氧化锌抗菌及降解有机污染物活性研究
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摘要
低维结构ZnO是近年来功能材料领域的研究热点,因其具有良好的生物相容性和环境安全性,基于ZnO的长效抗菌和环境净化材料更是吸引了学术界和工业界的广泛关注。ZnO的抗菌和光催化活性与其产生的羟基自由基(·OH)、超氧阴离子自由基(·02-)和过氧化氢(H202)等活性氧密切相关,而对于其产生活性氧的机理和影响因素的系统研究还很少,这恰恰是调控其功能活性的基础。本论文选择三种不同形貌的ZnO作为研究对象,以活性氧物种与ZnO材料学因素之间的关系作为研究主线,探讨了材料结构、形貌、比表面积等对其抗菌和降解有机污染物活性的影响规律和相关机理,在此基础上提出了ZnO的抗菌活性调控方法。
对微／痕量活性氧的特异反应进行了对比分析,根据本研究中对检测方法特异性、灵敏度以及可操作性等方面的要求,首先采用电子顺磁共振(EPR)法对ZnO体系中产生的自由基类活性氧(·OH和·O2)进行了定性分析；在此基础上,进一步开展了系列活性氧物种的定量检测方法研究,建立了适用于ZnO在水悬浮体系中产生典型活性氧物种(·OH、·O2-和H202)的定量检测方法,包括：基于对苯二甲酸羟基化-荧光光谱分析(TAH-F)的·OH检测、基于氯化硝基四氮唑蓝还原-分光光度分析(NBTR-S)的·O2-表征和基于淀粉碘量法-分光光度分析(SIM-S)的H2O2检测。实验研究发现：无光条件下,ZnO体系中没有·OH和·O2-产生,但是有H202产生；模拟日光下,·OH、·O2和H2O2三种活性氧都有产生；ZnO悬液在模拟日光下的·OH和·O2-累积产量均随时间的延长而增加,在无光和模拟日光条件下的H202产量也均随时间的延长而增加,且模拟日光照射下的H202产量高于无光下的产量。
分别对四针状ZnO晶须(T-ZnO)、纳米ZnO(n-ZnO)和微米ZnO(m-ZnO)这三种ZnO体系中产生的活性氧物种进行了研究,结果表明：其产生·OH的能力从大到小依次是T-ZnO、m-ZnO、n-ZnO,产生·O2-的能力从大到小依次是m-ZnO、T-ZnO、 n-ZnO,产生H2O2的能力从大到小依次是T-ZnO、n-ZnO、m-ZnO。对三种ZnO的材料学特性分析发现,比表面积不是影响ZnO悬液中·OH、·O2-和H2O2产量的主要因素；晶格畸变不利于ZnO体系产生-OH和·O2；表层晶格中的氧空位在H2O2的形成过程中发挥了重要作用,且有利于·OH的产生,而不利于·O2-的产生。
采用抑菌环试验和抗菌率测试法,评价了三种ZnO在模拟日光和无光条件下的抗菌性能,结果表明：在模拟日光和无光条件下,T-ZnO、n-ZnO和m-ZnO都对大肠杆菌具有明显抑制作用,且模拟日光下的抗菌活性比在无光条件下更高。在相同的光照条件下,不同形貌ZnO的抗菌活性也存在差异,无论是在模拟日光下还是在无光条件下,其抗菌活性都是从大到小依次为T-ZnO、n-ZnO、m-ZnO。结合三种ZnO产生活性氧物种和溶出Zn2+的研究结果,证实了H2O2的产生是ZnO抗菌的主要机理。进一步研究了环境中的O2和ZnO表层晶格氧空位对H2O2产生量的影响,结果表明,实验环境中的O2和ZnO表层的晶格氧空位浓度对H2O2的产生具有显著的影响,提出了一种基于氧空位控制的ZnO抗菌活性调控方法。
以甲基橙为降解底物,评价了ZnO光催化降解有机物的效果。结果表明：在模拟日光照射下,ZnO悬液中甲基橙的浓度随时间的延长而降低,三种ZnO降解甲基橙的活性从大到小依次为m-ZnO、T-ZnO、n-ZnO。结合ZnO产生活性物种的定量检测结果,发现此顺序与模拟日光下三种ZnO产生·O2-能力的大小顺序一致,与产生·OH能力的大小顺序不一致。说明甲基橙的降解不是以-OH氧化机理为主,而很有可能是空穴直接氧化机理。
以T-ZnO为载体材料,以酒石酸铜为前驱体,通过可控分解,在T-ZnO表面原位均匀地沉积了纳米Cu(粒径约为18nm)。发现沉积纳米Cu之后,模拟日光下·OH产量变化不大,而·O2-产量明显降低,说明有效捕获了光生电子；无光下H2O2产量没有明显变化,而模拟日光下的H2O2产量有所降低。在表面沉积了纳米Cu之后,T-ZnO在无光下的抗菌活性随纳米Cu沉积量的增大而显著提高,沉积量从0.2mol%到1.0mol%的5个样品,4h抗菌率都在98.5%以上,沉积量为1.0mol%样品的最小抑菌浓度(MIC)可达125mg/L,明显优于纯ZnO的500mg/L。进一步研究表明,纳米Cu沉积T-ZnO抗菌活性的增加不是因为H2O2产量的增加,也不主要源自纳米Cu溶出的Cu2+,而是来源于Cu与ZnO的协同抗菌效果。T-ZnO经纳米Cu沉积后的光催化降解甲基橙的活性没有明显变化,这可能是由于Cu沉积未能有效提高光生空穴的量。
