Activating Graphyne Nanosheet via sp-Hybridized Boron Modulation for Electrochemical Nitrogen Fixation

Exploring new metal-free catalysts with high activity for nitrogen reduction reaction (NRR) is highly desirable but remains a big challenge. Graphyne (GY) is a typical two-dimensional carbon material with many excellent properties. However, the NRR has rarely been envisaged on a GY-based metal-free catalyst up to now. Density functional theory calculations reveal that although pristine GY is inactive for N-2 reduction, boron modulation can endow it with efficient activity toward NRR Natural bond orbitals analysis, spin/charge density distributions, and free energy change diagrams are performed and discussed. Three boron doping formats including sp(2)-substituted, sp-substituted, and adsorbed configuration are considered. The obtained data show sp-substitution will induce local moderate spin and charge densities at the boron site on the GY surface, which is convenient for N-2 adsorption and activation, and conductive to N-related intermediates formation and transformation. Moreover, the incorporated sp-hybridized boron can provide one empty p orbital and one occupied p orbital around itself, which plays a key role as an electron reservoir to accept electrons from and donate electrons to the adsorbed N-related species, and thus facilitate N-2 reduction and ammonia synthesis. Henceforth, it provides more opportunities for preparing GY and other carbon materials as efficient catalysts toward renewable energy conversion and storage.