Catalyst Screening\nand Mechanism Elucidation of Two-Dimensional\nTransition Metal Coordinated Porphyrin-Analogue Materials for Nitrogen\nFixation

This paper reports the construction of a series of two-dimensional\n(2D) transition metal coordinated porphyrin-analogue catalytic materials\nand employs a combined strategy of the first-principles calculations\nand high-throughput screening to systematically investigate their\ncatalytic activity and reaction mechanisms of electrocatalytic nitrogen\nreduction reaction (NRR). Ninety metal porphyrin-analogue catalysts\nare obtained by embedding 30 transition metals (3–5d series)\ninto three classes of two-dimensional porphyrin-analogue substrates.\nHigh-throughput screening and full reaction pathway search reveal\nthat MoP<i>p</i>-β-<i>H</i>-<i>meso</i>-Diyne, MoP<i>p</i>-<i>meso</i>-<i>H</i>-β-Ph and MoP<i>p</i>-<i>meso</i>-<i>H</i>-β-Py are the optimal catalysts via the distal pathway\nwith onset potentials of −0.21, −0.26 and −0.28\nV, respectively. WP<i>p</i>-<i>meso</i>-<i>H</i>-β-Py and ReP<i>p</i>-β-<i>H</i>-<i>meso</i>-Diyne also exhibit good catalytic performance\nwith onset potentials of −0.46 and −0.46 V, respectively.\nAll five catalytic materials demonstrate good electronic conductivity\nand high stability. A volcano-shaped relationship is unveiled between\nthe free energy change of the first protonation step (Δ<i>G</i><sub>*N<sub>2</sub></sub> → <sub>*N<sub>2</sub>H</sub>) and the onset potential (<i>U</i><sub>onset</sub>), which\ncan be utilized to describe the catalytic activity of NRR and guide\nthe design and selection of efficient catalysts.