.5 to zero at total pressure of 8.1 MPa, suggesting the dissolved CO₂ in 3-nitrostyrene greatly promotes the dissolution of H₂ in the substrate, which is responsible for the high catalytic activity at the peak of the inverted V-curve.

Key words: Single-atom catalyst, Co-N-C, CO₂, Phase behavior, Chemoselective hydrogenation, 3-Nitrostyrene

Dan Zhou, Leilei Zhang, Wengang Liu, Gang Xu, Ji Yang, Qike Jiang, Aiqin Wang, Jianzhong Yin. Reaction kinetics and phase behavior in the chemoselective hydrogenation of 3-nitrostyrene over Co-N-C single-atom catalyst in compressed CO₂[J]. Chinese Journal of Catalysis, 2021, 42(9): 1617-1624.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63785-8

https://www.cjcatal.com/EN/Y2021/V42/I9/1617

Figures/Tables 8

Fig. 1. XRD pattern (a), low-magnification STEM (b) and high-resolution HAADF-STEM images (c) of the as-synthesized Co-N-C catalyst; HAADF-STEM image of the spent Co-N-C catalyst (d).

Fig. 2. The dependence of conversion and selectivity on H2 pressure (a), temperature (b) and CO2 pressure (c). Reaction conditions: 0.5 mmol 3-nitrostyrene, 30 mg Co-N-C catalyst, 60 °C (a,c), 3 MPa H2 (RT) (b,c), total pressure: 9.2 MPa (a,b), 8 h.

Fig. 3. Phase behaviour of 3-nitrostyrene (NS)-CO2-H2 ternary system: (a-d) visual observations, (e-h) images of the phase conditions when the view cell was irradiated by a laser beam, and (i-l) the corresponding illustration of the phases at the total pressure of 3.1 MPa (CO2-free), 8.1, 9.2 and 13.4 MPa, respectively. Other conditions: 0.5 mmol 3-nitrostyrene, 3 MPa H2 (RT), 60 °C.

Fig. 4. Photographs of volume expansion in CO2-nitrobenzene binary system taken at 60 °C under different pressures.

Fig. 5. Calculated H2 solubility in liquid substrate 3-nitrostyrene (NS) at 60 °C under different CO2 pressures.

Fig. 6. The dependence of reaction rate on the concentration of 3-nitrostyrene at total pressure of 8.1 (a) and 11.2 (b) MPa. Reaction conditions: Ptotal = 8.1 MPa, PH2 = 3.0 MPa (RT), 30 mg catalyst, 60 °C, reaction time was varied between 0.5-1 h to maintain the conversions below 30%.

Fig. 7. The dependence of reaction rate on the pressure of H2 at (a) CO2-free condition; (b) total pressure of 8.1 MPa; (c) total pressure of 11.2 MPa. Reaction conditions: 0.5 mmol 3-NS, 0.25 mmol o-xylene, 30 mg catalyst, 60 °C, and the reaction time was varied between 1?3 h to maintain the conversion below 30%.

Fig. 8. Durability of the Co-N-C catalyst. Condition: 3-nitrostyrene (0.5 mmol), Co-N-C catalysts (30 mg), o-xylene (0.25 mmol, as the internal standard), 60 °C, total pressure of 8.1MPa and H2 pressure of 3.0 MPa (RT), 8 h.

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Reaction kinetics and phase behavior in the chemoselective hydrogenation of 3-nitrostyrene over Co-N-C single-atom catalyst in compressed CO₂

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