CN115487816A - 一种基于蛭石的钼酸铁纳米酶及其制备方法和应用 - Google Patents
一种基于蛭石的钼酸铁纳米酶及其制备方法和应用 Download PDFInfo
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 60
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- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical group [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 1
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种基于蛭石的钼酸铁纳米酶及其制备方法和应用。制备方法采用蛭石为原料,在酸性水溶液中与钼酸盐通过简单的水热法得到类过氧化物酶活性增强的钼酸铁纳米酶。本发明采用蛭石作为原料,通过水热合成法,利用蛭石中的结构铁,与钼酸盐在酸性介质中合成Fe2(MoO4)3,蛭石不仅可以有效分散活性组分的分散性,而且减小Fe2(MoO4)3的尺寸,有利于增强了复合材料的类过氧化物酶活性。此外,该材料在中性条件下也具有类过氧化物酶活性。这些优势有利于复合材料产生更多的活性氧,使其满足中性条件下实现生物比色传感和抗菌的需求,有利于蛭石的高值化利用。此方法工艺简单,所用原料价格低廉、环保无毒,易于大规模生产。
Description
技术领域
本发明涉及矿物材料及纳米酶催化技术领域,尤其涉及一种基于蛭石的钼酸铁纳米酶及其制备方法和应用。
背景技术
自然界中的天然酶结构中含有活性Fe组分,如天然过氧化物酶的催化位点是铁卟啉结构。但是,天然酶提纯复杂,在高温和强酸强碱条件下易失活,使其应用受到极大限制。铁是地球上含量最丰富的过渡金属元素(58kg/吨),广泛存在于自然界的黏土矿物中,其中一类独特的具有类似天然酶催化活性和酶促反应动力学特征的铁纳米材料(铁基纳米酶),制备成本低、稳定性强,可以作为天然酶的替代者。虽然铁基纳米酶已有广阔的发展,但是其在中性条件下丧失催化活性,使其不能满足实际应用的需求(Anal.Chem.2019,91,11994-11999)。人工合成的铁基纳米酶所需铁源原料多为铁盐、铁氧化物,多经过加工得到,成本高。需要寻找天然的含铁原料,满足铁基纳米酶在中性条件下既具有较高类酶活性,还能够降低生产成本,增强铁基纳米酶的竞争力。
中国的蛭石(VMT)储量约占世界总储量的六分之一,储量丰富,价格低廉。蛭石是由外面两层[(Si,Al)O4]和中间一层[(Mg,Fe)O6]组成的2:1型层状硅酸盐黏土矿物。蛭石中间三八面体片层中存在Fe(III)和Fe(II)(Lagaly,1982)。蛭石产地不同,其含铁量也不相同,如河北灵寿蛭石矿物中Fe2O3含量为4.05wt%,Fe的含量均比我国潼关(7.38wt%)、张家口(6.40wt%)和灵宝(6.46wt%)等地的蛭石矿物低(杨雅秀和张乃娴,1994)。尽管蛭石中存在较多的铁,但是,这些Fe主要集中在中间的铁氧八面体结构层,利用困难。有研究通过球磨30min、接着氮气氛围中800℃煅烧2h、再在150℃下用NaOH水热蚀刻24h、最后超声5h离心得到蛭石中间的八面体结构层,得到具有类过氧化物酶的中间层(NATURECOMMUNICATIONS|(2021)12:1124),这些方法通过工艺调控设法提取并暴露蛭石的铁氧八面体结构层中的铁活性位点,以提高其类过氧化物酶,但工艺复杂,耗费时间,且并没有形成新的类过氧化物酶材料,因而不能充分利用蛭石的结构制备新材料,展示新型蛭石纳米酶的活性。
