CN114150317A - 一种抗氧化的铜基表面增强拉曼散射基底的制备方法 - Google Patents
一种抗氧化的铜基表面增强拉曼散射基底的制备方法 Download PDFInfo
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Abstract
本发明公开一种抗氧化的铜基表面增强拉曼散射基底的制备方法，通过甩带和脱合金法制备了双连续结构的纳米多孔铜条带，在纳米多孔铜表面包覆超薄的还原氧化石墨烯层，减小纳米多孔铜的氧化，从而保证还原氧化石墨烯/纳米多孔铜复合基底在拉曼检测中的稳定性。本发明制备方法工艺过程简单，成本低廉，所得的还原氧化石墨烯/纳米多孔铜作为复合基底的拉曼增强效果优异，稳定性好，可重复性高，可广泛应用于各种物质痕量检测领域。
Description
技术领域
本发明属于拉曼检测技术领域，具体涉及一种抗氧化的铜基表面增强拉曼散射基底的制备方法。
背景技术
表面增强拉曼散射(SERS)最早是Fleischman在1974年发现的，是在普通的拉曼散射的基础上发展起来的一种技术，它克服了传统拉曼光谱信号低的缺点，可以获得常规拉曼光谱所不易得到的结构信息，目前广泛地应用于生物医学、表面科学、生物传感、食品安全以及痕量分析检测等领域。常用的SERS基底主要是金属材料，如金、银、铜等。但是金和银是贵金属，价格昂贵，成本太高。
纳米多孔金属是近年发展起来的一种新型的纳米多孔材料体系，制备方法主要有模板法和去合金法。由双连续结构的纳米金属骨架组成，其特点为比表面积大、均匀性好、孔隙率高且结构大小可调，具有大面积均匀的电磁场。另外由于电磁场耦合效应，纳米多孔铜相邻的韧带结构可提供更强大的局域电磁场，通过激发表面等离子体共振和局域表面等离子体共振大大增强了SERS强度，在电化学生物传感器测试及SERS分子检测中具有优良的性能。传统的纳米多孔铜用作SERS基底存在着稳定性较差、存放时间较短、制备较为复杂、成本较高等缺点。
石墨烯是一层单原子层厚度的二维蜂窝状晶格结构的sp2杂化碳材料。一方面它的化学稳定性强，可以防止金属和金属合金氧化；另一方面较大的比表面积和优良的导电性，使其有利于吸附更多的探针分子,促进探针分子与石墨烯之间的电荷转移，增强拉曼信号。
发明内容
针对现有技术中存在的不足，本发明提供了一种抗氧化的铜基表面增强拉曼散射基底的制备方法，该方法简单易行且成本低，所制备的基底表面增强拉曼散射能力优异，且抗氧化能力强，稳定性高。
本发明是通过以下技术方案实现的：
一种抗氧化的铜基表面增强拉曼散射基底的制备方法，包括以下步骤：取纯度为99.99％的镁、铜颗粒于高频感应熔炼炉中熔炼冷却得到合金锭，然后进行破碎熔融，采用单辊快淬法将合金液喷到旋转的铜辊上制备出合金条带，将合金条带加入盐酸乙醇溶液中脱合金得到纳米多孔铜，再对所述纳米多孔铜进行酸洗，洗去氧化层后，再在所述纳米多孔铜表面旋涂氧化石墨烯溶液，随后立刻转移到管式炉中于氢气、氩气氛围下进行热还原，得到还原氧化石墨烯/纳米多孔铜的复合基底。
所述的镁和铜颗粒是按目标合金MgxCu100-x，33.3<x<66.6，组成原子的百分比进行定量称量。
所述的制备合金条带时旋转铜辊转速为1500～3000r/min，所得合金条带宽度为2～5mm、厚度为20～50μm。
所述的在盐酸乙醇溶液中脱合金的同时要通入惰性保护气体。
所述的脱合金所用的盐酸乙醇溶液的浓度为0.1～0.5M，脱合金时间为1～12h，温度为 10～40℃。
