Elucidating charge transfer process and enhancing electrochemical performance of laser-induced graphene via surface engineering with sustainable hydrogel membranes: An electrochemist's perspective.

Laser-induced graphene (LIG) has emerged as a promising solvent-free strategy for producing highly porous, 3D graphene structures, particularly for electrochemical applications. However, the unique character of LIG and hydrogel membrane (HM) coated LIG requires accounting for the specific conditions of its charge transfer process. This study investigates electron transfer kinetics and the electroactive surface area of LIG electrodes, finding efficient kinetics for the [Fe(CN) 6 ] 3-/4- redox process, with a high rate constant of 4.89 x 10 -3  cm/s. The impact of polysaccharide HM coatings (cationic chitosan, neutral agarose and anionic sodium alginate) on LIG's charge transfer behavior is elucidated, considering factors like ohmic drop across porous LIG and Coulombic interactions/permeability affecting diffusion coefficient (D), estimated from amperometry.It was found that D of redox species is lower for HM-coated LIGs, and is the lowest for chitosan HM. Chitosan coating results in increased capacitive share in the total current while does not apparently reduce Faradaic current. Experimental findings are supported by ab-initio calculations showing an electrostatic potential map's negative charge distribution upon chitosan chain protonation, having an effect in over a two-fold redox current increase upon switching the pH from 7.48 to 1.73. This feature is absent for other studied HMs. It was also revealed that the chitosan's band gap was reduced to 3.07 eV upon acetylation, due to the introduction of a new LUMO state. This study summarizes the operating conditions enhanced by HM presence, impacting redox process kinetics and presenting unique challenges for prospective LIG/HM systems' electrochemical applications.