Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 120, Issue 14, Pages -Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.2218261120
Keywords
Fe single atom; asymmetric coordination; -like carbon nanochannels; poke-like carbon nanochannels; epoxide ring-opening reaction; robust catalytic application
Categories
Ask authors/readers for more resources
This study reports a method for constructing Fe single-atom catalysts (SACs) with nitrogen (N) and phosphorus (P) asymmetric coordination using mesoporous carbon nanospheres (MCNs) with spoke-like nanochannels. The introduction of phosphorus atoms promotes the symmetry-breaking of common four nitrogen-coordinated iron sites, resulting in the formation of Fe-N3P-MCN catalysts with an asymmetric electronic configuration and superior catalytic capability. The Fe-N3P-MCN catalysts exhibit high catalytic activity for the ring-opening reaction of epoxide (97% yield) compared to Fe-N3P on nonporous carbon surface (91%) and Fe-N4 SACs on the same MCN support (89%). Density functional theory calculations reveal that Fe-N3P SACs lower the activation barrier for the C-O bond cleavage and the C-N bond formation, thus accelerating the ring-opening of epoxide. This study provides fundamental and practical insights into developing advanced catalysts in a simple and controllable manner for multistep organic reactions.
The ability to construct metal single-atom catalysts (SACs) asymmetrically coordi-nated with organic heteroatoms represents an important endeavor toward developing high-performance catalysts over symmetrically coordinated counterparts. Moreover, it is of key importance in creating supporting matrix with porous architecture for situating SACs as it greatly impacts the mass diffusion and transport of electrolyte. Herein, we report the crafting of Fe single atoms with asymmetrically coordinated nitrogen (N) and phosphorus (P) atoms scaffolded by rationally designed mesoporous carbon nanospheres (MCNs) with spoke-like nanochannels for boosting ring-opening reaction of epoxide to produce an array of pharmacologically important beta-amino alcohols. Notably, interfacial defects in MCN derived from the use of sacrificial tem-plate create abundant unpaired electrons, thereby stably anchoring N and P atoms and in turn Fe atoms on MCN. Importantly, the introduction of P atom promotes the symmetry-breaking of common four N-coordinated Fe sites, resulting in the Fe-N3P sites on MCN (denoted Fe-N3P-MCN) with an asymmetric electronic con-figuration and thus superior catalytic capability. As such, the Fe-N3P-MCN catalysts manifest a high catalytic activity for ring-opening reaction of epoxide (97% yield) over the Fe-N3P docked on nonporous carbon surface (91%) as well as the sole Fe-N4 SACs grounded on the same MCN support (89%). Density functional theory calculations reveal that Fe-N3P SAC lowers the activation barrier for the C-O bond cleavage and the C-N bond formation, thus accelerating the ring-opening of epoxide. Our study provides fundamental and practical insights into developing advanced catalysts in a simple and controllable manner for multistep organic reactions.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available