CN113324972B - A kind of quantitative analysis method of formaldehyde in water environment - Google Patents
A kind of quantitative analysis method of formaldehyde in water environment Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及一种水环境中甲醛的定量分析方法,属于环境检测技术领域。The invention relates to a quantitative analysis method for formaldehyde in a water environment, and belongs to the technical field of environmental detection.
背景技术Background technique
甲醛是一种常见的环境污染物,其常存在于在大气和水体中。由于水是人类不可缺少的资源,而环境水体中经常会受到工厂废弃物以及生活废弃物的污染,在众多污染物中,甲醛是十分常见的污染物,而过量的甲醛会对人类健康产生严重威胁。另外,甲醛是一些聚合材料的前驱物,一些不法产商为了降低成本,将生产过程中剩余的甲醛原料直接排入水源,这大大增加了水体受到甲醛污染的风险。因此建立一种准确、高效和经济的水环境中甲醛的分析方法具有重要意义。Formaldehyde is a common environmental pollutant that is often present in the atmosphere and water. Since water is an indispensable resource for human beings, environmental water is often polluted by factory waste and domestic waste. Among many pollutants, formaldehyde is a very common pollutant, and excessive formaldehyde will cause serious damage to human health. threaten. In addition, formaldehyde is a precursor of some polymeric materials. In order to reduce costs, some unscrupulous manufacturers directly discharge the remaining formaldehyde raw materials in the production process into the water source, which greatly increases the risk of water pollution by formaldehyde. Therefore, it is of great significance to establish an accurate, efficient and economical method for the analysis of formaldehyde in water environment.
目前,国内水环境中甲醛的检测方法主要为高效液相色谱法和紫外分光光度法,但存在耗时长、成本高等诸多问题,从而无法满足快速检测的需求。表面增强拉曼光谱(Surface-enhanced Raman scattering,英文简写:SERS)具有灵敏度高、特异性强、检测快速等诸多优点,并且容易实现快速快检。但在实际检测过程中,SERS分析检测的重现性与选择性都有所欠缺,而提高SERS分析检测重现性与选择性的关键是选择合适的SERS增强基底。At present, the detection methods of formaldehyde in the domestic water environment are mainly high performance liquid chromatography and ultraviolet spectrophotometry, but there are many problems such as time-consuming and high cost, which cannot meet the needs of rapid detection. Surface-enhanced Raman scattering (SERS) has many advantages, such as high sensitivity, strong specificity, rapid detection, etc., and it is easy to achieve rapid detection. However, in the actual detection process, the reproducibility and selectivity of SERS analysis and detection are lacking, and the key to improving the reproducibility and selectivity of SERS analysis and detection is to choose a suitable SERS-enhancing substrate.
目前常用的SERS增强基底是贵金属纳米粒子,具有制备简单、价格低廉、SERS增强效果明显等特点,但是也存在重现性差、不稳定以及选择性低等缺点,无法满足实际上包含复杂基质的样品的检测。因此,研制一种稳定性好、选择性高且容易保存的SERS增强基底显得十分重要。The currently commonly used SERS-enhancing substrates are noble metal nanoparticles, which have the characteristics of simple preparation, low price, and obvious SERS-enhancing effect. detection. Therefore, it is very important to develop a SERS-enhanced substrate with good stability, high selectivity and easy preservation.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种水环境中甲醛的定量分析方法,旨在利用SERS实现水样中甲醛的定量检测,本发明的检测方法具有理想的选择性和重现性。The purpose of the present invention is to provide a quantitative analysis method of formaldehyde in water environment, aiming to realize the quantitative detection of formaldehyde in water samples by SERS, and the detection method of the present invention has ideal selectivity and reproducibility.