采用高温固溶法对ZnO进行了Cu2+掺杂改性,表征结果表明,掺杂后ZnO的晶格常数发生了变化,对光的吸收阀值发生了红移,其中的Zn和O元素结合能发生了一定程度的偏移,说明Cu2+已掺杂到ZnO晶格中,并在ZnO中引入了杂质能级。掺杂改性后,ZnO体系中·OH、·O2-和H2O2的产量都急剧下降,其中·OH、·O2-的产量表现出同步下降规律,说明掺杂的Cu2+在ZnO中没有起到分离光生电子和空穴的作用,反而成为了光生电子和空穴的复合中心；Cu2+掺杂后的ZnO光催化降解甲基橙的活性也明显降低,这与活性氧的检测结果一致。掺杂后,ZnO的抗菌性能也有所下降,但针对所有掺杂样品而言,其抗菌性能随着Cu2+掺杂浓度的增加而增加,分析认为是掺杂进入ZnO晶格的Cu2+发挥了抗菌作用。
在上述研究的基础上,对含T-ZnO的抗菌材料在载人航天飞行器上的应用进行了前期探索。将改性T-ZnO添加到聚氨酯涂料中,用喷涂法分别在航天器用铝合金、舱壁布(天然纤维织物)和门帘布(合成纤维织物)表面制备了抗菌涂层,形貌观察显不：T-ZnO在涂层表面分布均匀,四针状结构基本保持完好。用双螺杆共混挤出和模压成型方法制备含改性T-ZnO的聚丙烯复合材料,研究表明：T-ZnO的四针状形貌多数被破坏,主要以单针状体形式存在。四种材料表层均露出有ZnO针状体(四针或单针),能够保证其表面抗菌作用的发挥。地面抗菌性能评价表明,添加4wt%T-ZnO的聚氨酯涂层和聚丙烯复合材料对大肠杆菌的抗菌率均在98%以上。以聚丙烯为对象,对T-ZnO抗菌剂添加量的研究结果表明：T-ZnO添加量达到2wt%时,抗菌率达到了96%以上,可满足其作为抗菌制品的使用要求。
Low-dimensional structure of ZnO is a hot research topic in the field of functional materials in recent years. Because of the good biocompatibility and environmental safety, ZnO-based long-term antibacterial and environmental purification materials have attracted lots of attentions of academia and industry. Antibacterial activity and photocatalytical activity of ZnO are closely related to the production of reactive oxygen species, such as hydroxyl radical (·OH), superoxide anion (·O2-) and hydroxyl peroxide (H2O2). However, the mechanism and affecting factors of generation of the reactive oxygen species in ZnO, which are distinctly the bases for adjusting its functional activity, are still lacking of systematically study. In this dissertation, we comparatively studied the productions and affecting mechanisms of reactive oxygen species, and related antibacterial and/or photocatalytical properties of selected three types of ZnO, and then proposed a facile approach to improve the antibacterial activity.
