Water stable Zr-benzenedicarboxylate metal-organic frameworks as photocatalysts for hydrogen generation.

The Zr-containing metal-organic frameworks (MOFs) formed by terephthalate (UiO-66) and 2-aminoterephthalate ligands [UiO-66(NH(2))] are two notably water-resistant MOFs that exhibit photocatalytic activity for hydrogen generation in methanol or water/methanol upon irradiation at wavelength longer than 300 nm. The apparent quantum yield for H(2) generation using monochromatic light at 370 nm in water/methanol 3:1 was of 3.5% for UiO-66(NH(2)). Laser-flash photolysis has allowed detecting for UiO-66 and UiO-66(NH(2)) the photochemical generation of a long lived charge separated state whose decay is not complete 300 µs after the laser flash. Our finding and particularly the influence of the amino group producing a bathochromic shift in the optical spectrum without altering the photochemistry shows promises for the development of more efficient MOFs for water splitting.

Layered double hydroxides as highly efficient photocatalysts for visible light oxygen generation from water.

Oxygen generation through photocatalytic water splitting under visible light irradiation is a challenging process. In this work we have synthesized a series of Zn/Ti, Zn/Ce, and Zn/Cr layered double hydroxides (LDH) at different Zn/metal atomic ratio (from 4:2 to 4:0.25) and tested them for the visible light photocatalytic oxygen generation. The most active material was found to be (Zn/Cr)LDH with an atomic ratio of 4:2 that exhibits two absorption bands in the visible region at lambda(max) of 410 and 570 nm. It was found that the efficiency of these chromium layered double oxides for oxygen generation increases asymptotically with the Cr content. Using iron oxalate as chemical actinometer we have determined that the apparent quantum yields for oxygen generation (Phi apparent = 4 x mol oxygen/mol incident photons) are of 60.9% and 12.2% at 410 and 570 nm, respectively. These quantum yields are among the highest values ever determined with visible light for solid materials in the absence of light harvesting dye. The overall efficiency of (Zn/Cr)LDH for visible light oxygen generation was found to be 1.6 times higher than that of WO(3) under the same conditions.