Photocatalytic Hydrogen Production from Glycerol Aqueous Solutions as Sustainable Feedstocks Using Zr-Based UiO-66 Materials under Simulated Sunlight Irradiation

Abstract

There is an increasing interest in developing cost-effective technologies to produce hydrogen from sustainable resources. Herein we show a comprehensive study on the use of metal–organic frameworks (MOFs) as heterogeneous photocatalysts for H2 generation from photoreforming of glycerol aqueous solutions under simulated sunlight irradiation. The list of materials employed in this study include some of the benchmark Zr-MOFs such as UiO-66(Zr)-X (X: H, NO2, NH2) as well as MIL-125(Ti)-NH2 as the reference Ti-MOF. Among these solids, UiO-66(Zr)-NH2 exhibits the highest photocatalytic H2 production, and this observation is attributed to its adequate energy level. The photocatalytic activity of UiO-66(Zr)-NH2 can be increased by deposition of small Pt NPs as the reference noble metal co-catalyst within the MOF network. This photocatalyst is effectively used for H2 generation at least for 70 h without loss of activity. The crystallinity of MOF and Pt particle size were maintained as revealed by powder X-ray diffraction and transmission electron microscopy measurements, respectively. Evidence in support of the occurrence of photoinduced charge separation with Pt@UiO-66(Zr)-NH2 is provided from transient absorption and photoluminescence spectroscopies together with photocurrent measurements. This study exemplifies the possibility of using MOFs as photocatalysts for the solar-driven H2 generation using sustainable feedstocks.

Keywords

• heterogeneous photocatalysis
• hydrogen generation
• metal–organic frameworks
• glycerol feedstock
• simulated sunlight irradiation