CN110935477A - 一种钛基复合材料在光催化降解霉菌毒素中的应用 - Google Patents
一种钛基复合材料在光催化降解霉菌毒素中的应用 Download PDFInfo
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Abstract
本发明申请提供了一种钛基复合材料在光催化降解霉菌毒素中的应用，属于纳米材料光催化技术领域。具体制备方法为：利用热分解法制备Y3+、Yb3+和Tm3+掺杂的β‑NaYF4上转换材料；接着使用CTAB修饰NaYF4:Yb,Tm，得到NaYF4:Yb,Tm分散液，向所得分散液加入氨水溶液调节pH，并加入TDAA的异丙醇溶液进行反应，将反应液进行离心并洗涤，得到NaYF4:Yb,Tm@TiO2，真空干燥随后退火处理得NaYF4:Yb,Tm@TiO2壳层光催化剂。该光催化剂应用于霉菌毒素的光催化降解中，本发明的光催化剂对霉菌毒素具有较强的光催化降解特性。
Description
技术领域
本发明属于纳米材料光催化技术领域，尤其是涉及一种钛基复合材料在光催化降解霉菌毒素中的应用。
背景技术
小麦、大米等谷物在田间或储存期间易被真菌侵染，导致霉菌毒素污染。常见的赭曲霉菌毒素是曲霉属和镰刀菌属的代谢产物，其中以赭曲霉菌毒素A(Ochratoxin，OTA)的毒性最大。OTA常见于谷物，咖啡，可可，香料，葡萄酒中。在家畜的一些器官和组织中，甚至在乳制品、血液中也发现了OTA。已知的OTA的毒性包括肾毒性，肝脏毒性，致畸性，遗传毒性和免疫毒性。OTA的危害性还体现在影响血液凝固，抑制蛋白质合成，促进细胞膜过氧化，破坏钙稳态并抑制线粒体呼吸。此外，国际癌症研究机构(IARC)将OTA列为潜在的人类致癌物(2B类)。OTA对于人类健康的危害及其对经济损失的影响使得寻找新型的脱毒方法对缓解OTA问题具有重大现实意义。
预防粮食中真菌生长和真菌毒素的产生通常被认为是阻止真菌毒素对动物和人类的有害影响的最佳方法，但对于已经产生的真菌毒素进行脱毒处理也是一项必要手段。现有的OTA脱毒方法可分为物理、化学、生物方法。物理方法如高温热处理使其失活、辐照降解技术或污染物通过提取和添加吸附剂等方式得以去除。常用的化学方法是碱处理法，使用碱性过氧化氢，氢氧化钠，甲胺和氢氧化钙等处理OTA。生物方法也被认为是一项有效脱毒的方法。许多微生物，如细菌，酵母和霉菌被证实具有降解OTA的能力。
采用物理方法可以有效降解OTA，但物理去除方法存在着成本高、操作难度系数大等缺点而难以投入到商业化大规模使用中去。此外，常用的添加吸附剂去除毒素的方法可能会造成营养价值的损失以及二次污染。
尽管化学方法能够达到有效去除毒素的目的，但化学方法在实际应用过程中存在一系列问题，首先是其安全性无法保障；其次是可能改变原料的性状，带来新污染；此外，可能会对环境造成污染等。
生物降解相比化学方法更加环保，在降解过程中对食物和环境不会造成污染，而且降解效率也很理想。因此，生物降解在脱毒方面具有很大的发展潜力。但目前生物降解的机理尚不明确，如何稳定菌种的降解能力，抑制菌种退化等问题都亟待解决。总之，现有的每种方法普遍存在不足之处，导致有限的应用。需要加大对OTA降解技术的研究，发展更加有效，更具发展前景的OTA降解手段。
纳米非均相光催化是一种先进的氧化技术，近些年来在空气净化、水消毒和废水处理中表现不凡。该技术利用纳米催化剂，在太阳光照射下受到刺激，为各类污染物的去除提供替代和节能的一个非常具有吸引力的解决方案。在各种半导体光催化剂中，二氧化钛(TiO2)凭借环境友好性，高光活性，优异的化学稳定性，低成本而备受青睐，广泛应用于水中有机污染物处理、空气污染物降解和抗菌处理上。针对用一般化学或者生物方法难以除去的物质如芳烃和芳香化合物类，纳米TiO2也表现出了令人满意的降解效果。TiO2光催化技术已成为环境污染物修复技术的重要方向。此外，相比其它的光催化剂，TiO2的低毒、物理和化学稳定性好和生物相容性，使其在许多消费产品，如牙膏，口红，食品添加剂和药物中得到了广泛应用。但TiO2在使用过程中存在着局限性，由于TiO2属于宽带隙半导体材料(禁带宽度约为3.2eV)，光催化所需的最大光致发光波长为387.5nm，而紫外光区在整个太阳光光谱中仅占一小部分，大部分是可见光区和红外光区，设法提高TiO2在可见光与红外光区的光利用率将大大拓宽TiO2的应用范围。稀土掺杂的上转换发光纳米颗粒可以通过双光子或多光子机制，吸收长波然后辐射出短波，在众多的上转换材料中，以Yb/Tm共掺的六方相NaYF4纳米颗粒的量子效率最高。