Firstly, specific reactions of the reactive oxygen species were reviewed and comparatively analyzed. Considering the requirements in specificity, sensitivity and operability of the detecting methods in this study, electron spin resonance was chosen for qualitatively study of the free radicals such as·OH and·O2-. Then, specific methods for quantificationally detecting the reactive oxygen species in ZnO suspensions were developed respectively. The typical measurements included terephthalic acid hydroxylation methods combining with fluorescence analysis (TAH-F) for·OH, nitro blue tetrazolium reduction method collaborating with spectrophotometry analysis (NBTR-S) for·O2-, and starch iodometric method incorporating with spectrophotometry analysis (SIM-S) for H2O2. The results indicated that, without light irradiation, there were no·OH or·O2-but H2O2generation in ZnO suspension; while under simulated sunlight,·OH,·O2-and H2O2all generated in ZnO suspension. The cumulative productions of·OH and·O2-both increased with time under simulated sunlight. The cumulative production of H2O2increased along with the extension of time either in dark or under simulated sunlight, and the yield of H2O2under simulated sunlight was higher than that in in dark.
The production of·OH,·O2-and H2O2of the three kinds of ZnO, which are tetrapod-like ZnO whisker (T-ZnO), nano-sized ZnO (n-ZnO) and micro-sized ZnO (m-ZnO), were comparatively tested in this work. The results showed that the activity forH production were T-ZnO, m-ZnO and n-ZnO in descending order, the activity for·O2-production were m-ZnO, T-ZnO and n-ZnO in descending order, and the activity for H2O2production were T-ZnO, n-ZnO and m-ZnO in descending order. By analyzing the material characteristics of the three typs of ZnO, it was found that the specific surface area was not the main factor on the production of·OH,·O2-and H2O2, and lattice distortion had a negative effect on the production of·OH and·O2-. Further investigations showed that oxygen vacancies in skin layers of the crystal played an important role in the formation of H2O2, and having a positive effect on the production of·OH and negative effect on·O2-.
The antibacterial properties of ZnO with different morphologies under simulated sunlight and in dark were respectively evaluated with Escherichia coli (E. coli) by zone of inhibition and bactericidal rate. The results indicated that T-ZnO, n-ZnO and m-ZnO all exhibited antibacterial effect against E. coli both under simulated sunlight and in dark, and the antibacterial activity under simulated sunlight condition was higher than that in dark. In the same condition, the antibacterial activity displayed differences among the three types of ZnO, which was sorted in descending order as T-ZnO, n-ZnO and m-ZnO either under simulated sunlight or in dark. Results of Zn2+dissolution and reactive oxygen species productions indicated that the H2O2generating was the main mechanism for antibacterial activity of ZnO. Furthermore, the effects of O2in atmosphere and oxygen vacancy in the skin layer of ZnO crystal on the production of H2O2were studied, and the results indicated that they both had significant role on H2O2formation. Based on the experimental studies, a method for adjusting the antibacterial activity by controlling oxygen vacancies concentration was preliminarily advised.
The activity of ZnO for decomposing organic contamination was evaluated using methyl orange as the substrate. The results showed that the concentration of methyl orange in ZnO suspensions decreased with time under simulated sunlight condition. The degradation rate of methyl orange in the aqueous suspensions displayed differences among the three types of ZnO, which was sorted in descending order as m-ZnO, T-ZnO, n-ZnO. Comparing the production of reactive oxygen species with the degradation rate of methyl orange, we concluded that the degradation of methyl orange in ZnO suspension was not consistent with the production of-OH, but showed the same order as the production of·O2-, which indicating that the degradation of methyl orange was not based on the·OH oxidation mechanism, but most likely based on the direct photo-generated hole oxidation mechanism.
