Green Synthesis of Ca-Doped ZnO Nanosheets with Tunable Band Structure via Cactus-Juice-Mediated Coprecipitation for Enhanced Photocatalytic H2 Evolution

The development of efficient, stable, and sustainably fabricated photocatalysts for solar-driven hydrogen evolution remains a critical challenge in the field. Herein, we report a novel green coprecipitation strategy to synthesize calcium-doped zinc oxide (Ca-ZnO) nanosheets, utilizing cactus juice as a natural, multifunctional medium for the coprecipitation process. This method enables the in situ, tunable incorporation of 3–7% Ca2+ ions into the wurtzite ZnO lattice without the use of harsh chemical reagents. Comprehensive characterization confirms that Ca2+ substitutionally replaces Zn2+, which preserves the intrinsic crystal structure of ZnO well while inducing the formation of uniform nanosheet morphology. This doping strategy effectively modulates the electronic band structure, progressively narrowing the bandgap from 3.19 eV to 2.90 eV and significantly enhancing visible-light absorption. Crucially, the incorporation of Ca2+ also generates oxygen vacancies, which serve as efficient electron traps to suppress photogenerated charge carrier recombination. The optimized 5%Ca-ZnO photocatalyst demonstrates a favorable hydrogen evolution rate of 889 μmol·g−1·h−1 under full-spectrum irradiation, with stability, retaining 94.8% of its activity after four cycles. This work not only provides a high-performance material but also establishes a generalizable, sustainable paradigm for the design of advanced semiconductor photocatalysts.