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Poor electrochemical communication between biocatalysts and electrodes is a ubiquitous limitation to bioelectrocatalysis efficiency. An extensive library of polymers has been developed to modify biocatalyst-electrode interfaces to alleviate this limitation. As such, conducting redox polymers (CRPs) are a versatile tool with high structural and functional tunability. While charge transport in CRPs is well characterized, the understanding of charge transport mechanisms facilitated by CRPs within decisively complex photobioelectrocatalytic systems remains very limited. This study is a comprehensive analysis that dissects the complex kinetics of photobioelectrodes into fundamental blocks based on rational assumptions, providing a mechanistic overview of charge transfer during photobioelectrocatalysis. We quantitatively compare two biohybrids of metal-free unbranched CRP (polydihydroxy aniline) and photobiocatalyst (intact chloroplasts), formed utilizing two deposition strategies ( “mixed” and “layered” depositions). The superior photobioelectrocatalytic performance of the “ layered” biohybrid compared to the “ mixed” counterpart is justified in terms of rate ( D app ), thermodynamic and kinetic barriers (H ≠ , E a ), frequency of molecular collisions ( D 0 ) during electron transport across depositions, and rate and resistance to heterogeneous electron transfer ( k 0 , R CT ). Our results indicate that the primary electron transfer mechanism across the biohybrids, constituting the unbranched CRP, is thermally activated intra- and inter-molecular electron hopping, as opposed to a non-thermally activated polaron transfer model typical for branched CRP- or conducting polymer (CP)-containing biohybrids in literature. This work underscores the significance of subtle interplay between CRP structure and deposition strategy in tuning the polymer-catalyst interfaces, and the branched/unbranched structural classification of CRPs in the bioelectrocatalysis context. 

Infrared and Raman spectroscopy techniques were applied to investigate the drying and aggregation behavior of Nafion ionomer particles dispersed in aqueous solution. Gravimetric measurements aided the identification of gel-phase development within a series of time-resolved spectra that tracked transformations of a dispersion sample during solvent evaporation. A spectral band characteristic of ionomer sidechain end group vibration provided a quantitative probe of the dispersion-to-gel change. For sets of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectra, adherence to Beer’s law was attributed to the relatively constant refractive index in the frequency region of hydrated -SO3 - group vibrations as fluorocarbon-rich ionomer regions aggregate in forming the structural framework of membranes and thin films. Although vibrational bands associated with ionomer backbone CF2 stretching vibrations were affected by distortion characteristic of wavelength-dependent refractive index change within a sample, the onset of band distortion signaled gel formation and coincided with ionomer mass % values just below the critical gelation point for Nafion aqueous dispersions. Similar temporal behavior was observed in confocal Raman microscopy experiments that monitored the formation of a thin ionomer film from an individual dispersion droplet. For the ATR FTIR spectroscopy and confocal Raman microscopy techniques, intensity in the water H-O-H bending vibrational band dropped sharply at the ionomer critical gelation point and displayed a time dependence consistent with changes in water content derived from gravimetric measurements. The reported studies lay groundwork for examining the impact of dispersing solvents and above-ambient temperatures on fluorinated ionomer transformations that influence structural properties of dispersion-cast membranes and thin films.