所述的对纳米多孔铜盐酸酸洗浓度为0.1～0.5M，酸洗时间为1～5min，温度为10～40℃。
所述的氧化石墨烯浓度为0.1～1.0M。
所述的热还原时通入H2、Ar的比例范围分别为10～50％、90～50％。
所述的热还原时间为1～4h，温度为220～300℃。
本发明的有益效果如下：
本发明的一种抗氧化的铜基表面增强拉曼散射基底的制备方法，所得到的还原氧化石墨烯/纳米多孔铜复合基底具有两种层次：内部为纳米多孔铜韧带/孔道结构，具有丰富的热点，有电磁场增强，因而具有优异的SERS性能；表面包覆了超薄的石墨烯层，不仅保护纳米多孔铜不被氧化，还能维持纳米多孔铜SERS能力，同时其本身具有化学增强效果，两者结合之后，基底的增强效果优异。该制备工艺简单易行，得到的还原氧化石墨烯/纳米多孔铜复合基底增强效果优异、探测灵敏度极高、空气稳定性好。
附图说明
图1为本发明所用到的MgCu合金条带XRD衍射图谱
图2为脱合金得到的纳米多孔铜条带的SEM图像
图3为纳米多孔铜条带对不同浓度结晶紫溶液的SERS图谱
图4为还原氧化石墨烯/纳米多孔铜复合条带的SEM图像
图5为还原氧化石墨烯/纳米多孔铜复合基底对不同浓度结晶紫溶液的SERS图谱
图6为还原氧化石墨烯/纳米多孔铜复合基底在空气中保存0-45天内的SERS图谱
图7为结晶紫溶液在纳米多孔金、纳米多孔铜和H2热还原还原氧化石墨烯/纳米多孔铜复合基底上保存45天内的检测限变化趋势图
具体实施方式
以下通过特定的具体实施例说明本发明的实施方式，本领域的技术人员可由本说明书所揭示的内容轻易地了解本发明的其他优点及功效。
本发明利用MgCu合金作为前驱体，通过感应熔炼和真空单辊快淬法制备了MgCu合金条带(图 1所示)，再在盐酸乙醇溶液中去合金得到纳米多孔铜(图2所示)，待去除表面氧化层后，在纳米多孔铜表面旋涂氧化石墨烯溶液，随后将纳米多孔铜转移到管式炉中还原，得到还原氧化石墨烯/纳米多孔铜复合基底(图4所示)，图3为纳米多孔铜条带对不同浓度结晶紫溶液的SERS图谱。在对纳米多孔铜与还原氧化石墨烯/纳米多孔铜的SERS测试中均产生了优良的SERS性能(图5所示)，另外还原氧化石墨烯/纳米多孔铜具有了较好的空气稳定性，保存45天后对结晶紫仍能保持10-9M左右的检测限，图6为还原氧化石墨烯/纳米多孔铜复合基底在空气中保存0-45天内的SERS图谱，图7为结晶紫溶液在纳米多孔金、纳米多孔铜和H2热还原还原氧化石墨烯/纳米多孔铜复合基底上保存45天内的检测限变化趋势图。本发明提出的一种抗氧化的铜基拉曼检测基底的制备方法包括以下步骤。
i)按目标合金MgxCu100-x组成原子的百分比定量称取纯度为99.99％的镁、铜颗粒，33.3<x<66.6。将称量好的金属原料放置于高频感应熔炼炉中，将所述高频感应熔炼炉内先抽真空，再充入适量的保护气体，最后加热熔化所述金属原料，恒温一定时间，使所述金属原料熔炼均匀，随后倒入铸型铜模中，冷却得到合金锭。
ii)将步骤i)中得到的合金锭破碎，并将所述破碎后的合金锭熔融后，采用单辊快淬法将合金液喷到旋转的铜辊上制备出合金条带。
iii)取步骤ii)中制备的合金条带加入盐酸乙醇溶液中在三口烧瓶内脱合金，同时在三口烧瓶一端对脱合金溶液通入氮气，脱合金后的条带即为纳米多孔铜。
iv)待步骤iii)中制备纳米多孔铜干燥后，再对纳米多孔铜进行盐酸酸洗，洗去表面氧化层。
v)待步骤iv)洗去氧化层后，再在纳米多孔铜表面旋涂氧化石墨烯溶液。
vi)将步骤v)中旋涂石墨烯后的纳米多孔铜转移到管式炉中于氢气、氩气氛围下进行热还原，得到还原氧化石墨烯/纳米多孔铜的复合基底。
