CN113231104B - 一种氨基酸改性纳米零价铁材料及其制备方法 - Google Patents
一种氨基酸改性纳米零价铁材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种氨基酸改性纳米零价铁材料和制备方法,属于材料及环境交叉技术领域。该材料中氨基酸吸附在纳米零价铁表面以实现纳米零价铁改性,从而增强纳米零价铁的分散和界面相互作用;与所述氨基酸中心碳原子连接的羧基上的碳原子、氧原子以及氨基上的氢原子与纳米零价铁通过静电相互作用连接,并形成稳定结构。优选地,氨基酸侧链上的氧原子和/或硫原子与纳米零价铁通过静电相互作用连接。利用氨基酸具有的氨基和羧基等特定官能团及多种支链来增强纳米颗粒在反应液中的分散和界面相互作用。该改性材料具有较高的催化反应活性及吸附性能,且制备方法简单,原料易得,对环境友好,仪器设备要求低,具有较大的应用前景。
Description
技术领域
本发明属于材料及环境交叉技术领域,更具体地,涉及一种氨基酸改性纳米零价铁材料和制备方法。
背景技术
随着研究的进展,人们发现均相芬顿反应存在适用pH范围较窄、产生大量化学污泥等缺点,于是非均相类芬顿反应逐渐成为研究热点。通过探索创新制备出效果较好的非均相催化剂,进而研究非均相类芬顿体系对废物的降解处理效果,确定反应的影响因素,找到最佳反应条件,以达到改善传统芬顿法的目的。非均相芬顿和类芬顿催化剂近年来受到广泛关注,迄今为止,研究主要集中在三类材料上:(1)铁氧系列化合物,如α-Fe2O3、α-FeOOH、Fe3O4和Fe0/Fe3O4等;(2)铁负载材料,其中电解质膜、聚乙烯膜、粉煤灰、聚电解质微球、碳、树脂、二氧化硅、粘土和Al2O3被用作固定铁的固体基质;(3)天然含铁材料,如褐铁矿和针铁矿等。另有一些双金属复合材料的研究,如nZVI、n-Ni/Fe、n-Pd/Fe等铁基纳米粒子。这些非均相类芬顿催化剂被证明可用于在更宽的适用酸碱度范围内处理水中的各种有机污染物,然而其中许多没有显示出良好的催化活性。通过引入特定官能团的表面功能化材料为各种可能的应用打开了大门,因此,使用官能团对纳米粒子进行表面改性引起了人们的兴趣,它可增强纳米颗粒的分散和界面相互作用,还可为纳米粒子提供特定的识别和结合能力。
由于氨基酸是天然存在、廉价的、对环境友好的分子,由至少一个氨基(-NH2)和一个羧基(-COOH)组成的氨基酸可改性纳米粒子材料的表面,氨基酸的氨基和羧基官能团可以作为与纳米材料相互作用的媒介,其具有两性性质、高稳定性和良好的生物相容性。生物分子显示出高水平的分子识别能力,其含有的官能团如氨基、羧基、硫醇和羟基与给定无机表面相互作用的特异性在许多应用中起着关键作用,例如生物成核、催化、医学诊断、医疗植入物和生物传感器等。氨基酸是肽和蛋白质的基本组成部分,是生物系统中反映复杂生物分子化学特性的两个主要结构单元,它们与不同纳米材料的相互作用正作为一类新材料被广泛探索。在许多理论和实验研究中已经报道了氨基酸在纳米粒子上的吸附,由于羧基官能团能参与金属表面的结合,氨基酸和金属表面之间的相互作用也成为可能,相互作用的强度主要取决于表面性质,但也可能受到氨基酸的类型的影响。自然界的生物系统中包含20种氨基酸,α-碳上含有的不同侧链通常可分为非极性侧链、极性侧链和带电侧链三种类型,由于不同的侧链基团,每个氨基酸具有不同的等电点,具有独特的净表面电荷。不同性质的纳米金属颗粒的表面官能化在催化剂应用中也很重要,从而提供开发这种改性纳米金属材料的进一步可能性。
