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Heterogeneous Iridium Single-Atom Molecular-like Catalysis for Epoxidation of Ethylene.
Yang, Hongling; Wang, Xiaoxu; Liu, Qinggang; Huang, Aijian; Zhang, Xun; Yu, Yi; Zhuang, Zewen; Li, Ganggang; Li, Yang; Peng, Qing; Chen, Xin; Xiao, Hai; Chen, Chen.
Afiliação
  • Yang H; Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing 100084, China.
  • Wang X; Beijing Key Laboratory for VOCs Pollution Prevention and Treatment Technology and Application of Urban Air, Beijing Municipal Research Institute of Eco-Environmental Protection, Beijing 100037, China.
  • Liu Q; DP Technology, Beijing 100080, China.
  • Huang A; Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing 100084, China.
  • Zhang X; Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing 100084, China.
  • Yu Y; School of Physical Science and Technology, Shanghai Tech University, Shanghai 201210, China.
  • Zhuang Z; School of Physical Science and Technology, Shanghai Tech University, Shanghai 201210, China.
  • Li G; Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing 100084, China.
  • Li Y; College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, China.
  • Peng Q; National Engineering Laboratory for VOCs Pollution Control Material & Technology, Research Center for Environmental Material and Pollution Control Technology, University of Chinese Academy of Sciences, Beijing 101408, China.
  • Chen X; Beijing Single-Atom Catalysis Technology Co., Ltd., Beijing 100094, China.
  • Xiao H; Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing 100084, China.
  • Chen C; Beijing Advanced Innovation Center for Materials Genome Engineering, Institute of Solid State Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
J Am Chem Soc ; 145(12): 6658-6670, 2023 Mar 29.
Article em En | MEDLINE | ID: mdl-36802612
Developing efficient and simple catalysts to reveal the key scientific issues in the epoxidation of ethylene has been a long-standing goal for chemists, whereas a heterogenized molecular-like catalyst is desirable which combines the best aspects of homogeneous and heterogeneous catalysts. Single-atom catalysts can effectively mimic molecular catalysts on account of their well-defined atomic structures and coordination environments. Herein, we report a strategy for selective epoxidation of ethylene, which exploits a heterogeneous catalyst comprising iridium single atoms to interact with the reactant molecules that act analogously to ligands, resulting in molecular-like catalysis. This catalytic protocol features a near-unity selectivity (99%) to produce value-added ethylene oxide. We investigated the origin of the improvement of selectivity for ethylene oxide for this iridium single-atom catalyst and attributed the improvement to the π-coordination between the iridium metal center with a higher oxidation state and ethylene or molecular oxygen. The molecular oxygen adsorbed on the iridium single-atom site not only helps to strengthen the adsorption of ethylene molecule by iridium but also alters its electronic structure, allowing iridium to donate electrons into the double bond π* orbitals of ethylene. This catalytic strategy facilitates the formation of five-membered oxametallacycle intermediates, leading to the exceptionally high selectivity for ethylene oxide. Our model of single-atom catalysts featuring remarkable molecular-like catalysis can be utilized as an effective strategy for inhibiting the overoxidation of the desired product. Implementing the concepts of homogeneous catalysis into heterogeneous catalysis would provide new perspectives for the design of new advanced catalysts.

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: J Am Chem Soc Ano de publicação: 2023 Tipo de documento: Article

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: J Am Chem Soc Ano de publicação: 2023 Tipo de documento: Article