本发明首先提供了一种固态表面增强拉曼散射基底的制备方法,所述方法包括:The present invention first provides a preparation method of a solid-state surface-enhanced Raman scattering substrate, the method comprising:
(1)制备类钙钛矿纳米材料:将硝酸铅溶液和硝酸铋溶液混合后,加入乙二醇和离子液体1-十六烷基-3-甲基咪唑溴盐,混合均匀后,在120-160℃下反应18-30h,之后洗涤、干燥即制备得到类钙钛矿纳米材料;(1) Preparation of perovskite-like nanomaterials: after mixing lead nitrate solution and bismuth nitrate solution, ethylene glycol and ionic liquid 1-hexadecyl-3-methylimidazolium bromide are added, and after mixing uniformly, at 120- React at 160°C for 18-30h, then wash and dry to prepare perovskite-like nanomaterials;
(2)制备金银纳米合金修饰的类钙钛矿复合材料:取步骤(1)制备得到的类钙钛矿纳米材料分散至水中,超声分散后加热至沸腾,加入氯金酸和硝酸银溶液,继续加热5-20min 后,再加入柠檬酸钠溶液,保持沸腾状态15-30min,降温后洗涤、干燥即可得到金银纳米合金修饰的类钙钛矿复合材料;(2) Preparation of gold-silver nanoalloy modified perovskite-like composite material: Disperse the perovskite-like nanomaterial prepared in step (1) into water, heat to boiling after ultrasonic dispersion, add chloroauric acid and silver nitrate solution , continue heating for 5-20min, then add sodium citrate solution, keep boiling for 15-30min, wash and dry after cooling to obtain gold-silver nanoalloy modified perovskite-like composite material;
(3)制备固态表面增强拉曼散射基底:取步骤(2)制备得到的金银纳米合金修饰的类钙钛矿复合材料配制成浓度为1.0-3.0mg mL-1的分散液,将其过滤在定性滤纸表面,即可获得固态表面增强拉曼散射基底。(3) Preparation of solid-state surface-enhanced Raman scattering substrate: take the gold-silver nanoalloy-modified perovskite-like composite material prepared in step (2) to prepare a dispersion with a concentration of 1.0-3.0 mg mL -1 , and filter it On the surface of qualitative filter paper, a solid surface-enhanced Raman scattering substrate can be obtained.
在本发明的一种实施方式中,步骤(1)中,所述硝酸铅和硝酸铋的摩尔比值为1~2:1~2,硝酸铅和1-十六烷基-3-甲基咪唑溴盐的摩尔比值为:1~2:1~2。In an embodiment of the present invention, in step (1), the molar ratio of lead nitrate and bismuth nitrate is 1-2:1-2, and lead nitrate and 1-hexadecyl-3-methylimidazole The molar ratio of bromine salt is: 1~2:1~2.
在本发明的一种实施方式中,步骤(1)中,所述洗涤为用无水乙醇和超纯水分别洗涤多次。In an embodiment of the present invention, in step (1), the washing is washing with absolute ethanol and ultrapure water for multiple times respectively.
在本发明的一种实施方式中,步骤(2)中,所述氯金酸和硝酸银的质量比为1~2:1,硝酸银和类钙钛矿纳米材料的质量比为1:8~16。In an embodiment of the present invention, in step (2), the mass ratio of the chloroauric acid and silver nitrate is 1-2:1, and the mass ratio of silver nitrate and perovskite-like nanomaterials is 1:8 ~16.
在本发明的一种实施方式中,步骤(2)中,柠檬酸钠与类钙钛矿纳米材料的质量比为 1.24:1-1.24:2。In one embodiment of the present invention, in step (2), the mass ratio of sodium citrate to perovskite-like nanomaterials is 1.24:1-1.24:2.
在本发明的一种实施方式中,所述洗涤为用超纯水洗涤数次。In one embodiment of the present invention, the washing is washing with ultrapure water several times.
本发明的第二个目的是提供上述方法制备得到的固态表面增强拉曼散射基底。The second object of the present invention is to provide the solid-state surface-enhanced Raman scattering substrate prepared by the above method.
本发明的第三个目的是提供一种水环境中甲醛的定量检测方法,所述方法包括以下步骤:The 3rd object of the present invention is to provide a kind of quantitative detection method of formaldehyde in water environment, and described method may further comprise the steps:
步骤S01:配制不同浓度的甲醛标准溶液,并采用上述固态表面增强拉曼散射基底进行检测,根据得到的不同浓度的甲醛的特征拉曼位移处峰值与甲醛标准溶液浓度绘制标准曲线;Step S01 : preparing standard solutions of formaldehyde with different concentrations, and using the above-mentioned solid surface-enhanced Raman scattering substrate for detection, and drawing a standard curve according to the obtained characteristic Raman shift peaks of the different concentrations of formaldehyde and the concentration of the standard solution of formaldehyde;
步骤S02:采用上述固态表面增强拉曼散射基底和对经过前处理的水样进行检测,并将获得的特征拉曼位移处峰值与所述标准曲线相比较,得到水样中甲醛的浓度。Step S02 : using the above solid surface-enhanced Raman scattering substrate and detecting the pretreated water sample, and comparing the obtained peak value at the characteristic Raman shift with the standard curve to obtain the concentration of formaldehyde in the water sample.
