CN113769768B - 一种双功能复合纳米材料及其制备方法和用途 - Google Patents
一种双功能复合纳米材料及其制备方法和用途 Download PDFInfo
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Abstract
本发明涉及模拟酶技术以及光催化,具体说是一种双功能复合纳米材料(溴化银、钼酸银复合物)及其制备方法和用途。通过银盐、钼盐与CTAB通过一步沉淀法获得双功能复合纳米材料。本发明制备的纳米材料具有合成方法简单、成本低、性能优异、可重复利用等优点,在纳米材料催化氧化领域中具有广阔的应用前景。
Description
技术领域
本发明涉及模拟酶技术以及光催化,具体说是一种双功能复合纳米材料(溴化银、钼酸银复合物)及其制备方法和用途。
背景技术
生物体内所含活性酶如HRP,具有高催化活性以及特异性,在有机合成、生物传感器、环境治理、废水处理、医疗领域中有较多的应用。纳米酶的类酶催化活性来自其自身的纳米结构,无需额外引入催化基团或天然酶;天然酶易受到温度、pH影响,相比之下纳米酶稳定性更高、成本较低且催化活性可调,因此开发这种模拟酶材料显得尤为重要。半导体光催化剂具有高效、稳定、环境友好的特点。在一系列半导体光催化剂材料中,TiO2无毒、结构稳定、活性高,但TiO2只能被紫外光激发,在实际应用中受到很大限制。铂/二氧化钛纳米粒子(Pt/TiO2NPs)具有类过氧化物酶活性,可以快速催化过氧化氢(H2O2)氧化3,3’,5,5’-四甲基联苯胺(TMB)显色。单独一种半导体材料性能受限,具有光生电子和空穴复合率高、对可见光吸收力差等缺点,复合半导体光催化剂大大减弱了这些缺点。
近年来,随着研究发现,越来越多的纳米材料或纳米复合材料被查证具有模拟酶的性质,如UsAuNPs/MOF[1]、CuO-HCSs[2]、CuS/GO[3]等;也有越来越多半导体异质结材料被证明具有光催化活性,如Ag3PO4/TiO2[4]等。相比于天然酶的获取方法,模拟酶材料一方面降低了材料成本,二是合成方法简便,单元操作易于实现,具有优异的耐久性、稳定性、生物相容性和可重复使用性;纳米酶也存在固有的缺点,纳米酶的微弱可见光响应限制了杀菌活性的应用,则需要对纳米复合材料进行改性使其具有光催化能力。相比于单一的半导体光催化剂,复合光催化剂提高了带隙宽度,光生电子和空穴分离效率也有很大提高;可见光下的光催化活性和黑暗环境中的类酶活性在杀菌应用中具有协同作用。因此,开发一种具有光催化和模拟酶活性的高效催化剂,在提高催化剂的利用率以及环境问题的应用方面具有重要意义。
1.HU WEN-CHAO,YOUNIS M R,ZHOU YUE,et al(2020)In situ fabrication ofultrasmall gold nanoparticles/2D MOFs hybrid as nanozyme for antibacterialtherapy.Small,2000553.
2.XI JU-QUN,WEO GEN,AN LAN-FANG,et al(2019)Copper/carbon hybridnanozyme:tuning catalytic activity by the copper state for antibacterialtherapy.Nano Letter 19(11):7645-7654.
3.WANG WAN-SHUN,LI BING-LIN,YANG HUI-LI,et al(2020)Efficientelimination of multidrug-resistant bacteria using copper sulfide nanozymesanchored to graphene oxide nanosheets.Nano Res 13(8):2156-2164.
4.LIU HUAN,LI DAO-RONG,YANG XIN-LI,et al(2019)Fabrication andcharacterization of Ag3PO4/TiO2 heterostructure with improved visible-lightphotocatalytic activity for the degradation of methyl orange andsterilization of E.coli.Materials Technology 34(4):192-203.
