TY - JOUR
T1 - Unprecedented Application of Covalent Organic Frameworks for Polymerization Catalysis
T2 - Rh/TPB-DMTP-COF in Polymerization of Phenylacetylene and Its Functional Derivatives
AU - Cao, Qingbin
AU - Zhang, Shaowen
AU - Zhang, Li
AU - Gao, Fei
AU - Chen, Jupeng
AU - Dong, Yuping
AU - Li, Xiaofang
N1 - Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/3/24
Y1 - 2021/3/24
N2 - Covalent organic frameworks (COFs) are applied widely in organic catalysis; however, no precedent has been reported in polymerization catalysis. Herein, we report the new application of COFs for polymerization catalysis. Different amounts of homogeneous Rh catalyst are incorporated into the COF via post-treatment to give a series of TPB-DMTP-COF-X wt % Rh (b-e) containing varying amounts of Rh from 2.74 to 11.38 wt %. In contrast to the known Rh catalysts, TPB-DMTP-COF-X wt % Rh (b-e) display an uncommon synergistic effect and exceptional steric confinement effect of nanochannels. Therefore, they possess the advantages of both homogeneous catalysts in high activity and selectivity and heterogeneous catalysts in stability and recyclability with extremely high activity up to 1.3 × 107 g·molRh-1·h-1 and cis-selectivity up to 99% and can be readily recycled and reused five times in the polymerization of phenylacetylene and its derivatives, affording cis-transoidal polyphenylacetylene and its derivatives having helical structures, aggregation-induced emission properties, or fluorescence properties with narrow molecular weight distributions.
AB - Covalent organic frameworks (COFs) are applied widely in organic catalysis; however, no precedent has been reported in polymerization catalysis. Herein, we report the new application of COFs for polymerization catalysis. Different amounts of homogeneous Rh catalyst are incorporated into the COF via post-treatment to give a series of TPB-DMTP-COF-X wt % Rh (b-e) containing varying amounts of Rh from 2.74 to 11.38 wt %. In contrast to the known Rh catalysts, TPB-DMTP-COF-X wt % Rh (b-e) display an uncommon synergistic effect and exceptional steric confinement effect of nanochannels. Therefore, they possess the advantages of both homogeneous catalysts in high activity and selectivity and heterogeneous catalysts in stability and recyclability with extremely high activity up to 1.3 × 107 g·molRh-1·h-1 and cis-selectivity up to 99% and can be readily recycled and reused five times in the polymerization of phenylacetylene and its derivatives, affording cis-transoidal polyphenylacetylene and its derivatives having helical structures, aggregation-induced emission properties, or fluorescence properties with narrow molecular weight distributions.
KW - alkyne
KW - covalent organic framework
KW - heterogeneous catalysis
KW - polymerization
KW - supported catalysts
UR - http://www.scopus.com/inward/record.url?scp=85103491449&partnerID=8YFLogxK
U2 - 10.1021/acsami.1c00512
DO - 10.1021/acsami.1c00512
M3 - Article
C2 - 33709703
AN - SCOPUS:85103491449
SN - 1944-8244
VL - 13
SP - 13693
EP - 13704
JO - ACS applied materials & interfaces
JF - ACS applied materials & interfaces
IS - 11
ER -