RESUMO
Heterogeneous light-driven catalysis is a cornerstone of sustainable energy conversion. Most catalytic studies focus on bulk analyses of the hydrogen and oxygen evolved, which impede the correlation of matrix heterogeneities, molecular features, and bulk reactivity. Here, we report studies of a heterogenized catalyst/photosensitizer system using a polyoxometalate water oxidation catalyst and a model, molecular photosensitizer that were co-immobilized within a nanoporous block copolymer membrane. Via operando scanning electrochemical microscopy (SECM), light-induced oxygen evolution was determined using sodium peroxodisulfate (Na2 S2 O8 ) as sacrificial electron acceptor. Ex situ element analyses provided spatially resolved information on the local concentration and distribution of the molecular components. Infrared attenuated total reflection (IR-ATR) studies of the modified membranes showed no degradation of the water oxidation catalyst under the reported light-driven conditions.
RESUMO
Polydopamine (PDA) films are interesting as smart functional materials, and their controlled structured formation plays a significant role in a wide range of applications ranging from cell adhesion to sensing and catalysis. A pulsed deposition technique is reported for micro-structuring polydopamine films using scanning electrochemical microscopy (SECM) in direct mode. Thereby, precise and reproducible film thicknesses of the deposited spots could be achieved ranging from 5.9 +/- 0.48 nm (1 pulse cycle) to 75.4 nm +/- 2.5 nm for 90 pulse cycles. The obtained morphology is different in comparison to films deposited via cyclic voltammetry or films formed by autooxidation showing a cracked blister-like structure for high pulse cycle numbers. The obtained polydopamine spots were investigated in respect to their electrochemical properties using SECM approach curves. Quantitative kinetic data in dependence of the film thickness, the substrate potential, and the used redox species were obtained.