Copper nanoparticles were uniformly deposited onto the surface of T-ZnO by in-situ decomposition of cupric tartrate. The productions of·OH, O2-and H2O2were determined. The results showed that the production of-OH did not change significantly. But, the production of·O2-decreased obviously, which indicated that Schottky barrier was formed and effective in trapping electrons. The production of H2O2in dark did obviously changed, but it decreased under simulated sunlight. The antibacterial activity in dark of the modified T-ZnO increased with the increase of loading amount of copper nanoparticles. The value of minimum inhibitory concentration (MIC) of the deposit-modified sample with1.0mol%of copper nanoparticles was125mg/L, which was significantly lower than the origianl T-ZnO of500mg/L. Further studies indicated that the improvement of antibacterial activity of T-ZnO after deposition of copper nanoparticles was attributed neither to increasing H2O2production nor to releasing Cu2+, but may be derived from the synergistic antibacterial effect between Cu and ZnO. Afte deposited with Cu nanoparticles, the activity of T-ZnO for decomposing methyl orange did not change significantly.
Cu2+doped ZnO was prepared by means of solid solution treatment. The change of lattice constants, the redshift of light absorption threshold and the offset of binding energy between Zn and O of the doped ZnO were investigated, and the results indicated that Cu2+had been successfully doped into the lattice of ZnO and the impurity level had been successfully introduced into ZnO. The productions of·OH,·O2-and H2O2all significantly decreased after doping. The similar level of decrease of·OH and·O2-illustrated that the doped Cu2+did not play the role in separating photogenerated electrons and holes in ZnO, but acted as recombination centers of the photo-induced electrons and holes. The activity of ZnO for decomposing methyl orange also decreased after Cu2+-doping, which was consistent with the measurements of reactive oxygen species. The antibacterial activity of ZnO decreased after doping, however, for the doped samples, the antibacterial activity increased with increase of doping concentration of Cu2+.
Finally, the application of ZnO as antibacterial materials for manned spacecraft was pre-explored. Antibacterial coatings were prepared and coated on the surfaces of aluminum alloys, bulkhead cloth and curtain cloth by spraying polyurethane (PU) varnish mixed with modified T-ZnO. Scanning electron microscopy (SEM) observations showed that T-ZnO was uniformly distributed on the surfaces, and the tetrapod-like structure was preserved. Polypropylene (PP) composites filled with modified T-ZnO were prepared by twin-screw extrusion and molding method. SEM analyses demonstrated that the tetrapod-like structure of T-ZnO was destroyed and mainly instead by single spicules or fragments existing in PP. A lot of ZnO needles exposed on the surfaces of the mentioned four kinds of materials, which could ensure contacting with bacteria and playing activity. The antibacteriral rates of PU coating and PP composite with4wt%T-ZnO against E. coli were all higher than98%. The effect of adding amount of T-ZnO onantibacteriral rate was studied with PP, and the result indicated that antibacteriral rates increased with the loading of T-ZnO increasing. The antibacteriral rate could get96%when T-ZnO was2wt%in the composites, which met the requirement of use as antimicrobial products.
