Methyl orange (MO) is an organic synthetic dye widely used in laboratory and industrial applications. In laboratory settings, it serves as an acid–base indicator due to its distinct color change in both acidic and alkaline environments. Industrially, it is primarily utilized in the textile industry for its ultraviolet (UV) absorption properties. However, the discharge and leakage of methyl orange into the environment can cause severe ecological damage and pose potential carcinogenic and teratogenic risks to human health. Therefore, detecting and quantifying the concentration of methyl orange in various matrices is crucial. This study reports the synthesis of graphene quantum dots (GQDs) from orange peel as a precursor, using ethanol and dimethylformamide (DMF) as solvents. Cyan (c-GQDs) and yellow (y-GQDs) graphene quantum dots were synthesized through a bottom-up hydrothermal method. The difference in color is attributed to the redshift caused by the varying ratio of pyridine nitrogen to pyrrole nitrogen. These GQDs exhibited notable optical properties, with c-GQDs emitting cyan fluorescence and y-GQDs emitting yellow fluorescence under UV light. To investigate fluorescence quenching effects, nine commonly used dyes were tested, and all were found to quench the fluorescence of y-GQDs, with methyl orange having the most significant effect. The fluorescence quenching of orange peel-derived GQDs in the presence of methyl orange is attributed to poor dispersion in DMF solution. Additionally, the GQDs possess high specific surface area, abundant surface functional groups, and excellent electronic conductivity, which contribute to their effective fluorescence quenching performance. The average thickness of y-GQDs (the vertical dimension from the substrate upwards) was 3.51 nm, confirming their graphene-like structure. They emitted yellow fluorescence within the wavelength range of 450–530 nm. Notably, a significant linear correlation was found between the concentration of methyl orange and the fluorescence intensity of y-GQDs (regression coefficient = 0.9954), indicating the potential of GQDs as effective sensing materials for organic pollutant detection.

Industrial dye wastewater poses serious environmental and health risks, demanding sustainable remediation strategies. Here, hierarchically porous hollow TiO₂ nanofibers (HNFTis) were fabricated and combined with blue, green, and orange graphene quantum dots (b-GQDs, g-GQDs, o-GQDs) to form heterojunction photocatalysts. Progressive fluorescence redshift of GQDs, induced by surface functionalization and S/B doping, narrows the bandgap and enhances visible-light absorption. Among the composites, 0.5 wt% o-GQDs/HNFTi exhibited the highest photocurrent and lowest charge-transfer resistance and degraded 99.5% of Methylene blue under visible light within 2 h, outperforming pristine HNFTi (77.7%). The synergistic effect of TiO₂ structural engineering and GQD fluorescence tuning demonstrates an effective strategy for designing high-performance photocatalysts for sustainable wastewater treatment.

Industrial dye wastewater poses severe environmental and health risks, creating an urgent demand for efficient and sustainable remediation technologies. Herein, hierarchically porous hollow TiO2 nanofibers (HNFTi) were constructed through electrospinning and coupled with blue-, green-, and orange-emissive graphene quantum dots (b-, g-, and o-GQDs) to fabricate visible-light-responsive heterojunction photocatalysts. By tailoring the surface functional groups and heteroatom doping of GQDs, a progressive fluorescence redshift was achieved, which effectively narrowed the bandgap and extended visible-light absorption. Benefiting from the synergistic effects of the hierarchically porous hollow TiO2 architecture and the fluorescence-tuned GQDs, the resulting composites exhibited enhanced light harvesting, accelerated charge separation, and improved interfacial charge transfer. Among them, the 0.5 wt% o-GQDs/HNFTi composite showed the best photocatalytic performance, delivering a methylene blue degradation efficiency of 99.5% within 2 h under visible-light irradiation, markedly higher than that of pristine HNFTi (77.7%). Photoelectrochemical and Kelvin probe force microscopy analyses further confirmed the promoted carrier dynamics and effective interfacial separation of photogenerated electron-hole pairs. This work provides a feasible strategy for integrating structural engineering and fluorescence modulation to develop high-performance TiO2-based photocatalysts for wastewater treatment.