Abstract
A series of conjugated microporous polymers (CMPs) based on 1,3,6,8-tetrabromocarbazole (N4CMP-1–5) is synthesized via Suzuki cross-coupling or Sonogashira polycondensation. The porosity properties and surface area of these polymer networks can be finely tuned by using a linker with different geometries or strut length. These polymers show the Brunauer-Emmett-Tellerthe (BET) surface areas ranging from 592 to 1426 m2 g−1. The dominant pore sizes of the polymers on the basis of the different linker are located between 0.36 and 0.61 nm. Gas uptake increases with BET surface area and micropore volume, N4CMP-3 polymer can capture CO2 with a capacity of 3.62 mmol g−1 (1.05 bar and 273 K) among the obtained polymers. All of the polymers show high isosteric heats of CO2 adsorption (25.5–35.1 kJ mol−1), and from single component adsorption isotherms, IAST-derived ideal CO2/N2 (28.7–53.8), CO2/CH4 (4.6–5.2) and CH4/N2 (5.7–10.5) selectivity. Furthermore, N4CMPs exhibit the high CO2 adsorption capacity of 542–800 mg g−1 at 318 K and 50 bar pressure. These data indicate that these materials are a promising potential for clean energy application and environmental field.
Highlights
In recent years, the global climate change mainly caused by excessive carbon dioxide (CO2) emissions has drawn great attentions and concerns[1]
Some reports have revealed that the introduction of some polar functional groups or heteroatoms into porous materials could enhance the binding affinity between the adsorbent and CO2 molecules, which leads to the increase of CO2 capture capacity[27,28,29,30]
We found that N4CMP-1 and N4CMP-2 have similar micropore surface area, N4CMP-1 shows the relatively higher CO2 uptake, possible reason is that N4CMP-1 has high micropore volume (Table S1)
Summary
The global climate change mainly caused by excessive carbon dioxide (CO2) emissions has drawn great attentions and concerns[1]. Introduction of the carbazole unit into the polymer skeleton makes the porous materials electron-rich to enhance CO2 uptake of porous polymers, and the steric configuration of linker monomer can effectively construct and adjust the microporous volume and reach outstanding gas storage and separation capacity[31,32,33]. With these considerations in mind, we prepared a series of CMPs (Fig. 1, N4CMP-1–5) based on 1,3,6,8-tetrabromocarbazole as the basic buliding block via Pd-catalyzed Suzuki cross-coupling or Sonogashira polycondensation. N4CMP polymer networks exhibit high CO2 adsorption capacity at high pressure condition
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