Single-atom catalysts (SACs) have demonstrated superior catalytic activity and selectivity compared to nanoparticle catalysts due to their high reactivity and atom efficiency. However, stabilizing SACs within hosting substrates and their controllable loading preventing single atom clustering remain the key challenges in this field. Moreover, the direct comparison of (co-) catalytic effect of single atoms vs nanoparticles is still highly challenging. Here, we present a novel ultrasound-driven strategy for stabilizing Pt single-atomic sites over highly ordered TiO2 nanotubes. This controllable low-temperature defect engineering enables entrapment of platinum single atoms and controlling their content through the reaction time of consequent chemical impregnation. The novel methodology enables achieving nearly 50 times higher normalized hydrogen evolution compared to pristine titania nanotubes. Moreover, the developed procedure allows the decoration of titania also with ultrasmall nanoparticles through a longer impregnation time of the substrate in a very dilute hexachloroplatinic acid solution. The comparison shows a 10 times higher normalized hydrogen production of platinum single atoms compared to nanoparticles. The mechanistic study shows that the novel approach creates homogeneously distributed defects, such as oxygen vacancies and Ti3+ species, which effectively trap and stabilize Pt2+ and Pt4+ single atoms. The optimized platinum single-atom photocatalyst shows excellent performance of photocatalytic water splitting and hydrogen evolution under one sun solar-simulated light, with TOF values being one order of magnitude higher compared to those of traditional thermal reduction-based methods. The single-atom engineering based on the creation of ultrasound-triggered chemical traps provides a pathway for controllable assembling stable and highly active single-atomic site catalysts on metal oxide support layers.

• Klíčová slova
• TiO2 nanotube arrays (TNTs), hydrogen evolution (H2), photocatalysis, reduced TiO2, single-atom catalysts,
• Publikační typ
• časopisecké články MeSH

The photoelectrochemical degradation of selected aromatic substances, acid orange 7 (AO7), salicylic acid (SA), benzoic acid (BA), and 4-chlorophenol (4-CP) was studied on hematite (α-Fe2O3) and compared with titanium dioxide (TiO2), both deposited as thin films on conducting substrates (FTO/glass). Batch type reactors were used under backside and front side illumination. Electrical bias was applied on the semiconducting electrodes, such that only valence band processes leading to oxidative pathways were followed. The initial Faradaic efficiency, f0, of degradation processes was determined from the UV-Vis absorbance decrease of the starting materials. f0 for 1 mM AO7 degradation in 0.01 M sulphuric acid was found to be 7.5%. When the pH of the solution was neutral (pH 7.2) or alkaline (pH 13), f0 decreased to 1.7%. For 1 mM SA, f0 was 6.2% on hematite photoanodes and 6.1% on titanium dioxide. For 1 mM benzoic acid and 4-chlorophenol, f0 was an order of magnitude lower, but only on hematite. This is ascribed to the lack of OH· radical formation on hematite, which seems to be essential for the photooxidation of these compounds.

• Klíčová slova
• Hematite, Organic substances, Photoelectrochemical oxidation, Spray pyrolysis,
• Publikační typ
• časopisecké články MeSH