In this study, we investigate the strategic spatial integration of a conducting polymer into lithium electrodes for energy storage applications. Poly(3,4-ethylenedioxythiophene) (PEDOT) was incorporated into 2D graphene-molybdenum disulfide (GM) heterolayers to enhance their electrochemical performance in lithium-ion hybrid capacitors (LHCs). Two design strategies were explored: (i) N-PGM with an intra-embedded 3D PEDOT network via vapor-phase polymerization (VDP), and (ii) L-PGM with an outer 2D PEDOT layer deposited in the final fabrication step. N-PGM exhibited improved rate capability over GM, while L-PGM achieved the highest specific capacity and excellent cycling stability, retaining over 95.3% of its capacity after 2000 cycles. PEDOT introduced an additional surface-driven charge storage mechanism, complementing the diffusion-limited redox behavior of MoS₂. Molecular dynamics simulations further revealed that PEDOT weakened direct Li⁺ binding but improved electrolyte compatibility and ion mobility. Notably, the spatial configuration of PEDOT critically influenced these effects: surface-localized PEDOT in L-PGM reduced Li⁺ adsorption energy and promoted faster ion diffusion, whereas embedded PEDOT in N-PGM maintained a balance between ion transport and retention. These findings highlight that spatially controlled polymer incorporation offers a promising route to optimizing ionic accessibility and charge transport in nanostructured electrodes.

Plant-derived molecules offer tunable coordination and surface chemistry for photoelectrochemical (PEC) water splitting. A Scopus survey retrieved 45 documents linking both topics in 2005–2025, equivalent to 0.34% of the PEC literature. A supplementary search added 15 records, and screening retained 26 research articles. The review organizes molecular functions into light harvesting, charge-transfer mediation, coordination of catalytic overlayers, and passivation. A molecular readiness scale and a validation protocol connect molecular identity to verified device performance. Hybrid layers combining plant ligands with Co, Ni, or Fe raised BiVO₄ photocurrents to approximately 3–6 mA cm⁻² at 1.23 V vs. the reversible hydrogen electrode (RHE). Comparable inorganic overlayers preclude a general claim of superior activity. Ambient solution processing and control of interfacial coordination provide the principal design opportunities. Two-electron phenol/quinone potentials do not establish the feasibility of one-electron hole relay, which requires independent kinetic and redox evidence. At a coverage of 0.1 nmol cm⁻², a chlorophyll layer has a calculated photocurrent upper bound of approximately 0.05 mA cm⁻² within 640–680 nm alone. Broadband enhancement requires wavelength-resolved attribution. Operation for 1000 h at 1 mA cm⁻² and a loading of 1 nmol cm⁻² corresponds to approximately 3.7 × 10⁷ electrons per initially loaded molecule. The proposed framework links molecular structure, interfacial function, and product verification to guide durable molecular photoelectrodes.