Abstract
We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water‐based acid solutions, protonation of free‐base porphyrin molecules is the driving force for crystal dissolution, whereas metal (ZnII) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π‐structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free‐base and metal porphyrin nanocrystals?In this work, by exploiting electrochemical atomic force microscopy (EC‐AFM), we monitor in situ and in real time the dissolution of both free‐base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential.
Highlights
Organic molecular aggregates represent the main dross in agricultural waste[1] and an important percentage of rubbish in industrial production.[2,3] Their treatment and disposal strategies can have a significant impact in the environment
The cyclic voltammetry (CV) is acquired in the traditional EC potential range where the oxidation of graphite is usually studied.[17,19]
The HOPG intercalation process has clear features in the CV: some shoulders appears above 1.0 V during the anodic swept and a broader peak characterizes the cathodic one.[17,18,19,20]
Summary
M. Campione Department of Earth and Environmental Sciences Università degli Studi di Milano-Bicocca Piazza della Scienza 4 20126 Milano (Italy). Trabattoni Department of Materials Science Università degli Studi di Milano-Bicocca v. L. Tortora Department of Science Roma Tre University via della Vasca Navale 84 00146 Rome (Italy). This analysis can confirm the role of porphyrin molecule oxidation as the driving force in organic crystal dissolution and, on the other hand, is helpful in defining differences between free-base and metal porphyrin species during the dissolution process
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