CN117323971B - SA@CDs/g-C3N4复合材料、其制备方法及在黄曲霉毒素脱除中的应用 - Google Patents
SA@CDs/g-C3N4复合材料、其制备方法及在黄曲霉毒素脱除中的应用 Download PDFInfo
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Abstract
本发明公开了SA@CDs/g‑C3N4复合材料、其制备方法及在黄曲霉毒素脱除中的应用,属于有机材料技术领域。所述SA@CDs/g‑C3N4复合材料的制备方法如下:将CDs/g‑C3N4复合物加入水中,超声处理,使其均匀分散;然后加入海藻酸钠,剧烈搅拌,充分混合,形成预凝胶溶液;将充分混合的预凝胶溶液转移到模具中,然后冷冻干燥,获得固体海绵;将固体海绵浸入CaCl2溶液中进行凝胶化,然后用去离子水洗涤,并冷冻干燥,获得SA@CDs/g‑C3N4复合材料。本发明制备的SA@CDs/g‑C3N4复合材料能够有效脱除食品中残留的黄曲霉毒素,作用温和,环保、安全。
Description
技术领域
本发明属于有机材料技术领域,具体涉及SA@CDs/g-C3N4复合材料、其制备方法及在黄曲霉毒素脱除中的应用。
背景技术
粮食、食用油和肉类等食品在种植、储存或饲养期间很容易受到环境污染,从而引发食品安全问题。除此之外,一些致病微生物也可以在这些食品中生长并形成真菌毒素,其中,最具代表性的真菌毒素为黄曲霉毒素(AFT),黄曲霉毒素会造成巨大的经济损失和健康风险。如何对其进行脱毒,是食品行业所面临的一大挑战。当前,脱除黄曲霉毒素的技术,包括物理和化学方法等。化学法一般采用强氧化剂(臭氧、双氧水等),这些强氧化剂处理农产品或食品能达到很好的去除黄曲霉毒素的效果,但也会破坏农产品营养和风味物质的结构,从而影响产品的风味和营养,且规模化也受到限制;物理法一般采用高温处理,而一些沸点低、不稳定的风味和营养物质经过高温处理后会被破坏。因此,这些方法存在效果不稳定、营养成分损失较大、引入新的有害成分等缺点,难以满足现代农产品产业发展的要求。因此,探索一种更环保、有效以及安全的方法来去除食品中的黄曲霉毒素具有重要意义。
发明内容
本发明提供了一种SA@CDs/g-C3N4复合材料的制备方法,步骤如下:
将CDs/g-C3N4复合物加入水中,超声处理,使其均匀分散;然后加入海藻酸钠,剧烈搅拌,充分混合,形成预凝胶溶液;将充分混合的预凝胶溶液转移到模具中,然后冷冻干燥,获得固体海绵;将固体海绵浸入CaCl2溶液中进行凝胶化,然后用去离子水洗涤,并冷冻干燥,获得SA@CDs/g-C3N4复合材料。
上述SA@CDs/g-C3N4复合材料的制备方法中,CDs/g-C3N4复合物与水的质量体积比选自1:300~1:800,优选为1:500,g/mL。
上述SA@CDs/g-C3N4复合材料的制备方法中,CDs/g-C3N4复合物与海藻酸钠的质量比选自1:4~1:10,优选为1:7.5。
上述SA@CDs/g-C3N4复合材料的制备方法中,CaCl2溶液的浓度选自1~8wt%,优选为3wt%。
本发明提供了上述CDs/g-C3N4复合物的制备方法,步骤如下:
将三聚氰胺和三硫代氰尿酸加入水中,搅拌均匀;然后加入CDs溶液,搅拌均匀;将混合溶液过滤、洗涤、干燥并转移到马弗炉中,进行高温煅烧,获得CDs/g-C3N4复合物。
上述CDs/g-C3N4复合物的制备方法中,三聚氰胺与三硫代氰尿酸的摩尔比选自1:0.5~1:1.5,优选为1:1。
