Single-atom catalysts based on polarization switching of ferroelectric In2Se3 for N2 reduction

doi:10.1016/S1872-2067(24)60084-7

Abstract

Abstract:

The polarization switching plays a crucial role in controlling the final products in the catalytic process. The effect of polarization orientation on nitrogen reduction was investigated by anchoring transition metal atoms to form active centers on ferroelectric material In₂Se₃. During the polarization switching process, the difference in surface electrostatic potential leads to a redistribution of electronic states. This affects the interaction strength between the adsorbed small molecules and the catalyst substrate, thereby altering the reaction barrier. In addition, the surface states must be considered to prevent the adsorption of other small molecules (such as *O, *OH, and *H). Furthermore, the V@↓-In₂Se₃ possesses excellent catalytic properties, high electrochemical and thermodynamic stability, which facilitates the catalytic process. Machine learning also helps us further explore the underlying mechanisms. The systematic investigation provides novel insights into the design and application of two-dimensional switchable ferroelectric catalysts for various chemical processes.

Key words: In₂Se₃ monolayer, Density functional theory, Ferroelectric switching, Single atom catalysts, Nitrogen reduction reaction, Machine learning

Nan Mu, Tingting Bo, Yugao Hu, Ruixin Xu, Yanyu Liu, Wei Zhou. Single-atom catalysts based on polarization switching of ferroelectric In₂Se₃ for N₂ reduction[J]. Chinese Journal of Catalysis, 2024, 63: 244-257.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60084-7

https://www.cjcatal.com/EN/Y2024/V63/I8/244

Figures/Tables 13

Fig. 1. (a) The top and side views of geometric structures of the α-In2Se3 monolayer with downward and upward polarization, respectively. Purple and green denote the In atom and Se atom, respectively. The red cycles, blue cycles, and black arrows represent selected TM anchored sites, different Se atoms, and polarization directions, respectively. (b) The partial density of states of the α-In2Se3 monolayer with spin up state. (c) The average potential energy for In2Se3 monolayer along the perpendicular direction. The black arrow represents the direction of the intrinsic electric field. (d) The partial density of states and labelled p band centers of V@↓-In2Se3 and V@↑-In2Se3.

Fig. 2. Dimensionality reduction for the binding energy of the TM@In2Se3 using multidimensional scaling (a) and spectral embedding algorithms (b).

Fig. 3. (a) Schematic of Distal, Alternating and Enzymatic Mechanisms for NRR. (b) Proposed screening strategy of NRR candidate catalysts. (c) N2 absorption free energies with end-on and side-on patterns. (d) The bonding schematic diagrams between N2 and TM. (e) The N-N bond length changes as a function of the excess electrons after N2 adsorption for TM@↑-In2Se3 and TM@↓-In2Se3 via the end-on configuration.

Fig. 4. Free energy changes of *N2 + H+ + e- → *N2H (a) and *NH2 + H+ + e- → *NH3 (b) on TM@↑-In2Se3 with end-on configuration. Free energy changes of *N2 + H+ + e- → *N2H and *NH2 + H+ + e- → *NH3 on TM@↓-In2Se3 with end-on configuration (c) and on TM@↑-In2Se3 with side-on configuration (d). (e) The Gibbs free energy change of PDS for TM@In2Se3. (f) The limiting potentials for NRR and HER of TM@In2Se3 via Distal pathway, Alternating pathway, and Enzymatic pathway.

Fig. 5. (a) The electrical conductivity of the V@In2Se3. (b) The calculated I-V curve for the V@In2Se3.

Fig. 6. The Free energy diagrams during the NRR on V@↓-In2Se3 (a) and V@↑-In2Se3 (b) via distal pathway. Gibbs free energy diagram of the HER on V@↓-In2Se3 (c), V@↑-In2Se3 (d), Mo@↓-In2Se3 (e), Mo@↑-In2Se3 (f).

Fig. 7. The partial density of states of V-3d on the V@↓-In2Se3 (a) and V@↑-In2Se3 (b). (c) Schematic diagram of TM-d orbitals splitting in the different crystal fields. The partial density of states of Mo-4d on the Mo@↓-In2Se3 (d) and Mo@↑-In2Se3 (e). (f) Schematic diagram of the crystal field effect between the dz2 orbital of V atom and the ligand of Se atoms with the FE polarization switching.

Fig. 8. (a) Schematics of N atomic orbitals and N2 molecular orbitals. (b) The partial density of states of free N2. The partial density of states and crystal orbital Hamilton populations of N2 on V@↓-In2Se3 (c) and V@↑-In2Se3 (d) via end-on configuration. The bonding and antibonding states are depicted by cyan and yellow, respectively.

Fig. 9. (a) Interaction diagram between the 2p orbital of N atom and the d orbital of the TM atom with end-on configuration. (b) Important features from the Random Forest model for ΔG*NNH. (c) The linear correlations between the d band center (εd) of TM atom and limiting potential by the distal mechanism on TM@In2Se3. (d) The linear correlations between the excess obtained electrons of N2 and limiting potential by the distal mechanism on TM@In2Se3. (e) Comparison of DFT-calculated UL values with the SISSO-predicted values.

Fig. 10. The configuration and ELF maps of V@↓-In2Se3 (a), *NN (end-on pattern) (b) and *NH2 on V@↓-In2Se3 (c).

Fig. 11. (a) The differential charge density plots of N2 adsorbed on V@↓-In2Se3 and V@↑-In2Se3. (b) The schematic diagram of three moieties on TM@In2Se3: moieties 1, 2, and 3 represent In2Se3, single TM atom, and adsorbed NxHy, respectively. The charge variations of the three moieties for the NRR on V@↓-In2Se3 (c) and V@↑-In2Se3 (d).

Fig. 12. Surface Pourbaix diagrams of V@↓-In2Se3 (a) and V@↑-In2Se3 (c); Competitive adsorption of *N2 and *H as well as *OH and *O at the V site on V@↓-In2Se3 (b) and V@↑-In2Se3 (d) as a function of electrode potential.

Fig. 13. Pourbaix diagrams (a) and the AIMD simulation (b) of V@↓-In2Se3.

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Single-atom catalysts based on polarization switching of ferroelectric In₂Se₃ for N₂ reduction

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