화학공학소재연구정보센터
Inorganic Chemistry, Vol.59, No.1, 472-483, 2020
Efficient Electrocatalytic Water Oxidation by Fe(salen)-MOF Composite: Effect of Modified Microenvironment
An efficient and robust heterogeneous electrocatalyst, FSWZ-8 ((Fe-(salen)(OH) + H-4[SiW12O40]-HCO@ZIF-8) for oxygen evolution reaction (OER) at the neutral pH, was developed by coencapsulation of Fe-salen (i.e., Fe(salen)Cl) and SiW12 (i.e., H-4[SiW12O40]) inside the cavity of zeolitic imidazolate framework-8 (ZIF-8) material by an in situ synthesis. Here ZIF-8 functions as a host, Fe-salen as the active catalyst, and SiW(12)( )helps in the charge transport by lowering the overall electrical resistance of the resulting composite system. High turnover frequency (similar to S s(-1)) and high Faradaic efficiency (similar to 94%) make the concerned composite an efficient catalyst toward water oxidation. This is the first report of one of the simplest known metal complexes, Fe-salen, to perfrom electrocatalytic OER as a heterogeneous catalyst in the neutral pH. This work also highlights the benefits of coencapsulation of the Keggin polyoxometalate (POM) along with the active catalyst Fe-salen species. Encapsulation of SiW(12)( )results in (i) faster formation of FSWZ-8 composite, (ii) higher loading of Fe-salen, and, most importantly, (iii) lowering of required overpotential for electrochemical OER by more than 150 mV. The Keggin POMs, located as discrete molecular oxides inside the cavity of ZIF-8 as well as on the surface of ZIF-8, facilitate electrical charge conduction in the ZIF-8 matrix and lower the overall charge-transfer resistance.