TY - JOUR
T1 - Ionic porous porphyrin cage as a superior catalyst for photocatalytic oxidization
AU - Li, Cheng
AU - Cui, Jing Wang
AU - Zhou, Jun Hao
AU - Xu, Yanqing
AU - Sun, Jian Ke
N1 - Publisher Copyright:
© 2024 The Royal Society of Chemistry.
PY - 2024/1/31
Y1 - 2024/1/31
N2 - Aggregation-induced deactivation has long been a challenge in the field of photocatalysis based on molecular porphyrin derivative-based photocatalysts. The development of polyhedral porphyrin cage-based heterogeneous catalysts has shown promise in addressing this issue by preventing intermolecular face-to-face packing. However, this shift towards heterogeneous catalysis comes at the cost of catalytic activity. Herein, we report the design and synthesis of an ionic porphyrin cage, TPPCage·8I, characterized with a high charge density within the skeleton. This strategy effectively circumvents spontaneous aggregation by harnessing the electrostatic repulsion that naturally occurs between adjacent cage hosts. Furthermore, the strategic incorporation of hydrophilic iodine counteranions surrounding the cage not only modulates their solubility, making them uniformly dispersed in the solvent, but also imparts an additional heavy-atom effect. These modifications lead to substantial enhancement in photophysical properties, resulting in extraordinary catalytic activity in the photocatalytic oxidation coupling reaction of benzylamines, with a remarkable conversion rate exceeding 99% and a record turnover frequency (TOF) of 1980.0 h−1, coupled with excellent stability. In addition, the current homogeneous photocatalyst offers ease of recycling through a straightforward exchange process with a robust hydrophobic anion (sodium dodecyl sulfate, SDS).
AB - Aggregation-induced deactivation has long been a challenge in the field of photocatalysis based on molecular porphyrin derivative-based photocatalysts. The development of polyhedral porphyrin cage-based heterogeneous catalysts has shown promise in addressing this issue by preventing intermolecular face-to-face packing. However, this shift towards heterogeneous catalysis comes at the cost of catalytic activity. Herein, we report the design and synthesis of an ionic porphyrin cage, TPPCage·8I, characterized with a high charge density within the skeleton. This strategy effectively circumvents spontaneous aggregation by harnessing the electrostatic repulsion that naturally occurs between adjacent cage hosts. Furthermore, the strategic incorporation of hydrophilic iodine counteranions surrounding the cage not only modulates their solubility, making them uniformly dispersed in the solvent, but also imparts an additional heavy-atom effect. These modifications lead to substantial enhancement in photophysical properties, resulting in extraordinary catalytic activity in the photocatalytic oxidation coupling reaction of benzylamines, with a remarkable conversion rate exceeding 99% and a record turnover frequency (TOF) of 1980.0 h−1, coupled with excellent stability. In addition, the current homogeneous photocatalyst offers ease of recycling through a straightforward exchange process with a robust hydrophobic anion (sodium dodecyl sulfate, SDS).
UR - http://www.scopus.com/inward/record.url?scp=85185171440&partnerID=8YFLogxK
U2 - 10.1039/d3cy01575k
DO - 10.1039/d3cy01575k
M3 - Article
AN - SCOPUS:85185171440
SN - 2044-4753
VL - 14
SP - 1558
EP - 1567
JO - Catalysis Science and Technology
JF - Catalysis Science and Technology
IS - 6
ER -