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• Bioinspired Mo tape-porphyrin exhibits high catalytic NRR activity. • The novel NRR catalyst is designed and easy to synthesize experimentally. • Selectivity and durability of Mo tape-porphyrin. The efficient N 2 fixation to NH 3 in the biological system benefits from the electron transfer and catalysis of nitrogenase under ambient conditions, where N 2 reduction occurs at Mo and Fe sites. Herein, the electrochemical N 2 reduction reaction (NRR) on bioinspired Mo tape-porphyrin (denoted as MoP) has been systematically investigated on the basis of first-principles calculations. The anchoring of Mo atom to the biomolecular porphyrin changes the charge distribution and activates more delocalized π electrons in the fully conjugated π-system. The results reveal that N 2 favourably coordinated with Mo atom in end-on configuration and the electronic and magnetic properties of MoP are changed. The most promising reaction pathway for NRR on MoP is via the distal route with overpotential of 0.22 V. The excellent conductivity, highly localized and spin-polarized Mo-4d states of MoP endow it preeminent NRR activity at room temperature. Furthermore, the competitive 2-electron hydrogen evolution reaction (HER) is sufficiently mitigated and circumvented during the NRR progress. The high symmetry of MoP enables a simple synthetic pathway. Our findings provide a ingenious strategy for catalytic N 2 reduction and a practical manufacturing method for designing efficient and selective electrocatalyst. [ABSTRACT FROM AUTHOR]

Carbon dioxide electrochemical reduction reaction (CO2RR) under ambient conditions provides an intriguing picture for conversion of CO2 to useful fuels and chemicals. Here by means of density functional theory (DFT) computations, the formation configuration and CO2RR catalytic activity of boron nitrogen cluster-doped graphdiyne (BN-doped GDY) were systematically investigated. The band structure and optical adsorption spectra reveal that BN-doped GDY exhibits semiconductor with the band gap of 0.902 eV and shows photothermal effect under visible and even infrared light irradiation. The BN-doped GDY could act as a hot spot to enhance CO2RR. The adsorption configurations of various reaction intermediates indicate that boron atoms are active sites, which can be further confirmed by charge analysis. Based on thermodynamic analysis, the reaction pathways and onset potentials were studied as compared with Cu(111) surface. For the production of CO, the onset potential for BN-doped GDY (−1.06 V) is higher than that for Cu(111) surface. While for the reduction of CO2 to HCOOH, CH4, CH3OH, and C2H4 on BN-doped GDY, the onset potentials are lower than that on Cu(111) surface, which are −0.57 V, −0.62 V, −0.57 V, and −0.82 V, respectively. Moreover, the onset potential of competitive hydrogen evolution reaction on BN-doped GDY is high to −0.82 V, which shows us a good selectivity towards to CO2RR rather than HER. Our results may pave a new avenue for the conversion of CO2 into high-value fuels and chemicals. [ABSTRACT FROM AUTHOR]