CN113324972B - Quantitative analysis method for formaldehyde in water environment - Google Patents

Quantitative analysis method for formaldehyde in water environment Download PDF

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CN113324972B
CN113324972B CN202110534734.8A CN202110534734A CN113324972B CN 113324972 B CN113324972 B CN 113324972B CN 202110534734 A CN202110534734 A CN 202110534734A CN 113324972 B CN113324972 B CN 113324972B
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CN113324972A (en
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顾颖
胡源苓
姜子烨
易伦朝
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Kunming University of Science and Technology
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Abstract

The invention discloses a quantitative analysis method for formaldehyde in a water environment, and belongs to the technical field of environment detection. The quantitative analysis method comprises the following steps: preparing a solid surface enhanced Raman scattering substrate by using a perovskite-like composite material modified by gold-silver nano alloy as a base material; preparing formaldehyde standard solutions with different concentrations, detecting by adopting the prepared solid surface enhanced Raman scattering substrate, and drawing a standard curve according to the peak value of the characteristic Raman shift position of the obtained standard solutions with different concentrations and the concentration of the formaldehyde standard solution; and detecting the water sample subjected to pretreatment by using the obtained solid surface enhanced Raman scattering substrate, comparing the detected water sample with the standard curve to obtain the concentration of formaldehyde in the water sample, and verifying the accuracy of the analysis method by using a high performance liquid chromatography. The method has the characteristics of high anti-interference capability, high sensitivity, stable signal, good reproducibility and the like for trace detection of a water sample, and can specifically select formaldehyde.

