84.0% energy-efficient nitrate conversion by a defective (Fe,Cu,Ni)2O3 electrocatalyst

• Published in: Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2024-12, Vol.12 (47), p.33023-33038
• Main Authors: Tadele Negash Gemeda, Dong-Hau, Kuo, Quoc-Nam Ha, Noto, Susanto Gultom, Wolde, Girma Sisay
• Format: Article
• Language: English
• Subjects: Ammonia; Atomic properties; Chemical reduction; Clean energy; Commercialization; Copper; Direct reduction; Electrocatalysts; Electrochemistry; Energy consumption; Energy conversion efficiency; Energy efficiency; Environmental cleanup; Environmental protection; Iron; Mass transfer; Nickel; Nitrates; Oxygen atoms; Reaction mechanisms; Trapping
• ISSN: 2050-7488; 2050-7496
• DOI: 10.1039/d4ta02801e

Decentralized ammonia (NH3) production as a way of environmental remediation for nitrate (NO3−) removal is a current issue due to the massive impact of nitrate on human well-being and the environment. Converting these contaminating NO3− species to valuable commodities such as NH3 in a green and sustainable way with a high NO3− conversion rate at low energy consumption efficiency can help to protect the environment and improve the livelihood of human beings. We synthesized an in situ grown and nanoflower-type (Fe,Cu,Ni)2O3−x electrocatalytic active material via a facile hydrothermal method. This catalyst exhibited a high NO3− conversion of 92.6% into a dominant ammonia with a selectivity of 98.3%. The NH3 was produced at a high yield rate of 9.2 mg h−1 cm−2 with faradaic efficiency (FE) of 94.8% at −0.3 V vs. the reversible hydrogen electrode (RHE) in an H-cell configuration. For a viable commercialization test, the scaled-up model of a single-stack flow cell electrolyzer was investigated and it accelerated the NH3 yield rate to 49.3 mg h−1 cm−2 and 96.0% FE while holding a high energy efficiency of 84.0% and a low energy consumption of 21.0 kW h kg−1. The NH3 yield exceeds that of the current state-of-the-art due to the reactants' continuous and high mass transfer rate on the trimetallic oxide active sites. The elucidated electrokinetic reaction mechanism reveals the direct reduction pathway enhanced by the abundant oxygen-vacancy (OV) sites in a synergetic trimetallic oxide system. These OV sites play a crucial role in the reaction mechanism by facilitating the trapping of oxygen atoms in NO3−, which are then surrounded by Fe2+/3+, Cu+, and Ni2+/3+ as sites of proton adsorption for NO3− hydrogenation. The trapping interaction enhancing the bond weakening of NO3− makes the electrochemical NO3− reduction reaction (eNO3−RR) mechanism meaningful.