posted on 2024-01-03, 20:14authored byHengyu Lin, Yihao Yang, Brian G. Diamond, Tian-Hao Yan, Vladimir I. Bakhmutov, Kelechi W. Festus, Peiyu Cai, Zhifeng Xiao, Mingwan Leng, Ibukun Afolabi, Gregory S. Day, Lei Fang, Christopher H. Hendon, Hong-Cai Zhou
3D metal–organic frameworks (MOFs) have gained
attention
as heterogeneous photocatalysts due to their porosity and unique host–guest
interactions. Despite their potential, MOFs face challenges, such
as inefficient mass transport and limited light penetration in photoinduced
energy transfer processes. Recent advancements in organic photocatalysis
have uncovered a variety of photoactive cores, while their heterogenization
remains an underexplored area with great potential to build MOFs.
This gap is bridged by incorporating photoactive cores into 2D MOF
nanosheets, a process that merges the realms of small-molecule photochemistry
and MOF chemistry. This approach results in recyclable heterogeneous
photocatalysts that exhibit an improved mass transfer efficiency.
This research demonstrates a bottom-up synthetic method for embedding
photoactive cores into 2D MOF nanosheets, successfully producing variants
such as PCN-641-NS, PCN-643-NS, and PCN-644-NS. The synthetic conditions
were systematically studied to optimize the crystallinity and morphology
of these 2D MOF nanosheets. Enhanced host–guest interactions
in these 2D structures were confirmed through various techniques,
particularly solid-state NMR studies. Additionally, the efficiency
of photoinduced energy transfer in these nanosheets was evidenced
through photoborylation reactions and the generation of reactive oxygen
species (ROS).