Three‐Dimensional Crystalline Covalent Triazine Frameworks via a Polycondensation Approach

Abstract

The growth of crystalline covalent triazine frameworks (CTFs) is still considered as a great challenge due to the less reversible covalent bonds of triazine linkages. The research studies of crystalline CTFs to date have been limited to two‐dimensional (2D) structures, and the three‐dimensional (3D) crystalline CTFs have never been reported before. Herein we report the design and synthesis of two 3D crystalline CTFs, termed 3D CTF‐TPM and 3D CTF‐TPA through a reversible/irreversible polycondensation approach. The targeted 3D CTFs adopt ctn topology, and show moderate crystallinity, relatively large surface area (ca. 2000 m2 g−1), and high CO2 uptake capacity (23.61 wt.%). Moreover, these 3D CTFs exhibit ultrastability in the presence of boiling water, strong acid (1 M HCl) and strong base (1 M NaOH). This contribution represents the first report of 3D crystalline CTFs, which not only extends their structural diversity but also offers a synthetic strategy and structural basis for expanding practical applications of CTF materials.

Carbonate-based hyper-cross-linked polymers with pendant versatile electron-withdrawing functional groups for CO2adsorption and separation

“…It is obvious that among these porous materials, polymer 3 possessing the highest BET surface area of 1367 m 2 g À1 as well as carbonyl and ester groups and nitrogen atoms has the best CO 2 uptake of 14.61 wt% at 273.15 K/1.00 bar. Although this is much lower than that of the topperforming N-containing scaffolds, [51][52][53][54][55][56] the determined CO 2 adsorption value of polymer 3, to our delight, is comparable or superior to some of the reported porous polymers, even those with larger BET surface areas or total pore volumes (Table 2), [57][58][59][60][61][62][63][64][65][66] which rmly indicates that the porosity parameters including high BET surface area, narrow pore size and pore size distribution, micropore volume, and pore volume along with the introduced functionalities such as nitrogen, carbonyl and ester groups play an essential role in increasing the CO 2 capturing performance. To gain further insight into the binding affinity of these functional polymers towards CO 2 molecules, the isosteric heat of adsorption (Q st ) of the polymers was calculated using the Clausius-Clapeyron equation according to the CO 2 adsorption isotherms measured at 273.15 K and 298.15 K. As revealed in Fig.…”

Metalated covalent organic frameworks: from synthetic strategies to diverse applications

“…75,76 However, 3D COFs have an abundant changeable topology. 77 3D COFs with ctn , 32,78 bor , 32 dia , 33,79 rra , 80 pts , 81–85 lon , 86 ljh , 87 and nbo 88 topologies have been formed based on four-connected monomers with tetrahedral T d symmetry. Six-connected monomers with trigonal prism D 3h symmetry led to stp , 89 ceq , 90 acs , 91–93 and hea 94 topologies, while D 3d - and C 3 -symmetric six-connected monomers have been implemented in the synthesis of 3D COFs with pcu 95 and soc 96 topologies, respectively.…”