上述CDs/g-C3N4复合物的制备方法中,三聚氰胺与水的摩尔体积比选自1:4000~1:8000,优选为1:6000,mol/mL。
上述CDs/g-C3N4复合物的制备方法中,CDs溶液与水的体积比选自1~7:60,优选为3:60。
上述CDs/g-C3N4复合物的制备方法中,高温煅烧的条件选自:以2~6℃/min的速率升温到550~650℃,并在此温度下煅烧3~6h;优选为:以3℃/min的速率升温到600℃,并在该温度下煅烧4h。
本发明提供了一种上述CDs溶液的制备方法,步骤如下:
将橙汁置于聚四氟乙烯内衬的反应器中,高温加热;待自然冷却后,将反应产物离心、过滤,形成透明的棕黄色碳量子点溶液,即CDs溶液。
上述CDs溶液的制备方法中,高温加热的条件选自180~210℃下加热8~12h;优选为200℃下加热10h。
本发明提供了由上述方法制备的SA@CDs/g-C3N4复合材料。
本发明提供了上述SA@CDs/g-C3N4复合材料在脱除食品中黄曲霉毒素中的应用。所述黄曲霉毒素选自黄曲霉毒素B1。
本发明的有益效果为:
本发明制备的SA@CDs/g-C3N4复合材料能够有效脱除食品中残留的黄曲霉毒素,作用温和,环保、安全且易循环,避免材料残留对食品品质的影响。
附图说明
图1为碳量子点溶液的XRD图谱和FTIR光谱;其中,a图为XRD图谱,b图为FTIR光谱;
图2为STCN和CSTCN-3的SEM图、TEM图、HRTEM图以及TEM-EDX元素映射图;其中,a图为STCN的SEM图,b和c图为STCN不同放大倍数下的TEM图像,d图为CSTCN-3的SEM图,e~g图为CSTCN-3不同放大倍数下的TEM图像,h图为HRTEM图(插图是SAED图像),i~l图为CSTCN-3的对应TEM-EDX元素图谱;
图3为实施例1中步骤(2)所得产物的XRD图谱(a图)、FT-IR光谱(b图)、UV-vis吸收光谱(c图)、PL光谱(d图)、EIS图(e图)以及瞬态光电流响应(f图);其中,c图中,曲线从上至下依次为CSTCN-7、CSTCN-5、CSTCN-3、CSTCN-1、STCN;d图中,曲线从上至下依次为STCN、CSTCN-3、CSTCN-1、CSTCN-5、CSTCN-7;e图中,曲线从左至右依次为CSTCN-3、CSTCN-7、CSTCN-5、STCN、CSTCN-1;f图中,曲线从上至下依次为CSTCN-3、CSTCN-5、CSTCN-7、CSTCN-1、STCN;
图4为STCN和CSTCN-3的高分辨率XPS光谱;
图5为SA@CSTCN海绵制备流程图(a图),SA海绵和SA@CSTCN海绵外观图(b图),SA@CSTCN海绵表面图(c图)以及SA@CSTCN海绵横截面(d图)。
具体实施方式
本发明所采用的其它材料,如无特殊声明,均可通过市售渠道获得。本发明所使用的其它术语,除非有另外说明,一般具有本领域普通技术人员通常理解的含义。下面结合具体实施例,并参照数据进一步详细的描述本发明。以下实施例只是为了举例说明本发明,而非以任何方式限制本发明的范围。
实施例1
制备SA@CDs/g-C3N4复合材料,步骤如下:
(1)碳量子点溶液的制备
将30mL新鲜橙子的橙汁置于100mL聚四氟乙烯内衬的反应器中,并在200℃下加热10h。自然冷却后,将反应产物离心并通过0.22μm聚醚砜过滤器过滤,形成透明的棕黄色碳量子点(CDs)溶液。
