Turning Colombian Banana Waste into a Lignocellulosic Carbocatalyst: A Green Photocatalytic Route for Mercury Remediation

Mercury pollution from artisanal and small-scale gold mining remains one of the most persistent environmental threats due to the high toxicity, mobility, and bioaccumulation of Hg(II). In this work, Colombian banana pseudostem waste is valorized into a lignocellulosic carbocatalyst through pyrolysis at 500 °C followed by MnCO3-derived MnOx functionalization, producing a sustainable material for Hg(II) remediation. The transformation of the biomass leads from a fibrous structure (~25 µm) to a pyrolyzed carbon matrix (9.56 µm), and finally to a heterogeneous Mn-modified system with bimodal particle distribution (~25 µm and ~0.85 µm), the latter being associated with highly dispersed MnOx redox-active domains. Structural and textural analyses reveal that Mn incorporation significantly enhances surface properties, increasing the BET surface area from 140.8 to 213 m2 g−1 while reducing pore size to the meso–microporous range (~1.9 nm). Importantly, the material retains intrinsic minerals such as Ca, Mg, K, and Si, which contribute to surface basicity and ion-exchange capacity, supporting additional Hg(II) interaction pathways. Optical and electronic characterization shows a wide band gap semiconductor behavior (≈3.4 eV) and a conduction band position at −0.892 V vs. NHE, sufficiently negative to thermodynamically drive Hg2+ reduction to Hg0 under UV-A irradiation. Hg(II) quantification was validated using a UV–Vis method based on the Hg2+–dipicolinic acid (DPA) complex, confirming stable complex formation with 1:2 stoichiometry (Hg2+:DPA) and high analytical reliability (R2 = 0.948, LOD = 1.85 mg L−1). Photocatalytic experiments demonstrated negligible Hg(II) reduction under UV-A light in the absence of catalyst, whereas the carbon-based materials enabled significant Hg transformation through adsorption-assisted photoinduced electron transfer. Electrochemical analyses (Rct ≈ 11 Ω) confirmed efficient charge transport, while cyclic voltammetry evidenced reversible Mn(IV)/Mn(III)/Mn(II) redox cycling, which sustains electron mediation during photocatalysis. Overall, pristine biochar acts primarily through adsorption driven by oxygenated functional groups and porous structure, whereas Mn-functionalized biochar operates via a synergistic adsorption–photocatalytic mechanism. In this system, MnOx species function as redox-active centers that facilitate electron transfer from the carbon matrix to Hg(II), while the conductive lignocellulosic-derived framework enhances charge mobility. The combination of structural carbon stability, dispersed Mn active sites, and inherent mineral functionality establishes a highly efficient and sustainable carbocatalyst, demonstrating a green and scalable approach for mercury remediation in mining-impacted regions.