对微／痕量活性氧的特异反应进行了对比分析,根据本研究中对检测方法特异性、灵敏度以及可操作性等方面的要求,首先采用电子顺磁共振(EPR)法对ZnO体系中产生的自由基类活性氧(·OH和·O2)进行了定性分析；在此基础上,进一步开展了系列活性氧物种的定量检测方法研究,建立了适用于ZnO在水悬浮体系中产生典型活性氧物种(·OH、·O2-和H202)的定量检测方法,包括：基于对苯二甲酸羟基化-荧光光谱分析(TAH-F)的·OH检测、基于氯化硝基四氮唑蓝还原-分光光度分析(NBTR-S)的·O2-表征和基于淀粉碘量法-分光光度分析(SIM-S)的H2O2检测。实验研究发现：无光条件下,ZnO体系中没有·OH和·O2-产生,但是有H202产生；模拟日光下,·OH、·O2和H2O2三种活性氧都有产生；ZnO悬液在模拟日光下的·OH和·O2-累积产量均随时间的延长而增加,在无光和模拟日光条件下的H202产量也均随时间的延长而增加,且模拟日光照射下的H202产量高于无光下的产量。
分别对四针状ZnO晶须(T-ZnO)、纳米ZnO(n-ZnO)和微米ZnO(m-ZnO)这三种ZnO体系中产生的活性氧物种进行了研究,结果表明：其产生·OH的能力从大到小依次是T-ZnO、m-ZnO、n-ZnO,产生·O2-的能力从大到小依次是m-ZnO、T-ZnO、 n-ZnO,产生H2O2的能力从大到小依次是T-ZnO、n-ZnO、m-ZnO。对三种ZnO的材料学特性分析发现,比表面积不是影响ZnO悬液中·OH、·O2-和H2O2产量的主要因素；晶格畸变不利于ZnO体系产生-OH和·O2；表层晶格中的氧空位在H2O2的形成过程中发挥了重要作用,且有利于·OH的产生,而不利于·O2-的产生。
采用抑菌环试验和抗菌率测试法,评价了三种ZnO在模拟日光和无光条件下的抗菌性能,结果表明：在模拟日光和无光条件下,T-ZnO、n-ZnO和m-ZnO都对大肠杆菌具有明显抑制作用,且模拟日光下的抗菌活性比在无光条件下更高。在相同的光照条件下,不同形貌ZnO的抗菌活性也存在差异,无论是在模拟日光下还是在无光条件下,其抗菌活性都是从大到小依次为T-ZnO、n-ZnO、m-ZnO。结合三种ZnO产生活性氧物种和溶出Zn2+的研究结果,证实了H2O2的产生是ZnO抗菌的主要机理。进一步研究了环境中的O2和ZnO表层晶格氧空位对H2O2产生量的影响,结果表明,实验环境中的O2和ZnO表层的晶格氧空位浓度对H2O2的产生具有显著的影响,提出了一种基于氧空位控制的ZnO抗菌活性调控方法。
以甲基橙为降解底物,评价了ZnO光催化降解有机物的效果。结果表明：在模拟日光照射下,ZnO悬液中甲基橙的浓度随时间的延长而降低,三种ZnO降解甲基橙的活性从大到小依次为m-ZnO、T-ZnO、n-ZnO。结合ZnO产生活性物种的定量检测结果,发现此顺序与模拟日光下三种ZnO产生·O2-能力的大小顺序一致,与产生·OH能力的大小顺序不一致。说明甲基橙的降解不是以-OH氧化机理为主,而很有可能是空穴直接氧化机理。
以T-ZnO为载体材料,以酒石酸铜为前驱体,通过可控分解,在T-ZnO表面原位均匀地沉积了纳米Cu(粒径约为18nm)。发现沉积纳米Cu之后,模拟日光下·OH产量变化不大,而·O2-产量明显降低,说明有效捕获了光生电子；无光下H2O2产量没有明显变化,而模拟日光下的H2O2产量有所降低。在表面沉积了纳米Cu之后,T-ZnO在无光下的抗菌活性随纳米Cu沉积量的增大而显著提高,沉积量从0.2mol%到1.0mol%的5个样品,4h抗菌率都在98.5%以上,沉积量为1.0mol%样品的最小抑菌浓度(MIC)可达125mg/L,明显优于纯ZnO的500mg/L。进一步研究表明,纳米Cu沉积T-ZnO抗菌活性的增加不是因为H2O2产量的增加,也不主要源自纳米Cu溶出的Cu2+,而是来源于Cu与ZnO的协同抗菌效果。T-ZnO经纳米Cu沉积后的光催化降解甲基橙的活性没有明显变化,这可能是由于Cu沉积未能有效提高光生空穴的量。
采用高温固溶法对ZnO进行了Cu2+掺杂改性,表征结果表明,掺杂后ZnO的晶格常数发生了变化,对光的吸收阀值发生了红移,其中的Zn和O元素结合能发生了一定程度的偏移,说明Cu2+已掺杂到ZnO晶格中,并在ZnO中引入了杂质能级。掺杂改性后,ZnO体系中·OH、·O2-和H2O2的产量都急剧下降,其中·OH、·O2-的产量表现出同步下降规律,说明掺杂的Cu2+在ZnO中没有起到分离光生电子和空穴的作用,反而成为了光生电子和空穴的复合中心；Cu2+掺杂后的ZnO光催化降解甲基橙的活性也明显降低,这与活性氧的检测结果一致。掺杂后,ZnO的抗菌性能也有所下降,但针对所有掺杂样品而言,其抗菌性能随着Cu2+掺杂浓度的增加而增加,分析认为是掺杂进入ZnO晶格的Cu2+发挥了抗菌作用。
在上述研究的基础上,对含T-ZnO的抗菌材料在载人航天飞行器上的应用进行了前期探索。将改性T-ZnO添加到聚氨酯涂料中,用喷涂法分别在航天器用铝合金、舱壁布(天然纤维织物)和门帘布(合成纤维织物)表面制备了抗菌涂层,形貌观察显不：T-ZnO在涂层表面分布均匀,四针状结构基本保持完好。用双螺杆共混挤出和模压成型方法制备含改性T-ZnO的聚丙烯复合材料,研究表明：T-ZnO的四针状形貌多数被破坏,主要以单针状体形式存在。四种材料表层均露出有ZnO针状体(四针或单针),能够保证其表面抗菌作用的发挥。地面抗菌性能评价表明,添加4wt%T-ZnO的聚氨酯涂层和聚丙烯复合材料对大肠杆菌的抗菌率均在98%以上。以聚丙烯为对象,对T-ZnO抗菌剂添加量的研究结果表明：T-ZnO添加量达到2wt%时,抗菌率达到了96%以上,可满足其作为抗菌制品的使用要求。
Low-dimensional structure of ZnO is a hot research topic in the field of functional materials in recent years. Because of the good biocompatibility and environmental safety, ZnO-based long-term antibacterial and environmental purification materials have attracted lots of attentions of academia and industry. Antibacterial activity and photocatalytical activity of ZnO are closely related to the production of reactive oxygen species, such as hydroxyl radical (·OH), superoxide anion (·O2-) and hydroxyl peroxide (H2O2). However, the mechanism and affecting factors of generation of the reactive oxygen species in ZnO, which are distinctly the bases for adjusting its functional activity, are still lacking of systematically study. In this dissertation, we comparatively studied the productions and affecting mechanisms of reactive oxygen species, and related antibacterial and/or photocatalytical properties of selected three types of ZnO, and then proposed a facile approach to improve the antibacterial activity.
