the values afforded by the homogeneous control [Ir(ppy) 2 (bpy)]Cl/K 2 PtCl 4 under
their respective conditions under the illumination of a 450 W Xe-lamp with a 420 nm
cutoff filter for 48 h.
In 2009, Kataoka et al. [15] detected the first example of open porous MOFs that
functioned as an activity site for the reduction of water into hydrogen molecules in
the presence of Ru(bpy) 3
2+ , MV
2+ , and EDTA–2Na under visible light irradiation.
Zhou et al. [11] synthesized and characterized a new metal–organic framework
(MOF-253-Pt) material through immobilizing a platinum complex in 2,20bipyridine-based microporous MOF (MOF-253) using a post-synthesis modification
strategy. The functionalized MOF-253-Pt serves both as a photosensitizer and a
photocatalyst for hydrogen evolution under visible light irradiation. The structure
and proposed mechanism are presented as shown in Fig. 17.2a, b, respectively.
Based on light irradiation, the MOF with TEOA’s presence firstly generates a oneelectron-reduced species MOF*(3MLCT) and holes. The MOF*(
3 MLCT) species is
reductively quenched to form MOF
À with the electrons stored on the bpy
À ligands.
After that, the reduced MOF
À further forms a Pt(III)-hydride intermediate via a
proton-coupled electron transfer (PCET), which contributes to the formation of the
hydride-diplatinum (II, III) intermediate by the synergistic effect of the nearing
anchored Pt(bpy)Cl 2 complex on framework, leading to H 2 production by a heterolytic coupling pathway.
The efficiency of electron–hole separation and charge-carrier utilization play a
central role in photocatalysis. Jiang et al. [16] prepared a representative MOF
UiO-66-NH 2 where Pt nanoparticles of ca. 3 nm are incorporated inside or supported
on. The resulting products are denoted as Pt@UiO-66-NH 2 and Pt/UiO-66-NH 2 ,
respectively. Finally, these materials are especially applied in photocatalytic
Fig. 17.2 (a) Model structure of MOF-253-Pt, through post-synthetic modification of MOF-253
with PtCl 2 . Key: Cyan octahedron represents Al atoms; while yellow, green, red, blue, and blank
circles represent Pt, Cl, O, N, and C atoms, respectively; H atoms are omitted for clarity. (b)
Proposed reaction mechanism for the photocatalytic H 2 evolution over MOF-253-Pt under visible
light irradiation. (Reprinted with the permission from Ref. [11], Copyright 2013, Royal Society of
Chemistry)
17.2 Hydrogen Production
405
their respective conditions under the illumination of a 450 W Xe-lamp with a 420 nm
cutoff filter for 48 h.
In 2009, Kataoka et al. [15] detected the first example of open porous MOFs that
functioned as an activity site for the reduction of water into hydrogen molecules in
the presence of Ru(bpy) 3
2+ , MV
2+ , and EDTA–2Na under visible light irradiation.
Zhou et al. [11] synthesized and characterized a new metal–organic framework
(MOF-253-Pt) material through immobilizing a platinum complex in 2,20bipyridine-based microporous MOF (MOF-253) using a post-synthesis modification
strategy. The functionalized MOF-253-Pt serves both as a photosensitizer and a
photocatalyst for hydrogen evolution under visible light irradiation. The structure
and proposed mechanism are presented as shown in Fig. 17.2a, b, respectively.
Based on light irradiation, the MOF with TEOA’s presence firstly generates a oneelectron-reduced species MOF*(3MLCT) and holes. The MOF*(
3 MLCT) species is
reductively quenched to form MOF
À with the electrons stored on the bpy
À ligands.
After that, the reduced MOF
À further forms a Pt(III)-hydride intermediate via a
proton-coupled electron transfer (PCET), which contributes to the formation of the
hydride-diplatinum (II, III) intermediate by the synergistic effect of the nearing
anchored Pt(bpy)Cl 2 complex on framework, leading to H 2 production by a heterolytic coupling pathway.
The efficiency of electron–hole separation and charge-carrier utilization play a
central role in photocatalysis. Jiang et al. [16] prepared a representative MOF
UiO-66-NH 2 where Pt nanoparticles of ca. 3 nm are incorporated inside or supported
on. The resulting products are denoted as Pt@UiO-66-NH 2 and Pt/UiO-66-NH 2 ,
respectively. Finally, these materials are especially applied in photocatalytic
Fig. 17.2 (a) Model structure of MOF-253-Pt, through post-synthetic modification of MOF-253
with PtCl 2 . Key: Cyan octahedron represents Al atoms; while yellow, green, red, blue, and blank
circles represent Pt, Cl, O, N, and C atoms, respectively; H atoms are omitted for clarity. (b)
Proposed reaction mechanism for the photocatalytic H 2 evolution over MOF-253-Pt under visible
light irradiation. (Reprinted with the permission from Ref. [11], Copyright 2013, Royal Society of
Chemistry)
17.2 Hydrogen Production
405