A combinatorial descriptor for volcano relationships of electrochemical nitrogen reduction reaction

doi:10.1016/S1872-2067(22)64128-7

Abstract

Abstract:

Though touted as a potential way to realize clean ammonia synthesis, electrochemical ammonia synthesis is currently limited by its catalytic efficiency. Great effort has been made to find catalysts with improved activity toward electrochemical nitrogen reduction reaction (eNRR). Rational screening of catalysts can be facilitated using the volcano relationship between catalytic activity and adsorption energy of an intermediate, namely, the activity descriptor. In this work, we propose ΔG_*NH2+ΔG_*NNH as a combinatorial descriptor, which shows better predictive power than traditional descriptors using the adsorption free energies of single intermediates. The volcano plots based on the combinatorial descriptor exhibits peak activity fixedly at the descriptor value corresponding to the formation free energy of NH₃, regardless of the catalyst types; while the descriptor values correspond to the top activities for eNRR on volcano plots based on single descriptors usually vary with the types of catalysts.

Key words: Electrocatalysis, Electrochemical nitrogen reduction reaction, Single atom catalyst, Single cluster catalyst, Scaling relationship

Ziyi Jiang, Youcheng Hu, Jun Huang, ShengLi Chen. A combinatorial descriptor for volcano relationships of electrochemical nitrogen reduction reaction[J]. Chinese Journal of Catalysis, 2022, 43(11): 2881-2888.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64128-7

https://www.cjcatal.com/EN/Y2022/V43/I11/2881

Figures/Tables 10

Fig. 1. (a) The top and side view of SCCs. (b) The top view of five types of SACs. Atoms in gray color represent C atoms, those in blue represent N and those in bluish violet represent metal atoms.

Fig. 2. (a) Diagram of three adsorption configurations of N2. (b) Reaction pathway for SCCs. (c) All possible reaction pathway for SACs.

Fig. 3. Scaling relationships between adsorption free energy of N, s-N2, *N-*N (a), s-NNH, s-NHNH (b), s-NHNH2, e-NNH, NH, NH2 (c) and adsorption free energy of N on SCCs. (d) Reaction free energy of each CPET and volcano curve based on single descriptor for SCCs, each point represents the maximum value of CPET free energy for catalyst, each dotted line represents the scaling relationship between the CPET free energy and the descriptor, the solid lines represent the volcano curve.

Fig. 4. Scaling relationships between adsorption free energy of N, NH, NH2 (a), NNH, NHNH, NNH2 (b), NHNH2, NH2NH2 (c) and adsorption free energy of N on SACs. (d) Reaction free energy of each CPET and volcano curve based on single descriptor for SACs, each point represents the maximum value of CPET free energy for catalyst, each dotted line represents the scaling relationship between the CPET free energy and the descriptor, the solid lines represent the volcano curve.

Fig. 5. Scaling relationship between adsorption free energy of N, s-N2, *N-*N (a), s-NNH, s-NHNH, s-NHNH2 (b), e-NNH, NH, NH2 (c) and combinatorial descriptor on SCCs. (d) Reaction free energy of each CPET and volcano curve based on combinatorial descriptor for SCCs, each point represents the maximum value of CPET free energy for catalyst, each dotted line represents the scaling relationship between the CPET free energy and the descriptor, the solid lines represent the volcano curve.

Fig. 6. Scaling relationship between adsorption free energy of N, NH, NH2 (a), NNH, NHNH, NNH2 (b), NHNH2, NH2NH2 (c) and combinatorial descriptor on SACs. (d) Reaction free energy of each CPET and volcano curve based on combinatorial descriptor for SACs, each point represents the maximum value of CPET free energy for catalyst, each dotted line represents the scaling relationship between the CPET free energy and the descriptor, and the solid lines represent the volcano curve.

Table 1 R2 value of scaling relationship between intermediates adsorption energy and single descriptor or combinatorial descriptor in and SCCs.

Descriptor	ΔG_*N	ΔG_*NH	ΔG_*NH2	ΔG_s-N2	ΔG_s-NNH	ΔG_s-NHNH	ΔG_s-NHNH2	ΔG_{N N}	ΔG_e-NNH
ΔG_*N	1	0.889	0.568	0.645	0.855	0.712	0.333	0.924	0.856
ΔG_NH2+ΔG_NNH	0.820	0.885	0.840	0.877	0.975	0.932	0.590	0.898	0.884

Table 2 R2 value of scaling relationship between intermediates adsorption energy and single descriptor or combinatorial descriptor in and SACs.

Descriptor	ΔG_*N	ΔG_*NH	ΔG_*NH2	ΔG_*NNH	ΔG_*NHNH	ΔG_*NNH2	ΔG_*NHNH2	ΔG_*NH2NH2
ΔG_*N	1	0.910	0.795	0.896	0.775	0.905	0.795	0.633
ΔG_NH2+ΔG_NNH	0.871	0.958	0.970	0.968	0.876	0.962	0.965	0.747

Fig. 7. Reaction energy of each CPET and Volcano relationship model based on combinatorial descriptor for side-on (a) and end-on (b) configuration for SACs from Ref. [34]. Each point represents the maximum value of CPET free energy for catalyst, each dotted line represents the scaling relationship between the CPET free energy and the descriptor, the solid lines represent the volcano curve.

Fig. 8. Summary of volcano curves based on combinatorial descriptor. Curves in red, blue represent volcano curves of SCCs and SACs. Curves in green and purple represent volcano curves end-on configuration and side-on configuration from Ref. [34], respectively.

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