Spin engineering of single-site metal catalysts
Zichuang Li, Ruguang Ma, Qiangjian Ju, Qian Liu, Lijia Liu, Yufang Zhu, Minghui Yang, Jiacheng Wang
Abstract
•Single-site FeN4 species are designed to dangle over axial carbon micropores (d-FeN4)•d-FeN4 shows much superior oxygen reduction reactivity to traditional FeN4•d-FeN4 facilitates the formation of singlet-state oxygen-containing species with optimized spin states by micropore•This work provides in-depth understanding of spin tuning for advanced catalyst design Single-site metal atoms (SMAs) on supports are attracting extensive interest as new catalytic systems because of maximized atom utilization and superior performance. However, rational design of configuration-optimized SMAs with high activity from the perspectives of fundamental electron spin is highly challenging. Herein, N-coordinated Fe single atoms are successfully distributed over axial carbon micropores to form dangling-FeN4 centers (d-FeN4). This unique d-FeN4 demonstrates much higher intrinsic activity toward oxygen reduction reaction (ORR) in HClO4 than FeN4 without micropore underneath and commercial Pt/C. Both theoretical calculation and electronic structure characterization imply that d-FeN4 endows central Fe with medium spin (t2g4 eg1), which provides a spin channel for electron transition compared with FeN4 with low spin. This leads to the facile formation of the singlet state of oxygen-containing species from triplet oxygen during the ORR, thus showing faster kinetics than FeN4. This work provides an in-depth understanding of spin tuning on SMAs for advanced energy catalysis. Single-site metal atoms (SMAs) on supports are attracting extensive interest as new catalytic systems because of maximized atom utilization and superior performance. However, rational design of configuration-optimized SMAs with high activity from the perspectives of fundamental electron spin is highly challenging. Herein, N-coordinated Fe single atoms are successfully distributed over axial carbon micropores to form dangling-FeN4 centers (d-FeN4). This unique d-FeN4 demonstrates much higher intrinsic activity toward oxygen reduction reaction (ORR) in HClO4 than FeN4 without micropore underneath and commercial Pt/C. Both theoretical calculation and electronic structure characterization imply that d-FeN4 endows central Fe with medium spin (t2g4 eg1), which provides a spin channel for electron transition compared with FeN4 with low spin. This leads to the facile formation of the singlet state of oxygen-containing species from triplet oxygen during the ORR, thus showing faster kinetics than FeN4. This work provides an in-depth understanding of spin tuning on SMAs for advanced energy catalysis.