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Methane Dehydrogenation and Coking Resistance on Ni(111) Surfaces of SOFC Anodes with Different Cu Doping Ratios under a Consistent DFT Framework

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Abstract

Carbon deposition on nickel-based anodes is a key problem for solid oxide fuel cells (SOFCs) using hydrocarbon fuels. One of the solutions is doping with other elements. In this work, DFT calculations were used to systematically study the processes of continuous CH4 dehydrogenation, carbon formation, and carbon elimination on Ni(111) surfaces doped with different amounts of Cu. The Cu doping concentrations on the Ni surface are set as 0, 1/9, 4/9, 5/9, 8/9, and 1 ml, namely Ni(111), NiCu1, NiCu4, NiCu5, NiCu8, and Cu9. The adsorption energies and adsorption sites of the important substances were obtained by calculation. In addition, the kinetics and thermodynamics of the main reactions and potential carbon removal pathways are discussed. Prior studies have shown that the introduction of Cu weakens the interaction between the Ni-based surface and the absorber, thereby enhancing the activity of various species on the surface of Ni-based catalysts. Second, the methane cracking path on the Ni-based surface is CH4 → CH3 → CH2 → CH, and the paths on the other five surfaces are the same. We found that the addition of Cu can weaken the adsorption of C, inhibit the activity of CH4 dehydrogenation, and promote the binding of C to the intermediate medium on the Ni-based surface, thus improving the ability of carbon deposition resistance. Finally, based on our DFT calculations, several potential carbon removal pathways are discussed in detail, and it is believed that the problem of carbon removal on SOFC anodes should focus on the oxidation of CH while preventing its direct cracking.

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Funding

This work was supported by National Natural Science Foundation of China (grants 51764028), Science and Technology Planning Project of Yunnan Province (202202AD080008).

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Authors and Affiliations

  1. Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, 650093, Kunming, Yunnan, China

    Xin Ding, Jie Yu, Feng Yu Chen, Shu Qiu Hu, Wei Tian Yang, Cui Qiao, Xiu Min Chen & Wen Hui Ma

  2. The Key Laboratory of Vacuum Metallurgy of Non-Ferrous Metals of Yunnan Province, 650093, Kunming, Yunnan, China

    Xin Ding, Jie Yu, Feng Yu Chen, Shu Qiu Hu, Wei Tian Yang, Cui Qiao, Xiu Min Chen & Wen Hui Ma

  3. School of Science and Technology, Pu’er University, 665000, Puer, Yunan, China

    Wen Hui Ma

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  1. Xin Ding
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Abbreviations and notation: SOFC, solid oxide fuel cell; TPB, three-phase boundary; SMR, steam methane reforming; DFF, density functional theory; DRM, dry methane reforming; fcc, face-centered cubic structures; hcp, hexagonal close-packed structures; PBE, Perdew–Burke–Ernzerhof functional; GGA, generalized gradient approximation; IS, initial state; TS, transition states; FS, final state; SCF, self-consistent field; LST, linear synchronous transit method; QST, quadratic synchronous transit method; RMS, root mean square (convergence criterion); \({{E}_{{{\text{adsorbates}}/{\text{slab}}}}}~\), total energy of adsorbates on the surface; \({{E}_{{{\text{adsorbates}}}}}\), total energy of the adsorbates; \({{E}_{{{\text{slab}}}}}\), total energy of the bare surface; \({{E}_{{\text{a}}}}\), energy barrier; ΔE, reaction heat; \({{E}_{{{\text{IS}}}}}\), \({{E}_{{{\text{TS}}}}}\), and \({{E}_{{{\text{FS}}}}}\), total energies of the initial state reactants, the transition states, and the final state products, respectively.

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Xin Ding, Yu, J., Chen, F.Y. et al. Methane Dehydrogenation and Coking Resistance on Ni(111) Surfaces of SOFC Anodes with Different Cu Doping Ratios under a Consistent DFT Framework. Kinet Catal 64, 371–389 (2023). https://doi.org/10.1134/S0023158423040146

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