Nano-Polycrystalline Cu Layer Interlaced with Ti3+-Self-Doped TiO2 Nanotube Arrays as an Electrocatalyst for Reduction of Nitrate to Ammonia

Abstract

The electrochemical nitrate reduction reaction (NO₃RR) is considered as a promising strategy to degrade nitrate-containing wastewater and synthesize recyclable ammonia at atmospheric pressure and room temperature. In this work, the copper oxides-derived nano-polycrystalline Cu (NPC Cu) was integrated with Ti³⁺-self-doped TiO₂ nanotube arrays (NTA) to fabricate the NPC Cu/H-TiO₂ NTA. Ti³⁺-self-doped TiO₂ NTAs and the NPC Cu facilitate electron transfer and mass transportation and create abundant active sites. The unique nanostructure in which Cu nano-polycrystals interlace with the TiO₂ nanotube accelerates the electron transfer from the substrate to surface NPC Cu. The density functional theory calculations confirm that the built-in electric field between Cu and TiO₂ improves the adsorption characteristic of the NPC Cu/H-TiO₂ NTA, thereby converting the endothermic NO₃^- adsorption step into an exothermic process. Therefore, the high NO₃^- conversion of 98.97%, the Faradic efficiency of 95.59%, and the ammonia production yield of 0.81 mg cm^-2 h^-1 are achieved at -0.45 V vs reversible hydrogen electrode in 10 mM NaNO₃ (140 mg L^-1)-0.1 M Na₂SO₄. This well-designed NPC Cu/H-TiO₂ NTA as an effective electrocatalyst for the 8e^- NO₃RR possesses promising potential in the applications of ammonia production.

Keywords: Ti3+-self-doping; TiO2 nanotube arrays; built-in electric field; electrochemical reduction of nitrate; nano-polycrystalline Cu.