Abstract
AbstractNitrogen‐doped, carbon‐supported transition metal catalysts are excellent for several reactions. Structural engineering of M−Nx sites to boost catalytic activity is rarely studied. Here, we demonstrate that the structural flexibility of Fe−N3 site is vital for tuning the electronic structure of Fe atoms and regulating the catalytic transfer hydrogenation (CTH) activity. By introducing carbon defects, we construct Fe−N3 sites with varying Fe−N bond lengths distinguishable by X‐ray absorption spectroscopy. We investigate the CTH activity by density‐functional theory and microkinetic calculations and reveal that the vertical displacement of the Fe atom out of the plane of the support, induced by the Fe−N3 distortion, raises the Fe orbital and strengthens binding. We propose that the activity is controlled by the relaxation of the reconstructed site, which is further affected by Fe−N bond length, an excellent activity descriptor. We elucidate the origin of the CTH activity and principles for high‐performing Fe−N−C catalysts by defect engineering.
Published Version
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
