CN113351256B - 一种乌贼黑色素基纳米银复合材料及其制备方法及催化应用 - Google Patents
一种乌贼黑色素基纳米银复合材料及其制备方法及催化应用 Download PDFInfo
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Abstract
本发明涉及一种乌贼黑色素基纳米银复合材料及其制备方法和催化应用,其制备方法包括如下步骤:S1.取乌贼墨囊,割破并挤出墨汁,加入去离子水浸泡处理后,离心,固液分离,真空干燥,得乌贼黑色素粉,然后超声分散至适量去离子水中,静置沉淀去除无法超声分散的大颗粒,取上层分散液;S2.将PVP粉末、去离子水和S1的乌贼黑色素分散液按比例投入反应容器中并超声分散,然后加入新制的银氨溶液,先通氮气脱除空气,然后氮气保护下,升温至70℃并维持,搅拌至反应完全,最后离心、水洗及真空干燥,即得。有益效果为,首次以乌贼黑色素为银纳米粒子的载体,制得了催化性能优良的载银复合材料;该复合材料的催化性能好,银纳米粒子在载体表面结合牢固,不易团聚或脱落。
Description
技术领域
本发明属于材料科学与催化领域,具体涉及一种乌贼黑色素基纳米银复合材料及其制备方法及催化应用。
背景技术
经济快速发展产生了大量染料有机污水,对自然环境和人体产生了极大的危害。粒径小、分散均匀的银纳米粒子(AgNPs)由于其较大的比表面积,是理想的处理性催化剂,凭借着其催化活性高、毒性低和易制备等优点而被广泛应用在多相催化领域。但是单一的AgNPs因为粒径小比表面积大,具有较高表面能,易发生团聚和氧化,导致催化活性降低和催化剂中毒等问题,而且难以回收和价格高等缺点也都制约着其在多相催化领域的发展。为了解决这一问题,最切实有效地方法就是掺AgNPs载于聚合物基体、金属氧化物等载体上,以提高纳米催化剂的分散性和稳定性。这通常就需要首先设计并构建一个有着可供AgNPs附着的含有大量活性位点的载体基底,再将前驱体银连接到载体上。
目前报导的AgNPs载体大多是共价有机骨架材料、金属有机框架材料、金属氧化物和无机非金属氧化物。它们要么是有着复杂且漫长的合成制备过程,要么就是基材本身缺乏活性位点负载效果差,难以有效地负载制备AgNPs。同时,上述常规载体一般都是采取如物理蒸发、粘接剂粘接法和电沉积等方法来连接AgNPs,涉及到繁琐的预处理程序,或者涉及到复杂的设备仪器使用,而且在实际操作过程中不可避免的会使用到有毒有害物质和较高的生产能耗。随着国家对于催化剂的高效节能、绿色环保和简便易行的可控合成等方面的要求越来越高,探究一种简单方法就可以制备的载体基纳米银催化剂十分具有实际应用前景。
发明内容
本发明所要解决的技术问题是提供一种乌贼黑色素基纳米银复合材料及其制备方法及催化应用,旨在克服现有技术中常规载体基纳米银催化剂存在的合成过程复杂、涉及复杂昂贵合成设备使用、能耗较高或者不环保等诸多不足。
本发明解决上述技术问题的技术方案如下:一种乌贼黑色素基纳米银复合材料的制备方法,其包括如下步骤:
S1.乌贼黑色素分散液的制备:取乌贼墨囊,割破并挤出墨汁,加入去离子水浸泡处理后,离心,固液分离,真空干燥分离出的固体,得乌贼黑色素粉,然后取乌贼黑色素粉超声分散至适量去离子水中,静置沉淀去除无法超声分散的大颗粒后得固含量为1.5-2%的乌贼黑色素分散液,备用;
S2.复合材料制备:将PVP粉末、去离子水和S1的乌贼黑色素分散液按照1-2g:30-60mL:4g的用量比例投入反应容器中并超声分散,然后加入新制的银氨溶液,加入的银氨溶液中含银量与乌贼黑色素分散液的质量之比为0.001-0.01mol:4g,先通氮气脱除空气,然后氮气保护下,升温至70℃并维持,搅拌至反应完全,最后离心、水洗及真空干燥,即得乌贼黑色素基纳米银复合材料。
在上述技术方案的基础上,本发明还可以做如下进一步的具体或更优选择。