发明内容
本发明针对现有类芬顿反应催化剂在有机物氧化降解过程中由于催化剂与水相和有机相的界面相互作用受限而导致的催化性能下降现象,提出了一种氨基酸改性纳米零价铁材料及其制备方法,该材料中氨基酸吸附在纳米零价铁表面以实现纳米零价铁改性,从而增强纳米零价铁的分散和界面相互作用。本发明中的氨基酸改性纳米零价铁材料具有更好的亲水性及氧化活性,作为非均相催化剂用于类芬顿反应降解水中有机物具有良好催化性能。
根据本发明的第一方面,提供了一种氨基酸改性纳米零价铁材料,该材料中氨基酸吸附在纳米零价铁表面以实现纳米零价铁改性,从而增强纳米零价铁的分散和界面相互作用;与所述氨基酸中心碳原子连接的羧基上的碳原子、与该中心碳原子连接的羧基上的氧原子以及与该中心碳原子连接的氨基上的氢原子分别与纳米零价铁通过静电相互作用连接并形成稳定结构。
优选地,所述氨基酸侧链上的氧原子和/或硫原子与纳米零价铁通过静电相互作用连接。
优选地,所述氨基酸为α-氨基酸。
优选地,所述α-氨基酸为甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、脯氨酸、苯丙氨酸、色氨酸、甲硫氨酸、半胱氨酸、天冬酰胺、丝氨酸、天冬氨酸、谷氨酸、赖氨酸或精氨酸。
优选地,所述氨基酸侧链上的氧原子为羟基、羧基或羰基上的氧原子。
按照本发明的另一方方面,提供了任一所述氨基酸改性纳米零价铁材料的制备方法,包括以下步骤:
(1)在通有非氧化性保护气氛的条件下,向二价铁盐水溶液中滴加硼氢化钾或硼氢化钠水溶液,所述硼氢化钾或硼氢化钠用于还原二价铁离子,并生成沉淀物纳米零价铁单质;
(2)向步骤(1)得到的沉淀物纳米零价铁单质中加入氨基酸水溶液进行接枝反应,即得到氨基酸改性纳米零价铁材料。
优选地,所述二价铁盐为七水合硫酸亚铁、四水合氯化亚铁或葡萄糖酸亚铁;所述氨基酸为α-氨基酸。
优选地,所述二价铁盐水溶液的初始浓度为0.02mol/L~0.08mol/L;所述的硼氢化钾水溶液或硼氢化钠水溶液的初始浓度与二价铁盐水溶液的初始浓度比为(4~6):1。
优选地,所述氨基酸与纳米零价铁单质的质量比为(1~3):1。
总体而言,通过本发明所构思的以上技术方案与现有技术相比,主要具备以下的技术优点:
(1)本发明中氨基酸的氨基和羧基官能团可以作为与纳米零价铁材料相互作用的媒介,氨基酸不同的侧链基团以及独特的表面净电荷,可通过静电相互作用吸附纳米零价铁材料,使纳米零价铁材料具有更强的亲水性,增强了纳米颗粒的分散和界面相互作用,该改性纳米铁材料具有一般非均相催化剂的优点,有更宽的酸碱度适用范围,不会产生化学污泥,且催化活性高,制备方法简单,操作方便,仪器设备要求低。
(2)本发明中的氨基酸改性纳米零价铁材料具有更好的亲水性及氧化活性,作为非均相催化剂用于类芬顿反应降解水中有机物具有良好催化性能,且所需催化剂用量少,原料易得,材料制备简单,对环境友好。
(3)本发明中用于改性纳米零价铁的氨基酸,优选地为自然界的生物系统中天然存在的α-氨基酸,包括甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、脯氨酸、苯丙氨酸、色氨酸、甲硫氨酸、半胱氨酸、天冬酰胺、丝氨酸、天冬氨酸、谷氨酸、赖氨酸、精氨酸,它们具有稳定性高、生物相容性好、廉价易得、对环境友好等技术优点。
附图说明
图1为丙氨酸改性纳米零价铁的结构图。
图2为氨基酸(以丙氨酸为例)改性纳米零价铁的制备流程图。
图3为丙氨酸改性纳米零价铁的ESP模拟图。
图4为丙氨酸改性纳米零价铁的EDAX表征。
