CN112574743A - 多掺杂型碳量子点的一步水热合成方法 - Google Patents
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Abstract
本发明公开了一种多掺杂型碳量子点的一步水热合成方法,以海产品加工废液为原料,在水热反应釜中加入去离子水或超纯水,在高温环境下进行水热反应,冷却得到多掺杂碳量子点粗产品;粗产品经滤膜过滤,透析袋透析得到多掺杂碳量子点提纯产品;海产品加工废液富含富蛋白质和氨基酸。该法以生物质废弃物海产品加工废液为碳源制备氮,磷,硫多掺杂型碳量子点,无需外加氮、磷、硫源,方法操作简单,绿色环保,所得碳量子点分散均匀,形貌可控。总之,本发明成本低廉、方便快速,易于工业化生产,产品可利用于多种领域,还解决了海产品加工废液的问题。
Description
技术领域
本发明属于碳量子点合成技术领域,尤其涉及一种多掺杂型碳量子点的一步水热合成方法。
背景技术
碳量子点(CQDs)作为碳纳米材料家族中最年轻的一员,具有毒性弱、生物相容性好、荧光效率高、水溶性好且对环境友好等特点,在生物、环境以及能源等方面都有广泛的应用。CQDs的合成方法多种多样,制备过程简易,原料易得,在光催化、元素检测和生物成像上有很高的应用价值,因此近些年来受到了研究者们越来越多的关注和青睐。生物质材料作为一种可循环使用的资源,对环境非常友好,其含碳量高达45~55%,经过热处理后其含碳量更为丰富,是合成CQDs的理想原料。经过十几年的发展,科学家们已经利用生物质材料合成了各种各样的CQDs,并且可以应用于各种领域,该法原料价廉且易得、制备过程简单、有利于资源循环利用。
然而,未经修饰的碳量子点,荧光效率不高,理化性质单一,缺乏特异性功能,这对它的推广与应用构成了限制。为了解决这一问题,异原子掺杂型碳量子点应运而生。异原子的掺杂可以有效地引入带隙,增加碳量子点的缺陷,从而对碳量子点的反应活性,电子结构和光学性质进行调控。碳量子点掺杂中常见的异原子有氮、磷、硫、硅、硼、锰等。对于碳量子点异原子的掺杂,目前常用的策略是添加含有该原子的化合物,如氮掺杂型碳量子点常常通过掺杂尿素、氨水、乙二胺,但是通过外加杂原子源实现的掺杂无疑增加了实验操作和实验成本。
广西北部湾地区(钦北防)富产海鲜,海产品加工及运输的过程产生了大量废水,如果能将这些资源运用起来,变废为宝,实现资源循环利用的同时,也减轻了对环境的压力。海鲜废水中多为海鲜代谢所产生的有机物,它富含蛋白质与氨基酸,碳含量丰富,是理想的碳源;同时,原料中富含氮硫、磷等元素,无需外加元素便可合成多掺杂型碳量子点,提高其光电性能。
发明内容
本发明要解决的技术问题是提供一种操作简单、绿色环保的多掺杂型碳量子点的一步水热合成方法。
为解决上述技术问题,本发明采用以下技术方案:
多掺杂型碳量子点的一步水热合成方法,以海产品加工废液为原料,在水热反应釜中加入去离子水或超纯水,在高温环境下进行水热反应,冷却得到多掺杂碳量子点粗产品;粗产品经滤膜过滤,透析袋透析得到多掺杂碳量子点提纯产品;海产品加工废液富含富蛋白质和氨基酸。
上述多掺杂型碳量子点的一步水热合成方法,按以下步骤进行操作:
步骤S1:将海产品加工废液和去离子水加入到水热反应釜中,盖好盖子并拧紧;
步骤S2:将步骤S1中的水热反应釜加热进行水热反应,冷却至室温,即得多掺杂碳量子点粗产品;
