Multivalent Sulfur Vacancy‐Rich NiCo<sub>2</sub>S<sub>4</sub>@MnO<sub>2</sub> Urchin‐Like Heterostructures for Ambient Electrochemical N<sub>2</sub> Reduction to NH<sub>3</sub>
Muhammad Asim Mushtaq, Anuj Kumar, Ghulam Yasin, Mohammad Tabish, Muhammad Arif, Saira Ajmal, Waseem Raza, Sajid Naseem, Jie Zhao, Pengyan Li, Hina Ghulam Ali, Shengfu Ji, Dongpeng Yan
Abstract
Abstract Innovative advances in the exploitation of effective electrocatalytic materials for the reduction of nitrogen (N 2 ) to ammonia (NH 3 ) are highly required for the sustainable production of fertilizers and zero‐carbon emission fuel. In order to achieve zero‐carbon footprints and renewable NH 3 production, electrochemical N 2 reduction reaction (NRR) provides a favorable energy‐saving alternative but it requires more active, efficient, and selective catalysts. In current work, sulfur vacancy (Sv)‐rich NiCo 2 S 4 @MnO 2 heterostructures are efficaciously fabricated via a facile hydrothermal approach followed by heat treatment. The urchin‐like Sv‐NiCo 2 S 4 @MnO 2 heterostructures serve as cathodes, which demonstrate an optimal NH 3 yield of 57.31 µg h −1 mg cat −1 and Faradaic efficiency of 20.55% at −0.2 V versus reversible hydrogen electrode (RHE) in basic electrolyte owing to the synergistic interactions between Sv‐NiCo 2 S 4 and MnO 2 . Density functional theory (DFT) simulation further verifies that Co‐sites of urchin‐like Sv‐NiCo 2 S 4 @MnO 2 heterostructures are beneficial to lowering the energy threshold for N 2 adsorption and successive protonation. Distinctive micro/nano‐architectures exhibit high NRR electrocatalytic activities that might motivate researchers to explore and concentrate on the development of heterostructures for ambient electrocatalytic NH 3 generation.