CN112619707B - 一种降解有机污染物用复合模拟酶凝胶及其制备方法和应用 - Google Patents
一种降解有机污染物用复合模拟酶凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种降解有机污染物用复合模拟酶凝胶及其制备方法和应用,该方法包括以下步骤:(1)将氨基酸溶于去离子水,配成氨基酸溶液,加入酸调节pH=6.5‑7.5,逐滴加入等体积的铜离子溶液,继续调节pH=6.5‑7.5后搅拌,洗涤数次后将产物进行冷冻干燥处理,得到模拟酶;(2)配置水性硅溶液,向水性硅溶液中添加模拟酶,得到混合液;搅拌溶解后调节pH=3.5‑7.5,老化,得到含有介孔或者微孔的降解有机污染物用复合模拟酶凝胶,并用于降解环境中的酚类和/或染料类有机污染物。与现有技术相比,本发明在不对环境造成额外污染的条件下,通过调控孔径的大小来控制酶降解的速度,从而达到长期、稳定、高效的降解效果,具有良好应用前景。
Description
技术领域
本发明涉及环境修护领域,具体涉及一种降解有机污染物用复合模拟酶凝胶及其制备方法和应用。
背景技术
随着我国经济的高速稳定发展,一些环境问题也开始凸显出来。人为活动产生的污染物进入土壤并积累到一定程度,引起土壤质量恶化,当土壤中有害物质过多,超过土壤的自净能力时,就会引起土壤的组成、结构和功能发生变化,微生物活动受到抑制,有害物质或其分解产物在土壤中逐渐积累,并且通过“土壤→植物→人体”或“土壤→水→人体”间接被人体吸收。土壤污染会导致农作物减产和农产品品质降低、农作物中某些指标超过国家标准、地下水和地表水污染、大气环境质量降低,并最终危害人体健康。
由于土壤性质差异较大,而且污染物在土壤中迁移慢,导致土壤中污染物分布不均匀,空间差异性较大。与大气和水体相比,治理土壤污染的成本高、周期长、难度大。如果想从土壤中将污染物分离,需要较为复杂解析手段,让污染物与土壤的结合性下降,之后再将污染物通过淋洗等手段从土壤中析出,需要大量的财力物力。同时也需要漫长的治理周期。如何低成本的处理受污染的土壤,同时不会破坏土壤环境,造成二次污染成为当今环保的重要问题。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种在不对环境造成额外污染的条件下,通过调控孔径的大小来控制酶降解的速度,从而达到长期、稳定、高效的降解效果,具有良好应用前景的降解有机污染物用复合模拟酶凝胶及其制备方法和应用。
本发明的目的可以通过以下技术方案来实现:
一种降解有机污染物用复合模拟酶凝胶的制备方法,该方法包括以下步骤:
(1)将氨基酸溶于去离子水,配成氨基酸溶液,加入酸调节pH=6.5-7.5,逐滴加入等体积的铜离子溶液,继续调节pH=6.5-7.5后搅拌,洗涤数次后将产物进行冷冻干燥处理,得到模拟酶——氨基酸配位铜产物;制得的中间产物模拟酶为蓝色的颗粒,溶于水;
(2)配置水性硅溶液,向水性硅溶液中添加模拟酶,得到混合液;搅拌溶解后调节pH=3.5-7.5,老化,溶胶胶粒依靠形成的Si-O-Si化学键相结合,连成极稳定的空间网络结构,得到含有介孔或者微孔的降解有机污染物用复合模拟酶凝胶。最后制得的复合凝胶冷冻干燥后,形貌是粉末、颗粒和块状中的一种或者多种,加入适量水中,会重新形成凝胶状。
本发明可以通过调节反应的条件,来控制生成的凝胶具有介孔或者微孔等不同的孔径大小,从而调整酶在环境体系中的降解速度,根据不同的需求,来达到在降解环境中长期、稳定、高效的降解作用。
本发明强调的可以通过调节反应的条件,来控制生成的凝胶具有介孔或者微孔等不同的孔径大小,从而调整酶在环境体系中的降解速度主要是配方的变化,工艺的变化主要是因为配方变了,同时改变了凝胶过程中的流变学性质,所以相应的工艺(比如凝胶时间)发生了变化。pH不同导致颗粒表面吸附的离子数不同,粒子之间的相互作用不同,形成的空间立体三维网状结构致密程度的不同。不同的配方导致凝胶产生的孔径的变化,而孔径的不同就导致了凝胶材料的比表面积的不同,从而改变了凝胶中模拟酶与污染物的接触面积,达到控制降解速率的作用。
进一步地,所述氨基酸溶液的浓度为0.1-5mol/L;所述铜离子溶液的浓度为0.1-2mol/L。
进一步地,所述搅拌的时间为1.5-2.5h。
进一步地,所述的混合液中模拟酶与SiO2的质量比为1:(5-500)。
