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Research Article

Ethane dehydrogenation over the g-C3N4 supported metal single-atom catalysts to enhance reactivity and coking-resistance ability

Yuan Zhang1,2, Baojun Wang1,2(), Maohong Fan3,4,5, Lixia Ling1,2, Riguang Zhang2()
College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China
Departments of Chemical and Petroleum Engineering, University of Wyoming, Laramie, WY 82071, USA
School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332, USA
School of Energy Resources, University of Wyoming, Laramie, WY 82071, USA
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Density functional theory (DFT) calculations and kinetic Monte Carlo (kMC) simulations were employed to predict the catalytic performance of ethane dehydrogenation over a series of metal single-atom anchored graphitic carbon nitride (g-C3N4) catalysts. Co/g-C3N4 catalyst is screened out to be the most potential with 100% C2H4(g) selectivity and the highest C2H4(g) formation activity at 673.15 K. The reaction free energy of C2H5* dehydrogenation to C2H4* is proposed as a simple descriptor to quantitatively and quickly evaluate C2H4(g) formation activity, and the catalyst with the reaction free energy approaching zero has higher C2H4(g) activity.

Abstract

Ethane dehydrogenation (EDH) to produce ethylene requires high operating temperature to achieve satisfactory ethylene yield, however, this process leads to coke formation and catalyst deactivation. Here, an active site isolation strategy was employed to inhibit side reaction and coke formation over fifteen types of metal single-atom metal/graphitic carbon nitride (M/g-C3N4) catalysts. Density functional theory (DFT) calculations completely describe reaction network of ethane dehydrogenation. On-lattice kinetic Monte Carlo simulations were carried out to evaluate catalytic performance under the realistic conditions. The Co/g-C3N4, Rh/g-C3N4, and Ni/g-C3N4 catalysts were screened out to exhibit higher C2H4(g) formation activity and C2H4(g) selectivity close to or equal to 100%. The low reactant partial pressure 0%–5% at atmospheric pressure facilitates ethane dehydrogenation, and the appropriate temperatures over Co/g-C3N4, Rh/g-C3N4, and Ni/g-C3N4 catalysts are 673.15, 723.15, and 723.15 K, respectively. Especially, Co/g-C3N4 catalyst presents the highest C2H4(g) formation activity, attributing to the appropriate anti-bonding strength between C atom and metal single-atom. Further, a simple descriptor, the reaction energy of C2H5* dehydrogenation to C2H4*, was proposed to quantitatively and quickly evaluate C2H4(g) formation activity. The present study laid a solid foundation for efficient design and development of single-atom catalysts with high-performance for selective dehydrogenation of alkanes.

Keywords

ethane dehydrogenationsingle-atom catalystgraphitic carbon nitridesdensity functional theory (DFT) calculationskinetic Monte Carlo

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Nano Research
Volume 16 Issue 5,
May 2023
Pages 6142-6152
DOI: 10.1007/s12274-022-5187-4
Cite this article:
Zhang Y, Wang B, Fan M, et al. Ethane dehydrogenation over the g-C3N4 supported metal single-atom catalysts to enhance reactivity and coking-resistance ability. Nano Research, 2023, 16(5): 6142-6152. https://doi.org/10.1007/s12274-022-5187-4
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