步骤S3:将步骤S2中得到的多掺杂碳量子点粗产品先通过0.22μm滤膜除去大颗粒物质,再通过透析袋透析除去未反应的原料,得到多掺杂碳量子点提纯产品溶液。
步骤S1中海产品加工废液为1~10mL、去离子水为0~9mL,步骤S2中水热反应在140~240℃下进行2~12h,透析采用500~1000Da的透析袋透析12~36h。
步骤S1中海产品加工废液为9mL、去离子水为1mL,步骤S2中水热反应在220℃下进行5h,透析采用1000Da的透析袋透析24h。
水热反应采用数显式干燥箱加热或油浴加热。
上述一步水热合成方法得到的多掺杂型碳量子点。
上述多掺杂型碳量子点,在紫外灯照射下发出明亮的蓝色荧光。
上述多掺杂型碳量子点,在237nm和335nm处各有一个激发峰,其对应的发射峰位于420nm左右。
上述多掺杂型碳量子点用于铬(Ⅵ)的可视化检测。
针对目前海产品加工废液和碳量子点制备中存在的问题,发明人建立了一种多掺杂型碳量子点的一步水热合成方法,以海产品加工废液为原料,在水热反应釜中加入去离子水或超纯水,在高温环境下进行水热反应,冷却得到多掺杂碳量子点粗产品;粗产品经滤膜过滤,透析袋透析得到多掺杂碳量子点提纯产品;海产品加工废液富含富蛋白质和氨基酸。该法以生物质废弃物海产品加工废液为碳源制备氮,磷,硫多掺杂型碳量子点,无需外加氮、磷、硫源,方法操作简单,绿色环保,所得碳量子点分散均匀,形貌可控(粒径2~10nm,平均粒径约3.5nm)。总之,本发明成本低廉、方便快速,易于工业化生产,产品可利用于多种领域,还解决了海产品加工废液的问题。
与现有技术相比,本发明至少具有如下优势:
(1)由于广西北部湾地区(钦北防)沿海,富产海鲜,而在海产品加工及运输的过程将产生大量废水,本发明可将这些废水利用起来,实现资源循环利用的同时也减轻了对环境的压力。
(2)海产品加工废水中,富含蛋白质与氨基酸。其中,碳含量丰富,是合成碳量子点的理想碳源;同时,原料中富含氮硫、磷等元素,无需外加元素便可合成多掺杂型碳量子点,提高其光电性能。
(3)本发明制得的碳量子点具有良好的pH稳定性,光稳定性和盐稳定性。所得碳量子点在pH 3~12的范围荧光发射强度基本保持不变,经过3小时的365nm紫外灯照射仍具有87.3%的荧光,在0~1.0mol/L NaCl和KCl溶液中依然保持良好的荧光想能。
(4)本发明所制得的多掺杂型碳量子点可应用于六价铬的可视化检测,且不受Fe3 +,Co2+,Ni2+,Cu2+,NH4 +,Bi3+,Na+,Cl-,SO4 2-,HPO4 2-常见阴阳离子的影响,对Cr6+表现出较强的选择性。
附图说明
图1是本发明实施例1得到的多掺杂型碳量子点的高倍电子显微镜图(HRTEM)
图2是本发明实施例1得到的多掺杂型碳量子点的荧光激发光谱和在不同激发波长下的荧光发射光谱。
图3是本发明实施例1得到的多掺杂型碳量子点的傅里叶转换红外光谱(FT-IR)。
图4是本发明实施例1得到的多掺杂型碳量子点的X射线衍射谱图(XRD)
图5是本发明实施例1得到的多掺杂型碳量子点的X射线光电子能谱(XPS)
图6是本发明实施例1得到的多掺杂型碳量子点在pH 1~14范围内的荧光强度变化情况。
图7是本发明实施例1得到的多掺杂型碳量子点在365nm紫外灯照射0~180min内照射的荧光变化情况。
图8是本发明实施例1得到的多掺杂型碳量子点在0~1mol/L的NaCl溶液中的荧光变化情况。
图9是本发明实施例1得到的多掺杂型碳量子点在0~1mol/L的KCl溶液中的荧光变化情况。