Description

Quantitative analysis method for formaldehyde in water environment
Technical Field
The invention relates to a quantitative analysis method for formaldehyde in a water environment, and belongs to the technical field of environment detection.
Background
Formaldehyde is a common environmental pollutant that is often found in the atmosphere and in water bodies. As water is an indispensable resource for human beings, environmental water is often polluted by factory wastes and domestic wastes, among many pollutants, formaldehyde is a very common pollutant, and excessive formaldehyde can seriously threaten human health. In addition, formaldehyde is a precursor of some polymeric materials, and in order to reduce cost, some illegal manufacturers directly discharge the residual formaldehyde raw materials in the production process into a water source, so that the risk of formaldehyde pollution to the water body is greatly increased. Therefore, the method for accurately, efficiently and economically analyzing the formaldehyde in the water environment has important significance.
At present, the detection method of formaldehyde in domestic water environment mainly adopts high performance liquid chromatography and ultraviolet spectrophotometry, but has the problems of long time consumption, high cost and the like, so that the requirement of quick detection cannot be met. Surface-enhanced Raman spectroscopy (SERS, abbreviated in english) has many advantages such as high sensitivity, strong specificity, and rapid detection, and is easy to realize rapid detection. However, in the actual detection process, the reproducibility and selectivity of SERS analysis and detection are all lacking, and the key to improve the reproducibility and selectivity of SERS analysis and detection is to select a suitable SERS enhancing substrate.
The conventional SERS enhancement substrate is a noble metal nanoparticle, has the characteristics of simple preparation, low price, obvious SERS enhancement effect and the like, has the defects of poor reproducibility, instability, low selectivity and the like, and cannot meet the requirement of detecting a sample containing a complex matrix actually. Therefore, it is very important to develop a SERS enhancing substrate with good stability, high selectivity and easy preservation.
Disclosure of Invention
The invention aims to provide a quantitative analysis method for formaldehyde in a water environment, which aims to realize quantitative detection of formaldehyde in a water sample by SERS (surface enhanced Raman scattering), and the detection method has ideal selectivity and reproducibility.
The invention firstly provides a preparation method of a solid surface enhanced Raman scattering substrate, which comprises the following steps:
(1) preparing a perovskite-like nano material: mixing a lead nitrate solution and a bismuth nitrate solution, adding ethylene glycol and ionic liquid 1-hexadecyl-3-methylimidazolium bromide, uniformly mixing, reacting at the temperature of 120-160 ℃ for 18-30h, and then washing and drying to obtain the perovskite-like nano material;
(2) preparing a perovskite-like composite material modified by gold-silver nano alloy: dispersing the perovskite-like nano material prepared in the step (1) into water, performing ultrasonic dispersion, heating to boil, adding chloroauric acid and silver nitrate solution, continuing heating for 5-20min, adding sodium citrate solution, keeping the boiling state for 15-30min, cooling, washing and drying to obtain the gold-silver nano alloy modified perovskite-like composite material;
(3) preparing a solid surface enhanced Raman scattering substrate: preparing the gold-silver nano-alloy modified perovskite-like composite material prepared in the step (2)The concentration is 1.0-3.0mg mL -1 The dispersion liquid is filtered on the surface of qualitative filter paper, and then the solid surface enhanced Raman scattering substrate can be obtained.
In one embodiment of the present invention, in the step (1), the molar ratio of the lead nitrate to the bismuth nitrate is 1-2: 1-2, wherein the molar ratio of the lead nitrate to the 1-hexadecyl-3-methylimidazole bromine salt is as follows: 1-2: 1 to 2.
In one embodiment of the present invention, in the step (1), the washing is performed by washing with absolute ethanol and ultrapure water respectively for a plurality of times.
In one embodiment of the invention, in the step (2), the mass ratio of the chloroauric acid to the silver nitrate is 1-2: 1, the mass ratio of silver nitrate to the perovskite-like nano material is 1: 8 to 16.
In one embodiment of the invention, in step (2), the mass ratio of sodium citrate to perovskite-like nanomaterial is 1.24:1 to 1.24: 2.
In one embodiment of the present invention, the washing is washing with ultrapure water several times.
The second purpose of the invention is to provide the solid-state surface-enhanced Raman scattering substrate prepared by the method.
The third purpose of the invention is to provide a quantitative detection method of formaldehyde in water environment, which comprises the following steps:
step S01: preparing formaldehyde standard solutions with different concentrations, detecting by adopting the solid surface enhanced Raman scattering substrate, and drawing a standard curve according to the peak value of the characteristic Raman shift position of the obtained formaldehyde with different concentrations and the concentration of the formaldehyde standard solution;
step S02: and detecting the water sample subjected to pretreatment by using the solid surface enhanced Raman scattering substrate, and comparing the peak value of the obtained characteristic Raman shift position with the standard curve to obtain the concentration of formaldehyde in the water sample.
In one embodiment of the present invention, the standard formaldehyde solution prepared in step S01 may be 20. mu.g.L -1 、50 μg·L -1 、100μg·L -1 、200μg·L -1 、400μg·L -1 、500μg·L -1 The gradient change solution can also be a standard solution with other concentrations, and the smaller the prepared concentration gradient is, the closer the standard curve obtained by the solution is to the real value.
In one embodiment of the present invention, the formaldehyde standard solution or water sample needs to be derivatized before detection by the solid-state surface enhanced raman scattering substrate.
In one embodiment of the invention, the derivatization comprises the steps of: adding a 4-amino-5-hydrazino-3-mercapto-1, 2, 4-triazole solution and a sodium hydroxide solution into a solution containing formaldehyde, and then incubating for 10-60 min.
In one embodiment of the invention, the pretreatment step of the water sample comprises natural sedimentation, centrifugation and membrane filtration.
In one embodiment of the invention, the filtration membrane used for the membrane filtration is a commercial 0.22 μm nylon membrane.
In an embodiment of the present invention, the pretreatment of the water sample specifically includes: natural sedimentation is adopted for 12-36h, then centrifugation is carried out for 5-10min under the condition of 5000 and 7000 revolutions per minute, and finally the treatment is carried out by adopting a mode of 0.22 mu m nylon membrane filtration.
The fourth purpose of the invention is to provide the application of the quantitative detection method in the environmental field.
The invention has the beneficial effects that:
