Experimental Prototyping and Atomistic Modeling of Graphene Quantum Dot-Sensitized Solar Cells.

In the era of global energy transition, the development of third-generation photovoltaic technologies, such as dye-sensitized solar cells, has emerged as a paramount challenge in materials engineering. This study is dedicated to the synthesis and implementation of graphene quantum dots as eco-friendly sensitizers within DSSC architectures. The GQDs were synthesized via a microwave-assisted hydrothermal route using biodegradable organic precursors, providing a "green" alternative to conventional, toxic heavy-metal-based materials. The nanocrystalline structure and optoelectronic properties of the sensitizer were verified through UV-Vis and visual photoluminescence assessment. A focal point of this research was the optimization of the GQD concentration on the mesoporous surface of the titanium dioxide photoanode. Measurements were conducted utilizing a custom-designed experimental setup integrated with 3D-printed (FDM) components and an Arduino microcontroller, ensuring precise data acquisition under controlled illumination conditions (405-625 nm). The results indicated an optimal operational point at a fivefold dilution of the stock solution (0.4 g/dm3), which yielded the highest open-circuit voltage (Voc) of 545.4 mV under UV irradiation. The decline in photovoltaic performance observed at higher concentrations was attributed to excessive nanostructure agglomeration, which effectively blocked the mesopores of the semiconductor. Furthermore, the demonstrated high chemical capacitance of the system imparts electrochemical capacitor-like characteristics to the cell, enabling energy stabilization under fluctuating illumination. To elucidate the underlying sensitization mechanisms at the atomic level, computational simulations were conducted utilizing the MACE machine-learning potential and the GFN2-xTB semi-empirical method. The theoretical models revealed that the formation of stable covalent Ti-O-C bridges (chemisorption) is imperative for establishing strong interfacial electronic coupling. Solvation models and molecular dynamics (MD) at 300 K confirmed the thermodynamic and operational robustness of the hybrid system in an aqueous electrolyte. Ultimately, this combined experimental and theoretical work conclusively demonstrates that graphene quantum dots represent an efficient, highly stable, and non-toxic alternative to classic molecular dye sensitizers.