发明内容
本申请针对现有技术的不足，本发明提供了一种钛基复合材料在光催化降解霉菌毒素中的应用。本发明工艺简单，制备得到的光催化剂可以有效降解OTA。
本发明的技术方案如下：
一种用于高效降解霉菌毒素的钛基复合材料，所述复合材料为NaYF4:Yb,Tm@TiO2壳层纳米结构。
所述的复合材料在光催化降解霉菌毒素中的应用。
所述霉菌毒素包括赭曲霉菌毒素A、呕吐毒素、烟曲霉毒素。
所述霉菌毒素为赭曲霉菌毒素A，所述应用包括以下步骤：将所述复合材料与赭曲霉菌毒素A溶液在避光条件下搅拌混匀，随后在波长为200-2500nm光源下进行光催化降解。
所述复合材料NaYF4:Yb,Tm@TiO2的用量为6-12mg/mL，赭曲霉菌毒素A溶液浓度为5μg/mL，避光搅拌时间为1-4h，所述光催化降解反应时间为5-30min。
本发明有益的技术效果在于：
在具有将近红外光转换成可见光、甚至更高能量的紫外光这一特殊光学性能的材料中，稀土元素掺杂的β-NaYF4上转换材料被认为是最有效，在该领域引起了很多关注。NaYF4:Yb,Tm@TiO2光催化降解OTA的原理见图1，从图中可知NaYF4:Yb,Tm中的Yb3+先被近红外光激发，Yb3+上的能量转移到Tm3+的3H5能级。Tm3+中1I6→3F4(345nm)和1D2→3H6(361nm)的能量大于TiO2的禁带宽度，可以通过Tm3+离子的跃迁过程激发TiO2。TiO2中的电子经过光子激发，产生电子–空穴对，导带(CB)上的电子与光催化材料表面吸附物种结合，使吸附物种还原，价带(VB)空穴夺走光催化材料表面吸附物种的电子，使吸附物种氧化，产生的活性氧自由基能与OTA反应，破坏OTA的结构，达到脱毒的目的。
基于稀土掺杂的上转换发光纳米颗粒在近红外光激发下，能够发射紫外光的特性与TiO2的光催化活性，本发明制备出结合稀土离子高效上转换发光特性与TiO2高光催化活性的复合材料，该复合光催化剂能够有效利用太阳光，达到对粮食中的污染物赭曲霉菌毒素—OTA的有效去除，缓解由真菌毒素引起的食品安全问题，为食品质量与安全提供有力的保障。
物理方法中，如热处理，OTA在200℃下加热40min的最大降解率为64％，而在140℃下降解率为21％，缺点是高温会改变食品的感官性状。生物方法中，液体发酵条件下，在含有赭曲霉菌毒素A终浓度20μg/L的发酵培养液中，48h菌株CW574对赭曲霉菌毒素A的降解率为90.1％，生物转化相对安全有效，对食品品质的损害较小，但微生物容易受到温度、湿度等环境的影响，降解过程也相对缓慢，很难在短时间内实现大规模推广。目前，光催化技术应用较少，本发明采用NaYF4:Yb,Tm@TiO2光催化剂，除吸收紫外光外，还将太阳光中的近红外作为光催化的驱动源，在UV-NIR光(200nm-2500nm)照射下，其光催化活性约为纯TiO2的3.75倍，对复合材料用量进行优化，在30min内可以实现98.7％的OTA降解，与其他的方法相比，本研究显示出更高的降解率，更短的处理时间和环境可持续性。
附图说明
图1为本发明NaYF4:Yb,Tm@TiO2光催化降解OTA的原理图；
图2为本发明实施例1中制备得到的NaYF4:Yb,Tm(a)和NaYF4:Yb,Tm@TiO2(b)的TEM图；
图3本发明实施例1中制备得到的NaYF4:Yb,Tm(a)和NaYF4:Yb,Tm@TiO2(b)的XRD图谱；
图4为本发明实施例1中制备得到的NaYF4:Yb,Tm和NaYF4:Yb,Tm@TiO2的紫外可见吸收光谱(a)上转换发射光谱图(b)；
图5为本发明实施例1中制备得到的NaYF4:Yb,Tm@TiO2在不同光源下OTA的光催化降解效果：UV 200-400nm(a)NIR 780-2500nm(b)UV-NIR 200-2500nm(c)；
图6为本发明实施例1中制备得到的NaYF4:Yb,Tm@TiO2不同用量对OTA降解效果的影响；