在本发明的一种实施方式中,步骤S01中,配制的甲醛标准溶液可以是20μg·L-1、50 μg·L-1、100μg·L-1、200μg·L-1、400μg·L-1、500μg·L-1的梯度变化溶液,也可以是其他浓度的标准溶液,配制的浓度梯度越小,其所能获得的标准曲线与真实值越接近。In an embodiment of the present invention, in step S01, the prepared formaldehyde standard solution can be 20 μg·L -1 , 50 μg·L -1 , 100 μg·L -1 , 200 μg·L -1 , 400 μg·L -1 . 1. The gradient solution of 500 μg·L -1 can also be standard solutions of other concentrations. The smaller the prepared concentration gradient, the closer the standard curve that can be obtained is to the real value.
在本发明的一种实施方式中,甲醛标准溶液或水样在固态表面增强拉曼散射基底进行检测前需要进行衍生化。In one embodiment of the present invention, the formaldehyde standard solution or water sample needs to be derivatized before the solid surface-enhanced Raman scattering substrate is detected.
在本发明的一种实施方式中,所述衍生化包括以下步骤:向含有甲醛的溶液中加入4-氨基-5-肼基-3-巯基-1,2,4-三唑溶液和氢氧化钠溶液,然后孵育10~60min即可。In one embodiment of the present invention, the derivatization comprises the steps of: adding a solution of 4-amino-5-hydrazino-3-mercapto-1,2,4-triazole and hydroxide to a solution containing formaldehyde sodium solution, and then incubate for 10 to 60 min.
在本发明的一种实施方式中,所述水样的前处理步骤包括自然沉降、离心、膜过滤。In an embodiment of the present invention, the pretreatment steps of the water sample include natural sedimentation, centrifugation, and membrane filtration.
在本发明的一种实施方式中,所述膜过滤所用的滤膜为商品化0.22μm尼龙膜。In one embodiment of the present invention, the filter membrane used in the membrane filtration is a commercial 0.22 μm nylon membrane.
在本发明的一种实施方式中,所述水样的前处理具体包括:采用自然沉降12-36h,然后在5000-7000转/分条件下离心5-10min,最后采用0.22μm尼龙膜过滤的方式进行处理。In an embodiment of the present invention, the pretreatment of the water sample specifically includes: using natural sedimentation for 12-36 hours, then centrifuging at 5000-7000 rpm for 5-10 minutes, and finally using a 0.22 μm nylon membrane to filter way of processing.
本发明的第四个目的是提供上述定量检测方法在环境领域的应用。The fourth object of the present invention is to provide the application of the above quantitative detection method in the environmental field.
本发明的有益效果:Beneficial effects of the present invention:
(1)相对于现有技术,本发明提供的水环境中甲醛的定量分析方法,由于固态增强基底“热点”分布均匀、制备方便、稳定性好,对水样中甲醛的检测具有抗干扰能力高、灵敏度高、信号稳定、重现性好等特点,能够对甲醛具有特异性选择。(1) with respect to the prior art, the quantitative analysis method of formaldehyde in the water environment provided by the invention has the anti-interference ability to the detection of formaldehyde in the water sample due to the uniform distribution of solid-state enhanced substrate "hot spots", convenient preparation and good stability It has the characteristics of high sensitivity, stable signal, and good reproducibility, and can have specific selection for formaldehyde.
(2)固态表面增强拉曼散射基底的制备方法简单快速,成本低,携带方便,易储存;检出限较低(2.6μg·L-1),更适用于痕量检测;水样前处理步骤简单,且适用于SERS检测;此外,由于衍生化试剂的高选择性,使得固态表面增强拉曼散射基底在一定范围内,对甲醛具有特定选择性。(2) The preparation method of the solid-state surface-enhanced Raman scattering substrate is simple, fast, low-cost, convenient to carry, and easy to store; the detection limit is low (2.6μg·L -1 ), which is more suitable for trace detection; water sample pretreatment The steps are simple and suitable for SERS detection; in addition, due to the high selectivity of the derivatization reagent, the solid-state surface-enhanced Raman scattering substrate has a specific selectivity to formaldehyde within a certain range.
附图说明Description of drawings
为了更清楚地说明本发明的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to illustrate the technical solutions of the present invention more clearly, the following briefly introduces the accompanying drawings used in the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention, which are common in the art. As far as technical personnel are concerned, other drawings can also be obtained based on these drawings without any creative effort.
图1是实施例1制备得到的金银纳米合金修饰的类钙钛矿复合材料的透射电子显微镜照片。1 is a transmission electron microscope photograph of the gold-silver nanoalloy modified perovskite-like composite material prepared in Example 1.
