Details

Autor(en) / Beteiligte

• Herrera, Facundo C
• Caraballo, Rolando M
• Vensaus, Priscila
• Soler Illia, Galo J. A. A
• Hamer, Mariana

Titel

Fe-Ni porphyrin/mesoporous titania thin film electrodes: a bioinspired nanoarchitecture for photoelectrocatalysis

Ist Teil von

• RSC advances, 2024-05, Vol.14 (23), p.15832-15839

Ort / Verlag

England: Royal Society of Chemistry

Erscheinungsjahr

2024

Quelle

Free E-Journal (出版社公開部分のみ）

Beschreibungen/Notizen

• Porphyrin and porphyrinoid derivatives have been extensively studied in the assembly of catalysts and sensors, seeking biomimetic and bioinspired activity. In particular, Fe and Ni porphyrins can be used for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by immobilization of these molecular catalysts on semiconductor materials. In this study, we designed a hybrid material containing a crystalline mesoporous TiO 2 thin film in which the catalytic centres are Ni-porphyrin (NiP), Fe-porphyrin (FeP), and a NiP/FeP bimetallic system to assess whether the coexistence of both metalloporphyrins improves the OER activity. The obtained photoelectrodes were physicochemically and morphologically characterized through high-resolution FE-SEM images, UV-vis and Raman spectroscopies, cyclic voltammetry, and impedance measurements. The results show a differential behavior of the mono- and bimetallic porphyrin systems, where the Fe( iii ) centre in FeP may increase the acidity and lower the reduction potential of the Ni 2+/3+ couple when co-deposited with NiP leading to an improved photoelectrochemical water-oxidation performance. We have validated the cooperative effect of both metal complexes within this novel system, where the μ-peroxo-bridged interaction between Fe and Ni is integrated into a supramolecular heterometallic structure of porphyrins. Mesoporous TiO 2 thin films with a crystalline structure were effectively produced and analyzed after modification with Fe and Ni porphyrins. The collaborative impact of these metal complexes was evaluated to determine if the simultaneous presence of both metalloporphyrins enhances the OER activity.