Tunable Surface Area, Porosity, and Function in Conjugated Microporous Polymers

Abstract

Simple inorganic salts are used to tune N‐containing conjugated microporous polymers (CMPs) synthesized by Buchwald–Hartwig (BH) cross‐coupling reactions. Poly(triphenylamine), PTPA, initially shows a broad distribution of micropores, mesopores, and macropores. However, the addition of inorganic salts affects all porous network properties significantly: the pore size distribution is narrowed to the microporous range only, mimicking COFs and MOFs; the BET surface area is radically improved from 58 m2 g−1 to 1152 m2 g−1; and variations of the anion and cation sizes are used to fine‐tune the surface area of PTPA, with the surface area showing a gradual decrease with an increase in the ionic radius of salts. The effect of the salt on the physical properties of the polymer is attributed to adjusting and optimizing the Hansen solubility parameters (HSPs) of solvents for the growing polymer, and named the Beijing–Xi'an Jiaotong (BXJ) method.

Exploiting Hansen solubility parameters to tune porosity and function in conjugated microporous polymers

“…The materials were initially a light brown colour under a N 2 atmosphere during the polymerization, but gradually turned dark with increasing exposure to air, conrming the successful construction of C-N bonds and a PANi-type structure by BH coupling. 22 Additionally, their molecular structures were conrmed by Fourier transform infrared (FTIR) and solid-state 13 C cross-polarization magic angle spinning nuclear magnetic resonance (SS 13 C CP/MAS NMR). As shown in Fig.…”

“…14,15 Moreover, such materials possessed unexpectedly low micropore volumes and broad pore size distributions (PSDs) when compared, for example, with structurally similar poly(aryleneethynylene)s (PAEs). 14,15 To address this unexpected challenge, we have shown in a recent paper 22 that the surface area of a model BHsynthesized CMP, polytriphenylamine (PTPA), could be netuned and optimized by the addition of inorganic salts to the reaction mixtures. This approach, termed the Bristol-Xi'an Jiaotong (BXJ) approach, yielded PTPA with a 20 times higher surface area than the standard reaction.…”

“…Our developed approaches therefore present an opportunity to tune surface area and porosity, potentially for a range of amorphous polymers. However, this potentially impactful methodology has only been applied in one specic instance in our rst published study, 22 and its general applicability to create a design tool for wider application remains to be fully explored.…”

High‐Yield Synthesis of Pyridyl Conjugated Microporous Polymer Networks with Large Surface Areas: From Molecular Iodine Capture to Metal‐Free Heterogeneous Catalysis

“…The C 1s core-level XPS spectra reflects that the nitrogen atoms are attributed to CN, CCN, CCC, CH and sp 2 satellite of CC (Figure 1e), respectively. [25] Thermal analyses suggest that PCMP-Y2, 3, 4, 5, and 6 are more stable than the pure polymers PCMP-Y1 and PCMP-Y7 ( Figure S4, Supporting Information). Therefore, above analyses verify the successful syntheses of the designed CMPs with different pyridine contents.…”

Molecular Expansion for Constructing Porous Organic Polymers with High Surface Areas and Well‐Defined Nanopores

“…[8] In addition to predetermined building units and various synthetic methods,h igh surface areas and well-defined nanopores are also important inherent properties of POPs,w hich endow POPs with unique potentials and novel phenomena in nanoscale areas. [9] Specially,t he high surface area can provide large nanometer-sized space for storage, [10][11][12] enhance catalytic performance, [13] improve membrane permeability and separation performance, [14,15] and facilitate charge dynamics and photoenergy conversions. [16,17] Notably,t hree-dimensional (3D) porous networks recently attracted much attention owing to their high surface area and well-defined nanopores.…”