Electrocatalytic and Photocatalytic N Fixation Using Carbon Catalysts.

Carbon catalysts have shown promise as an alternative to the currently available energy-intensive approaches for nitrogen fixation (NF) to urea, NH, or related nitrogenous compounds. The primary challenges for NF are the natural inertia of nitrogenous molecules and the competitive hydrogen evolution reaction (HER). Recently, carbon-based materials have made significant progress due to their tunable electronic structure and ease of defect formation. These properties significantly enhance electrocatalytic and photocatalytic nitrogen reduction reaction (NRR) activity. While transition metal-based catalysts have solved the kinetic constraints to activate nitrogen bonds via the donation-back-π approach, there is a problem: the d-orbital electrons of these transition metal atoms tend to generate H-metal bonds, inadvertently amplifying unwanted HER. Because of this, a timely review of defective carbon-based electrocatalysts for NF is imperative. Such a review will succinctly capture recent developments in both experimental and theoretical fields. It will delve into multiple defective engineering approaches to advance the development of ideal carbon-based electrocatalysts and photocatalysts. Furthermore, this review will carefully explore the natural correlation between the structure of these defective carbon-based electrocatalysts and photocatalysts and their NF activity. Finally, novel carbon-based catalysts are introduced to obtain more efficient performance of NF, paving the way for a sustainable future.