The electronic interaction of encapsulating graphene layers with FeCo alloy promotes efficient CO2 Hydrogenation to light olefins

doi:10.1016/S1872-2067(24)60188-9

Abstract

Abstract:

CO₂ hydrogenation to value-added light olefins (C_2-4⁼) is crucial for the utilization and cycling of global carbon resource. Moderate CO₂ activation and carbon chain growth ability are key factors for iron-based catalysts for efficient CO₂ conversion to target C_2-4⁼ products. The electronic interaction and confinement effect of electron-deficient graphene inner surface on the active phase are effective to improve surface chemical properties and enhance the catalytic performance. Here, we report a core-shell FeCo alloy catalyst with graphene layers confinement prepared by a simple sol-gel method. The electron transfer from Fe species to curved graphene inner surface modifies the surface electronic structure of the active phase χ-(Fe_xCo_1-_x)₅C₂ and improves CO₂ adsorption capacity, enhancing the efficient conversion of CO₂ and moderate C-C coupling. Therefore, the catalyst FeCoK@C exhibits C_2-4⁼ selectivity of 33.0% while maintaining high CO₂ conversion of 52.0%. The high stability without obvious deactivation for over 100 h and unprecedented C_2-4⁼ space time yield (STY) up to 52.9 mmol_CO2·g^-1·h^-1 demonstrate its potential for practical application. This work provides an efficient strategy for the development of high-performance CO₂ hydrogenation catalysts.

Key words: CO₂ hydrogenation, Light olefins, Graphene layers, Cobalt-iron alloy carbide, Electronic interaction

Miao Zhang, Limin Zhang, Mingrui Wang, Guanghui Zhang, Chunshan Song, Xinwen Guo. The electronic interaction of encapsulating graphene layers with FeCo alloy promotes efficient CO₂ Hydrogenation to light olefins[J]. Chinese Journal of Catalysis, 2025, 68: 366-375.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60188-9

https://www.cjcatal.com/EN/Y2025/V68/I1/366

Figures/Tables 6

Fig. 1. Synthesis and microscopic analysis of Fe-based catalysts. (A) Schematic illustration of the synthesis of the samples. TEM and HRTEM images of fresh FeCoK@C (B,E), FeCoK-1 (C,F), and FeCoK-2 (D,G) catalysts.

Fig. 2. Structural characterizations of fresh catalysts. (A) XRD patterns of fresh Fe-based catalysts. C 1s (B) and Fe 2p (C) XPS spectra of fresh catalysts.

Fig. 3. Surface chemical properties of activated catalysts. C 1s (A) and Fe 2p (B) XPS spectra of activated FeCoK@C, FeCoK-1 and FeCoK-2. (C) CO2-TPD profiles of all activated Fe-based catalysts.

Fig. 4. Catalytic performances of the catalysts. (A) CO2 conversion and product selectivity over different Fe-based catalysts in CO2 hydrogenation. (B) C2-4= STY, C2-4 O/P, and chain growth factor α of different Fe-based catalysts. (C) Comparison between C2-4= STY over FeCoK@C and other Fe-based catalysts in previous reports. (D) Catalytic performance of FeCoK@C for 100 h stability test. Reaction conditions: 320 °C, 3.0 MPa, space velocity = 18000 mL·g-1·h-1, H2/CO2/N2 = 9/3/2, TOS = 8 h.

Fig. 5. EDS Mapping and HRTEM images of spent catalysts. (A,D) FeCoK@C; (B,E) FeCoK-1; (C,F) FeCoK-2.

Fig. 6. Structural characterizations of spent catalysts and comparison of carburizing rates of catalysts from in-situ XRD during CO2 hydrogenation. (A) XRD patterns of spent catalysts. (B) The intensity ratio of the XRD peaks at 43.5° and 44.7° during CO2 hydrogenation. C 1s (C) and Fe 2p (D) XPS spectra of spent catalysts.

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The electronic interaction of encapsulating graphene layers with FeCo alloy promotes efficient CO₂ Hydrogenation to light olefins

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