Synergistic effects of biomass-derived carbon quantum dots and Cu Co-doping on TiO2 nanocomposite for enhanced visible-light photocatalysis

Abstract

The development of sustainable approaches for enhancing the visible-light activity of TiO2-based photocatalysts has attracted considerable research interest. In this work, carbon quantum dots (CQDs)-Cu co-modified TiO2 nanocomposites were synthesized via a hydrothermal method using butterfly pea ( Clitoria ternatea ) flowers as a biomass-derived carbon source. The Cu content was fixed at 1.5 mol% relative to Ti, while the CQDs loading was controlled by varying the butterfly pea precursor concentration from 0.25 to 1.25 g L−1, yielding 1C–Cu–TiO2, 3C–Cu–TiO2, and 5C–Cu–TiO2 samples. The prepared materials were characterized by electron microscopy, X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy, photoluminescence (PL), and X-ray absorption spectroscopy (XAS). High-resolution transmission electron microscopy revealed CQDs with an average size of approximately 4.29 nm and an interplanar spacing of approximately 0.23 nm. All composites retained the anatase TiO2 phase after Cu incorporation and CQDs modification. Enhanced visible-light absorption was observed and is attributed to the formation of Cu-related sub-band-gap states and the sensitization effect of CQDs. PL analysis showed an emission peak at ∼415 nm under 660 nm excitation, suggesting the presence of upconversion photoluminescence behavior in the CQDs. Conventional PL spectra further suggested reduced charge-carrier recombination in the modified composites. Photocatalytic activity was evaluated through Rhodamine B (RhB) degradation under visible-light irradiation. Among all samples, 1C–Cu–TiO2 exhibited the highest performance, achieving degradation efficiency of 99.28% within 50 min. The apparent reaction rate constant reached 0.1038 min−1, which was 2.23, 1.96, and 2.90 times higher than those of pristine TiO2, Cu–TiO2, and 3C–Cu–TiO2, respectively. Radical scavenging experiments indicated that •OH and h+ were the dominant reactive species, while •O2− also participated in the degradation process. The enhanced photocatalytic performance is attributed to the synergistic effects of Cu and biomass-derived CQDs in improving visible-light harvesting and charge separation, providing an effective approach for developing visible-light-responsive TiO2 photocatalysts.