图7为本发明实施例1中制备得到的NaYF4:Yb,Tm@TiO2纳米材料循环利用降解OTA图。
具体实施方式
下面结合附图和实施例，对本发明进行具体描述。
实施例1
称取YCl3·6H2O(0.2410g)，YbCl3·6H2O(0.0775g)，TmCl3·6H2O(0.0019g)到三口烧瓶中，加入6mL OA和15mL 1-ODE。在磁力搅拌下，通入N2 15min，将溶液加热到160℃并保持30min。加入含有0.1g NaOH与0.148g NH4F的10mL甲醇溶液，升温至50℃，保持30min，再升温至70℃。在N2保护下，加热至300℃，持续1h。加入乙醇沉淀NaYF4:Yb,Tm，离心收集，取0.05g上述的NaYF4:Yb,Tm分散在10mL环己烷中。称取0.02g CTAB分散在20mL去离子水中，将含有NaYF4:Yb,Tm纳米粒子的环己烷溶液加入到CTAB水溶液中，放入80℃水浴锅蒸去环己烷。离心收集CTAB修饰的NaYF4:Yb,Tm，分散在10mL异丙醇中。
为了进一步的得到核壳结构的NaYF4:Yb,Tm@TiO2光催化材料，向异丙醇溶液中加入2.5mL H2O和0.3mL氨水(28wt％)，搅拌均匀，将含有10μL TDAA的10mL异丙醇加入到上述溶液，搅拌10h，乙醇洗涤，离心收集NaYF4:Yb,Tm@TiO2并于60℃进行真空干燥。将干燥后的样品在350℃退火3h获得晶态NaYF4:Yb,Tm@TiO2光催化纳米材料。
将24mg的光催化剂NaYF4:Yb,Tm@TiO2粉末加入到3mL OTA溶液中(5μg/mL)。在实验过程中，分别配置0.8mg/mL TiO2和8mg/mL NaYF4:Yb,Tm@TiO2的溶液(保证TiO2与NaYF4:Yb,Tm@TiO2光催化剂中的TiO2保持相同的摩尔浓度)，并设置空白组(不加光催化剂，只光照)作为对照。光照前，暗环境中搅拌2h以达到材料对OTA吸附-解吸平衡。在紫外(200-400nm)、近红外(780-2500nm)、全波长(200-2500nm)三种不同光源下进行OTA的光催化降解实验，取光催化降解时间为0min，5min，10min，15min，20min，30min的反应液200μL，离心，过0.22μm的有机滤膜。滤膜后采用高效液相色谱法定量OTA浓度。实验结果：在全波长光(200-2500nm)照射下，不加任何催化剂的空白组照射30min后OTA的降解率为43.8％，添加有TiO2和NaYF4:Yb,Tm@TiO2的实验组在照射30min后OTA降解率分别为68.9％和85.1％，相比TiO2，NaYF4:Yb,Tm@TiO2可以利用全波长光中TiO2无法利用的近红外光从而实现更高的光催化降解率。
测试例1材料表征
将实施例1中制备得到的NaYF4:Yb,Tm以及NaYF4:Yb,Tm@TiO2通过透射电子显微镜(TEM)表征材料的形貌以及通过X射线衍射仪(XRD)表征材料的晶型，表征结果见图2和图3：从图2可以看出，图2(a)中合成得到的NaYF4:Yb,Tm呈六方相，形貌规则，尺寸分布均匀，约为50nm，图2(b)中的NaYF4:Yb,Tm@TiO2具有明显核壳结构，经过退火处理，壳层的TiO2颗粒晶化，围在NaYF4:Yb,Tm纳米粒子表面，内核NaYF4:Yb,Tm的形态、尺寸经退火后无明显变化。从图3(a)中可以看出，NaYF4:Yb,Tm纳米粒子的衍射峰与β-NaYF4标准卡片(JCPDS 16-0334)相一致，未观察到其他杂质的衍射峰，表明所制备的样品的六方相晶型的形成。图3(b)中NaYF4:Yb,Tm@TiO2除具有β-NaYF4的衍射峰外，在2θ为25.2°处有较为明显的衍射峰，对应于锐钛矿型TiO2的101面的特征衍射峰(JCPDS 21-1272)，这表明经过500℃煅烧，锐钛矿TiO2的形成。此外，内核NaYF4:Yb,Tm粒子的特征衍射峰的位置和强度未观察到明显变化，因此采用500℃高温煅烧处理不会影响NaYF4:Yb,Tm的晶相结构。
测试例2光谱分析
