Orbital symmetry matching: Achieving superior nitrogen reduction reaction over single-atom catalysts anchored on Mxene substrates

doi:10.1016/S1872-2067(20)63643-9

Abstract

Abstract:

The nitrogen reduction reaction (NRR) under ambient conditions is still challenging due to the inertness of N₂. Herein, we report a series of superior NRR catalysts identified by examining Ti₂NO₂ MXenes embedded with 28 different single-atom catalysts using first-principles calculations. The stability of this system was first verified using formation energies, and it is discovered that N₂ can be effectively adsorbed due to the synergistic effect between single atom catalysis and the Ti atoms. Examination of the electronic structure demonstrated that this design satisfies orbital symmetry matching where “acceptor-donor” interaction scenario can be realized. A new “enzymatic-distal” reaction mechanism that is a mixture of the enzymatic and distal pathways was also discovered. Among all of the candidates, Ni anchored on MXene system achieves an onset potential as low as -0.13 V, which to the best of our knowledge is the lowest onset potential value reported to date. This work elucidates the significance of orbital symmetry matching and provides theoretical guidance for future studies.

Key words: Orbital symmetry matching, Single atom catalysis, Nitrogen reduction reaction, MXene substrate, Potential determining step

Jiale Qu, Jiewen Xiao, Hetian Chen, Xiaopeng Liu, Tianshuai Wang, Qianfan Zhang. Orbital symmetry matching: Achieving superior nitrogen reduction reaction over single-atom catalysts anchored on Mxene substrates[J]. Chinese Journal of Catalysis, 2021, 42(2): 288-296.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63643-9

https://www.cjcatal.com/EN/Y2021/V42/I2/288

Figures/Tables 5

Fig. 1. (a) Side and top views of the atomic configurations of the SAC@MXene design (upper panel) and the general features of the partial density of states (lower panel); (b) 28 kinds of single-atom catalysts (cyan) considered for screening and the corresponding formation energies.

Fig. 2. N2 binding strength for the (a) side-on and (e) end-on adsorption patterns. Partial density of states (PDOS) for the (b) side-on and (f) end-on adsorption patterns. Crystal occupation Hamiltonian population (COHP) for the (c) side-on and (g) end-on adsorption patterns. Spatial charge distribution for the (d) side-on and (h) end-on adsorption patterns. The adsorption configuration is shown in the inset of the left panel.

Fig. 3. Free energy evolution process for the (a) distal, (b) alternating, (c) enzymatic-distal, and (d) enzymatic reaction mechanisms, where structural evolution is shown in the top bar of each panel.

Fig. 4. (a) Free energy evolution for the HER process, where the H adsorption configuration is shown in the inset. (b) Comparison of the electrochemical performances of the NRR and HER processes. The dashed line represents equal onset potentials for HER and NRR, while for the elements below this line, NRR is preferred to HER.

Fig. 5. COHP and partial density of states for the (a) *NH2 adsorption system in the enzymatic-distal reaction path and (c) *NNH adsorption system in the distal reaction path, where the spatial charge distribution in each energy interval is shown in the inset with the isosurface set to 0.008 e/?3. The scaling relations between the onset potential and the binding strength of a single N atom for the (b) enzymatic-distal reaction and (d) distal reaction.

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