具体的,步骤S1中浸泡处理墨汁时加入的去离子水的体积为墨汁体积的1-3倍,浸泡处理的时间为3-10h,真空干燥分离出的固体的具体条件为:控制温度在45±1℃,抽真空且持续处理24h以上;静置沉淀去除无法超声分散的大颗粒时静置的时间为10-14h,沉淀完成后上层液体即为所述分散液。
具体的,步骤S2中,新制银氨溶液的浓度为0.1-1mol/L。
具体的,步骤S2中,PVP粉末的K值在26-35之间。
具体的,步骤S2中,通氮气脱除空气时,持续通氮气的时间不少于1h,搅拌反应的转速为200rpm,反应时间为7h以上,离心时的转速为10000rpm,真空干燥的具体条件为:控制温度在50±1℃,抽真空且持续处理24h以上。
本发明还提供一种乌贼黑色素基纳米银复合材料,其通过上述的方法制备得到。
本发明还提供了上述的乌贼黑色素基纳米银复合材料的催化应用,具体为应用于废水中亚甲基蓝和硝基酚类化合物的催化降解。
与现有技术相比,本发明的有益效果是:
首次以乌贼黑色素为银纳米粒子的载体,并制得了催化性能优良的载银复合材料;取自乌贼墨囊的天然黑色素(SE)成球形粒径较小且分布均一,表面有着大量的活性羟基和氨基,表面Zeta电位为较高负电位,在低固含量时,SE可以在水溶液中相对稳定的分散,其通过较强的静电吸引作用吸附银氨络合离子到SE表面,再通过自身活性羟基的弱还原性和外加还原剂的作用就可以在SE表面生纳米银(AgNPs),AgNPs在SE表面均匀负载并牢牢锚定形成乌贼黑色素基纳米银复合材料。该复合材料的催化性能好,AgNPs在SE表面结合牢固,不易团聚或脱落,催化性能较为稳定。
附图说明
图1为本发明实施例1中得到的SE粉末的SEM图;
图2为本发明实施例1制得的SE粉末及实施例1至3制备的复合材料各自对应的TEM图(图中a、b、c和d分别对应SE粉末、SE/Ag-0.1、SE/Ag-0.3和SE/Ag-1复合材料);
图3为本发明实施例1至3制备的复合材料催化亚甲基蓝降解时测得的紫外吸收图谱(图中a、b和c分别对应SE/Ag-0.1、SE/Ag-0.3和SE/Ag-1复合材料)。
具体实施方式
以下结合附图及具体实施例对本发明作进一步的详细描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
为免赘述,以下实施例中用到的药品原料若无特别说明则均为市售产品,用到的方法若无特别说明则均为常规方法。
实施例1
一种乌贼黑色素基纳米银复合材料,其制备方法包括如下步骤:
S1.乌贼黑色素分散液的制备:取乌贼墨囊,割破并挤出墨汁,加入2倍体积的去离子水浸泡处理10h后,10000rmp离心,固液分离,去除滤液及其内的可溶成分,余下固体,在45℃下、抽真空至-0.08MPa,干燥处理24h,得乌贼黑色素粉,然后取乌贼黑色素粉0.2000g加入至9.8265g的去离子水中,超声震荡至分散均匀,静置沉淀10-14h,缓慢吸取上层液体(沉淀部分干燥后质量约0.0265g),即得固含量约为1.735%的乌贼黑色素分散液,备用;
S2.复合材料制备:将PVP粉末1g、去离子水30mL和S1的乌贼黑色素分散液4g的投入三颈烧瓶中并超声分散均匀,然后在室温下加入新制的0.1mol/L的银氨溶液10mL,先在氮气脱氧1h后,将温度升至70℃在氮气氛保护下200r/min加热搅拌7h,再10000rmp离心、水洗分散三次,在50℃下、抽真空至-0.08MPa,干燥处理24h后,即得乌贼黑色素基纳米银复合材料,命名为SE/Ag-0.1。
实施例2
一种乌贼黑色素基纳米银复合材料,其制备方法包括如下步骤:
S1.乌贼黑色素分散液的制备:取乌贼墨囊,割破并挤出墨汁,加入2倍体积的去离子水浸泡处理10h后,10000rmp离心,固液分离,去除滤液及其内的可溶成分,余下固体,在45℃下、抽真空至-0.08MPa,干燥处理24h,得乌贼黑色素粉,然后取乌贼黑色素粉0.2000g加入至9.8265g的去离子水中,超声震荡至分散均匀,静置沉淀10-14h,缓慢吸取上层液体(沉淀部分干燥后质量约0.0285g),即得固含量约为1.715%的乌贼黑色素分散液,备用;
