Effective Photogeneration of Singlet Oxygen and High Photocatalytic and Antibacterial Activities of Porous Mn-Doped ZnO-ZrO2 Nanocomposites

S. Evstropiev, A. Shelemanov, Igor Bagrov, A. Karavaeva, Kseniya Portnova, N. Nikonorov
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Abstract

Disperse porous Mn-doped ZnO-ZrO2 nanocomposites were prepared using the facile polymer-salt method. The effect of Mn content on the crystal structure, composite morphologies, their ability to photogenate the singlet oxygen, luminescence properties, and bactericidal activities were studied. The crystal structure and morphology of these materials were investigated using XRD and SEM analysis. It was found that obtained nanocomposites consist of small (~9 nm) hexagonal ZnO and fine ZrO2 crystals and the embedding of Mn ions expands the crystal cells of ZnO crystals. Photoluminescence spectra indicate the presence of different structural defects (interstitial Zn ions and oxygen vacancies in ZnO and oxygen vacancies in ZrO2 crystals). Mn-doped ZnO-ZrO2 nanocomposites can photogenerate singlet oxygen under visible (λ = 405 nm) irradiation. The increased power density of the exciting blue (λ = 405 nm) light significantly enhances the singlet oxygen photogeneration by prepared composites. The dependence of the intensity of singlet oxygen photogeneration by composites on the power density of exciting radiation (at its variation in the range 0.8 ÷ 1.6 W/cm2) is close to linear. Mn-doped ZnO-ZrO2 composites demonstrate superior antibacterial activity against the gram-positive bacteria Staphylococcus aureus ATCC 209P. It was found that highly dispersed porous Mn-doped ZnO-ZrO2 nanocomposites are promising for practical environmental and medical applications.
多孔掺锰 ZnO-ZrO2 纳米复合材料的有效单线态氧光生成及高光催化和抗菌活性
采用简便的聚合物-盐法制备了分散多孔的掺锰 ZnO-ZrO2 纳米复合材料。研究了锰含量对晶体结构、复合形貌、光生化单线态氧的能力、发光特性和杀菌活性的影响。采用 XRD 和 SEM 分析方法研究了这些材料的晶体结构和形态。研究发现,所获得的纳米复合材料由小(约 9 nm)六方氧化锌和细 ZrO2 晶体组成,锰离子的嵌入扩展了氧化锌晶体的晶胞。光致发光光谱显示存在不同的结构缺陷(ZnO 晶体中的间隙锌离子和氧空位以及 ZrO2 晶体中的氧空位)。掺锰的 ZnO-ZrO2 纳米复合材料可在可见光(λ = 405 纳米)照射下光生成单线态氧。增加激发蓝光(λ = 405 nm)的功率密度可显著提高所制备复合材料的单线态氧光生成能力。复合材料的单线态氧光生成强度与激发辐射的功率密度(在 0.8 ÷ 1.6 W/cm2 范围内变化)的关系接近线性。掺锰的 ZnO-ZrO2 复合材料对革兰氏阳性菌金黄色葡萄球菌 ATCC 209P 具有卓越的抗菌活性。研究发现,高分散多孔掺锰 ZnO-ZrO2 纳米复合材料在实际环境和医疗应用中大有可为。
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