Effect of POSS Size on the Porosity and Adsorption Performance of Hybrid Porous Polymers

Abstract

Polyhedral oligomeric silsesquioxanes (POSS), with unique cage-like three-dimensional (3D) structures, have been considered as promising nanoblocks for novel hybrid porous polymers (HPPs). To date, T 8 POSS-based HPPs have been extensively studied, while the potential of larger POSS remains elusive and intriguing. Herein, we report the synthesis of a series of T 8 , T 10 , and T 12 POSS-based HPPs (T 8 TPM, T 10 TPM, and T 12 TPM) and investigate their size-dictated structure−property relationships. These novel HPPs with identical composition yet distinct framework topologies are available through Friedel−Crafts polymerization of octa-, deca-, and dodeca-vinyl POSS with triptycene in a fixed mass ratio. It is found that the structures and properties of these materials are highly related to the POSS type and, more importantly, display an almost linear increase with increasing POSS size. Specifically, the surface area, pore volume, and adsorption capacity of T 12 TPM are 1214.8 m 2 g −1 , 1.00 cm 3 g −1 , and 4462.4 mg g −1 (Rhodamine B), showing an increase of 13.2, 56.3, and 37.9% compared with T 8 TPM, respectively. These results demonstrate the profound influence of the POSS size on the structure−property relationship of HPPs and could be used to predict the property of larger T 14 , T 16 , and T 18 POSS-based HPPs. This calls for future endeavors in the exploration of larger POSSbased HPPs.

High‐Performance Low‐k Poly(dicyclopentadiene) Nanocomposites as Achieved via Reactive Blending with Norbornene‐Functionalized Larger POSS

“…[5,45] As for PT 10 N 10 and PT 12 N 12 , it is obviously that they possess lower k values than PT 8 N 8 even at same T n N n loadings (Figure 3c), it may be due to the incorporation of larger cavity from larger POSS. [15,28,32,40] Among them, PT 12 N 12 -40 has the minimum k value (2.10 at 10 3 Hz). Compared with the decrease rates of the k values (compared to the k value of PT 8 N 8 -x) for PT n N n materials, we deduce that the contribution of larger POSS to the k values is considerable even only 5 wt% T n N n contained (consists of ≈0.9 wt% POSS cage).…”

“…have been considered as ideal pore generators for reducing the materials' k values. [15,[25][26][27][28][29][30][31][32] Meanwhile, the organic-inorganic hybrid nature and high reactivity of POSSs endow the resulting materials high thermal [28,[32][33][34][35] and mechanical performance, [36,37] large surface area and pore volume, [38][39][40][41] and unique surface properties. [42,43] Recently, we demonstrated that larger POSS (i.e., T 10 and T 12 POSSs) is better nano-building block and filler for fabricating thermally and mechanically robust low-k materials.…”

Rationally Engineered Ultrastable Three-Dimensional (3D) Conjugated Microporous Polymers Containing Triptycene, Tetraphenylethene, and Benzothiadiazole Units as Exceptional High-Performance Organic Electrodes for Supercapacitors

“…45 In addition, Fu et al have reported the different functional POSS such as (T 8 , T 10 , and T 12 ) units with the triptycene components to form organic/inorganic hybrid POPs. 46 Energy density, power capacity, and long cycle stability are essential requirements for an electrode material in energy storage devices. Considering these three factors, we inserted a highly functional unit into a network structure to be a new material and made it a component of an energy storage device.…”

“…Benefiting from the extensive functional sites, Fang et al synthesized a 3D stp-topologized COFs with a porphyrin or metalloporphyrin building unit . In addition, Fu et al have reported the different functional POSS such as ( T 8 , T 10 , and T 12 ) units with the triptycene components to form organic/inorganic hybrid POPs …”

Cation Adsorption in TiO2 Nanotubes: Implication for Water Decontamination

“…However, the undesired consequence is the production of waste, which has to be further processed. The new strategies for water remediation are based on carbon, polymeric and organic materials, inorganic composites, and hybrid inorganic–organic materials. − The aforementioned materials are employed as adsorbents, photocatalysts, and biocatalysts in water recovery processes. Although numerous methods are available for water remediation, adsorption has been recognized as a method of choice, due to its efficiency, simple design, and performance.…”