图10是本发明实施例1得到的多掺杂型碳量子点在365nm紫外灯照射下,在Cr6+,Fe3+,Co2+,Na+,Cu2+,Bi3+,NH4 +存在下的荧光图及单纯碳量子点溶液的荧光图。
具体实施方式
经检测,实施例所用海产品加工废液富含蛋白质与氨基酸,其中蛋白质和16种氨基酸的含量分别为:蛋白质2.41g/100g,天门冬氨酸0.14g/100g,苏氨酸0.046g/100g,丝氨酸0.048g/100g,谷氨酸0.24g/100g,甘氨酸0.36g/100g,丙氨酸0.11g/100g,缬氨酸0.064g/100g,蛋氨酸0.021g/100g,异亮氨酸0.045g/100g,亮氨酸0.080g/100g,酪氨酸0.041g/100g,苯丙氨酸0.056g/100g,赖氨酸0.074g/100g,组氨酸0.027g/100g,精氨酸0.21g/100g,脯氨酸0.36g/100g。
实施例1
取8mL海产品加工废液和2mL去离子水于PPL内衬的聚四氟乙烯反应釜中,在220℃条件下水热反应5h,冷却至室温,得到多掺杂碳量子点粗产品。将得到的粗产品先通过0.22μm滤膜,然后在1000Da的透析袋中透析24h,得到纯化的多掺杂型碳量子点水溶液。
实施例2
实施例2与实施例1操作相同,唯一不同的是水热反应时间为3h。
实施例3
实施例3与实施例1操作相同,唯一不同的是水热反应时间为4h。
实施例4
实施例4与实施例1操作相同,唯一不同的是水热反应时间为6h。
实施例5
实施例5与实施例1操作相同,唯一不同的是水热温度为180℃。
实施例6
实施例6与实施例1操作相同,唯一不同的是水热温度为200℃。
实施例7
实施例7与实施例1操作相同,唯一不同的是水热温度为210℃。
实施例8
实施例8与实施例1操作相同,唯一不同的是水热温度为230℃。
实施例9
实施例9与实施例1操作相同,唯一不同的是水热温度为240℃。
水热时间考察实验结果表明,当水热时间从3h增加到5h时,着随着反应时间的增加,所得CQDs的荧光强度增强,反应时间5h其荧光强度达到最大,而当水热时间超过5h后,反应时间增加荧光强度降低。因此,最佳水热时间为5h。
水热温度考察实验结果表明,当水热温度从180℃增加至220℃时,所得多掺杂型碳量子点的荧光强度随着水热温度的增加而增加,当水热温度超过220℃之后,继续提高反应温度,其荧光强度下降。因此,最佳水热温度为220℃。
如图1所示,本发明多掺杂型碳量子点为类球型结构,其粒径为15nm左右。在高倍电子显微镜下可清楚观察到其晶格条纹,条纹间隙为0.23nm左右,对应于(100)石墨平面晶格。
如图2所示,本发明多掺杂型碳量子点有两个激发峰,分别为237nm和335nm,两个激发峰对应的荧光发射光谱都在420nm左右。
如图3所示,在3345cm-1出现宽的吸收峰为—OH的伸缩振动峰,2920cm-1处出现的峰为—CH的伸缩振动峰。1645cm-1出现的特征吸收峰为—C=O。1402cm-1处出现的为—C=C或—C=N,说明碳源在高温水热下形成CQDs的过程可能发生碳化从而产生共轭结构。1088cm-1为—C-O的振动峰。以上结果表明CQDs中有含氧官能团、含氮官能团的存在。
如图4所示,XRD在2θ=21°处有一个尖锐的强衍射峰,对应于石墨(002)面,这说明实施例1得到的多掺杂型碳量子点石墨化程度较高,并且具有一定的晶型结构。