图2:a是本发明实施例1制备类钙钛矿的紫外-可见消光光谱,b是实施例1制备的类钙钛矿/纳米金银合金复合材料的紫外-可见消光光谱。Figure 2: a is the ultraviolet-visible extinction spectrum of the perovskite-like prepared in Example 1 of the present invention, and b is the ultraviolet-visible extinction spectrum of the perovskite-like/nano-gold-silver alloy composite material prepared in Example 1.
图3是甲醛分析的SERS响应图。Figure 3 is a graph of the SERS response for formaldehyde analysis.
图4是实施例1甲醛各浓度在840cm-1处峰值与响应浓度标准曲线图。Fig. 4 is the standard curve diagram of peak value and response concentration at 840cm -1 for each concentration of formaldehyde in Example 1.
图5是本发明实施例1和实施例2水样实际样品测试SERS谱图。FIG. 5 is the SERS spectrum of the actual sample test of the water samples of Example 1 and Example 2 of the present invention.
图6是本发明实施例1制备得到的固态表面增强拉曼散射基底对一系列甲醛结构类似物的SERS响应图。6 is a graph showing the SERS response of the solid-state surface-enhanced Raman scattering substrate prepared in Example 1 of the present invention to a series of formaldehyde structural analogs.
图7是本发明实施例1制备得到的固态表面增强拉曼散射基底对一系列甲醛结构类似物与甲醛共存的SERS响应图。7 is a graph showing the SERS response of the solid-state surface-enhanced Raman scattering substrate prepared in Example 1 of the present invention to the coexistence of a series of formaldehyde structural analogs and formaldehyde.
图8a是本发明连续11次SERS测试响应图,图8b是随机11点SERS测试响应图,图 8c是11批固态表面增强拉曼散射基底SERS测试响应图,图8d是11天固态表面增强拉曼散射基底SERS测试响应图。Fig. 8a is the response diagram of 11 consecutive SERS tests of the present invention, Fig. 8b is the response diagram of the random 11-point SERS test, Fig. 8c is the SERS test response diagram of 11 batches of solid-state surface-enhanced Raman scattering substrates, and Fig. 8d is the 11-day solid-state surface-enhanced Raman scattering test response diagram. Mann scattering substrate SERS test response plot.
具体实施方式Detailed ways
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
实施例1Example 1
一种水环境中甲醛的定量分析方法,包括以下步骤:A quantitative analysis method for formaldehyde in a water environment, comprising the following steps:
1)固态表面增强拉曼散射基底的制备;1) Preparation of solid-state surface-enhanced Raman scattering substrates;
分别向50mL圆底烧瓶中加入2mmol硝酸铅与2mmol硝酸铋,随即加入40mL乙二醇和2mmol离子液体1-十六烷基-3-甲基咪唑溴盐并搅拌30min,随即转移至50mL聚四氟乙烯反应釜,在140℃下反应24h。最终用无水乙醇和超纯水分别清洗3次后烘干即可得到直径约为800nm类钙钛矿纳米材料。Add 2mmol of lead nitrate and 2mmol of bismuth nitrate to a 50mL round-bottomed flask, then add 40mL of ethylene glycol and 2mmol of ionic liquid 1-hexadecyl-3-methylimidazolium bromide and stir for 30min, then transfer to 50mL of polytetrafluoroethylene Ethylene reactor, react at 140 ° C for 24 h. Finally, the perovskite-like nanomaterials with a diameter of about 800 nm were obtained by washing with absolute ethanol and ultrapure water for three times respectively and drying.
取100mg类钙钛矿分散到72mL超纯水中,超声分散30min,然后加热至沸腾,同时加入4mL 15mmol·L-1氯金酸和硝酸银,继续加热10min,然后加入8mL 60mmol·L-1柠檬酸钠溶液,保持沸腾状态20min,随即降温至室温,并用超纯水清洗3次后烘干即可得到金银纳米合金修饰的类钙钛矿复合材料。采用透射电子显微镜对金银纳米合金修饰的类钙钛矿复合材料,从图1可以看出金银纳米合金均匀修饰在类钙钛矿表面,从而可以确保较好的 SERS增强效果。另外,采用紫外-消光光谱对类钙钛矿和金银纳米合金修饰的类钙钛矿复合材料表征,如图2所示,与类钙钛矿相比,金银纳米合金修饰的类钙钛矿复合材料在492nm 处出现显著的吸收峰,表明金银纳米合金修饰的类钙钛矿的成功合成。Disperse 100 mg of perovskite into 72 mL of ultrapure water, ultrasonically disperse for 30 min, then heat to boiling, add 4 mL of 15 mmol L -1 chloroauric acid and silver nitrate at the same time, continue heating for 10 min, and then add 8 mL of 60 mmol L -1 The sodium citrate solution was kept in a boiling state for 20 min, then cooled to room temperature, washed with ultrapure water for 3 times, and dried to obtain a gold-silver nanoalloy modified perovskite-like composite material. The perovskite-like composites decorated with gold-silver nano-alloys were examined by transmission electron microscopy. From Figure 1, it can be seen that the gold-silver nano-alloys are uniformly modified on the perovskite-like surface, which can ensure a better SERS enhancement effect. In addition, the perovskite-like and gold-silver nanoalloy-modified perovskite-like composites were characterized by UV-extinction spectroscopy, as shown in Fig. The ore composite showed a significant absorption peak at 492 nm, indicating the successful synthesis of perovskite-like modified gold-silver nanoalloys.