发明内容
本发明的目的在于提供一种双功能复合纳米材料(溴化银、钼酸银复合物)及其制备方法和用途。
为实现上述目的,本发明采用的技术方案为:
一种双功能复合纳米材料的制备方法,通过银盐、钼盐与CTAB通过一步沉淀法获得双功能复合纳米材料。
进一步的说:
将银盐、钼盐和CTAB粉末混合,再加入去离子水得混合液,将混合溶液在黑暗环境下磁力搅拌1-2小时,将得到的材料清洗并离心,离心后将得到的复合材料在60-80℃下真空干燥6-8小时,最终得到含银、钼的纳米复合材料;其中,钼盐、CTAB的摩尔比为1:1。
所述将银盐加入蒸馏水进行磁力搅拌获得含银溶液,钼盐与CTAB依次加入蒸馏水进行磁力搅拌获得含钼混合溶液,将含钼混合溶液缓慢滴加至含银溶液中,滴加后黑暗环境下磁力搅拌1-2小时进行反应。
所述黑暗环境下磁力搅拌反应后依次经无水乙醇和蒸馏水各清洗2-3次,清洗后离心,收集黄色沉淀后于60℃-80℃真空干燥6-8小时,并将干燥后的粉末进行研磨得双功能复合纳米材料。
所述银盐为硝酸银;钼盐为钼酸铵。
一种双功能纳米复合材料,所述方法制备获得含银、钼的不规则纳米球状颗粒的双功能复合纳米材料,其中,复合纳米材料粒径均达到100-250nm,溴化银呈9-20nm规则纳米球状负载于100-250nm钼酸银不规则纳米球状颗粒表面。
一种双功能纳米复合材料的应用,所述含银、钼的双功能复合纳米材料在作为模拟酶或光催化剂在经可见光条件下对染料进行降解中的应用。
所述含银、钼的双功能复合纳米材料作为模拟酶材料,在酸性条件下对底物进行催化氧化还原反应中的应用。
所述底物为TMB和H2O2。
所述染料为罗丹明B和/或盐酸四环素(TC)。
本发明与现有技术相比,具有以下优点及突出性效果:
本发明通过简单可行的溶剂沉淀法得到含银、钼的复合纳米材料,该材料具有模拟酶和光催化活性的双功能。本发明所得材料与一些现有材料相比光催化活性较高且可同时降解罗丹明B和TC,同时具有氧化物酶活性及过氧化物酶活性;成本低、制备方法简单、重复性高、易于保存;该材料可作为一种新型材料在工程防污实践、免疫分析、生物检测和临床诊断等领域具有潜在的应用价值,在新型催化氧化分析中具有广阔的应用前景。
附图说明:
图1为本发明实施案例提供的纳米材料的TEM图;
图2为本发明实施案例提供的定性分析材料成分的X-射线衍射图;
图3为本发明实施例提供的纳米材料模拟酶催化测试图。
图4为本发明实施例提供的纳米材料光催化降解图像,其中,a为降解罗丹明B的光催化降解图像,b为降解TC的光催化降解图像。
具体实施方式
以下通过具体的实施例对本发明作进一步说明,有助于本领域的普通技术人员更全面的理解本发明,但不以任何方式限制本发明。
实施例1:
将1mmol AgNO3放入烧杯中加入20mL蒸馏水,磁力搅拌20min,使其溶解于蒸馏水中获得含银溶液;将0.036mmol(NH4)6Mo7O24·4H2O、0.25mmol CTAB放入烧杯加入20mL蒸馏水,磁力搅拌20min,使其溶解于蒸馏水中获得含钼混合溶液;将所得含钼混合溶液缓慢滴加到上述AgNO3溶液中,并在黑暗条件下搅拌1h得到产物。所得产物用蒸馏水和无水乙醇分别清洗产物3次,清洗后以6000r/min离心,收集黄色沉淀将其放于真空干燥箱60℃干燥6h,得到1:1AgBr/Ag2MoO4复合纳米材料(参见图1),并对所得材料经XRD测试(参见图2)。
由图1可看出,复合纳米材料平均粒径达到189nm,平均粒径16nm的溴化银呈规则纳米球状负载于平均粒径189nm的钼酸银不规则纳米球状颗粒表面。由图2可以看出合成的复合材料的成分与AgBr标准卡片(JCPDS No.79-0149)、Ag2MoO4标准卡片(JCPDS No.08-0473)相吻合,即复合纳米材料中产物含AgBr和Ag2MoO4。
实施例2-4:
制备过程:
将1mmol AgNO3放入烧杯中加入20mL蒸馏水,磁力搅拌20min,使其溶解于蒸馏水中获得含银溶液。将表1记载的不同比例(NH4)6Mo7O24·4H2O、CTAB放入烧杯加入20mL蒸馏水,磁力搅拌20min,使其溶解于蒸馏水中获得含钼混合溶液;将所得含钼混合溶液缓慢滴加到上述AgNO3溶液中,并在黑暗条件下搅拌1h得到产物。用蒸馏水和无水乙醇分别清洗产物3次,清洗后以6000r/min离心,收集黄色沉淀将其放于真空干燥箱60℃干燥6h,实施例2-4分别得到1:2AgBr/Ag2MoO4、2:1AgBr/Ag2MoO4和3:1AgBr/Ag2MoO4复合纳米材料。
