Ti-doped iron phosphide nanoarrays grown on carbon cloth as a self-supported electrode for enhanced electrocatalytic nitrogen reduction

The electrocatalytic nitrogen reduction reaction (eNRR) has been widely recognized as a promising method for green ammonia synthesis. However, the inert NN bond, inferior catalytic activity and small electrochemically active area impede its practical application. To circumvent these problems, we proposed self-supported Ti-doped iron phosphide (FeP) nanorod arrays grown on carbon cloth (Ti-FeP/CC) as an electrode for eNRR. The introduction of Ti doping sites regulated the electron structure of FeP, leading to electron migration from Fe to P, which facilitated N₂-to-NH₃ conversion. The as-prepared Ti-FeP/CC showed an enhancement of electrochemical surface area (ECSA), high electrical conductivity and well-exposed active sites. Ti-FeP/CC was capable of producing a high NH₃ yield of 10.93 μg h^-1 cm^-2 and faradaic efficiency of 10.77% at an optimal voltage of -0.3 V (vs. RHE) in a 0.1 M Na₂SO₄ solution with excellent stability and durability during the eNRR process. This work not only presents a promising electrode material for eNRR, but also provides a new insight into rational heteroatom doping for electrocatalysis.