CN116422319A - 一种铈单原子纳米酶及其制备方法和海洋抗污损应用 - Google Patents
一种铈单原子纳米酶及其制备方法和海洋抗污损应用 Download PDFInfo
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Abstract
本发明公开了一种铈单原子纳米酶的制备方法，先将一定量的钴基金属化合物分散于溶剂中，再将一定浓度的铈盐逐滴滴入上述分散液，搅拌均匀后经过混合物体系处理获得铈单原子纳米酶。采用本发明方法制备的铈单原子纳米酶，利用金属铈以单位点状态牢固地锚定在基底上，不仅使原子利用率最大化且单原子的引入使得基底化合物中存在更多的不饱和配位非金属键，且基底边缘暴露更丰富的活性位，从而促使酶催化反应动力学加快，最终提升其抗海洋生物污损能力。本发明方法简易，易于规模生产，为制备新型环保、低成本和高效的海洋防污损材料提供新的思路。
Description
技术领域
本发明涉及海洋抗污损纳米材料领域，尤其涉及一种铈单原子纳米酶及其制备方法和海洋抗污损应用。
背景技术
海洋生物污损是指细菌、藻类、硬壳类(如贝壳、藤壶)等生物在潮湿表面的附着和生长，而浸入海洋中的任何表面均受海洋生物污损的影响。传统的防污涂层材料由于含有毒物质而逐渐被世界各国禁用，因此开发新型绿色、高效的防污涂层材料成为装备表面防护所面临的重大技术难题。
根据目前文献报道，海洋中某些藻类已经进化出天然的污损防御机制，某些藻类利用自主分泌的钒卤代过氧化物酶可将海水中的卤素离子催化为具有抗菌和抵制生物膜附着效果的次卤酸，从而实现抵抗生物污损目的。但天然酶的应用存在提取成本高、易降解及获取条件苛刻等问题。
单原子纳米酶是一种原子级分散活性位点的纳米酶，其更类似于金属蛋白酶，不仅具有普通纳米酶的优势，且催化活性更高。由于单原子纳米酶具有明确的原子级金属分散性和独特的电子/几何结构，较高的原子利用率和丰富的活性位点，近年来在仿生化学中被用于模拟蛋白酶，但传统纳米酶仍然面临着元素组成不均匀、活性位点密度低及催化机制复杂等巨大挑战。
因此，开发出一种新型环保、低成本和高效的海洋防污损材料是很有必要的。
发明内容
有鉴于此，本发明提供了一种铈单原子纳米酶的制备方法，解决现有技术存在的问题。
本发明一方面提供一种铈单原子纳米酶的制备方法，包括以下步骤：先将一定量的钴基金属化合物分散于溶剂中，再将一定浓度的铈盐逐滴滴入上述分散液，搅拌均匀后经过混合物体系处理获得铈单原子纳米酶。
优选地，金属化合物选自磷化钴、氧化钴、硫化钴、硒化钴和氮化钴中的一种。
优选地，铈盐选自草酸铈、氯化铈、硝酸铈、硝酸铈铵、三氟甲磺酸铈和硬脂酸铈中的一种。
优选地，钴基金属化合物的质量为100-500mg。
优选地，铈盐体积为2-9mL，浓度为0.05-2mM。
优选地，混合物体系处理的方式为在130℃的条件下水热生长10h。
另一方面本发明提供一种铈单原子纳米酶及在制备海洋抗生物污损材料中的应用。
采用本发明所提供的一种铈单原子纳米酶的制备方法，步骤简易、成本低、可大批量生产。且利用本发明方法制备的铈单原子纳米酶，利用金属铈以单位点状态牢固地锚定在基底上，不仅使原子利用率最大化且单原子的引入使得基底化合物中存在更多不饱和配位非金属键，而且基底边缘暴露更丰富的活性位，从而促使类酶催化反应动力学加快，最终展现出优异的抗海洋生物污损能力。
进一步地，相对于现有防污技术，本发明技术方案制备的铈单原子纳米酶清洁、环保，不存在毒害海洋生态系统的二次污染问题。
附图说明
图1为利用实施例一的方法制备的铈单原子纳米酶的扫描电子显微镜(SEM)图片；
图2为利用实施例一的方法制备的铈单原子纳米酶的透射电子显微镜(TEM)图片；
图3为利用实施例一的方法制备的铈单原子纳米酶的扫描透射电子显微镜(HADDF)图片；
图4为利用实施例一的方法制备的铈单原子纳米酶的扫描透射电子显微镜(HADDF)图片；
图5为利用实施例一的方法制备的铈单原子纳米酶分别催化苯酚红溴化过程的酶促反应动力曲线，其中(a)根据Br-浓度改变做出的曲线，(b)根据H2O2浓度改变做出的曲线；
图6为利用实施例一的方法制备的铈单原子纳米酶在H2O2和Br-存在时孵育大肠杆菌的对照图片；
图7为利用实施例一的方法制备的铈单原子纳米酶在真实海洋环境中挂板92天的照片。
具体实施方式
以下结合附图对本发明的原理和特征进行描述，所举实施例只用于解释本发明，并非用于限定本发明的范围。
实施例一：一种铈单原子纳米酶的制备方法，包括以下步骤：
将300mg磷化钴超声分散于200mL超纯水中，再将4mL浓度为0.5mM的硝酸铈铵溶液使用注射泵逐滴滴入上述分散液，搅拌5h后离心、洗涤并转移至50mL水热釜，在130℃的条件下反应10h，最后离心干燥获得铈单原子纳米酶。
