Improved Ammonia Synthesis and Energy Output from Zinc-Nitrate Batteries by Spin-State Regulation in Perovskite
Hele Guo1,2, Yazhou Zhou3,4, Kaibin Chu1,2
1The Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China.
Abstract:
Electrocatalytic nitrate reduction to ammonia (eNRA) is a promising route toward environmental sustainability and clean energy. However, its efficiency is often limited by the slow conversion of intermediates due to spin-forbidden processes. Here, we introduce a novel A-site high-entropy strategy to develop a new perovskite oxide (La0.2Pr0.2Nd0.2Ba0.2Sr0.2)CoO3-δ (LPNBSC) for eNRA. The LPNBSC possesses a higher concentration of high-spin (HS) cobalt-active centers, resulting from an increased concentration of [CoO5] structural motifs compared to conventional LaCoO3. Consequently, this material exhibits a significantly improved electrocatalytic performance toward ammonia (NH3) production, resulting in a 3-fold increase in yield rate (129 μmol h-1 mgcat.-1) and a 2-fold increase in Faradaic efficiency (FE, 76%) compared to LaCoO3 at the optimal potential. Furthermore, the LPNBSC-based Zn-nitrate battery reaches a maximum FE of 82% and an NH3 yield rate of 57 μmol h-1 cm-2. Density functional theory calculations reveal that A-site high-entropy management in perovskites facilitates nitrate activation and potentially optimizes the thermodynamic rate-determining step of the eNRA process, namely, *HNO3 + H+ + e- → *NO2 + H2O. This work presents an efficient concept for modulating the spin state of the B-site metal in perovskites and offers valuable insights for the design of high-performance eNRA catalysts.
