Photoelectrochemical (PEC) water splitting has been widely regarded as one of the most promising routes for hydrogen production from water. Titanium dioxide (TiO2) and TiO2– based) materials were mostly used for that purpose. However, performance limitations require innovative strategies to maximize the efficiency of such systems. Nano-structuration and surface modification of TiO2 substrates are both necessary to optimize water splitting under solar light. In this work, we successfully decorated TiO2 nanorods (TNRs) arrays with thin layers of a nickel metal organic framework (MOF) using a layer-by-layer growth process. Ni-BDC (NBF) was selected as a surface photosensitizer and co-catalyst for the oxygen evolution reaction (OER). The morphology of the final product contains vertically-oriented TNRs decorated with NBF nanoparticles, forming a thin layer nanostructure. The loading concentration of NBF was found to impact the resistance, electrons transfer and photo-response of the photo-electrode, and fine tuning was required to optimize the photoactivity. After optimization, this unique architecture of NBF@TNRs photoanodes shows an enhanced OER photo-activity, with a photocurrent of 0.46 mA cm-2 under 100 mW/cm2 UV + Visible light intensity (42.4 µA cm-2 under 63 mW/cm2 intensity of visible light &gt;420 nm) which are ~20 times higher than on bare TNRs. The high PEC performance was attributed to the presence of NBF, which enhances the visible light absorption, but also to the large surface area of the interface, that provides efficient charge separation and high carrier mobility. Based on the analysis of experimental UV and visible optical response, electrochemical impedance spectroscopy, and chrono-amperometry, a microscopic mechanism was proposed to explain the observed activity of these systems.

Thin layer Ni-MOF as efficient photosensitizer for TiO2 nanorods array and application to photoelectrochemical water splitting

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.