配制1.5mg·mL-1的金银纳米合金修饰的类钙钛矿复合材料,用注射器取4mL上述溶液,通过过滤的方式将金银纳米合金修饰的类钙钛矿复合材料负载在直径为13mm定性滤纸上即得到固态表面增强拉曼散射基底。Prepare 1.5 mg·mL -1 of gold-silver nanoalloy-modified perovskite-like composite material, take 4 mL of the above solution with a syringe, and load the gold-silver nanoalloy-modified perovskite-like composite material in a diameter of 13 mm by filtration. The solid surface-enhanced Raman scattering substrate is obtained on the qualitative filter paper.
2)甲醛标准曲线的绘制:2) Drawing of formaldehyde standard curve:
分别配制浓度为20μg·L-1、50μg·L-1、100μg·L-1、200μg·L-1、400μg·L-1、500μg·L-1甲醛标准溶液。另外,甲醛衍生化步骤为:向0.5mL甲醛标准溶液中加入0.2mL 10mg·L-1 4- 氨基-5-肼基-3-巯基-1,2,4-三唑和0.2mL 1mol·L-1氢氧化钠,然后孵育20min。吸取5-10μL 衍生化后溶液,采用Delta Nu拉曼仪直接检测,激发强度为48mV,积分时间为5s,每个浓度的溶液连续检测3次,取平均值和相对偏差,并绘制840cm-1拉曼位移处峰值-甲醛浓度标准曲线,见图3和图4。以能检测到3倍信噪比信号的最低浓度为检出限,检出限为2.6μg·L-1 (S/N=3),此方法线性范围和检出限能满足实际样品分析的需要。Formaldehyde standard solutions with concentrations of 20μg·L -1 , 50μg·L -1 , 100μg·L -1 , 200μg·L -1 , 400μg·L -1 , and 500μg·L -1 were prepared respectively. In addition, the formaldehyde derivatization step is: add 0.2 mL of 10 mg·L -1 4-amino-5-hydrazino-3-mercapto-1,2,4-triazole and 0.2 mL of 1 mol·L to 0.5 mL of standard formaldehyde solution -1 NaOH, then incubated for 20min. Aspirate 5-10μL of the derivatized solution, and use the Delta Nu Raman instrument for direct detection. The excitation intensity is 48mV and the integration time is 5s. The solution of each concentration is continuously detected 3 times, the average value and relative deviation are taken, and 840cm -1 is drawn. The peak at Raman shift-formaldehyde concentration standard curve is shown in Figures 3 and 4. The detection limit is the lowest concentration that can detect three times the signal-to-noise ratio signal, and the detection limit is 2.6μg·L -1 (S/N=3). The linear range and detection limit of this method can meet the requirements of actual sample analysis. need.
3)水样中甲醛的检测:3) Detection of formaldehyde in water samples:
取10mL湖水,首先自然沉降24h,然后在5000转/分条件下离心5min,最后采用0.22μm尼龙膜过滤的方式进行处理,最终取0.5mL与0.2mL 10mg·L-1 4-氨基-5-肼基-3-巯基 -1,2,4-三唑以及0.2mL 1mol·L-1氢氧化钠孵育20min,最终进行SERS检测。测得SERS信号如图5所示,连续测试3次,并计算3个数据的840cm-1处峰值平均值和相对标准偏差,代入标准曲线,表明得到该湖水样品中甲醛浓度为207.6μg·L-1。Take 10mL of lake water, first settle it naturally for 24h, then centrifuge at 5000 rpm for 5min, and finally filter it with a 0.22μm nylon membrane, and finally take 0.5mL and 0.2mL of 10mg·L -1 4-amino-5- Hydrazino-3-mercapto-1,2,4-triazole and 0.2 mL of 1 mol·L -1 sodium hydroxide were incubated for 20 min, and finally SERS detection was performed. The measured SERS signal is shown in Figure 5. The test was performed three times in a row, and the average value and relative standard deviation of the peak at 840cm -1 of the three data were calculated and substituted into the standard curve, indicating that the concentration of formaldehyde in the lake water sample was 207.6 μg·L -1 .
