Boosting photocatalytic nitrogen reduction to ammonia by dual defective -C=N and K-doping sites on graphitic carbon nitride nanorod arrays

Bi-defective g-C3N4 (K and-C equivalent to N) nanorod arrays with favorable light absorption through multiple light scattering/reflections were designed for photocatalytic N-2 reduction. The highest record of NH3 production, 23.5 mmol/(h.g(cat)), was achieved when dual defects are present at the nanoarrays without any cocatalysts, which is about two orders higher than its counterpart. The N-2 reduction rate is proportional to-C equivalent to N, unveiling its role as active sites. Its synergistic effect with K was observed. Theoretical calculations support that-C equivalent to N site is crucial to N-2 activation by donating electrons, while cation like K center traps electrons. Consequently, modification with such dual defects in conjunction with nanoarray configuration creates a favorable electron-dominated structure to overcome the energy barrier for activating inert nitrogen, enhancing charge separation and light absorption effectively. The present work underlines the impetus of defects engineering and nanoarray configuration for the rational of active for efficient fixation.

Automated summary

Bi-defective g-C3N4 nanorod arrays with enhanced light absorption were used for photocatalytic N2 reduction. The presence of dual defects without any cocatalysts resulted in the highest NH3 production rate of 23.5 mmol/(h.g(cat)), which is two orders higher than the counterpart. The-C equivalent to N site plays a crucial role in N2 activation through electron donation, while cations like K trap electrons. The combination of dual defects and nanoarray configuration creates an electron-dominated structure to enhance charge separation and light absorption, overcoming the energy barrier for activating inert nitrogen.