将实施例1中制备得到的NaYF4:Yb,Tm以及NaYF4:Yb,Tm@TiO2分别测试其紫外可见漫反射情况，结果见图4，从图中可知，相对于NaYF4:Yb,Tm，NaYF4:Yb,Tm@TiO2在380nm处具有明显的吸收峰，与锐钛矿TiO2在380nm(3.2eV)的特征吸收峰一致。980nm激光照射下，NaYF4:Yb,Tm和NaYF4:Yb,Tm@TiO2的荧光光谱见图4(b)。其中，NaYF4:Yb,Tm纳米粒子在289.6nm、344.6nm、360.4nm、450.8nm、475.4nm产生发射峰都来自激活剂Tm3+离子辐射跃迁。NaYF4:Yb,Tm纳米粒子在混入或包覆了TiO2后产生了明显的光谱差异，表明有效的能量转移的发生。与NaYF4:Yb,Tm的上转换光谱相比，在紫外区，NaYF4:Yb,Tm@TiO2与NaYF4:Yb,Tm与TiO2的混合材料在354nm处的发射强度显著减少，参考锐钛矿TiO2的特征吸收峰及图4(a)NaYF4:Yb,Tm@TiO2复合材料的紫外可见漫反射光谱，这种现象可归因于TiO2主要吸收紫外光这一固有特性。NaYF4:Yb,Tm@TiO2中，NaYF4:Yb,Tm与TiO2紧密结合，通过辐射再吸收过程和荧光共振能量转移过程进行能量传递。NaYF4:Yb,Tm与TiO2仅物理混合时，能量通过辐射再吸收过程进行传递。NaYF4:Yb,Tm@TiO2中的TiO2能更好地吸收NaYF4:Yb,Tm的上转换紫外发射光，从而导致NaYF4:Yb,Tm@TiO2在紫外区的荧光光谱强度下降更明显。
测试例3不同光源对OTA光催化降解效果的影响
将实施例1制备得到的纳米光催化剂NaYF4:Yb,Tm@TiO2应用于光催化降解过程中，具体实验步骤为：OTA在不同光源下的降解情况见图5。从图中可得，在UV光(200-400nm)照射下，归因于OTA在紫外波段有光吸收，不加任何催化剂的空白组在照射30min后由于光降解效应，OTA的降解率达到41.2％。由于TiO2的光催化效应，添加有TiO2和NaYF4:Yb,Tm@TiO2的实验组在光降解与光催化降解的协同作用，照射30min后OTA的降解率分别为70.0％和67.8％，高于空白组。在NIR光(780-2500nm)照射下，不加任何催化剂的空白组照射30min后OTA的降解率为3.2％。添加有TiO2和NaYF4:Yb,Tm@TiO2的实验组在照射30min后OTA降解率分别为2.9％和16.5％。仅在添加了NaYF4:Yb,Tm@TiO2复合材料的实验组中，OTA有较为明显的降解。在UV-NIR光(200-2500nm)照射下，不加任何催化剂的空白组照射30min后OTA的降解率为43.8％，添加有TiO2和NaYF4:Yb,Tm@TiO2的实验组在照射30min后OTA降解率分别为68.9％和85.1％。从上述结果中可以看出，相比TiO2，NaYF4:Yb,Tm@TiO2可以利用近红外光，从而在近红外光和全波长光照射下，有效降解OTA，实现比TiO2更高的光催化效率。
测试例4NaYF4:Yb,Tm@TiO2光催化材料稳定性的研究
将实施例1中制备得到的NaYF4:Yb,Tm@TiO2光催化剂在全波长照射下，NaYF4:Yb,Tm@TiO2重复多次使用的光催化表现如图7所示。光催化剂经过1次使用，降解效率为98.7％；经过4次循环，降解效率为98.2％。4次实验后催化活性略下降，考虑到材料回收过程中不可避免的损失，表明合成的复合光催化剂稳定性良好。
Claims (5)
1.一种钛基复合材料，其特征在于，所述复合材料为NaYF4:Yb,Tm@TiO2壳层纳米结构。
2.一种如权利要求1中所述的复合材料在光催化降解霉菌毒素中的应用。
3.根据权利要求2所述的应用，其特征在于，所述霉菌毒素包括赭曲霉菌毒素A、呕吐毒素、烟曲霉毒素。
4.根据权利要求3所述的应用，其特征在于，所述霉菌毒素为赭曲霉菌毒素A，所述应用包括以下步骤：将所述复合材料与赭曲霉菌毒素A溶液在避光条件下搅拌混匀，随后在波长为200-2500nm光源下进行光催化降解。
5.根据权利要求4所述的应用，其特征在于，所述复合材料NaYF4:Yb,Tm@TiO2的用量为6-12mg/mL，赭曲霉菌毒素A溶液浓度为5μg/mL，避光搅拌时间为1-4h，所述光催化降解反应时间为5-30min。
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