S2.复合材料制备:将PVP粉末1g、去离子水30mL和S1的乌贼黑色素分散液4g的投入三颈烧瓶中并超声分散均匀,然后在室温下加入新制的0.5mol/L的银氨溶液10mL,先在氮气脱氧1h后,将温度升至70℃在氮气氛保护下200r/min加热搅拌7h,再10000rmp离心、水洗分散三次,在50℃下、抽真空至-0.08MPa,干燥处理24h后,即得乌贼黑色素基纳米银复合材料,命名为SE/Ag-0.5。
实施例3
一种乌贼黑色素基纳米银复合材料,其制备方法包括如下步骤:
S1.乌贼黑色素分散液的制备:取乌贼墨囊,割破并挤出墨汁,加入2倍体积的去离子水浸泡处理10h后,10000rmp离心,固液分离,去除滤液及其内的可溶成分,余下固体,在45℃下、抽真空至-0.08MPa,干燥处理24h,得乌贼黑色素粉,然后取乌贼黑色素粉0.2000g加入至9.8265g的去离子水中,超声震荡至分散均匀,静置沉淀10-14h,缓慢吸取上层液体(沉淀部分干燥后质量约0.0305g),即得固含量约为1.695%的乌贼黑色素分散液,备用;
S2.复合材料制备:将PVP粉末1g、去离子水30mL和S1的乌贼黑色素分散液4g的投入三颈烧瓶中并超声分散均匀,然后在室温下加入新制的1mol/L的银氨溶液10mL,先在氮气脱氧1h后,将温度升至70℃在氮气氛保护下200r/min加热搅拌7h,再10000rmp离心、水洗分散三次,在50℃下、抽真空至-0.08MPa,干燥处理24h后,即得乌贼黑色素基纳米银复合材料,命名为SE/Ag-1。
实施例4
一种乌贼黑色素基纳米银复合材料,其制备方法包括如下步骤:
S1.乌贼黑色素分散液的制备:取乌贼墨囊,割破并挤出墨汁,加入1倍体积的去离子水浸泡处理3h后,10000rmp离心,固液分离,去除滤液及其内的可溶成分,余下固体,在45℃下、抽真空至-0.08MPa,干燥处理24h,得乌贼黑色素粉,然后取乌贼黑色素粉0.2000g加入至9.8265g的去离子水中,超声震荡至分散均匀,静置沉淀10-14h,缓慢吸取上层液体(沉淀部分干燥后质量约0.0225g),即得固含量约为1.775%的乌贼黑色素分散液,备用;
S2.复合材料制备:将PVP粉末2g、去离子水60mL和S1的乌贼黑色素分散液4g的投入三颈烧瓶中并超声分散均匀,然后在室温下加入新制的1mol/L的银氨溶液10mL,先在氮气脱氧1h后,将温度升至70℃在氮气氛保护下200r/min加热搅拌7h,再10000rmp离心、水洗分散三次,在50℃下、抽真空至-0.08MPa,干燥处理24h后,即得乌贼黑色素基纳米银复合材料。
产品表征:
以实施例1步骤S1中干燥后获得的乌贼黑色素粉(SE)为样品,喷金处理后做SEM电镜图观察其形貌特征,结果如图1所示,从图1可以看出,这种来源广泛的天然乌贼黑色素品质较高,经统计计算这些SE微球的平均直径为180nm,且粒径分度跨度较小;另外,本发明还提供了上述的乌贼黑色素粉的TEM电镜图,结果如图2a所示,从图2a同样可看出,这种简单易得的SE微球大小合适粒径均一。SEM及TEM均表明通过本发明提供的简易方法可以得到形貌规整的高品质基底材料。
SE的表面富含大量的活性羟基和氨基,有利于增强其在水中分散的稳定性,当固含量相对较低时(2%以下),可得到相对稳定的分散液,同时这些活性羟基和氨基也有利于吸附锚定小粒径的AgNPs,从而制备较大比表面积的银基催化材料。以实施例1、2和3制得的乌贼黑色素基纳米银复合材料为测试样品,分别得到了TEM电镜图,如图2b、图2c和图2d所示,从图中可以看出,SE/Ag-0.1、SE/Ag-0.5和SE/Ag-1已经成功在SE微球表面均匀的负载了AgNPs,绝大部分的AgNPs粒径分布在6-8nm之间,同时还有少量粒径在60-80nm大颗粒AgNPs粒子,总体的统计平均粒径在7-9nm,相比其它的银基复合材料,其粒径更小,预示着其催化性能更优秀。
