Synthetic strategies to incorporate Ru-terpyridyl water oxidation catalysts into MOFs : direct synthesis vs. post-synthetic approach

• Incorporating molecular catalysts into metal-organic frameworks (MOFs) is a promising strategy for improving their catalytic longevity and recyclability. In this article, we investigate and compare synthetic routes for the incorporation of the potent water oxidation catalyst Ru(tda)(pyCO(2)H)(2) (tda = 2,2':6',2 ''-terpyridine-6,6 ''-dicarboxylic acid, pyCO(2)H = iso-nicotinic acid) as a structural linker into a Zr-based UiO-type MOF. The task is challenging with this particular metallo-linker because of the equatorial dangling carboxylates that can potentially compete for Zr-coordination, as well as free rotation of the pyCO(2)H groups around the HO(2)Cpy center dot center dot center dot Ru center dot center dot center dot pyCO(2)H axis. As a consequence, all attempts to synthesize a MOF with the metallo-linker directly under solvothermal conditions led to amorphous materials with the Ru(tda) (pyCO(2)H)(2) linker coordinating to the Zr nodes in ill-defined ways, resulting in multiple waves in the cyclic voltammograms of the solvothermally obtained materials. On the other hand, an indirect post-synthetic approach in which the Ru(tda)(pyCO(2)H)(2) linker is introduced into a preformed edba-MOF (edba = ethyne dibenzoic acid) of UiO topology results in the formation of the desired material. Interestingly, two distinctly different morphologies of the parent edba-MOF have been discovered, and the impact that the morphological difference has on linker incorporation is investigated.

Ämnesord

NATURVETENSKAP  -- Kemi -- Oorganisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)

NATURVETENSKAP  -- Kemi -- Organisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Organic Chemistry (hsv//eng)

Publikations- och innehållstyp

ref (ämneskategori)

art (ämneskategori)