进一步地,所述老化的温度为40-70℃,时间为2-16h。
进一步地,所述的氨基酸包括甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、甲硫氨酸(蛋氨酸)、脯氨酸、色氨酸、丝氨酸、酪氨酸、半胱氨酸、苯丙氨酸、天冬酰胺、谷氨酰胺、苏氨酸、天冬氨酸、谷氨酸、赖氨酸、精氨酸或组氨酸中的一种或多种;
所述的铜离子溶液包括氯化铜溶液、二水合氯化铜溶液、硫酸铜溶液或五水合硫酸铜溶液中的一种或多种。
进一步地,所述的配置的水性硅溶胶是以水玻璃、单质硅或SiO2为原料,用离子交换法、单质硅一步溶解法、电解电渗析法、直接酸化法、分散法或胶溶法制成。
进一步地,所述水性硅溶胶的SiO2质量分数在10-40%,粒径在5-100nm,pH=8.5-10的碱性硅溶胶或者pH=2-3的酸性硅溶胶。配置的水性硅溶胶在pH>7.5或者pH<3.5时,溶液呈现出稳定的溶胶状态,不会发生凝胶现象。
一种如上所述的方法制备的降解有机污染物用复合模拟酶凝胶。
一种如上所述的降解有机污染物用复合模拟酶凝胶的应用,该复合模拟酶凝胶用于降解环境中的酚类和/或染料类有机污染物,应用时向复合模拟酶凝胶所在的环境中添加适量双氧水(H2O2)。双氧水(H2O2)会使模拟酶产生具有活性的羟基自由基,从而高效降解酚类、染料类等有机污染物,向降解过污染物的凝胶环境中添加适量双氧水(H2O2),复合的Arg-Cu(II)会被还原成Arg-Cu(I),从而重新具备降解活性。
与现有技术相比,本发明具有以下优点:
(1)本发明可以通过调节反应的条件,来控制生成的凝胶具有介孔或者微孔等不同的孔径大小,从而调整酶在环境体系中的降解速度,根据不同的需求,来达到在降解环境中长期、稳定、高效的降解作用;
(2)本发明具有步骤简单、结构稳定、用料便宜、低碳环保、降解高效、可循环使用等优点,能够降低土壤或水体中的部分污染,具有潜在的大规模生产应用价值;
(3)本发明中的模拟酶凝胶利用SiO2水系凝胶不仅作为载体,而且可以通过不同的配比来调控孔径,从而达到控制降解速度的效果。此外,本发明的凝胶是在水体系下形成的,与传统的乙醇体系不同,相比之下制备简单且具有更高的实用价值。
附图说明
图1为实施例1制得的复合模拟酶凝胶图片;
图2为实施例1制得的复合模拟酶凝胶的作用机理示意图;
图3为实施例1制得的复合模拟酶凝胶的氮气吸脱附曲线和孔径分布图;
图4为实施例1制得的复合模拟酶凝胶对亚甲基蓝的降解测试。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
将L-精氨酸(Arg)溶于去离子水,配成1mol/L精氨酸溶液,加入酸调节pH为7,逐滴加入等体积的氯化铜溶液(0.5mol/L),继续调节pH约为7搅拌1h,然后洗涤数次后将产物进行冷冻干燥处理,得到模拟酶——精氨酸配位铜(Arg-Cu)产物;向SiO2质量分数为30%,粒径在20nm,pH为8.5的碱性硅溶胶中添加模拟酶,使酶与SiO2的质量比为1:500。搅拌溶解后用调节pH到5,在60℃条件下,老化2h,得到一种具有降解功能的复合凝胶。该复合凝胶经过BET测试,比表面积在191m2/g,孔径大小为1.04nm,配置50μg/ml的亚甲基蓝溶液作为降解测试对象,向亚甲基蓝溶液中加入H2O2,使得H2O2浓度为50mmol/l,放入200g制得的模拟酶凝胶,凝胶在降解环境中能够保持30天的降解活性。
实施例2
将L-精氨酸(Arg)溶于去离子水,配成1mol/L精氨酸溶液,加入酸调节pH为7,逐滴加入等体积的氯化铜溶液(1mol/L),继续调节pH约为7搅拌8h,然后洗涤数次后将产物进行冷冻干燥处理,得到模拟酶——精氨酸配位铜(Arg-Cu)产物;向配置好的SiO2质量分数为30%,颗粒在20nm,pH为8.5的碱性硅溶胶中添加模拟酶,使酶与SiO2的质量比为1:50。搅拌溶解后用酸调节pH到7,在60℃条件下,老化12h,得到一种具有降解功能的复合凝胶。该复合凝胶经过BET测试,比表面积在320m2/g,孔径大小为6.08nm,配置50μg/ml的亚甲基蓝溶液作为降解测试对象,向亚甲基蓝溶液中加入H2O2,使得H2O2浓度为50mmol/l,放入200g制得的模拟酶凝胶,凝胶在降解环境中能够保持14天的降解活性。
实施例3