随后对样品进行加标处理,加标样品为向迁移液中添加20μg·L-1、50μg·L-1和200μg·L-1量甲醛标准溶液,随即进行SERS检测,连续测试3次,并计算3个数据的840cm-1处峰值平均值和相对偏差,代入标准曲线,从而得到加标样品中甲醛浓度,计算得到样品加标回收率101.0-103.0%,相对标准偏差为2.4-4.6%。Then, the samples were spiked with standard solutions of 20μg·L -1 , 50μg·L -1 and 200μg·L -1 of formaldehyde standard solution added to the migration solution, and then SERS detection was carried out. Calculate the peak mean value and relative deviation at 840cm -1 of the three data, and substitute them into the standard curve to obtain the formaldehyde concentration in the spiked sample.
通过高效液相色谱法(HPLC)验证所建立的SERS分析方法检测的准确性。取5mL前处理后的湖水,加入5mL 3mg·mL-1 2,4-二硝基苯肼溶液,在60℃下孵育1h。然后过0.22μm微孔滤膜,滤液供HPLC测定。高效液相色谱仪配二极管阵列检测器(日本岛津公司),其检测波长为360nm,所选色谱柱为DiamonsilC18柱(250mm×4.6mm,5μm)。流动相选用0.1%三氟乙酸(A)-乙腈(B),采用梯度洗脱,洗脱条件为:0-5min:流动相B从30%升至70%; 5-10min:流动相B从70%升至80%;10-12min:流动相B从80%降至30%;12-17min:流动相B维持在30%;流速为1.0mL/min,进样量为20μL。经HPLC检测,得到该湖水样品中甲醛浓度为209.1(±0.4)μg·L-1,与SERS分析方法相对偏差为4.9%,证明了本发明定量分析方法的可靠性。The detection accuracy of the established SERS analytical method was verified by high performance liquid chromatography (HPLC). Take 5mL of pre-treated lake water, add 5mL of 3mg·
为了验证固态表面增强拉曼散射基底对甲醛具有特异性选择和抗干扰性,采用本发明的方法对于甲醛结构相似的物质:丙酮、甲醇、乙醇、乙腈、乙醛、乙酸、乙酸乙酯进行检测,其SERS谱图如图6所示。从图6可知,采用本发明的固态表面增强拉曼散射基底对上述八种物质进行检测,丙酮、甲醇、乙醇、乙腈、乙醛、乙酸、乙酸乙酯的SERS响应均较弱。另外,图7为上述一系列甲醛结构类似物与甲醛共存的SERS响应图,从图7可知,当甲醛与上述干扰物同时存在时,SERS响应几乎没有变化,由此可见本发明的方法可以准确测定甲醛的含量。In order to verify that the solid surface-enhanced Raman scattering substrate has specific selection and anti-interference for formaldehyde, the method of the present invention is used to detect substances with similar structure of formaldehyde: acetone, methanol, ethanol, acetonitrile, acetaldehyde, acetic acid, ethyl acetate , and its SERS spectrum is shown in Figure 6. It can be seen from FIG. 6 that the SERS responses of acetone, methanol, ethanol, acetonitrile, acetaldehyde, acetic acid, and ethyl acetate are all weak in the detection of the above-mentioned eight substances using the solid surface-enhanced Raman scattering substrate of the present invention. In addition, Figure 7 is the SERS response diagram of the above-mentioned series of formaldehyde structural analogs coexisting with formaldehyde. It can be seen from Figure 7 that when formaldehyde and the above-mentioned interfering substances coexist, the SERS response hardly changes. It can be seen that the method of the present invention can accurately Determination of formaldehyde content.