发明内容
本发明的目的在于,蛭石结构铁的有效利用与纳米酶中性条件下活性低的问题,提出一种蛭石组分调控合成的类过氧化物酶活性增强的钼酸铁纳米酶及其制备方法和应用。
本发明的一种基于蛭石的钼酸铁纳米酶及其制备方法,采用蛭石、钼酸盐为原料,在酸性介质中通过水热合成法得到产物,待产物冷却至室温,使用去离子水多次清洗干净,冷冻干燥,既可得到蛭石组分调控合成的钼酸铁纳米酶。
进一步的,所述酸性介质溶液0.1M-1.0M HCl溶液。
进一步的,所述钼酸盐:蛭石的质量比为2.4-120:1。
进一步的,所述蛭石的质量百分比SiO2为30-43%,Fe2O3为15-21%、Al2O3为5-15%,MgO为5-11%,K2O<6%,CaO<3%,其他元素<1%。
进一步的,所述水热合成法温度为120-190℃,时间保持8-24h。
进一步的,合成的改性钼酸铁纳米酶可以催化H2O2产生活性氧物种,如单线态氧。
进一步的,合成的钼酸铁纳米酶可以用于生物比色传感、抗菌等领域。
一种采用上述的制备方法制备的钼酸铁纳米酶。
一种钼酸铁纳米酶在比色传感上的应用,以钼酸铁纳米酶作为类过氧化物酶,在H2O2存在条件下,与显色底物发生显色反应,将溶液吸光度值变化与目标待检测还原物浓度关联,从而建立起比色传感平台,用于检测待检测还原物的浓度。
一种钼酸铁纳米酶在比色传感上的应用,所述显色底物为氧化3,3’5,5’-四甲基联苯胺、2,2'-联氮双(3-乙基苯并噻唑啉-6-磺酸)二铵盐或邻苯二胺。
一种钼酸铁纳米酶的抗菌应用,所述钼酸铁纳米酶催化H2O2分解产生具有强氧化能力的羟基自由基和单线态氧,用于有效杀死细菌。
因此,本文采用具有独特2:1型层状结构和结构铁组分丰富的蛭石黏土矿物作为铁源,在酸性介质中采用简单的水热合成法,使得蛭石结构铁和钼酸盐反应在蛭石片上生成新的物质相钼酸铁(Fe2(MoO4)3),蛭石可以有效分散活性组分的分散性,而且减小Fe2(MoO4)3的尺寸,增强了蛭石结构铁的有效利用,有利于增强了复合材料的类过氧化物酶活性,而且显著提升了钼酸铁纳米酶在中性条件下的类过氧化物酶活性,可以用于生物传感与抗菌应用,这些优势有利于复合材料产生更多的活性氧,使其满足中性条件下实现生物比色传感和抗菌的需求,有利于蛭石的高值化利用;本工作为黏土矿物纳米酶的合成与纳米酶活性调控提供新方法,为黏土矿物高值化利用提供新途径,而且此方法工艺简单,所用原料价格低廉、环保无毒,易于大规模生产。
附图说明
图1为实施例1制备的钼酸铁纳米酶、原矿蛭石、MoO3和空白组的类过氧化物酶活性测试结果图;
图2为原矿蛭石、MoO3和实施例1制备的钼酸铁纳米酶的XRD图;
图3为原矿蛭石、酸处理蛭石、MoO3和实施例1制备的钼酸铁纳米酶的电镜图;
图4为实施例1制备的钼酸铁纳米酶在中性和酸性介质下的类过氧化物酶活性测试结果图;
图5为实施例2制备的钼酸铁纳米酶的类过氧化物酶活性测试结果图;
图6为实施例3制备的钼酸铁纳米酶的类过氧化物酶活性测试结果图;
图7为实施例4制备的钼酸铁纳米酶的类过氧化物酶活性测试结果图;
图8为实施例5制备的钼酸铁纳米酶的类过氧化物酶活性测试图;