催化性能测试:
先配置浓度为0.06mmol/L的亚甲基蓝溶液和60mmol/L的硼氢化钠溶液。在依次取2mg的SE/Ag-0.1、SE/Ag-0.3和SE/Ag-1各自与4mL的去离子水混合超声20分钟分散均匀后,各自取0.1mL加入到装有2mL配置的0.06mmol/L亚甲基蓝溶液的石英比色皿中,摇晃静止30s待分散均匀,再加入新制的60mmol/L的硼氢化钠溶液1mL,即每隔1分钟测一组紫外吸收数据。测得的紫外吸收图谱如图3所示,在图3中,在保障还原剂硼氢化钠过量的情况,随着硝酸银的用量加大对应的SE/Ag复合材料对亚甲基蓝的催化还原速率越快。在图3a中可以看出由于SE表面载银量较少需要约14分钟才能催化反应完全,而在图3c中仅7分钟就能催化反应到完全。从图3中可得出,在相对低硝酸银用量的情况下本发明制备的催化材料就可以高效催化还原亚甲基蓝。另外,还以同样的方法测试了实施例4制备出的乌贼黑色素基纳米银复合材料,其催化性能亦较好,与实施例3接近。为测试催化剂的稳定性,以实施例1制备的复合材料为测试对象,放大催化试验,且每次催化亚甲蓝完成后,离心回收催化剂,反复10次后,回收的催化剂仍保留原本首次使用时80%以上的催化能力。
以上所述仅为本发明的较佳实施例,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、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种乌贼黑色素基纳米银复合材料的制备方法,其特征在于,包括如下步骤:
S1.乌贼黑色素分散液的制备:取乌贼墨囊,割破并挤出墨汁,加入去离子水浸泡处理后,离心,固液分离,真空干燥分离出的固体,得乌贼黑色素粉,然后取乌贼黑色素粉超声分散至适量去离子水中,静置沉淀10-14h,缓慢吸取上层液体,得固含量为1.5-2%的乌贼黑色素分散液,备用;浸泡处理墨汁时加入的去离子水的体积为墨汁体积的1-3倍,浸泡处理的时间为3-10h,真空干燥分离出的固体的具体条件为:控制温度在45±1℃,抽真空且持续处理24h以上;
S2.复合材料制备:将PVP粉末、去离子水和S1的乌贼黑色素分散液按照1-2g:30-60mL:4g的用量比例投入反应容器中并超声分散,然后加入新制的银氨溶液,加入的银氨溶液中含银量与乌贼黑色素分散液的质量之比为0.001-0.01mol:4g,先通氮气脱除空气,然后氮气保护下,升温至70℃并维持,搅拌至反应完全,最后离心、水洗及真空干燥,即得乌贼黑色素基纳米银复合材料。
2.根据权利要求1所述的一种乌贼黑色素基纳米银复合材料的制备方法,其特征在于,步骤S2中,新制银氨溶液的浓度为0.1-1mol/L。
3.根据权利要求1所述的一种乌贼黑色素基纳米银复合材料的制备方法,其特征在于,步骤S2中,PVP粉末的K值在26-35之间。
4.根据权利要求1所述的一种乌贼黑色素基纳米银复合材料的制备方法,其特征在于,步骤S2中,通氮气脱除空气时,持续通氮气的时间不少于1h,搅拌反应的转速为200rpm,反应时间为7h以上,离心时的转速为10000rpm,真空干燥的具体条件为:控制温度在50±1℃,抽真空且持续处理24h以上。
5.一种乌贼黑色素基纳米银复合材料,其特征在于,通过权利要求1至4任一项所述的方法制备得到。
6.一种如权利要求5所述的乌贼黑色素基纳米银复合材料的催化应用,其特征在于,用于废水中亚甲基蓝和硝基酚类化合物的催化降解。
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