为了验证固态表面增强拉曼散射基底对甲醛检测具有较好的重复性和重现性,分别对固态表面增强拉曼散射基底进行连续11次SERS测试,随机11点SERS测试,11批固态表面增强拉曼散射基底SERS测试以及连续11天固态表面增强拉曼散射基底SERS测试,其结果如图8a-8d所示。从图8可知,采用本发明的固态表面增强拉曼散射基底对甲醛检测具有较好的重复性和重现性,可以用于水环境中甲醛含量的测试。In order to verify that the solid-state surface-enhanced Raman scattering substrate has good repeatability and reproducibility for formaldehyde detection, 11 consecutive SERS tests, random 11-point SERS tests, and 11 batches of solid-state surface-enhanced Raman scattering substrates were performed on the solid-state surface-enhanced Raman scattering substrate. The results of the Raman scattering substrate SERS test and the solid-state surface-enhanced Raman scattering substrate SERS test for 11 consecutive days are shown in Figures 8a-8d. It can be seen from FIG. 8 that the solid surface-enhanced Raman scattering substrate of the present invention has good repeatability and reproducibility for formaldehyde detection, and can be used for the test of formaldehyde content in water environment.
实施例2Example 2
一种水环境中甲醛的定量分析方法,包括以下步骤:A quantitative analysis method for formaldehyde in a water environment, comprising the following steps:
1)固态表面增强拉曼散射基底的制备;1) Preparation of solid-state surface-enhanced Raman scattering substrates;
分别向50mL圆底烧瓶中加入1.5mmol硝酸铅与1.5mmol硝酸铋,随即加入30mL乙二醇和1.5mmol离子液体1-十六烷基-3-甲基咪唑溴盐并搅拌40min,随机转移至50mL聚四氟乙烯反应釜,在150℃下反应22h。最终用无水乙醇和超纯水分别清洗3次后烘干即可得到直径约为800nm类钙钛矿纳米材料。1.5mmol of lead nitrate and 1.5mmol of bismuth nitrate were respectively added to the 50mL round-bottomed flask, then 30mL of ethylene glycol and 1.5mmol of ionic liquid 1-hexadecyl-3-methylimidazolium bromide were added and stirred for 40min, and then randomly transferred to 50mL Teflon reaction kettle, react at 150°C for 22h. Finally, the perovskite-like nanomaterials with a diameter of about 800 nm were obtained by washing with absolute ethanol and ultrapure water for three times respectively and drying.
取80mg类钙钛矿分散到58mL超纯水中,超声分散40min,然后加热至沸腾,同时加入2mL 15mmol·L-1氯金酸和硝酸银,继续加热15min,然后加入8mL 30mmol·L-1柠檬酸钠溶液,保持沸腾状态25min,随机降温至室温,并用超纯水清洗3次后烘干即可得到金银纳米合金修饰的类钙钛矿复合材料。采用透射电子显微镜对金银纳米合金修饰的类钙钛矿复合材料。Disperse 80 mg of perovskite into 58 mL of ultrapure water, ultrasonically disperse for 40 min, then heat to boiling, add 2 mL of 15 mmol L -1 chloroauric acid and silver nitrate at the same time, continue heating for 15 min, and then add 8 mL of 30 mmol L -1 The sodium citrate solution was kept in a boiling state for 25 min, randomly cooled to room temperature, washed with ultrapure water for 3 times, and then dried to obtain a gold-silver nanoalloy modified perovskite-like composite material. Perovskite-like composites decorated with gold-silver nanoalloys by transmission electron microscopy.
配制2mg·mL-1的金银纳米合金修饰的类钙钛矿复合材料,用注射器取3mL上述溶液,通过过滤的方式将金银纳米合金修饰的类钙钛矿复合材料负载在13mm定性滤纸上即得到固态表面增强拉曼散射基底。Prepare 2 mg·mL -1 of gold-silver nanoalloy-modified perovskite-like composites, take 3 mL of the above solution with a syringe, and load the gold-silver nanoalloy-modified perovskite-like composites on 13 mm qualitative filter paper by filtration That is, a solid surface-enhanced Raman scattering substrate is obtained.
