Design and Optimization of ZnO–ZnCr2O4 Heterojunction for Enhanced Solar-Light Photocatalytic Degradation of Rhodamine B

ZnO–ZnCr2O4 heterojunction nanocomposites were synthesized via co-precipitation with nominal spinel loadings of 10, 20, and 30 wt.% (denoted ZnCr-10, ZnCr-20, ZnCr-30) to evaluate structure–property–performance relationships in photocatalytic dye degradation. Rietveld refinement of XRD data revealed actual crystalline phase fractions of 12.1%, 32.4%, and 39.9% ZnCr2O4, respectively, with systematic morphological evolution from dispersed nanoparticles (ZnCr-10) to densely agglomerated structures (ZnCr-30) observed by SEM. Optical analysis demonstrated that ZnCr-10 (apparent band gap 3.09 eV) retains ZnO-dominated absorption with moderate interfacial electronic coupling, while ZnCr-20 shows enhanced visible response (2.89 eV) through interface-mediated transitions. ZnCr-30 exhibits strong sub-bandgap absorption (1.63 eV) originating from defect states rather than intrinsic band narrowing. Photoluminescence studies under UV excitation revealed optimal radiative recombination suppression in ZnCr-10, consistent with efficient interfacial charge separation, whereas excessive loading (ZnCr-30) introduced defect-mediated recombination centers. Photocatalytic degradation of Rhodamine B (5 mg/L, 0.5 g/L catalyst, solar irradiation) followed the order: ZnCr-10 (k = 0.0307 min−1) > ZnO (0.0203 min−1) > ZnCr-20 (0.0230 min−1) > ZnCr2O4 (0.0166 min−1) > ZnCr-30 (0.0113 min−1). The optimal ZnCr-10 performance is attributed to balanced interfacial contact between phases enabling charge separation without excessive agglomeration or defect accumulation. Operational parameters (pH 7, 50 mg/100 mL, 100 µL H2O2) were optimized, achieving 98% degradation in 60 min. This study demonstrates that photocatalytic enhancement in ZnO–spinel heterojunctions is governed by interfacial architecture and defect management rather than optical absorption alone, providing design principles for efficient solar-driven environmental remediation.