实施例1
按Mg58Cu42组成原子的百分比定量称取纯度为99.99％的镁、铜颗粒。将称量好的金属原料放置于高频感应熔炼炉中，将所述高频感应熔炼炉内先抽真空，再充入适量的保护气体Ar，最后加热熔化所述金属原料，恒温5分钟，使所述金属原料熔炼均匀，随后倒入铸型铜模中，冷却得到合金锭。随后将合金锭破碎，并将所述破碎后的合金锭熔融后，采用单辊快淬法将合金液喷到转速为1500r/min的旋转铜辊上制备出宽度为5mm、厚度为50μm合金条带。将合金条带加入盐酸乙醇溶液中在三口烧瓶内脱合金，脱合金浓度为0.1M，脱合金时间为12h，温度为10℃，同时在三口烧瓶一端对脱合金溶液通入氮气，脱合金后的条带即为纳米多孔铜条带。脱合金结束对纳米多孔铜条带用乙醇、水反复清洗3遍。待将纳米多孔铜干燥后，再对纳米多孔铜进行盐酸酸洗，浓度为0.1M，酸洗时间为5min，温度为10℃，洗去表面氧化层，再在纳米多孔铜表面旋涂0.1M的氧化石墨烯溶液，干燥后再旋涂0.1M的氧化石墨烯溶液。随后马上将纳米多孔铜转移到管式炉中于H2：Ar＝33:67氛围下220℃还原，热还原时间为2h，得到还原氧化石墨烯/纳米多孔铜的复合基底。
实施例2
按Mg58Cu42组成原子的百分比定量称取纯度为99.99％的镁、铜颗粒。将称量好的金属原料放置于高频感应熔炼炉中，将所述高频感应熔炼炉内先抽真空，再充入适量的保护气体Ar，最后加热熔化所述金属原料，恒温5分钟，使所述金属原料熔炼均匀，随后倒入铸型铜模中，冷却得到合金锭。随后将合金锭破碎，并将所述破碎后的合金锭熔融后，采用单辊快淬法将合金液喷到转速为3000r/min的旋转铜辊上制备出宽度为2mm、厚度为20μm合金条带。将合金条带加入盐酸乙醇溶液中在三口烧瓶内脱合金，脱合金浓度为0.25M，脱合金时间为4h，温度为20℃，同时在三口烧瓶一端对脱合金溶液通入氮气，脱合金后的条带即为纳米多孔铜条带。脱合金结束对纳米多孔铜条带用乙醇、水反复清洗3遍。待将纳米多孔铜干燥后，再对纳米多孔铜进行盐酸酸洗，浓度为0.25M，酸洗时间为3min，温度为20℃，洗去表面氧化层，再在纳米多孔铜表面旋涂0.25M的氧化石墨烯溶液，干燥后再旋涂0.25M的氧化石墨烯溶液。随后马上将纳米多孔铜转移到管式炉中于H2：Ar＝17:83氛围下220℃还原，热还原时间为3h，得到还原氧化石墨烯/纳米多孔铜的复合基底。
实施例3
按Mg58Cu42组成原子的百分比定量称取纯度为99.99％的镁、铜颗粒。将称量好的金属原料放置于高频感应熔炼炉中，将所述高频感应熔炼炉内先抽真空，再充入适量的保护气体Ar，最后加热熔化所述金属原料，恒温5分钟，使所述金属原料熔炼均匀，随后倒入铸型铜模中，冷却得到合金锭。随后将合金锭破碎，并将所述破碎后的合金锭熔融后，采用单辊快淬法将合金液喷到转速为1500r/min的旋转铜辊上制备出宽度为5mm、厚度为50μm合金条带。将合金条带加入盐酸乙醇溶液中在三口烧瓶内脱合金，脱合金浓度为0.25M，脱合金时间为4h，温度为30℃，同时在三口烧瓶一端对脱合金溶液通入氮气，脱合金后的条带即为纳米多孔铜条带。脱合金结束对纳米多孔铜条带用乙醇、水反复清洗3遍。待将纳米多孔铜干燥后，再对纳米多孔铜进行盐酸酸洗，浓度为0.25M，酸洗时间为3min，温度为30℃，洗去表面氧化层，再在纳米多孔铜表面旋涂0.5M的氧化石墨烯溶液，干燥后再旋涂0.5M的氧化石墨烯溶液。随后马上将纳米多孔铜转移到管式炉中于H2：Ar＝25:75氛围下250℃还原，热还原时间为2h，得到还原氧化石墨烯/纳米多孔铜的复合基底。
