Incorporation of a [Ru(dcbpy)(bpy)₂]²⁺ photosensitizer and a Pt(dcbpy)Cl₂ catalyst into metal–organic frameworks for photocatalytic hydrogen evolution from aqueous solution

Abstract

UIO-67 MOFs functionalized with a [Ru(dcbpy)(bpy)2]2+ photosensitizer and a Pt(dcbpy)Cl2 catalyst display enhanced photocatalytic activity, due to the facile electron transfer from the Ru- to Pt-centers in the MOFs.

Self-Healing of Molecular Catalyst and Photosensitizer on Metal–Organic Framework: Robust Molecular System for Photocatalytic H2 Evolution from Water

“…[19][20][21] For example, molecular catalyst and photosensitizer were embedded in water-stable MOF and showed far more enhanced activity and stability in H2 evolution reaction (HER) than homogeneous counterpart. [22][23][24] As an additional step forward, we herein report an original strategy of using MOF as a self-healing system that not only proceeds HER, but also spontaneously repairs embedded molecular catalyst and photosensitizer during the photocatalytic process. Water-stable bipyridineembedded UiO-67 MOF, namely BUiO, was selected as a selfhealing platform, and was functionalized with a molecular Pt(II) catalyst and a Ir(III) photosensitizer to yield Ptn_Ir_BUiO (Scheme 1).…”

“…Pt1.0_BUiO and Pt0.1_BUiO showed prominent absorption peak at 418 nm which corresponds to metalto-ligand (Pt(dπ) → dcbpy(π*)) charge transfer (MLCT) transition for H2Pt Pt Pt Pt in DMF. 22 The Cl/Pt ratio was further quantified with energy dispersive x-ray spectrometer (EDS) and inductively coupled plasma-mass spectroscopy (ICP-MS) ( Figure S1 and Table S2). Additionally, electron binding energy of Pt(II) 4f7/2 and 4f5/2 was very close to that of analogous MOF ( Figure S5) and Ptn_Ir_BUiO suspension showed orange to olive green color change after the beginning of photocatalysis which is known to be observed when Pt(II)-diimine type complexes are reduced ( Figure S6).…”

“…Additionally, electron binding energy of Pt(II) 4f7/2 and 4f5/2 was very close to that of analogous MOF ( Figure S5) and Ptn_Ir_BUiO suspension showed orange to olive green color change after the beginning of photocatalysis which is known to be observed when Pt(II)-diimine type complexes are reduced ( Figure S6). 22,27 The amount of each component in Ptn_Ir_BUiO was determined by ICP-MS and 1 H NMR ( Figure S3), and field-emission scanning electron microscope (FE-SEM) showed that the size of MOF particles ranged from 50 to 200 nm ( Figure S7). Figure 2.…”

Photochemical Hydrogen Production with Metal–Organic Frameworks

“…Employing a different framework (UiO-67(Zr)) but using the same catalyst, Hou et al [49] reported the incorporation of Pt(dcbpy)Cl 2 together with a photosensitizer Ru(dcbpy)(bpy) 2 Cl 2 into a MOF. Both molecules were introduced during the solvothermal synthesis in a mix-and-match approach taking advantage of the matching linker topology of dcbpy and 4,4 0 biphenyl-dicarboxylic acid of the parent framework.…”

“…3 MOF with dual functionality. In the depicted example by Hou and coworkers [49], two molecular species were co-incorporated into the MOF irradiation. In comparison with the homogeneous control, the dual functionalized MOF showed enhanced hydrogen formation.…”