Synergistic interaction of Nb atoms anchored on g-C3N4 and H+promoting high-efficiency nitrogen reduction reaction

doi:10.1016/S1872-2067(21)63950-5

Abstract

Abstract:

Nowadays catalytic nitrogen reduction reaction (NRR) by electrochemistry has attracted much attention because of its key role in producing the basic chemical product ammonia with low energy consumption. A stable and environmentally-friendly single- or multi-atom catalyst with good performance in activity and selectivity is highly desired for NRR. From density functional theory calculations, the NRR mechanisms catalyzed by Nb monomer, dimer, trimer and tetramer anchored on graphitic carbon nitride (Nb_x@g-C₃N₄, x = 1, 2, 3, 4) have been deeply explored. It has been found that Nb₃@g-C₃N₄ exhibits the best catalytic ability among the four catalysts with the introduction of H⁺. A more stable intermediate (*NH₂+*H) can be found to reduce the huge free energy barrier of forming *NH₃ from *NH₂ directly in a multi-atom system. By analyzing the density of states and projected crystal orbital Hamilton population, a synergistic effect among Nb atoms and the adsorbed H⁺is responsible for reducing the overpotential of NRR. Furthermore, the competitive hydrogen evolution reaction is suppressed effectively. This work introduces a new insight in the reaction pathway in multi-atoms for developing high-efficiency NRR catalysts.

Key words: Catalysis, N₂ fixation, Nitrogen reaction, H⁺absorption, Selectivity

Shaokang Yang, Chaonan Zhang, Dewei Rao, Xiaohong Yan. Synergistic interaction of Nb atoms anchored on g-C₃N₄ and H⁺promoting high-efficiency nitrogen reduction reaction[J]. Chinese Journal of Catalysis, 2022, 43(4): 1139-1147.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63950-5

https://www.cjcatal.com/EN/Y2022/V43/I4/1139

Figures/Tables 5

Fig. 1. Optimized structure of Nb1@g-C3N4 (a), Nb2@g-C3N4 (b), Nb3@g-C3N4 (c), and Nb4@g-C3N4 (d); The computed PDOS of Nb1@g-C3N4 (e), Nb2@g-C3N4 (f), Nb3@g-C3N4 (g) and Nb4@g-C3N4 (h); The energy profiles of the formation and dissociation (i) and the AIMD result (j) at 500 K for Nb3@g-C3N4. The Fermi level was shifted to zero. The brown, silver and green balls represent C, N and Nb atoms, respectively.

Fig. 2. The computed charge density difference and projected density of states of Nb1@g-C3N4 (a), Nb2@g-C3N4 (b), Nb3@g-C3N4 (c) and Nb4@g-C3N4 (d) after N2 adsorbed on the surface while the bonding and antibonding states in COHP depicted by up and down in blue shaded areas. The contributions by the orbitals of N2 and the d orbitals of Nb atom are shown in blue and green, respectively. The brown, silver and green balls denote C, N and Nb atoms, respectively. The isosurface is set to 0.004 e/Å3and the red area represents the accumulation of electrons, the green area represents the loss of electrons.

Fig. 3. Gibbs free energy diagram and the reaction intermediates for NRR through the mixed mechanism on Nb3@g-C3N4. The brown, silver, green and white balls denote C, N, Nb and H atoms, respectively.

Fig. 4. (a) The structure of *NH2 + *H (up) and *NH2 (down); (b) the PDOS of *NH2 + *H (up) and *NH2 (down) species in the system of Nb3@g-C3N4. The green area represents the contribution of Nb atoms. The blue, sky blue, yellow and pink lines indicate the orbitals of N, H1, H2 and H3, respectively. (c,d) The COHP between two metal atoms (NbI, NbII) and the N in *NH2 species in the system of Nb3@g-C3N4; (e,f) The COHP between the two metal atoms (NbI, NbII) and the N in *NH2 + *H species in the system of Nb3@g-C3N4; (g) The correlation between the ICOHP of Nb?N and ΔE(*NH2).

Fig. 5. (a) Gibbs free energy diagrams of HER on Nb1@g-C3N4, Nb2@g-C3N4, Nb3@g-C3N4 and Nb4@g-C3N4; (b) Compare the selectivity of NRR versus HER.

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Synergistic interaction of Nb atoms anchored on g-C₃N₄ and H⁺promoting high-efficiency nitrogen reduction reaction

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