| Institution: | 1. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001 China
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049 China;2. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001 China;3. Department of Materials Science and Engineering, Beijing Jiaotong University, Beijing, 100044 China;4. University of Saskatchewan, Saskatoon, Canada |
| Abstract: | A fundamental understanding of the nature of nuclearity effects is important for the rational design of superior sub-nanocatalysts with low nuclearity, but remains a long-standing challenge. Using atomic layer deposition, we precisely synthesized Fe sub-nanocatalysts with tunable nuclearity (Fe1–Fe4) anchored on N,O-co-doped carbon nanorods (NOC). The electronic properties and spin configuration of the Fe sub-nanocatalysts were nuclearity dependent and dominated the H2O2 activation modes and adsorption strength of active O species on Fe sites toward C?H oxidation. The Fe1-NOC single atom catalyst exhibits state-of-the-art activity for benzene oxidation to phenol, which is ascribed to its unique coordination environment (Fe1N2O3) and medium spin state (t2g4eg1); turnover frequencies of 407 h?1 at 25 °C and 1869 h?1 at 60 °C were obtained, which is 3.4, 5.7, and 13.6 times higher than those of Fe dimer, trimer, and tetramer catalysts, respectively. |
