Photocatalytic nitrogen fixation under an ambient atmosphere using a porous coordination polymer with bridging...

The design of highly electron-active and stable heterogeneous catalysts for the ambient nitrogen reduction reaction is challenging due to the inertness of the N₂ molecule. Here, we report the synthesis of a zinc-based coordination polymer that features bridging dinitrogen anionic ligands, {[Zn(L)(N₂)_0.5(TCNQ-TCNQ)_0.5]·(TCNQ)_0.5}_n (L is tetra(isoquinolin-6-yl)tetrathiafulvalene and TCNQ is tetracyanoquinodimethane), and show that it is an efficient photocatalyst for nitrogen fixation under an ambient atmosphere. It exhibits an ammonia conversion rate of 140 μmol g^-1 h^-1 and functions well also with unpurified air as the feeding gas. Experimental and theoretical studies show that the active [Zn²⁺-(N≡N)^--Zn²⁺] sites can promote the formation of NH₃ and the detachment of the NH₃ formed creates unsaturated [Zn²⁺···Zn⁺] intermediates, which in turn can be refilled by external N₂ sequestration and fast intermolecular electron migration. The [Zn²⁺···Zn⁺] intermediates stabilized by the sandwiched cage-like donor-acceptor-donor framework can sustain continuous catalytic cycles. This work presents an example of a molecular active site embedded within a coordination polymer for nitrogen fixation under mild conditions.