The development of novel protocols and techniques for waste treatment represents the state of the art in the so‐called “green conversion”. Chemical wastes deriving from industrial and power‐station processes, which involve organic crystals, can be very hazardous for the environment. Studying their dissolution mechanism, both theoretically and experimentally, represents a mandatory step in the critical task of their disposal. Surprisingly, most of the studies are focused on millimeter scale length, from which one could estimate the crystal dissolution rate. In these studies, where no information about the dissolution mechanism on a molecular scale is provided, etch‐pit formation is recognized as the ultimate mechanism of crystal dissolution.
In this work, we show the morphological evolution of organic nanocrystals on the sub‐micrometer scale range in a reactive dissolution process controlled by pH. This approach allows us to explore ranges of high undersaturation, whereby crystal dissolution occurs even though etch‐pit formation is suppressed. Adopting different surface and bulk‐sensitive techniques (atomic force microscopy, time‐of‐flight secondary ion mass spectroscopy and X‐ray/electron diffraction, Raman spectroscopy, respectively), we investigate the dissolution process of porphyrin thin films deposited on the basal plane of highly oriented pyrolytic graphite, proving that such films constitute a model system to unveil the dissolution mechanism of organic nanocrystals.
Flexible and economic sensor devices are the focus of increasing interest for their potential and wide applications in medicine, food analysis, pollution, water quality, etc. In these areas, the possibility of using stable, reproducible, and pocket devices can simplify the acquisition of data. Among recent prototypes, sensors based on laser-induced graphene (LIGE) on Kapton represent a feasible choice. In particular, LIGE devices are also exploited as electrodes for sensing in liquids. Despite a characterization with electrochemical (EC) methods in the literature, a closer comparison with traditional graphite electrodes is still missing. In this study, we combine atomic force microscopy with an EC cell (EC-AFM) to study, in situ, electrode oxidation reactions when LIGE or other graphite samples are used as anodes inside an acid electrolyte. This investigation shows the quality and performance of the LIGE electrode with respect to other samples. Finally, an ex situ Raman spectroscopy analysis allows a detailed chemical analysis of the employed electrodes.
Reflectance anisotropy spectroscopy (RAS) coupled to an electrochemical cell represents a powerful tool to correlate changes in the surface optical anisotropy to changes in the electrochemical currents related to electrochemical reactions. The high sensitivity of RAS in the range of the absorption bands of organic systems, such as porphyrins, allows us to directly correlate the variations of the optical anisotropy signal to modifications in the solid-state aggregation of the porphyrin molecules. By combining in situ RAS to electrochemical techniques, we studied the case of vacuum-deposited porphyrin nanocrystals, which have been recently observed dissolving through electrochemical oxidation in diluted sulfuric acid. Specifically, we could identify the first stages of the morphological modifications of the nanocrystals, which we could attribute to the single-electron transfers involved in the oxidation reaction; in this sense, the simultaneous variation of the optical anisotropy with the electron transfer acts as a precursor of the dissolution process of porphyrin nanocrystals.
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