Revealing the electrocatalytic mechanism of layered crystalline CoMoO4 for water splitting: A theoretical study from facet selecting to active site engineering

doi:10.1016/S1872-2067(23)64458-4

Abstract

Abstract:

Deciphering the atomic-level properties and mechanism of electrocatalysts for water splitting is vital for the development of highly active non-noble-metal catalysts. Herein, we conduct a detailed study of layered crystalline CoMoO₄ using density functional theory (DFT) calculations. The layered arrangement of CoMoO₄ along the [110] lattice direction is observed, and the two thermodynamically stable and most exposed (110)A and (001)A crystal facets are selected among all low-index facets by surface energy calculations and Wulff construction to study the electrocatalytic activity for alkaline water splitting and corresponding mechanism. CoMoO₄ with an exposed (110)A facet (i.e., CMO (110)A) exhibited a high hydrogen evolution reaction (HER) activity, with a ΔG_H* of 0.22 eV, which is similar to that of Pt because the adsorbed H is allowed to interact with two oxygen atoms (O3 and O_adj). The (110)A facet also possesses better H₂O adsorption and dissociation abilities than the (001)A facet, benefiting the HER performance in alkaline solutions. Moreover, the overpotential of the (110)A facet for the electrocatalytic oxygen evolution reaction (OER) is only 0.74 V according to the Gibbs free-energy calculation, this overpotential is lower than that of the (001)A facet (0.84 V) owing to the stronger binding and more stable adsorption states between Co and O for the intermediate *O. By allowing us to identify highly active facets and sites, this approach guided the selective synthesis of CoMoO₄ and its isostructural substances, such as Mn(Ni, Fe)MoO₄ nanocatalysts, for alkaline water splitting.

Key words: Density functional theory, Water splitting, Layered crystalline CoMoO₄, Facet selecting, Active-site engineering

Shipeng Geng, Liming Chen, Haixin Chen, Yi Wang, Zhao-Bin Ding, Dandan Cai, Shuqin Song. Revealing the electrocatalytic mechanism of layered crystalline CoMoO₄ for water splitting: A theoretical study from facet selecting to active site engineering[J]. Chinese Journal of Catalysis, 2023, 50: 334-342.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64458-4

https://www.cjcatal.com/EN/Y2023/V50/I7/334

Figures/Tables 6

Fig. 1. (a) Optimized unit cell of bulk monoclinic CoMoO4 (CMO) and top view along the C axis. Surface energies (b) and corresponding surface models (c) for different low-index facets of CMO. (d) Thermodynamic equilibrium shape of CMO obtained by the Wulff construction and area percentage of the different facets.

Fig. 2. Different H adsorption sites and corresponding ΔGH* for (110)A facet (a) and (001)A facet (b). (c) Volcano plot of exchange current as a function of ΔGH* for (110)A and (001)A facets of CMO. (d) Optimized structure having the best ΔGH* in the (110)A facet.

Fig. 3. Partial DOS of different O sites in the (110)A (a) and (001)A (b) facets. The Bader charge analysis and the charge-density difference of the top layer for the H adsorption structure possesses the optimal ΔGH* for the (110)A (c) and (001)A (d) facets. The colors cyan and yellow are associated with the depletion and accumulation of the total valence electrons, respectively. The isosurface value is 0.005 e bohr?3.

Fig. 4. H2O adsorption energies and corresponding charge-density differences for (110)A (a) and (001)A (b) facets. The colors yellow and cyan correspond to the accumulation and depletion of total valence electrons, respectively. The isosurface value is 0.01 e bohr?3. (c) H2O dissociation barrier for the reaction pathway of the (110)A facet. The insets show the structure of the corresponding initial state (IS), transition state (TS), and final state (FS). (d) Calculated free-energy diagrams of HER pathways for (110)A and (001)A facets.

Fig. 5. OER free-energy diagrams for the (110)A (a) and (001)A (b) facets, and structural diagrams of the optimized intermediates *, *OH, *O, and *OOH for the (110)A (c) and (001)A (d) facets.

Fig. 6. Bader charge analysis of Co for the slab model *; optimized local structures of *OH, *O, and *OOH; and corresponding bond lengths in the (110)A facet (a) and (001)A facet (b).

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Revealing the electrocatalytic mechanism of layered crystalline CoMoO₄ for water splitting: A theoretical study from facet selecting to active site engineering

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