Highly Proton Conductive Phosphoric Acid Porous Organic Polymers via Knitting Method

Abstract

Phosphoric acid group, which possesses a low energy barrier for proton conduction and high water bonding energy, favors proton conduction and water retention. In this study, a phosphoric acid porous organic polymer (PAPOP) with high proton conductivity was synthesized. The diethyl benzylphosphonate (DBP) monomer and the benzyl monomer were directly knitted via the Friedel–Crafts alkylation reaction to form a porous scaffold. The phosphate ester group on DBP not only enhanced the monomer reactivity but also realized the in situ introduction of the phosphoric acid group precursor during the formation of the porous scaffold. It is found that p-dichloroxylene (DCX) monomer, due to its higher electrophilic activity, is easier to react with DBP and thus easier to introduce phosphoric acid groups. The higher ratio of DCX leads to a more continuous hydrogen-bond network within the scaffold, which facilitates the proton-conducting process. The resultant porous organic polymers exhibited high hydrophilicity and excellent stability in strong acid as well as antiswelling ability in water. The highest ion-exchange capacity reached 2.68 mmol g–1, much higher than that of most reported polymers. The proton conductivity of powders reached the highest value of 7.09 × 10–2 S cm–1 at 348 K and 98% relative humidity.

Phosphine Oxide Porous Organic Polymers Incorporating Cobalt(II) Ions: Synthesis, Characterization, and Investigation of H2 Production

“…These materials encompass purely inorganic zeolites, hybrid metal organic-frameworks (MOFs, crystalline), − and purely organic materials like covalent organic frameworks (COFs, crystalline). , The functional properties of these materials are strongly determined by the permanent porosity, large accessible surface, and size and shape of the pores. ,− More recently, amorphous porous organic polymers (POPs) have been developed, showing a higher stability than MOFs and COFs, and they can be prepared with a number of chemical functionalities within the cavities. Symmetric aromatic synthons, with tetrahedral- or trigonal-planar geometries, condensed through controlled and directional synthetic methodologies, produced porous materials with uniform pore size distribution and high capacity. − POPs can also be prepared with more conformationally flexible monomers with nonunivocal position of the linkage bond between monomers and linkers. , Similar to other porous materials, POPs can be prepared by incorporating into the framework Lewis basic sites that can serve as electron-donor systems for metal centers, and thus are suitable for proton transport, or the capture of volatile species …”

“…12−17 POPs can also be prepared with more conformationally flexible monomers with nonunivocal position of the linkage bond between monomers and linkers. 18,19 Similar to other porous materials, POPs can be prepared by incorporating into the framework Lewis basic sites that can serve as electron-donor systems for metal centers, and thus are suitable for proton transport, 20 or the capture of volatile species. 21 Additionally, POPs have been investigated in the domain of heterogeneous catalysis, 18,22−25 usually after the incorporation of metal centers.…”

Alkoxy phosphonic acid-functionalized conjugated microporous polymers for efficient and multi-environmental proton conduction

“…4e and Table S1, ESI †). 23,24,27,28,30,41,[43][44][45]49,[64][65][66][67][68][69][70][71][72][73][74][75] According to this result, CMP-Cx-P-H performs well with an excellent electrochemical stability under humid conditions. In the meantime, it demonstrates that CMP-Cx-P-H not only shows high efficiency and stability in anhydrous proton conduction, but is also promising for application in proton conduction under relative humidity.…”

“…So far, for proton conduction, among POPs doped with an additional proton source such as acid, their highest humid and anhydrous proton conductivities are revealed as B10 À1 S cm À1 for SPAF-1 and B10 À3 S cm À1 for H 3 PO 4 @CMP-F6-60%, respectively. 27,28,30,[41][42][43][44][45] For operation above 80 1C and below À5 1C, the research and development of guest-induced anhydrous proton-conductors is the top priority. Thus far, PA@TpBpy-MC and H 3 PO 4 @TPB-DMeTP-COF have been reported to achieve high anhydrous proton conductivities of B10 À4 and B10 À1 S cm À1 at À40 1C and 160 1C, respectively.…”

Highly Cationized and Porous Hyper-cross-linked Polymer Nanospheres for Composite Anion Exchange Membranes

“…Therefore, we surmise that HCP is a potentially attractive electrolyte material for anion conduction. Until now, only a few reports have focused on proton conductive HCP electrolytes, 19,20 to the best of our knowledge, and HCP has not been exploited as an anion conductive electrolyte yet. Due to the insoluble network structures, the fabrication of POM particles into thin free-standing AEMs is challenging.…”