Boosting Electrocatalytic Ammonia Synthesis via Synergistic Effect of Iron-Based Single Atoms and Clusters
Li Xu, Tong Liu, Dong Liu, Airong Xu, Sicong Wang, Hui Huang, Xiaokang Liu, Mei Sun, Qiquan Luo, Xusheng Zheng, Tao Ding, Tao Yao
Abstract
Electrocatalytic reduction of nitrate to ammonia (NO 3 RR) is gaining attention for low carbon emissions and environmental protection. However, low ammonia production rate and poor selectivity have remained major challenges in this multi-proton coupling process. Herein, we report a facile strategy toward a novel Fe-based hybrid structure composed of Fe single atoms and Fe 3 C atomic clusters that demonstrates outstanding performance for synergistic electrocatalytic NO 3 RR. By operando synchrotron Fourier transform infrared spectroscopy and theoretical computation, we clarify that Fe single atoms serve as the active site for NO 3 RR, while Fe 3 C clusters facilitate H 2 O dissociation to provide protons (*H) for continued hydrogenation reactions. As a result, the Fe-based electrocatalyst exhibits ammonia Faradaic efficiency of nearly 100%, with a corresponding production rate of 24768 μg h –1 cm –2 at −0.4 V vs RHE, exceeding most reported metal-based catalysts. This research provides valuable guidance toward multi-step reactions.