Achieving high-efficiency charge separation and strong oxidizing capacity are of great significance for photodegradation of organic pollutants . Herein, novel self-doped Zr 3+ -ZrO 2 nanoclusters and AgCl@Zr 3+ -ZrO 2 heterostructures with high surface areas were fabricated for photodegradation of organic pollutants under visible-light illumination. The experimental results revealed that self-doped Zr 3+ -ZrO 2 clusters were formed during a carbothermal reduction process, and the adsorbed surface chlorine promoted the adhesions of Ag + to form AgCl over the surface of Zr 3+ -ZrO 2 clusters. The obtained AgCl@Zr 3+ -ZrO 2 heterojunctions displayed ultrahigh-performance degradation of norfloxacin under visible-light illumination, and the prepared AgCl@Zr 3+ -ZrO 2 -11 heterojunction presented the highest photocatalytic performance with a rate constant of 0.21989 min −1 , which was approximately 62.12 times that of Zr 3+ -ZrO 2 clusters and 21.95 times that of AgCl and far better than that of commercial ZrO 2 . The formation of Zr 3+ self-doping, strongly combined interfaces, and high surface areas highly promoted charge separation for highly enhanced photodegradation of organic pollutants.
Broadband solar light absorption and visible light photocatalysis of surface modified ultrawide bandgap semiconductors are receiving wide attentions because of their more negative conduction band potential and positive valence band potential for refractory organics degradation. Here, we reported a novel modified solvothermal strategy by the introduction of distilled water into small molecular alcohols to synthesize crystallized carbon-coated Zr 3+ -ZrO 2 composites for enhanced visible light absorption and visible light photocatalytic tetracycline degradation, in which the distilled water favored for the crystallization of Zr 3+ -ZrO 2 and the formed ultrathin carbon layers derived from the polymerization of small molecular alcohols were contributing to the generation of Zr 3+ species and well dispersion of Zr 3+ self-doped ZrO 2 nanoparticles. The experimental results also showed that carbon-coated Zr 3+ -ZrO 2 composites exhibited enhanced visible light absorption, long-lived charges, efficient visible light photocatalytic performance and good recyclable stability. Besides, possible photocatalytic mechanism and antibiotic degradation pathways over carbon-coated Zr 3+ -ZrO 2 composites under visible light irradiation were also proposed in detail.
Zirconium dioxide (ZrO 2 ) is extensively investigated for the remediation of antibiotic pollution in aquatic environments, owing to its environmental compatibility and favorable electronic structure. However, its ultrawide band gap energy severely restricts visible-light harvesting and visible-light photocatalysis. To overcome these limitations, visible-light-active Zn/Zr 3+ -ZrO 2 and AgI@Zn/Zr 3+ -ZrO 2 nanostructures were synthesized through a calcination-chemical deposition strategy for levofloxacin degradation. The obtained AgI@Zn/Zr 3+ -ZrO 2 composites demonstrated a high specific surface area of approximately 100.65 m 2 g −1 and enhanced visible-light absorption, featuring a red-shifted absorption edge extending to approximately 460 nm. The AgI@Zn/Zr 3+ -ZrO 2 -30% heterojunction exhibited the highest photocatalytic levofloxacin degradation efficiency under visible-light irradiation, achieving a remarkable 80.51% degradation within 18 min. The apparent rate constant was 0.10042 min −1 , which was 5.66 times and 31.28 times of AgI (0.01772 min −1 ) and Zn/Zr 3+ -ZrO 2 (0.00321 min −1 ), respectively. Additionally, the AgI@Zn/Zr 3+ -ZrO 2 composites demonstrated remarkable cycling stability for levofloxacin degradation, retaining 94.67% of the initial performance after three reuse cycles. Crucially, Zr 3+ doping and Step-scheme (S-scheme) heterostructure synergistically enhances interfacial charge dynamics and chemical stability of the AgI@Zn/Zr 3+ -ZrO 2 composites, offering a viable design strategy for high-performance photocatalysis.
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