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Identification of the Electronic and Structural Dynamics of Catalytic Centers in Single-Fe-Atom Material

Journal Article · · Chem
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [8];  [5];  [9];  [6];  [10];  [10];  [11];  [4];  [3];  [9];  [2];  [7];  [12] more »;  [7];  [5] « less
  1. Nanyang Technical Univ. (Singapore); Chinese Academy of Sciences (CAS), Dalian (China). Dalian Inst. of Chemical Physics, State Key Lab. of Catalysis
  2. Tsinghua Univ., Beijing (China). Key Lab. of Organic Optoelectronics & Molecular Engineering
  3. National Taiwan Univ., Taipei (Taiwan)
  4. National Synchrotron Radiation Research Center, Hsinchu (Taiwan)
  5. Nanyang Technical Univ. (Singapore)
  6. Chinese Academy of Sciences (CAS), Dalian (China). Dalian Inst. of Chemical Physics, Mössbauer Effect Data Center
  7. Chinese Academy of Sciences (CAS), Dalian (China). Dalian Inst. of Chemical Physics, State Key Lab. of Catalysis
  8. Inst. of Chemical and Engineering Sciences (Singapore)
  9. Nanyang Technological Univ. (Singapore)
  10. Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
  11. Chinese Academy of Sciences (CAS), Beijing (China). Inst. of High Energy Physics (IHEP), Beijing Synchrotron Radiation Facility
  12. Tsinghua Univ., Beijing (China). Key Lab. of Organic Optoelectronics & Molecular Engineering; Southern Univ. of Science and Technology, Shenzhen (China)
+ Show Author Affiliations
The lack of model single-atom catalysts (SACs) and atomic-resolution operando spectroscopic techniques greatly limits our comprehension of the nature of catalysis. Herein, based on the designed model single-Fe-atom catalysts with well-controlled microenvironments, we have explored the exact structure of catalytic centers and provided insights into a spin-crossover-involved mechanism for oxygen reduction reaction (ORR) using operando Raman, X-ray absorption spectroscopies, and the developed operando 57Fe Mössbauer spectroscopy. In combination with theoretical studies, the N-FeN4C10 moiety is evidenced as a more active site for ORR. Moreover, the potential-relevant dynamic cycles of both geometric structure and electronic configuration of reactive single-Fe-atom moieties are evidenced via capturing the peroxido (*O2-) and hydroxyl (*OH-) intermediates under in situ ORR conditions. Overall, we anticipate that the integration of operando techniques and SACs in this work shall shed some light on the electronic-level insight into the catalytic centers and underlying reaction mechanism.
Research Organization:
Argonne National Laboratory (ANL)
Sponsoring Organization:
Chinese Academy of Sciences (CAS) - Strategic Priority Research Program; Nanyang Technological University (NTU); National Natural Science Foundation of China (NSFC); USDOE
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1823273
Journal Information:
Chem, Journal Name: Chem Journal Issue: 12 Vol. 6; ISSN 2451-9294
Publisher:
Cell Press, ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Mössbauer
Single-atom catalysis
dynamic cycles
electrocatalysis
electronic structure
intermediates
operando
oxygen reduction reaction