碳量子点溶液的XRD图谱和FTIR光谱如图1所示。由图1可知,所制备的碳量子点为非晶结构,且表面含有羰基、羟基等官能团。
(2)CDs/g-C3N4复合物的制备
将1.26g三聚氰胺(0.01mol)和3.16g三硫代氰尿酸(0.01mol)添加到60mL去离子水中并搅拌1h以获得均匀的混合溶液,将一定体积(分别设置为1mL、3mL、5mL和7mL)的CDs溶液加入上述混合溶液中并继续搅拌12h。将混合溶液过滤、洗涤、干燥并转移到马弗炉中,以3℃/min的速率升温到600℃,并在此温度下煅烧4h,获得CDs/g-C3N4复合物,简称为CSTCN-x光催化剂,其中,x=1、3、5和7,即分别在1mL、3mL、5mL和7mL CDs溶液制备条件下所获得的产物。
作为比较,本发明设置了在不添加CDs溶液的情况下通过相同条件制备获得的产物,简称为STCN。
对所制备的CSTCN-3和STCN进行物理特征鉴定,如图2所示。其中,a图为STCN的SEM图,b和c图为STCN不同放大倍数下的TEM图像,d图为CSTCN-3的SEM图,e~g图为CSTCN-3不同放大倍数下的TEM图像,h图为HRTEM图(插图是SAED图像),i~l图为CSTCN-3的对应TEM-EDX元素图谱。
通过SEM图可观察STCN和CSTCN-3的微观形态。由图2a可知,STCN具有纳米棒结构,而由图2d图可知,在掺杂CDs后,CSTCN-3保持了纳米棒结构,但表面产生大量孔。由图2b和e的TEM图可清楚地看见STCN和CSTCN-3都是中空结构,而由图2c和f可知,CSTCN-3具有较薄的壁,这可能归因于煅烧过程中释放的大量气体。由图2g所示的CSTCN-3的放大TEM图像可知,CD被成功地掺杂到STCN中。由图2h可知,HRTEM中出现属于碳(001)晶面的晶格条纹,这进一步表明CDs与STCN的紧密结合。此外,由图2i-l所示的CSTCN-3的相关TEM-EDX元素图谱可知,C、N、O和S在样品中均匀分布。上述结果证实了由柑橘衍生的CDs成功地锚定在g-C3N4纳米管上。
图3为上述步骤(2)所得产物的XRD图谱(a图)、FT-IR光谱(b图)、UV-vis吸收光谱(c图)、PL光谱(d图)、EIS图(e图)以及瞬态光电流响应(f图)。
通过XRD光谱可知所制备的g-C3N4材料的晶体结构,如图3a所示,所有样品都呈现出相似的两个特征衍射峰,13.1°处的宽峰对应于三-s-三嗪环的平面内重复基序,27.3°处的尖锐峰归属于共轭芳香单元的面层堆叠。与XRD图像类似,所有样品的FT-IR光谱显示出几乎相同的特征峰,如图3b所示,816cm-1处的尖锐峰归因于庚嗪的形成,在1100-1750cm-1处的多个峰归因于C-N杂环的拉伸振动。在3000-3500cm-1范围内的宽峰归属于吸附水和N-H拉伸振动。CDs修饰的CSTCN-x曲线与STCN相比没有显著变化,表明复合材料中STCN的晶体和分子结构不受CDs的影响。
增强光吸收是提高光催化剂催化性能的最有效方法之一,如图3c所示,由于CDs的量子效应,CSTCN-x复合材料的光吸收能力显著增强。此外,它还随着量子点浓度的增加而进一步增强。样品的颜色逐渐从黄色变为棕色。利用光致发光和时间分辨光致发光测量了光生载流子的分离和转移效率。如图3d所示,在引入CDs后,CSTCN-x复合材料表现出比STCN更低的PL强度。结果表明,CD的引入可以有效地促进载体的分离。
