Polymeric carbon nitride with frustrated Lewis pair sites for enhanced photofixation of nitrogen

The bottleneck of photocatalytic nitrogen fixation lies in the rate-limiting reductive activation of robust N equivalent to N triple bonds with high bond energy. Herein, polymeric carbon nitride with frustrated-Lewis-pairs was constructed by intercalation of electron-deficient boron (B) into metal-free carbon nitride. NH3-temperature programmed desorption (TPD) and pyridine-adsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results demonstrated that B heteroatoms (Lewis acid) and proximal amino groups (Lewis base) were more likely to form frustrated Lewis pairs, which would capture, activate and reduce N(2)to NH(3)through a pull-push effect. Molybdenum-based oxide was further employed as a co-catalyst to improve the charge separation efficiency of site-engineered photocatalysts. The synergistic effect between intercalated B and defective MoO(2)resulted in an 8-fold increased photoactivity of carbon nitride for N(2)fixation. This work provides a new avenue for the rational design and engineering of frustrated Lewis pair sites on polymeric photocatalysts toward efficient N(2)fixation.