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.

This work deals with the synthesis of metal-free and porphyrin-based covalent organic polymers (COPs) by the Suzuki–Miyaura coupling carbon-carbon bond forming reaction to study the photocatalytic overall water splitting performance. Apart from using 5,10,15,20-Tetrakis-(4-bromophenyl)porphyrin, we have chosen different cross-linker monomers to induce 2-dimensional (2D) or 3-dimensional (3D) and different rigidity in their resulting polymeric molecular structure. The synthesised COPs were extensively characterised to reveal that the dimensionality and flexibility of the molecular structure play an intense role in the physical, photochemical, and electronic properties of the polymers. Photoinduced excited state of the COPs was evaluated by nanosecond time-resolved laser transient absorption spectroscopy (TAS) by analysing excited state kinetics and quenching experiments, photocurrent density measurements and photocatalytic deposition of Ru³⁺ to RuO_2, and photocatalysis. In summary, TAS experiments demonstrated that the transient excited state of these polymers has two decay kinetics and exhibit strong interaction with water molecules. Moreover, photocurrent and photocatalytic deposition experiments proved that charges are photoinduced and are found across the COP molecular network, but more important charges can migrate from the surface of the COP to the medium. Among the various COPs tested, COP–3 that has a flexible and 3D molecular structure reached the best photocatalytic performances, achieving a photocatalytic yield of 0.4 mmol H₂ × g_COP–3⁻¹ after 3 h irradiation.