电化学表征用于进一步评估CSTCN-x中有效的光生载流子分离和转移效率,图3e显示了所制备的催化剂的电化学阻抗谱(EIS),与STCN相比,CSTCN-3表现出更短的电弧半径,表明了具有更小的电荷转移电阻和更有效的电荷分离效率。此外,如图3f所示,CSTCN-3在“开关”照明的重复周期中表现出最高的光电流响应强度,表明其在可见光中载流子传输速率更快。由此可见,CSTCN-3具有最佳的光催化性能。然而,随着CDs掺杂浓度的增加,光电流响应强度降低,这可能归因于CDs的增加引入了新的复合位点。
图4为STCN和CSTCN-3的高分辨率XPS光谱。使用XPS光谱分析所制备的样品的表面成分和元素组成。图4a中的高分辨率C1s光谱可以被去卷积为两个结合能分别为284.7和287.9eV的峰,分别归因于C-C/C=C和N-C=N。如图4b所示,N1s光谱可以拟合到位于398.4、399.9和401.1eV的三个峰。这些峰分别对应于C-N=C、N-(C)3和N-Hx。图4c显示了在高分辨率O1s光谱中获得的三个峰,分别归属于531.5eV的C=O、532.2eV的C-O和533.3eV的O-H/吸附水。值得注意的是,与STCN相比,CSTCN-3表面C=O和C-O的含量显著增加,这可能归因于CD表面存在大量含氧官能团。在高分辨率S2p光谱中发现了弱S元素信号。163.4eV处的峰被认为是S-N键,而162.8eV的峰被确定为硫氧化物的产生。此外,CSTCN-3中O1s的所有峰都向较低的结合能移动,表明电子流存在于复合材料中的CDs中。
由于CSTCN-3具有最佳的光催化性能,因此,本发明直接采用CSTCN-3来制备SA@CSTCN复合物,如下述步骤(3)所示。
(3)SA@CDs/g-C3N4复合材料的制备
将0.1g CSTCN-3光催化剂加入50mL去离子水中,超声处理30min,使其均匀分散。随后,加入0.75g海藻酸钠(SA)并剧烈搅拌6h,充分混合,形成预凝胶溶液。将充分混合的预凝胶溶液转移到模具中,然后冷冻干燥24h,获得固体海绵。将固体海绵浸入300mL 3wt%CaCl2溶液中6h以凝胶化。用去离子水彻底洗涤并冷冻干燥36h后,获得CSTCN-3附着的海藻酸钠凝胶片,即SA@CDs/g-C3N4复合材料,因其物理形态呈海绵状,亦可称之为SA@CSTCN海绵。
作为比较,本发明设置了在不添加CSTCN光催化剂的情况下通过相同条件制备获得的SA海绵。
图5为SA@CSTCN海绵制备流程图(a图),SA海绵和SA@CSTCN海绵外观图(b图),SA@CSTCN海绵表面SEM图(c图)以及SA@CSTCN海绵横截面SEM图(d图)。
SA@CSTCN海绵的制备示意图如图5a所示,通过冷冻干燥过程,SA凝胶内的冰晶升华,形成孔洞。随后,加入Ca2+交联并固化凝胶,使其具有一定的机械强度。在不存在光催化剂的情况下,制备的SA海绵显示出半透明性,表明光可以很好地穿过SA凝胶基质。
与SA海绵相比,SA@CSTCN海绵显示黄色,表明催化剂分散良好(图5b)。SA@CSTCN海绵如图5c和d所示,较大的孔不仅有利于光子的反射,而且提供了更多的反应活性位点。此外,丰富的孔洞赋予海绵漂浮的特性,保证了氧气的持续供应,促进了ROS的产生。
应用例1
花生中黄曲霉毒素B1的脱除:
取5份花生,每份1kg。向花生中分别加入1g CSTCN(包括CSTCN-1、CSTCN-3、CSTCN-5和CSTCN-7)和3g SA@CSTCN,以230rpm匀速搅拌8min混匀,加入纯水400kg混匀,光照6h,静置至固液分离,弃去上清,晾干,脱除花生中黄曲霉毒素B1。