图5为丙氨酸改性纳米零价铁的扫描电镜结构图。
图6为纳米零价铁改性前后与水的接触角表征。
图7为甲硫氨酸改性纳米零价铁的结构图。
图8为丝氨酸改性纳米零价铁的结构图。
图9为天冬氨酸改性纳米零价铁的结构图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明中氨基酸改性纳米零价铁材料,该材料为粉末状,氨基酸通过静电相互作用吸附在纳米零价铁表面,实现了纳米颗粒的表面功能化,增强了纳米颗粒的分散和界面相互作用,且该改性材料中含有氨基和羧基等极性基团,使纳米零价铁材料具有更好的亲水性,氨基酸特异性的支链还可与有机分子产生相互作用力,具有较高的催化反应活性及吸附性能。
本发明中的氨基酸改性纳米零价铁材料的结构特点与性质如下:氨基酸的氨基和羧基是与铁原子发生相互作用的主要位点,侧链几乎不参与氨基酸与金属的相互作用,当侧链含有含氧官能团时也会出现与铁相互作用的情况。氨基酸与铁发生作用后,氨基酸的形状结构和电荷分布均会发生变化。铁原子倾向于将电子转移到氨基酸的羧基,因此羧基是最有效的吸附位点。受铁原子的吸附力作用,氨基氢原子和羧基氧原子、碳原子倾向于与铁原子形成较稳定的三齿结构,以丙氨酸为例改性纳米零价铁的结构如图1所示。
本发明中氨基酸(以丙氨酸为例)改性纳米零价铁材料的制备过程如图2所示,采用液相还原法和接枝法制备,方法如下:室温下,在通有氮气保护和电动搅拌的情况下,向二价铁盐水溶液中以2mL/min的速度滴加硼氢化钾水溶液,还原反应2h后,静置沉淀;用无氧去离子水洗涤沉淀三次,之后向沉淀中加入一定浓度的氨基酸水溶液进行接枝反应,将混合液低速搅拌1h后静置沉淀,随后将沉淀放入真空冷冻干燥箱中干燥1~2天,全程应避免材料与氧气的接触。还原反应的搅拌转速为300~500r/min;接枝反应的搅拌转速为100~200r/min。
实施例1:丙氨酸改性纳米零价铁的制备
室温下,在通有氮气保护和电动搅拌的情况下,向100mL 0.04mol/L的FeSO4水溶液中以2mL/min的流速滴加100ml 0.2mol/L的硼氢化钾水溶液,在500r/min的搅拌速度下反应2h后,静置沉淀,用无氧去离子水洗涤沉淀三次,之后向沉淀中加入50mL溶有0.5345g丙氨酸的水溶液,将混合液以150r/min低速搅拌1h后静置沉淀,随后将沉淀放入冷冻干燥箱中干燥1~2天,全程应避免材料与氧气的接触。干燥后得到约0.35g黑色粉末状丙氨酸改性纳米零价铁粉。
丙氨酸改性纳米零价铁的结构如图1所示,其中,氨基氢原子和羧基氧原子、碳原子倾向于与铁原子形成较稳定的三齿结构。丙氨酸通过静电相互作用与纳米零价铁结合,由图3可知,铁在带负电荷羧基的和带正电荷的氨基之间处于静电平衡状态,使氨基酸改性纳米零价铁处于稳定结构。图4为丙氨酸改性纳米零价铁的EDAX表征图,图4中的(a)和(b)分别为丙氨酸改性纳米零价铁的实时面分布图及N元素分布图,可以看出改性后的纳米材料中N元素占有较大的比例,表明氨基酸接枝的成功。从图5的丙氨酸改性纳米零价铁的扫描电镜结构图中可以看出,丙氨酸改性纳米零价铁具有粒径约为50~100nm的微观结构。由图6中的(a)可知,纳米零价铁与水的接触角为41.6°和41.8°;由图6中的(b)所示,经过氨基酸改性后,与水的接触角为37.4°和38.4°,表明经氨基酸改性后的材料表现出更好的亲水性,更易于与有机物结合氧化降解有机物。
实施例2:甲硫氨酸改性纳米零价铁的制备