表1
(NH4)6Mo7O24·4H2O/mmol | CTAB/mmol | |
实施例1 | 0.036 | 0.25 |
实施例2 | 0.047 | 0.16 |
实施例3 | 0.023 | 0.33 |
实施例4 | 0.018 | 0.375 |
上述实施例2-4获得的复合纳米材料粒径达到170-210nm,溴化银呈12-18nm规则纳米球状负载于170-210nm钼酸银不规则纳米球状颗粒表面。
应用例1
在0.5mM H2O2,4mM TMB,上述实例1获得的1:1AgBr/Ag2MoO4纳米材料作为模拟酶三种物质,在不同条件下(TMB、过氧化氢和TMB、过氧化氢和模拟酶材料、TMB和模拟酶材料或过氧化氢和TMB和模拟酶材料)加入至pH为4的醋酸钠醋酸缓冲液,共1mL体系中测试模拟酶性能,各物质加入后等待5min后进行溶液颜色观察,在652nm波长下进行吸光度测试。当体系中只有过氧化氢和TMB时,溶液呈无色透明;当体系中只有过氧化氢和模拟酶材料1:1AgBr/Ag2MoO4,未加入TMB时,溶液呈无色透明;当向TMB和过氧化氢体系中加入模拟酶材料1:1AgBr/Ag2MoO4时以及当体系中只有TMB与模拟酶材料1:1AgBr/Ag2MoO4时,溶液变为较深蓝色,证明TMB已经被氧化为蓝色的oxTMB;结合图3吸光度数据,可见本发明提供的纳米材料具有较高的氧化物酶和过氧化物模拟酶活性。
应用例2
处理1:向40mL的10mg/L罗丹明B中分别加入40mg的1mg/mL上述各实施例获得的AgBr/Ag2MoO4,而后加入具有底部滤光片的石英管中进行可见光光催化降解实验,首先在暗态条件下以250r/min的速度搅拌30min达到吸附-脱附平衡,随后打开氙灯光源每隔30min取一次反应溶液,将1mL反应溶液在6000r/min的速度下离心后进行吸光度测试。空白组可见光下反应120min后体系颜色无明显变化,实验组则由紫红色变为无色,根据图4结果也能够说明对罗丹明B降解率达100%(图4a)。
处理2:向40mL的10mg/L TC中分别加入40mg的1mg/mL上述各实施例获得的AgBr/Ag2MoO4加入具有底部滤光片的石英管中进行可见光光催化降解实验,首先在暗态条件下以250r/min的速度搅拌30min达到吸附-脱附平衡,随后打开氙灯光源每隔30min取一次反应溶液,将1mL反应溶液在6000r/min的速度下离心后进行吸光度测试。空白组可见光下反应120min后体系颜色无明显变化,实验组则由淡黄色变为接近无色,120min内对TC的降解率达到73%(图4b)。可见本发明提供的纳米材料具有优异的光催化活性,可以对染料罗丹明B以及抗生素TC进行降解;由于其同时具有模拟酶活性,所以是一种新型高效的双功能催化材料。
Claims (6)
1.一种双功能复合纳米材料的应用,其特征在于:将AgBr/Ag2MoO4作为模拟酶材料,在酸性条件下对底物进行催化氧化还原反应;所述底物为TMB和H2O2;所述AgBr/ Ag2MoO4复合材料通过银盐、钼盐与CTAB通过一步沉淀法获得。
2.按权利要求1所述双功能复合纳米材料的应用,其特征在于:
将银盐、钼盐和CTAB粉末混合,再加入去离子水得混合液,将混合溶液在黑暗环境下磁力搅拌1-2小时,将得到的材料清洗并离心,离心后将得到的复合材料在60-80℃下真空干燥6-8小时,最终得到含银、钼的纳米复合材料;其中,钼盐、CTAB的摩尔比为1:1。
3.按权利要求1所述双功能复合纳米材料的应用,其特征在于:将银盐加入蒸馏水进行磁力搅拌获得含银溶液,钼盐与CTAB依次加入蒸馏水进行磁力搅拌获得含钼混合溶液,将含钼混合溶液缓慢滴加至含银溶液中,滴加后黑暗环境下磁力搅拌1-2小时进行反应。
4.按权利要求2所述双功能纳米复合材料的应用,其特征在于:所述黑暗环境下磁力搅拌反应后依次经无水乙醇和蒸馏水各清洗2-3次,清洗后离心,收集黄色沉淀后于60℃-80℃真空干燥6-8小时,并将干燥后的粉末进行研磨得双功能复合纳米材料。
5.按权利要求1-3任意一项所述双功能纳米复合材料的应用,其特征在于:所述银盐为硝酸银;钼盐为钼酸铵。
6.按权利要求1所述双功能纳米复合材料的应用,其特征在于:所述AgBr/ Ag2MoO4复合材料中溴化银呈9-20nm规则纳米球状负载于100-250nm钼酸银不规则纳米球状颗粒表面。
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