取按上述方法脱毒前后的花生各5g,加入10mL的冷甲醇洗脱,静置,取1mL悬浮液于离心管中,涡旋震荡2min,在4℃,10000rpm条件下离心10min,利用高效液相色谱法(HPLC)分析上清液中黄曲霉毒素浓度,若毒素浓度降低85%及以上,则达到国标要求,记为脱除成功。
试验结果如表1所示:
表1
上述试验结果表明,本发明制备的CSTCN能够有效降解脱除花生中的黄曲霉毒素。将CSTCN与SA结合形成SA@CSTCN后,可使材料呈海绵状,易于循环利用,从而对食品品质影响较小。
应用例2
花生油中黄曲霉毒素B1的脱除:
取5份花生油,每份1kg。向花生油中分别加入1g CSTCN(包括CSTCN-1、CSTCN-3、CSTCN-5和CSTCN-7)和3g SA@CSTCN,加入纯水10kg,经35min震荡,在光照下搅拌6h,10000rpm离心10min,静置,弃去水层,即脱除不溶于水的花生油中黄曲霉毒素B1。
取按上述方法脱毒前后的花生油各5mL,加入5mL的乙腈,静置,取1mL上清液于离心管中,13000rpm,4℃下离心10min,利用高效液相色谱法(HPLC)分析上清液中黄曲霉毒素浓度,若毒素浓度降低85%及以上,则达到国标要求,记为脱除成功。
试验结果如表2所示:
表2
上述试验结果表明,本发明制备的CSTCN和SA@CSTCN海绵对花生油中的黄曲霉毒素也具有有效的降解脱除效果。
以上所述,仅是本发明的较佳实施例而已,并非是对本发明作其它形式的限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型,仍属于本发明技术方案的保护范围。
Claims (3)
1.一种SA@CDs/g-C3N4复合材料的制备方法,步骤如下:
将CDs/g-C3N4复合物加入水中,超声处理,使其均匀分散;然后加入海藻酸钠,剧烈搅拌,充分混合,形成预凝胶溶液;将充分混合的预凝胶溶液转移到模具中,然后冷冻干燥,获得固体海绵;将固体海绵浸入CaCl2溶液中进行凝胶化,然后用去离子水洗涤,并冷冻干燥,获得SA@CDs/g-C3N4复合材料;
所述CDs/g-C3N4复合物与水的质量体积比选自1:300~1:800,g/mL;所述CDs/g-C3N4复合物与海藻酸钠的质量比选自1:4~1:10;所述CaCl2溶液的浓度选自1~8wt%;
所述CDs/g-C3N4复合物的制备方法,步骤如下:
将三聚氰胺和三硫代氰尿酸加入水中,搅拌均匀;然后加入CDs溶液,搅拌均匀;将混合溶液过滤、洗涤、干燥并转移到马弗炉中,进行高温煅烧,获得CDs/g-C3N4复合物;
所述三聚氰胺与三硫代氰尿酸的摩尔比选自1:0.5~1:1.5;所述高温煅烧的条件选自:以2~6℃/min的速率升温到550~650℃,并在此温度下煅烧3~6h;
所述CDs溶液的制备方法,步骤如下:
将橙汁置于聚四氟乙烯内衬的反应器中,180~210℃下加热8~12h;待自然冷却后,将反应产物离心、过滤,形成透明的棕黄色碳量子点溶液,即CDs溶液。
2.权利要求1所述方法制备的SA@CDs/g-C3N4复合材料。
3.权利要求2所述的SA@CDs/g-C3N4复合材料在脱除食品中黄曲霉毒素中的应用。
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