Firstly, specific reactions of the reactive oxygen species were reviewed and comparatively analyzed. Considering the requirements in specificity, sensitivity and operability of the detecting methods in this study, electron spin resonance was chosen for qualitatively study of the free radicals such as·OH and·O2-. Then, specific methods for quantificationally detecting the reactive oxygen species in ZnO suspensions were developed respectively. The typical measurements included terephthalic acid hydroxylation methods combining with fluorescence analysis (TAH-F) for·OH, nitro blue tetrazolium reduction method collaborating with spectrophotometry analysis (NBTR-S) for·O2-, and starch iodometric method incorporating with spectrophotometry analysis (SIM-S) for H2O2. The results indicated that, without light irradiation, there were no·OH or·O2-but H2O2generation in ZnO suspension; while under simulated sunlight,·OH,·O2-and H2O2all generated in ZnO suspension. The cumulative productions of·OH and·O2-both increased with time under simulated sunlight. The cumulative production of H2O2increased along with the extension of time either in dark or under simulated sunlight, and the yield of H2O2under simulated sunlight was higher than that in in dark.
The production of·OH,·O2-and H2O2of the three kinds of ZnO, which are tetrapod-like ZnO whisker (T-ZnO), nano-sized ZnO (n-ZnO) and micro-sized ZnO (m-ZnO), were comparatively tested in this work. The results showed that the activity forH production were T-ZnO, m-ZnO and n-ZnO in descending order, the activity for·O2-production were m-ZnO, T-ZnO and n-ZnO in descending order, and the activity for H2O2production were T-ZnO, n-ZnO and m-ZnO in descending order. By analyzing the material characteristics of the three typs of ZnO, it was found that the specific surface area was not the main factor on the production of·OH,·O2-and H2O2, and lattice distortion had a negative effect on the production of·OH and·O2-. Further investigations showed that oxygen vacancies in skin layers of the crystal played an important role in the formation of H2O2, and having a positive effect on the production of·OH and negative effect on·O2-.
The antibacterial properties of ZnO with different morphologies under simulated sunlight and in dark were respectively evaluated with Escherichia coli (E. coli) by zone of inhibition and bactericidal rate. The results indicated that T-ZnO, n-ZnO and m-ZnO all exhibited antibacterial effect against E. coli both under simulated sunlight and in dark, and the antibacterial activity under simulated sunlight condition was higher than that in dark. In the same condition, the antibacterial activity displayed differences among the three types of ZnO, which was sorted in descending order as T-ZnO, n-ZnO and m-ZnO either under simulated sunlight or in dark. Results of Zn2+dissolution and reactive oxygen species productions indicated that the H2O2generating was the main mechanism for antibacterial activity of ZnO. Furthermore, the effects of O2in atmosphere and oxygen vacancy in the skin layer of ZnO crystal on the production of H2O2were studied, and the results indicated that they both had significant role on H2O2formation. Based on the experimental studies, a method for adjusting the antibacterial activity by controlling oxygen vacancies concentration was preliminarily advised.
