Triazatruxene-Based Ordered Porous Polymer: High Capacity CO2, CH4, and H2 Capture, Heterogeneous Suzuki–Miyaura Catalytic Coupling, and Thermoelectric Properties

A. E. Sadak*, E. Karakuş*, Y. Chumakov, N. A. Dogan, C. T. Yavuz 
ACS Appl. Energy Mater., 3, 5, 4983–4994 (2020). 

A hypercrosslinked ultramicroporous and ordered organic polymer network was synthesized from a planar trimer indole building block called triazatruxene (TAT) through anhydrous FeCl3 catalyzed Friedel–Crafts alkylation using methylal as a crosslinker. The polymer network is stable in a variety of chemicals and thermally durable. The hypercrosslinked network TATHCP shows a high BET (Brunauer–Emmet–Teller) specific surface area of 997 m2 g–1 with CO2 uptake capacity of 12.55 wt % at 273 K, 1.1 bar. Gas selectivities of 38.4 for CO2/N2, 7.8 for CO2/CH4, 40.6 for CO2/O2, and 32.1 for CO2/CO were achieved through IAST calculation. The PXRD analysis has revealed that TATHCP has a fully eclipsed structure in full agreement with Pawley refinement. The ordered 2D layers provide anisotropy that could be used in catalysis and thermoelectric measurements. After loading with Pd(II), TATHCP-Pd showed high catalytic activity in Suzuki–Miyaura cross coupling reaction with a wide range of reagents and excellent reaction yields of 90–98% with good recyclability. The structure of TATHCP-Pd was found to have two independent molecules of Pd(OAc)2 in the asymmetric unit cell which are arranged between two TATHCP layers. Thermoelectric properties of TATHCP showed a high Seebeck coefficient and ZT, a first and promising example in HCPs with applications in all-organic thermal energy recovery devices.
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