图9为实施例6制备的钼酸铁纳米酶的类过氧化物酶活性测试图。
具体实施方式
以下是本发明的具体实施例并结合附图,对本发明的技术方案作进一步的描述,但本发明并不限于这些实施例。
实施例1:
本实施例以最优条件下的钼酸铁纳米酶为例:将质量比Na2MoO4·2H2O:原矿蛭石=12:1(Na2MoO4·2H2O为1.2g,原矿蛭石为0.1g)放入100mL烧杯中,然后依次加入43mL去离子水,加入浓盐酸(最后盐酸浓度0.3M),接着转入到100mL聚四氟乙烯内衬中,装入反应釜,在180℃的卧式鼓风干燥箱中反应24h,待溶液冷却至室温,用去离子水充分洗涤后,冷冻干燥,既可得到钼酸铁纳米酶。做类过氧化物酶活性测试。
上述技术方案中,类过氧化物酶检测:以无色3,3’5,5’-四甲基联苯胺(TMB)为显色底物,其氧化态在652nm处有吸收,pH=4.0的0.1M醋酸-醋酸钠缓冲液(超纯水、NaCl溶液),材料浓度66.66μg/mL、H2O2浓度10mM、TMB浓度1mM,使用酶标仪隔30s测一次溶液在652nm处的吸光度值,循环6次。
参见附图1,相比于蛭石,蛭石制备的钼酸铁类过氧化物酶活性显著增强。
参见附图2,原矿蛭石(PDF#42-1413)在2θ=8.7°和27.5°时的两个强衍射峰归因于蛭石的特征峰(001)和(003)。MoO3的结构与PDF#05-0508吻合。Fe2(MoO4)3结构与PDF#35-0183吻合。
参见附图3,原矿蛭石具有片层状结构且表面较为平整,酸处理蛭石变为细小碎片,MoO3是棒状结构,长约2μm,直径约200nm。Fe2(MoO4)3形貌为片状和棒状复合形貌,尺寸减小。处理后的蛭石原先完整的片层架构遭到破坏,却有利于Fe2(MoO4)3的尺寸减少和分散。
参见附图4,钼酸铁纳米酶在中性介质去离子水和生理盐水中的活性优于其在酸性条件下的催化活性。蛭石原料制备的Fe2(MoO4)3纳米酶不仅在酸性条件下具有类过氧化物酶活性,而且在中性介质中的类过氧化物酶活性更高。
实施例2:
本实施例制备不同酸性介质条件下的钼酸铁纳米酶:将Na2MoO4·2H2O:原矿蛭石=12:1(质量比)放入100mL烧杯中,然后依次加入43mL去离子水,加入浓盐酸(最后盐酸浓度0.1-1.0M),接着转入到100mL聚四氟乙烯内衬中,装入反应釜,在180℃的卧式鼓风干燥箱中反应24h,待溶液冷却至室温,用去离子水充分洗涤后,冷冻干燥,既可得到钼酸铁纳米酶。做类过氧化物酶活性测试。
参见附图5,钼酸铁纳米酶的类过氧化物酶活性在0.3M HCl下活性最高。
实施例3
本实施例制备不同钼酸盐:原矿蛭石质量比的钼酸铁纳米酶:将将Na2MoO4·2H2O:原矿蛭石(质量比)=2.4-120:1(原矿蛭石为0.1g)放入100mL烧杯中,然后依次加入43mL去离子水,加入浓盐酸(最后盐酸浓度0.3M),接着转入到100mL聚四氟乙烯内衬中,装入反应釜,在180℃的卧式鼓风干燥箱中反应24h,待溶液冷却至室温,用去离子水充分洗涤后,冷冻干燥,既可得到钼酸铁纳米酶。做类过氧化物酶活性测试。
参见附图6,钼酸铁纳米酶的类过氧化物酶活性在钼酸盐:蛭石=12:1时的活性最优。
实施例4:
本实施例制备不同温度下的钼酸铁纳米酶:将将Na2MoO4·2H2O:原矿蛭石(质量比)=12:1放入100mL烧杯中,然后依次加入43mL去离子水,加入浓盐酸(最后盐酸浓度0.3M),接着转入到100mL聚四氟乙烯内衬中,装入反应釜,在120-190℃的卧式鼓风干燥箱中反应24h,待溶液冷却至室温,用去离子水充分洗涤后,冷冻干燥,既可得到钼酸铁纳米酶。做类过氧化物酶活性测试。
