Spin-state regulation by secondary coordination sphere for improved oxygen evolution activity of LaCo1-xNixO3 perovskite

Abstract

The evolution of oxygen evolution reaction (OER) remains a pivotal challenge in the realm of oxygen electrocatalysis. Recently, the proposition of regulating spin states has emerged as a novel avenue for enhancing the efficiency of electrocatalytic reactions. Presently, accurately modulating the metal active center into immediate spin (IS) remains a formidable challenge. Here, our research has achieved a breakthrough in precise spin state control and catalytic performance enhancement of Co3+ through the utilization of Ni-substituted LaCo1-xNixO3 perovskite. This achievement is primarily attributed to the fine regulation of both the secondary coordination sphere (SCS) and primary coordination sphere (PCS), i.e., Co6-y-[Co]-Niy (y = 0–6) and Co-O lengths, respectively. Our findings reveal that LaCo7/9Ni2/9O3 consisted of the SCS (y ≤ 2) with the eg1 fillings of IS Co3+ exhibits an optimal OER activity. Additionally, adjusting the Co-O bond length in PCS to approximately 1.89 Å proves to be more conducive to the transition of Co3+ spin states from high spin (HS) and low spin (LS) to IS. These discoveries present new approach to precisely modulating the spin state, offering promising prospects for the development of high-efficiency OER catalysts.