Melanin
is a group of heterogeneous polymeric pigments that has
been proposed to perform various biological functions and is attracting
increasing technological interest as a sustainable electronic material
for energy storage and bioelectronics. Here, we prepared a semitransparent
hydrogel film from a soluble melanin obtained from the black soldier
fly (Hermetia illucens; BSF) and applied
an operando spectroelectrochemical approach to investigate the molecular-level
changes that occur when electrons are “flowing” through
this melanin (i.e., while electron transfer processes are “in
operation”). Like other natural and synthetic melanins, we
observed that the BSF melanin has reversible redox activities in the
mid-physiological redox potential range. We report that electron transfer
can occur through an indirect (mediator-based) mechanism and also
through a direct mechanism involving an extrinsic electron exchange
with conducting graphene. In both mechanisms, we show that electron
transfer is correlated to a reversible switching of the melanin’s
redox state. Finally, we provide evidence to support a chemical disorder
model, which suggests that the properties of melanin may involve diverse
structural and mechanistic features that occur over various length
scales. Overall, we show that operando spectroelectrochemical measurements
can bridge traditional bottom-up and top-down methods to facilitate
the characterization of melanin.