室温下,在通有氮气保护和电动搅拌的情况下,向100mL 0.04mol/L的FeSO4水溶液中以2mL/min的流速滴加100mL 0.2mol/L的硼氢化钾水溶液,在500r/min的搅拌速度下反应2h后,静置沉淀,用无氧去离子水洗涤沉淀三次,之后向沉淀中加入50mL溶有0.8952g甲硫氨酸的水溶液,将混合液以150r/min低速搅拌1h后静置沉淀,随后将沉淀放入冷冻干燥箱中干燥1~2天,全程应避免材料与氧气的接触。干燥后得到约0.38g黑色粉末状甲硫氨酸改性纳米零价铁粉,其具有粒径约为50~100nm的微观结构,且表现出更好的亲水性。甲硫氨酸改性纳米零价铁的结构如图7所示,甲硫氨酸通过静电相互作用与纳米零价铁结合,其中甲硫氨酸的羧基氧原子以及支链上的硫原子是可能与铁发生作用的主要位点,可能形成较为稳定的Fe-S键,增强吸附结合的强度。
实施例3:丝氨酸改性纳米零价铁的制备
室温下,在通有氮气保护和电动搅拌的情况下,向100mL 0.04mol/L的FeSO4水溶液中以2mL/min的流速滴加100mL 0.2mol/L的硼氢化钾水溶液,在500r/min的搅拌速度下反应2h后,静置沉淀,用无氧去离子水洗涤沉淀三次,之后向沉淀中加入50mL溶有0.6305g丝氨酸的水溶液,将混合液以150r/min低速搅拌1h后静置沉淀,随后将沉淀放入冷冻干燥箱中干燥1~2天,全程应避免材料与氧气的接触。干燥后得到约0.37g黑色粉末状丝氨酸改性纳米零价铁粉,其具有粒径约为50~100nm的微观结构,且表现出更好的亲水性。丝氨酸改性纳米零价铁的结构如图8所示,丝氨酸通过静电相互作用与纳米零价铁结合,其中丝氨酸的氨基和羧基以及支链上的羟基是可能与铁发生作用的主要位点。
实施例4:天冬氨酸改性纳米零价铁的制备
室温下,在通有氮气保护和电动搅拌的情况下,向100mL 0.04mol/L的FeSO4水溶液中以2mL/min的流速滴加100mL 0.2mol/L的硼氢化钾水溶液,在500r/min的搅拌速度下反应2h后,静置沉淀,用无氧去离子水洗涤沉淀三次,之后向沉淀中加入50mL溶有0.1505g天冬氨酸的水溶液,将混合液以150r/min低速搅拌1h后静置沉淀,随后将沉淀放入冷冻干燥箱中干燥1~2天,全程应避免材料与氧气的接触。干燥后得到约0.32g黑色粉末状天冬氨酸改性纳米零价铁粉,其具有粒径约为50~100nm的微观结构,且表现出更好的亲水性。天冬氨酸改性纳米零价铁的结构如图9所示,天冬氨酸通过静电相互作用与纳米零价铁结合,其中天冬氨酸主链上的羧基以及支链上的羧基是可能与铁发生作用的主要位点。
实施例5:苯丙氨酸改性纳米零价铁的制备
室温下,在通有氮气保护和电动搅拌的情况下,向100mL 0.04mol/L的FeSO4水溶液中以2mL/min的流速滴加100mL 0.2mol/L的硼氢化钾水溶液,在500r/min的搅拌速度下反应2h后,静置沉淀,用无氧去离子水洗涤沉淀两次,之后向沉淀中加入50mL溶有0.9911g苯丙氨酸的水溶液,将混合液以150r/min低速搅拌1h后静置沉淀,随后将沉淀放入冷冻干燥箱中干燥1~2天,全程应避免材料与氧气的接触。干燥后得到约0.34g黑色粉末状苯丙氨酸改性纳米零价铁粉,其具有粒径约为50~100nm的微观结构,表现出更好的界面作用。苯丙氨酸通过静电相互作用与纳米零价铁结合,其中苯丙氨酸主链上有亲水的氨基和羧基基团,支链上有疏水的苯环,因此能够进一步促进苯丙氨酸改性纳米零价铁与水相和有机相界面的作用。
实施例6:氨基酸改性纳米零价铁的催化性能