实施例4
按Mg58Cu42组成原子的百分比定量称取纯度为99.99％的镁、铜颗粒。将称量好的金属原料放置于高频感应熔炼炉中，将所述高频感应熔炼炉内先抽真空，再充入适量的保护气体Ar，最后加热熔化所述金属原料，恒温5分钟，使所述金属原料熔炼均匀，随后倒入铸型铜模中，冷却得到合金锭。随后将合金锭破碎，并将所述破碎后的合金锭熔融后，采用单辊快淬法将合金液喷到转速为3000r/min的旋转铜辊上制备出宽度为2mm、厚度为20μm合金条带。将合金条带加入盐酸乙醇溶液中在三口烧瓶内脱合金，脱合金浓度为0.5M，脱合金时间为1h，温度为40℃，同时在三口烧瓶一端对脱合金溶液通入氮气，脱合金后的条带即为纳米多孔铜条带。脱合金结束对纳米多孔铜条带用乙醇、水反复清洗3遍。待将纳米多孔铜干燥后，再对纳米多孔铜进行盐酸酸洗，浓度为0.5M，酸洗时间为1min，温度为40℃，洗去表面氧化层，再在纳米多孔铜表面旋涂0.25M的氧化石墨烯溶液，干燥后再旋涂一次0.25M的氧化石墨烯溶液。随后马上将纳米多孔铜转移到管式炉中于H2：Ar＝20:80氛围下300℃还原，热还原时间为2h，得到还原氧化石墨烯/纳米多孔铜的复合基底.
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)
1.一种抗氧化的铜基表面增强拉曼散射基底的制备方法，其特征在于，包括以下步骤：
取纯度为99.99％的镁、铜颗粒于高频感应熔炼炉中熔炼冷却得到合金锭，然后进行破碎熔融，采用单辊快淬法将合金液喷到旋转的铜辊上制备出合金条带，将合金条带加入盐酸乙醇溶液中脱合金得到纳米多孔铜，再对所述纳米多孔铜进行酸洗，洗去氧化层后，再在所述纳米多孔铜表面旋涂氧化石墨烯溶液，随后立刻转移到管式炉中于氢气、氩气氛围下进行热还原，得到还原氧化石墨烯/纳米多孔铜的复合基底。
2.根据权利要求1所述的一种抗氧化的铜基表面增强拉曼散射基底的制备方法，其特征在于，所述镁和铜颗粒是按目标合金MgxCu100-x，33.3<x<66.6，组成原子的百分比进行定量称量。
3.根据权利要求1所述的一种抗氧化的铜基表面增强拉曼散射基底的制备方法，其特征在于，制备所述合金条带时旋转铜辊转速为1500～3000r/min，所得合金条带宽度为2～5mm、厚度为20～50μm。
4.根据权利要求1所述的一种抗氧化的铜基表面增强拉曼散射基底的制备方法，其特征在于，在所述盐酸乙醇溶液中脱合金的同时要通入惰性保护气体。
5.根据权利要求1所述的一种抗氧化的铜基表面增强拉曼散射基底的制备方法，其特征在于，脱合金所用的所述盐酸乙醇溶液的浓度为0.1～0.5M，脱合金时间为1～12h，温度为10～40℃。
6.根据权利要求1所述的一种抗氧化的铜基表面增强拉曼散射基底的制备方法，其特征在于，所述对纳米多孔铜酸洗盐酸浓度为0.1～0.5M，酸洗时间为1～5min，温度为10～40℃。
7.根据权利要求1所述的一种抗氧化的铜基表面增强拉曼散射基底的制备方法，其特征在于，所述氧化石墨烯浓度为0.1～1.0M。
8.根据权利要求1所述的一种抗氧化的铜基表面增强拉曼散射基底的制备方法，其特征在于，所述热还原时通入H2、Ar的比例范围分别为10～50％、90～50％。
9.根据权利要求1所述的一种抗氧化的铜基表面增强拉曼散射基底的制备方法，其特征在于，所述热还原时间为1～4h，温度为150～300℃。
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