2)甲醛标准曲线的绘制:2) Drawing of formaldehyde standard curve:
分别配制浓度为20μg·L-1、50μg·L-1、100μg·L-1、200μg·L-1、400μg·L-1、500μg·L-1甲醛标准溶液。另外,甲醛衍生化步骤为:向0.5mL甲醛标准溶液中加入0.2mL 10mg·L-1 4- 氨基-5-肼基-3-巯基-1,2,4-三唑和0.2mL 1mol·L-1氢氧化钠,然后孵育20min。吸取5-10μL 衍生化后溶液,采用Delta Nu拉曼仪直接检测,激发强度为48mV,积分时间为5s,每个浓度的溶液连续检测3次,取平均值和相对偏差,并绘制840cm-1拉曼位移处峰值-甲醛浓度标准曲线,以能检测到3倍信噪比信号的最低浓度为检出限,检出限为2.6μg·L-1(S/N=3),此方法线性范围和检出限能满足实际样品分析的需要。Formaldehyde standard solutions with concentrations of 20μg·L -1 , 50μg·L -1 , 100μg·L -1 , 200μg·L -1 , 400μg·L -1 , and 500μg·L -1 were prepared respectively. In addition, the formaldehyde derivatization step is: add 0.2 mL of 10 mg·L -1 4-amino-5-hydrazino-3-mercapto-1,2,4-triazole and 0.2 mL of 1 mol·L to 0.5 mL of standard formaldehyde solution -1 NaOH, then incubated for 20min. Aspirate 5-10μL of the derivatized solution, and use the Delta Nu Raman instrument for direct detection. The excitation intensity is 48mV and the integration time is 5s. The solution of each concentration is continuously detected 3 times, the average value and relative deviation are taken, and 840cm -1 is drawn. The peak value at Raman shift-formaldehyde concentration standard curve, the detection limit is the lowest concentration that can detect three times the signal-to-noise ratio signal, the detection limit is 2.6μg·L -1 (S/N=3), this method is linear The range and detection limit can meet the needs of actual sample analysis.
3)水样中甲醛的检测:3) Detection of formaldehyde in water samples:
取10mL水库水,首先自然沉降24h,然后在6000转/分条件下离心7min,最后采用0.22μm尼龙膜过滤的方式进行处理,最终取0.5mL与0.2mL 10mg·L-1 4-氨基-5-肼基-3-巯基-1,2,4-三唑以及0.2mL 1mol·L-1氢氧化钠孵育20min,最终进行SERS检测。测得SERS 信号如图5所示,连续测试3次,并计算3个数据的840cm-1处峰值平均值和相对标准偏差,代入标准曲线,表明得到该湖水样品中甲醛浓度为181.9μg·L-1。Take 10mL of reservoir water, first settle naturally for 24h, then centrifuge at 6000 rpm for 7min, and finally filter it with a 0.22μm nylon membrane, and finally take 0.5mL and 0.2mL of 10mg·L -1 4-amino-5 - Hydrazino-3-mercapto-1,2,4-triazole and 0.2mL 1mol·L -1 sodium hydroxide were incubated for 20min, and finally SERS detection was performed. The measured SERS signal is shown in Figure 5, and the test was performed three times in a row, and the average value and relative standard deviation of the peak at 840cm -1 of the three data were calculated and substituted into the standard curve, indicating that the formaldehyde concentration in the lake water sample was 181.9μg·L -1 .
随后对样品进行加标处理,加标样品为向迁移液中添加20μg·L-1、50μg·L-1和200μg·L-1量甲醛标准溶液,随即进行SERS检测,连续测试3次,并计算3个数据的840cm-1处峰值平均值和相对偏差,代入标准曲线,从而得到加标样品中甲醛浓度,计算得到样品加标回收率93.3-100.3%,相对标准偏差3.3-5.7%。Then, the samples were spiked with standard solutions of 20μg·L -1 , 50μg·L -1 and 200μg·L -1 of formaldehyde standard solution added to the migration solution, and then SERS detection was carried out. Calculate the peak mean value and relative deviation at 840cm -1 of the three data, and substitute them into the standard curve to obtain the formaldehyde concentration in the spiked sample.
通过高效液相色谱法(HPLC)验证所建立的SERS分析方法检测的准确性。取5mL前处理后的水库水,加入5mL 3mg·mL-1 2,4-二硝基苯肼溶液,在60℃下孵育1h。然后过0.22μm微孔滤膜,滤液供HPLC测定。高效液相色谱仪配二极管阵列检测器(日本岛津公司),其检测波长为360nm,所选色谱柱为DiamonsilC18柱(250mm×4.6mm,5μm)。流动相选用 0.1%三氟乙酸(A)-乙腈(B),采用梯度洗脱,洗脱条件为:0-5min:流动相B从30%升至70%;5-10min:流动相B从70%升至80%;10-12min:流动相B从80%降至30%;12-17min:流动相B维持在30%;流速为1.0mL/min,进样量为20μL。经HPLC检测,得到该湖水样品中甲醛浓度为186.4(±1.7)μg·L-1,与SERS分析方法相对偏差为6.9%,证明了该分析方法的可靠性。The detection accuracy of the established SERS analytical method was verified by high performance liquid chromatography (HPLC). Take 5mL of pre-treated reservoir water, add 5mL of 3mg·
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, The protection scope of the present invention should be defined by the claims.
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