参见附图7,钼酸铁纳米酶的类过氧化物酶活性在180℃时的活性最优。
实施例5
本实施例制备不同时间下的钼酸铁纳米酶:将将Na2MoO4·2H2O:原矿蛭石(质量比)=12:1放入100mL烧杯中,然后依次加入43mL去离子水,加入浓盐酸(最后盐酸浓度0.3M),接着转入到100mL聚四氟乙烯内衬中,装入反应釜,在180℃的卧式鼓风干燥箱中反应8-24h,待溶液冷却至室温,用去离子水充分洗涤后,冷冻干燥,既可得到钼酸铁纳米酶。做类过氧化物酶活性测试。
参见附图8,钼酸铁纳米酶的类过氧化物酶活性在16h活性达到平稳。
实施例6
本实施例测试反应过程中的活性氧物种,以糠醇作为单线态氧(1O2)的淬灭剂,钼酸铁+H2O2+TMB作为显色体系,在酶标仪上测定吸光度值随时间的变化。
图9为单线态氧测试的结果图。
以上未涉及之处,适用于现有技术。
虽然已经通过示例对本发明的一些特定实施例进行了详细说明,但是本领域的技术人员应该理解,以上示例仅是为了进行说明,而不是为了限制本发明的范围,本发明所属技术领域的技术人员可以对所描述的具体实施例来做出各种各样的修改或补充或采用类似的方式替代,但并不会偏离本发明的方向或者超越所附权利要求书所定义的范围。本领域的技术人员应该理解,凡是依据本发明的技术实质对以上实施方式所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围。
Claims (9)
1.一种基于蛭石的钼酸铁纳米酶的制备方法,其特征在于:采用蛭石、钼酸盐为原料,在酸性介质中通过水热合成法得到产物,待产物冷却至室温,使用去离子水多次清洗干净,冷冻干燥,既可得到钼酸铁纳米酶。
2.如权利要求1所述的一种基于蛭石的钼酸铁纳米酶的制备方法,其特征在于:所述酸性介质溶液为0.1M-1.0M HCl。
3.如权利要求1所述的一种基于蛭石的钼酸铁纳米酶的制备方法,其特征在于:所述钼酸盐:蛭石的质量比为2.4-120:1。
4.如权利要求1所述的一种基于蛭石的钼酸铁纳米酶的制备方法,其特征在于:所述蛭石的质量百分比SiO2为30-43%,Fe2O3为15-21%、Al2O3为5-15%,MgO为5-11%,K2O<6%,CaO<3%,其他元素<1%。
5.如权利要求1所述的一种基于蛭石的钼酸铁纳米酶的制备方法,其特征在于:所述水热合成法温度为120℃-190℃;并保持8-24h。
6.一种采用权利要求1-5任一项所述的制备方法制备的钼酸铁纳米酶。
7.如权利要求6所述的一种钼酸铁纳米酶在比色传感上的应用,其特征在于:以钼酸铁纳米酶作为类过氧化物酶,在H2O2存在条件下,与显色底物发生显色反应,将溶液吸光度值变化与目标待检测还原物浓度关联,从而建立起比色传感平台,用于检测待检测还原物的浓度。
8.如权利要求6所述的一种钼酸铁纳米酶在比色传感上的应用,其特征在于:所述显色底物为氧化3,3’5,5’-四甲基联苯胺、2,2'-联氮双(3-乙基苯并噻唑啉-6-磺酸)二铵盐或邻苯二胺。
9.如权利要求6所述的一种钼酸铁纳米酶的抗菌应用,其特征在于:所述钼酸铁纳米酶催化H2O2分解产生具有强氧化能力的羟基自由基和单线态氧,用于有效杀死细菌。
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