在95℃恒温水浴加搅拌的条件下,对10mL有机溶剂进行氧化降解,反应开始时分别以2mL/min的速度同时滴加150mL 30%H2O2和50mL 2M H2SO4溶液,加入0.3g氨基酸改性纳米零价铁材料作为氧化反应的催化剂,反应2h后测量剩余有机溶剂体积及反应残液的COD值。结果显示,使用氨基酸改性纳米零价铁材料作为催化剂时,有6.4mL有机溶剂被氧化降解,且反应残液COD为104mg/L;使用未改性的纳米零价铁材料作为催化剂时,有5.4mL有机溶剂被氧化降解,且反应残液COD为729mg/L;对比可知,氨基酸改性纳米零价铁有更好的催化性能,可将反应的氧化效率提高10%左右,且反应残液的COD值更低,能达到更高要求。
本领域的技术人员容易理解,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作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种氨基酸改性纳米零价铁材料,其特征在于,该材料中氨基酸吸附在纳米零价铁表面以实现纳米零价铁改性,从而增强纳米零价铁的分散和界面相互作用;与所述氨基酸中心碳原子连接的羧基上的碳原子、与该中心碳原子连接的羧基上的氧原子以及与该中心碳原子连接的氨基上的氢原子分别与纳米零价铁通过静电相互作用连接并形成稳定结构;
所述氨基酸改性纳米零价铁材料通过以下步骤制备得到:
(1)在通有非氧化性保护气氛的条件下,向二价铁盐水溶液中滴加硼氢化钾或硼氢化钠水溶液,所述硼氢化钾或硼氢化钠用于还原二价铁离子,并生成沉淀物纳米零价铁单质;
(2)向步骤(1)得到的沉淀物纳米零价铁单质中加入氨基酸水溶液进行接枝反应,即得到氨基酸改性纳米零价铁材料。
2.如权利要求1所述的氨基酸改性纳米零价铁材料,其特征在于,所述氨基酸侧链上的氧原子和/或硫原子与纳米零价铁通过静电相互作用连接。
3.如权利要求1所述的氨基酸改性纳米零价铁材料,其特征在于,所述氨基酸为α-氨基酸。
4.如权利要求3所述的氨基酸改性纳米零价铁材料,其特征在于,所述α-氨基酸为甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、脯氨酸、苯丙氨酸、色氨酸、甲硫氨酸、半胱氨酸、天冬酰胺、丝氨酸、天冬氨酸、谷氨酸、赖氨酸或精氨酸。
5.如权利要求2所述的氨基酸改性纳米零价铁材料,其特征在于,所述氨基酸侧链上的氧原子为羟基、羧基或羰基上的氧原子。
6.如权利要求1-5任一所述氨基酸改性纳米零价铁材料的制备方法,其特征在于,包括以下步骤:
(1)在通有非氧化性保护气氛的条件下,向二价铁盐水溶液中滴加硼氢化钾或硼氢化钠水溶液,所述硼氢化钾或硼氢化钠用于还原二价铁离子,并生成沉淀物纳米零价铁单质;
(2)向步骤(1)得到的沉淀物纳米零价铁单质中加入氨基酸水溶液进行接枝反应,即得到氨基酸改性纳米零价铁材料。
7.如权利要求6所述氨基酸改性纳米零价铁材料的制备方法,其特征在于,所述二价铁盐为七水合硫酸亚铁、四水合氯化亚铁或葡萄糖酸亚铁;所述氨基酸为α-氨基酸。
8.如权利要求6所述氨基酸改性纳米零价铁材料的制备方法,其特征在于,所述二价铁盐水溶液的初始浓度为0.02mol/L~0.08mol/L;所述的硼氢化钾水溶液或硼氢化钠水溶液的初始浓度与二价铁盐水溶液的初始浓度比为(4~6):1。
9.如权利要求6所述氨基酸改性纳米零价铁材料的制备方法,其特征在于,所述氨基酸与纳米零价铁单质的质量比为(1~3):1。
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