将L-亮氨酸(Leu)溶于去离子水,配成1mol/L亮氨酸溶液,加入酸调节pH为7,逐滴加入等体积的氯化铜溶液(0.5mol/L),继续调节pH约为7搅拌1h,然后洗涤数次后将产物进行冷冻干燥处理,得到模拟酶——亮氨酸配位铜(Leu-Cu)产物;向SiO2质量分数为20%,颗粒在20nm,pH为2的酸性硅溶胶中添加模拟酶,使酶与SiO2的质量比为1:500。搅拌溶解后用酸调节pH到5,在60℃条件下,老化2h,得到一种具有降解功能的复合凝胶。该复合凝胶经过BET测试,比表面积在179m2/g,孔径大小为1.01nm,配置50μg/ml的亚甲基蓝溶液作为降解测试对象,向亚甲基蓝溶液中加入H2O2,使得H2O2浓度为50mmol/l,放入200g制得的模拟酶凝胶,凝胶在降解环境中能够保持30天的降解活性。
实施例4
将L-精氨酸(Arg)溶于去离子水,配成1mol/L精氨酸溶液,加入酸调节pH为7,逐滴加入等体积的氯化铜溶液(0.5mol/L),继续调节pH约为7搅拌1h,然后洗涤数次后将产物进行冷冻干燥处理,得到模拟酶——精氨酸配位铜(Arg-Cu)产物;向SiO2质量分数为30%,颗粒在50nm,pH为8.5的碱性硅溶胶中添加模拟酶,使酶与SiO2的质量比为1:500。搅拌溶解后用酸调节pH到4,在60℃条件下,老化12h,得到一种具有降解功能的复合凝胶。该复合凝胶经过BET测试,比表面积在152m2/g,孔径大小为1.25nm,配置50μg/ml的亚甲基蓝溶液作为降解测试对象,向亚甲基蓝溶液中加入H2O2,使得H2O2浓度为50mmol/l,放入200g制得的模拟酶凝胶,凝胶在降解环境中能够保持30天的降解活性。
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 (9)
1.一种降解有机污染物用复合模拟酶凝胶的制备方法,其特征在于,该方法包括以下步骤:
(1)将氨基酸溶于去离子水,配成氨基酸溶液,加入酸调节pH=6.5-7.5,逐滴加入等体积的铜离子溶液,继续调节pH=6.5-7.5后搅拌,洗涤数次后将产物进行冷冻干燥处理,得到模拟酶——氨基酸配位铜产物;
(2)配制水性硅溶胶,所述的水性硅溶胶是以水玻璃、单质硅或SiO2为原料,用离子交换法、单质硅一步溶解法、电解电渗析法、直接酸化法、分散法或胶溶法中的一种制成;向水性硅溶胶中添加模拟酶,得到混合液;搅拌溶解后调节pH=3.5-7.5,老化,得到含有介孔或者微孔的降解有机污染物用复合模拟酶凝胶,制得的复合凝胶冷冻干燥后,形貌是粉末、颗粒和块状中的一种或者多种,加入适量水中,会重新形成凝胶状。
2.根据权利要求1所述的一种降解有机污染物用复合模拟酶凝胶的制备方法,其特征在于,所述氨基酸溶液的浓度为0.1-5 mol/L;所述铜离子溶液的浓度为0.1-2 mol/L。
3.根据权利要求1所述的一种降解有机污染物用复合模拟酶凝胶的制备方法,其特征在于,所述搅拌的时间为1.5-2.5 h。
4.根据权利要求1所述的一种降解有机污染物用复合模拟酶凝胶的制备方法,其特征在于,所述的混合液中模拟酶与SiO2的质量比为1: (5-500)。
5.根据权利要求1所述的一种降解有机污染物用复合模拟酶凝胶的制备方法,其特征在于,所述老化的温度为40-70℃,时间为2-16 h。
6.根据权利要求1所述的一种降解有机污染物用复合模拟酶凝胶的制备方法,其特征在于,所述的氨基酸包括甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、甲硫氨酸、脯氨酸、色氨酸、丝氨酸、酪氨酸、半胱氨酸、苯丙氨酸、天冬酰胺、谷氨酰胺、苏氨酸、天冬氨酸、谷氨酸、赖氨酸、精氨酸或组氨酸中的一种或多种;
所述的铜离子溶液包括氯化铜溶液、二水合氯化铜溶液、硫酸铜溶液或五水合硫酸铜溶液中的一种或多种。
7.根据权利要求1所述的一种降解有机污染物用复合模拟酶凝胶的制备方法,其特征在于,所述水性硅溶胶为SiO2质量分数在10-40%,粒径在5-100 nm,pH=8.5-10的碱性硅溶胶或者pH=2-3的酸性硅溶胶。
8.一种如权利要求1-7任一项所述的方法制备的降解有机污染物用复合模拟酶凝胶。
9.一种如权利要求8所述的降解有机污染物用复合模拟酶凝胶的应用,其特征在于,该复合模拟酶凝胶用于降解环境中的酚类和/或染料类有机污染物,应用时向复合模拟酶凝胶所在的环境中添加适量双氧水。
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