如图5所示,在285eV处出现了C1s峰,400eV处出现N1s峰,525eV处出现的强峰为O1s。此外,在134eV处出现一个微弱的峰为P 2p,在169eV出现的弱峰为S 2p。其中,C,N,O,P,S的含量分别为52%,5%,41.6%,0.98%,0.49%。实施例1制得的碳量子点除C,O以外还含有N,P,S元素,证实了实施例1在未添加外加原料的情况下,通过一步水热法合成了N,P,S多掺杂型碳量子点。
如图6所示,在强酸(pH 1~2)强碱(pH 13~14)范围内,制得的多掺杂型碳量子点荧光较弱。而在pH 3~12的范围内,其荧光基本保持稳定,说明实施例1制备的多掺杂型碳量子点能够适应较宽的pH值范围。
如图7所示,随着紫外光照时间的增加,碳量子点荧光强度会逐渐下降。经过3小时365nm的紫外灯照射,碳量子点的荧光猝灭率为12.7%,仍保持83.7%的荧光,表明实施例1得到的多掺杂型碳量子点具有良好的光稳定性。
如图8和图9所示,在不同浓度的盐溶液中,本发明的多掺杂型碳量子点的荧光强度几乎不变,可见其具有良好的盐稳定性,可以应用于高盐环境中。
如图10所示,实施例1得到的多掺杂型碳量子点在365nm紫外灯照射下发出明亮的蓝白色荧光。在Fe3+,Co2+,Na+,Cu2+,Bi3+,NH4 +这些常见的阴阳离子(各离子的浓度均为5μg/mL)存在下,碳量子点的365nm紫外灯照射下的荧光基本保持不变,而当Cr6+存在时则可观察到明显的荧光猝灭现象。因此,本发明的多掺杂型碳量子点对Cr6+表现出了良好的选择性,可应用于的Cr6+可视化检测。
Claims (9)
1.一种多掺杂型碳量子点的一步水热合成方法,其特征在于:以海产品加工废液为原料,在水热反应釜中加入去离子水或超纯水,在高温环境下进行水热反应,冷却得到多掺杂碳量子点粗产品;粗产品经滤膜过滤,透析袋透析得到多掺杂碳量子点提纯产品;所述海产品加工废液富含蛋白质和氨基酸。
2.根据权利要求1所述的多掺杂型碳量子点的一步水热合成方法,其特征在于按以下步骤进行操作:
步骤S1:将海产品加工废液和去离子水加入到水热反应釜中,盖好盖子并拧紧;
步骤S2:将步骤S1中的水热反应釜加热进行水热反应,冷却至室温,即得多掺杂碳量子点粗产品;
步骤S3:将步骤S2中得到的多掺杂碳量子点粗产品先通过0.22μm滤膜,再通过透析袋透析,得到多掺杂碳量子点提纯产品溶液。
3.根据权利要求2所述的多掺杂型碳量子点的一步水热合成方法,其特征在于步骤S1中海产品加工废液为1~10mL、去离子水为0~9mL,步骤S2中水热反应在140~240℃下进行2~12h,透析采用500~1000Da的透析袋透析12~36h。
4.根据权利要求3所述的多掺杂型碳量子点的一步水热合成方法,其特征在于步骤S1中海产品加工废液为9mL、去离子水为1mL,步骤S2中水热反应在220℃下进行5h,透析采用1000Da的透析袋透析24h。
5.根据权利要求4所述的多掺杂型碳量子点的一步水热合成方法,其特征在于:所述水热反应采用数显式干燥箱加热或油浴加热。
6.权利要求1所述一步水热合成方法得到的多掺杂型碳量子点。
7.根据权利要求6所述的多掺杂型碳量子点,其特征在于在紫外灯照射下发出明亮的蓝色荧光。
8.根据权利要求7所述的多掺杂型碳量子点,其特征在于在237nm和335nm处各有一个激发峰,其对应的发射峰位于420nm。
9.权利要求6所述的多掺杂型碳量子点用于铬(Ⅵ)的可视化检测。
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