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

Suitably functionalized porous matrices represent versatile platforms to support well-dispersed catalytic centers. In the present study, porous organic polymers (POPs) containing phosphine oxide groups were fabricated to bind transition metals and to be investigated for potential electrocatalytic applications. Cross-linking of mono- and di-phosphine monomers with multiple phenyl substituents was subject to the Friedel-Crafts (F-C) reaction and the oxidation process, which generated phosphine oxide porous polymers with pore capacity up to 0.92 cm(3)/g and a surface area of about 990 m(2)/g. The formation of the R3P center dot BH3 borohydride adduct during synthesis allows to extend the library of phosphine-based monomeric entities when using FeCl3. The porous polymers were loaded with 0.8-4.2 w/w % of cobalt(II) and behaved as hydrogen evolution reaction (HER) catalysts with a Faradaic efficiency of up to 95% (5.81 x 10(-5) mol H-2 per 11.76 C) and a stable current density during repeated controlled potential experiments (CPE), even though with high overpotentials (0.53-0.68 V to reach a current density of 1 mA.cm(-2)). These studies open the way to the effectiveness of tailored phosphine oxide POPs produced through an inexpensive and ecofriendly iron-based catalyst and for the insertion of transition metals in a porous architecture, enabling electrochemically driven activation of small molecules.

Automated summary

Suitably functionalized porous matrices have been developed as versatile platforms for catalytic applications. In this study, porous organic polymers (POPs) with phosphine oxide groups were synthesized and used as electrocatalysts. The loaded polymers showed high efficiency for hydrogen evolution reaction, indicating their potential in electrochemical activation of small molecules.