The activity of ZnO for decomposing organic contamination was evaluated using methyl orange as the substrate. The results showed that the concentration of methyl orange in ZnO suspensions decreased with time under simulated sunlight condition. The degradation rate of methyl orange in the aqueous suspensions displayed differences among the three types of ZnO, which was sorted in descending order as m-ZnO, T-ZnO, n-ZnO. Comparing the production of reactive oxygen species with the degradation rate of methyl orange, we concluded that the degradation of methyl orange in ZnO suspension was not consistent with the production of-OH, but showed the same order as the production of·O2-, which indicating that the degradation of methyl orange was not based on the·OH oxidation mechanism, but most likely based on the direct photo-generated hole oxidation mechanism.
Copper nanoparticles were uniformly deposited onto the surface of T-ZnO by in-situ decomposition of cupric tartrate. The productions of·OH, O2-and H2O2were determined. The results showed that the production of-OH did not change significantly. But, the production of·O2-decreased obviously, which indicated that Schottky barrier was formed and effective in trapping electrons. The production of H2O2in dark did obviously changed, but it decreased under simulated sunlight. The antibacterial activity in dark of the modified T-ZnO increased with the increase of loading amount of copper nanoparticles. The value of minimum inhibitory concentration (MIC) of the deposit-modified sample with1.0mol%of copper nanoparticles was125mg/L, which was significantly lower than the origianl T-ZnO of500mg/L. Further studies indicated that the improvement of antibacterial activity of T-ZnO after deposition of copper nanoparticles was attributed neither to increasing H2O2production nor to releasing Cu2+, but may be derived from the synergistic antibacterial effect between Cu and ZnO. Afte deposited with Cu nanoparticles, the activity of T-ZnO for decomposing methyl orange did not change significantly.
Cu2+doped ZnO was prepared by means of solid solution treatment. The change of lattice constants, the redshift of light absorption threshold and the offset of binding energy between Zn and O of the doped ZnO were investigated, and the results indicated that Cu2+had been successfully doped into the lattice of ZnO and the impurity level had been successfully introduced into ZnO. The productions of·OH,·O2-and H2O2all significantly decreased after doping. The similar level of decrease of·OH and·O2-illustrated that the doped Cu2+did not play the role in separating photogenerated electrons and holes in ZnO, but acted as recombination centers of the photo-induced electrons and holes. The activity of ZnO for decomposing methyl orange also decreased after Cu2+-doping, which was consistent with the measurements of reactive oxygen species. The antibacterial activity of ZnO decreased after doping, however, for the doped samples, the antibacterial activity increased with increase of doping concentration of Cu2+.
Finally, the application of ZnO as antibacterial materials for manned spacecraft was pre-explored. Antibacterial coatings were prepared and coated on the surfaces of aluminum alloys, bulkhead cloth and curtain cloth by spraying polyurethane (PU) varnish mixed with modified T-ZnO. Scanning electron microscopy (SEM) observations showed that T-ZnO was uniformly distributed on the surfaces, and the tetrapod-like structure was preserved. Polypropylene (PP) composites filled with modified T-ZnO were prepared by twin-screw extrusion and molding method. SEM analyses demonstrated that the tetrapod-like structure of T-ZnO was destroyed and mainly instead by single spicules or fragments existing in PP. A lot of ZnO needles exposed on the surfaces of the mentioned four kinds of materials, which could ensure contacting with bacteria and playing activity. The antibacteriral rates of PU coating and PP composite with4wt%T-ZnO against E. coli were all higher than98%. The effect of adding amount of T-ZnO onantibacteriral rate was studied with PP, and the result indicated that antibacteriral rates increased with the loading of T-ZnO increasing. The antibacteriral rate could get96%when T-ZnO was2wt%in the composites, which met the requirement of use as antimicrobial products.
引文
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