(1)分别利用扫描电镜和透射电镜对本实施例制备的铈单原子纳米酶进行测试表征，从图1和2的结果可以看出，本实施例制备的铈单原子纳米酶具有二维纳米薄片结构，且纳米片上没有观察到铈相关的纳米颗粒或团簇。
(2)利用球差电镜对本实施例制备的铈单原子纳米酶进行测试，从图3结果可看出，铈以不到1纳米的大小且孤立的原子形态分布于载体上，且载体上不存在铈物种相关的团簇或颗粒，表明铈单原子纳米酶的成功制备。
(3)利用X射线衍射的表征对本实施例制备的铈单原子纳米酶进行测试，从图4中看出，本实施例的铈单原子纳米酶与纯的磷化钴基底的衍射峰相同，没有其他峰出现，进一步表明铈原子在基底上的负载量较少且粒径极小。
(4)本实施例制备的铈单原子纳米酶在H2O2和溴源共存时，以苯酚红为显色剂，观察其酶促反应动力曲线。当分别改变H2O2或溴源的浓度，其他底物浓度保持常量。从图5的结果表明：本实施例制备的铈单原子纳米酶对H2O2和Br-均表现出典型的米氏行为。根据Lineaweaver-Burk双倒数作图，得到纳米酶模拟卤代过氧化物酶催化过程的米氏常数(Km)，本实施例制备的铈单原子纳米酶对H2O2底物较低的Km值(221.9μM)，表明其对H2O2较强的结合亲和力。
(5)本实施例制备得到的铈单原子纳米酶在H2O2和Br-存在的前提下，与稀释的细菌菌液与共孵育12h，如图6结果对比发现：经过铈单原子纳米酶涂覆过的培养基基板上菌落数明显低于基底材料，表明铈纳米酶催化Br-氧化产生的HOBr可有效抑制细菌生物膜的生长繁殖。
(7)按照5％的重量比例将本实施例的铈单原子纳米酶与商用船舶涂料混匀并涂覆于不锈钢板上，悬挂于真实海洋环境中52天，如图7的结果对比发现：经铈单原子纳米酶处理过的钢板(b)污损情况相比于纯基底材料(a)大为减少，充分证明了本发明铈单原子纳米酶具有良好的海洋防生物污损特性。
在另外一个实施例中，金属化合物选自磷化钴、氧化钴、硒化钴、氮化钴中的一种。
在另外一个实施例中，铈盐选自草酸铈、氯化铈、硝酸铈、三氟甲磺酸铈和硬脂酸铈中的一种。
在另外一个实施例中，钴基金属化合物的质量为100-500mg。
在另外一个实施例中，铈盐体积为2-9mL，浓度为0.05-2mM。
综上所述，采用本发明所提供的方法制备的铈单原子纳米酶，金属铈以单位点状态牢固地锚定在基底上，使原子利用率最大化且单原子的引入使得基底化合物中存在更多的不饱和配位非金属键，基底边缘暴露更丰富的活性位，促使酶催化反应动力学加快。进一步地，本发明制备的铈单原子纳米酶模拟钒溴代过氧化物酶，在H2O2氧化剂存在时，可有效催化Br-产生HOBr，从而将细菌中的信号分子卤化失活，抑制细胞间的交流，有效阻止微生物的附着。进一步地，本发明制备铈单原子纳米酶展现了良好的海洋防生物污损特性。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明保护的范围之内。
Claims (9)
1.一种铈单原子纳米酶的制备方法，其特征在于包括以下步骤：先将一定量的钴基金属化合物分散于溶剂中，再将一定浓度的铈盐逐滴滴入上述分散液，搅拌均匀后经过混合物体系处理获得铈单原子纳米酶。
2.根据权利要求1所述的一种铈单原子纳米酶的制备方法，其特征在于：所述金属化合物选自磷化钴、氧化钴、硫化钴、硒化钴和氮化钴中的一种。
3.根据权利要求1所述的一种铈单原子纳米酶的制备方法，其特征在于：所述铈盐选自草酸铈、氯化铈、硝酸铈、硝酸铈铵、三氟甲磺酸铈和硬脂酸铈中的一种。
4.根据权利要求1所述的一种铈单原子纳米酶的制备方法，其特征在于：所述钴基金属化合物的质量为100-500mg。
5.根据权利要求1所述的一种铈单原子纳米酶的制备方法，其特征在于：所述铈盐体积为2-9mL，浓度为0.05-2mM。
6.根据权利要求1所述的一种铈单原子纳米酶的制备方法，其特征在于：所述混合物体系处理为在130℃的条件下水热生长10h。
7.根据权利要求1所述的一种铈单原子纳米酶的制备方法，其特征在于包括以下步骤：将300mg磷化钴超声分散于200mL超纯水中，再将4mL浓度为0.5mM的硝酸铈铵溶液使用注射泵逐滴滴入上述分散液，搅拌5h后离心洗涤并转移至50mL水热釜，在130℃的条件下水热反应10h，最后离心干燥获得铈单原子纳米酶。
8.一种根据权利要求1至7任一项所述的方法制备的铈单原子纳米酶。
9.权利要求8所述的铈单原子纳米酶在制备海洋抗生物污损材料中的应用。
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