Functionalization of UiO-66 Metal−Organic Framework and Highly Cross-Linked Polystyrene with Cr(CO)₃: In Situ Formation, Stability, and Photoreactivity

Abstract

The formation and stability of (arene)Cr(CO) 3 species inside two highly porous materials;UiO-66, which is a recently synthesized metal-organic framework, and a cross-linked poly(styrene-codivinylbenzene) resin;are investigated in detail by means of complementary spectroscopic techniques and theoretical calculations. In particular, Fourier transform infrared (FT-IR), ultravioletvisible (UV-vis), and X-ray absorption near-edge structure (XANES) spectroscopies, coupled with theoretical calculations, allow the formation of the (arene)Cr(CO) 3 species to be followed in situ, starting from the Cr(CO) 6 precursor, monitoring the changes in the vibrational and electronic properties of the materials. EXAFS spectroscopy gives the structural evidence of the functionalized unities. Finally, the photoinduced reactivity of Cr(CO) 3 in UiO-66 is also explored, by following the substitution of one CO ligand with a N 2 molecule. The overall presented data would become the starting point for the development of a systematic procedure for investigating functionalized porous matrices.

Pilot-scale synthesis of a zirconium-benzenedicarboxylate UiO-66 for CO2 adsorption and catalysis

“…Kim et al first reported the modification of UiO-66-Br to UiO-66-CN via microwave irradiation [26] as well as tandem functionalization with a mixed ligand UiO-66-(Br)(NH 2 ) [27]. A large number of functionalized UiO-66 studies were followed afterwards using mono-, multi-functional and mixed ligand [28][29][30]. Yang et al examined the effect of functional groups on gas uptake and separation using the functionalized UiO-66 ( Br, NH 2 , −2,5-(OH) 2 , NO 2 , SO 3 H, −2,5-(CF 3 ) 2 ) [31].…”

Tailoring the photocatalytic reaction rate of a nanostructured TiO2 matrix using additional gas phase oxygen

“…, as evaluated by N 2 adsorption at 77 K, and a pore size distribution centered at approximately 16 Å [25]. The water was double distilled and produced in our laboratory.…”

Metal‐Organic Frameworks: Metal‐Uptake

“…Cr(CO) 3 fragments can also be grafted onto arene groups of MOF [Zr 6 O 4 (OH) 4 (bdc) 6 ] (UiO-66). 23 Similarly, the MOF [Ni 2 (dhbd)] (dhbd = 2,5-dihydroxybenzene-1,4-dicarboxylate) can be metallated through chemical vapor deposition (CVD) with sublimation of Mo(CO) 6 into the MOF pores. 24 Again infrared spectroscopy supports the formation of (dhbd)Mo(CO) 3 species on the MOF framework, and microanalysis indicates that half of the dhbd 2− ligands are metallated.…”