(1) compared with the prior art, the quantitative analysis method for the formaldehyde in the water environment provided by the invention has the characteristics of high anti-interference capability, high sensitivity, stable signal, good reproducibility and the like for detecting the formaldehyde in the water sample due to the fact that the solid-state enhanced substrate hot spots are uniformly distributed, the preparation is convenient, and the stability is good, so that the method can specifically select the formaldehyde.
(2) The preparation method of the solid surface enhanced Raman scattering substrate is simple and rapid, low in cost, convenient to carry and easy to store; the detection limit is low (2.6 mu g.L) -1 ) The method is more suitable for trace detection; the pretreatment step of the water sample is simple, and the method is suitable for SERS detection; in addition, due to the high selectivity of the derivatization reagent, the solid-state surface enhanced Raman scattering substrateWithin a certain range, has specific selectivity to formaldehyde.
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In order to more clearly illustrate the technical solution of the present invention, the drawings required to be used in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a transmission electron microscope photograph of the gold-silver nano-alloy modified perovskite-like composite material prepared in example 1.
FIG. 2: a is the ultraviolet-visible extinction spectrum of the perovskite-like alloy prepared in the embodiment 1 of the invention, and b is the ultraviolet-visible extinction spectrum of the perovskite-like/nano gold-silver alloy composite material prepared in the embodiment 1.
Fig. 3 is a graph of SERS response of formaldehyde analysis.
FIG. 4 shows the respective concentrations of formaldehyde in example 1 at 840cm -1 Peak to response concentration standard curve.
Fig. 5 is a SERS spectrum measured from an actual sample of water samples according to example 1 and example 2 of the present invention.
FIG. 6 is a graph showing SERS responses of the solid-state surface-enhanced Raman scattering substrate prepared in example 1 of the present invention to a series of formaldehyde structural analogs.
FIG. 7 is a graph showing 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 in the presence of formaldehyde.
FIG. 8a is a response graph of 11 consecutive SERS tests of the present invention, FIG. 8b is a response graph of a random 11-point SERS test, FIG. 8c is a response graph of an 11-batch SERS test using a solid-state surface-enhanced Raman scattering substrate, and FIG. 8d is a response graph of an 11-day SERS test using a solid-state surface-enhanced Raman scattering substrate.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A quantitative analysis method for formaldehyde in a water environment comprises the following steps:
1) preparing a solid surface enhanced Raman scattering substrate;
2mmol of lead nitrate and 2mmol of bismuth nitrate are respectively added into a 50mL round-bottom flask, 40mL of ethylene glycol and 2mmol of ionic liquid 1-hexadecyl-3-methylimidazolium bromide are added and stirred for 30min, and then the mixture is transferred to a 50mL polytetrafluoroethylene reaction kettle and reacted for 24h at 140 ℃. Finally, respectively cleaning the perovskite nano material with the diameter of about 800nm by using absolute ethyl alcohol and ultrapure water for 3 times, and drying the washed perovskite nano material.
Dispersing 100mg of perovskite into 72mL of ultrapure water, ultrasonically dispersing for 30min, heating to boil, and simultaneously adding 4mL of 15 mmol.L -1 Heating chloroauric acid and silver nitrate for 10min, adding 8mL 60mmol L -1 And (3) keeping the sodium citrate solution in a boiling state for 20min, immediately cooling to room temperature, cleaning for 3 times by using ultrapure water, and drying to obtain the gold-silver nano alloy modified perovskite-like composite material. The perovskite-like composite material modified by the gold-silver nano alloy by adopting a transmission electron microscope can be seen from figure 1 that the gold-silver nano alloy is uniformly modified on the surface of the perovskite-like composite material, so that a better SERS enhancement effect can be ensured. In addition, ultraviolet-extinction spectroscopy is adopted to characterize the perovskite-like composite material modified by the perovskite-like and the gold-silver nano-alloy, as shown in fig. 2, compared with the perovskite-like, the perovskite-like composite material modified by the gold-silver nano-alloy has a remarkable absorption peak at 492nm, which indicates the successful synthesis of the perovskite-like modified by the gold-silver nano-alloy.
Preparation of 1.5 mg/mL -1 The perovskite-like composite material modified by the gold-silver nano alloy is prepared by taking 4mL of the solution by using an injector, and loading the perovskite-like composite material modified by the gold-silver nano alloy on qualitative filter paper with the diameter of 13mm in a filtering mode to obtain the solid surface enhanced Raman scattering substrate.
2) And (3) drawing a formaldehyde standard curve:
are prepared separatelyThe concentration is 20 mug.L -1 、50μg·L -1 、100μg·L -1 、200μg·L -1 、400μg·L -1 、500μg·L -1 Formaldehyde standard solution. In addition, the formaldehyde derivatization step is as follows: 0.2mL of 10 mg. L was added to 0.5mL of the formaldehyde standard solution -1 4-amino-5-hydrazino-3-mercapto-1, 2, 4-triazole and 0.2mL of 1 mol. L -1 Sodium hydroxide, followed by incubation for 20 min. Sucking 5-10 μ L of the derivatized solution, detecting directly with Delta Nu Raman spectrometer with excitation intensity of 48mV and integration time of 5s, detecting each concentration of solution for 3 times, taking average value and relative deviation, and drawing 840cm -1 The peak-formaldehyde concentration standard curve at the raman shift is shown in fig. 3 and 4. The lowest concentration capable of detecting 3 times of signal-to-noise ratio is taken as the detection limit, and the detection limit is 2.6 mu g.L -1 (S/N is 3), the linear range and detection limit of the method can meet the requirement of practical sample analysis.
3) Detecting formaldehyde in a water sample:
taking 10mL lake water, naturally settling for 24h, centrifuging for 5min at 5000 r/min, and filtering with 0.22 μm nylon membrane to obtain 0.5mL lake water and 0.2mL 10 mg.L -1 4-amino-5-hydrazino-3-mercapto-1, 2, 4-triazole and 0.2mL of 1 mol. L -1 And (5) incubating for 20min by using sodium hydroxide, and finally carrying out SERS detection. The SERS signal was measured as shown in FIG. 5, and measured 3 times in succession, and 840cm of 3 data was calculated -1 Substituting the average value and the relative standard deviation of the peak value into the standard curve to show that the concentration of the formaldehyde in the lake water sample is 207.6 mu g.L -1 。
Subsequently, the sample was subjected to a labeling treatment in which 20. mu.g.L of the sample was added to the migration solution -1 、50μg·L -1 And 200. mu.g.L -1 Measuring standard formaldehyde solution, performing SERS detection, continuously measuring for 3 times, and calculating 840cm of 3 data -1 And substituting the average value and the relative deviation of the peak values into a standard curve to obtain the concentration of the formaldehyde in the standard adding sample, and calculating to obtain the standard adding recovery rate of the sample of 101.0-103.0% and the relative standard deviation of 2.4-4.6%.
Verification of established SERS analysis method by High Performance Liquid Chromatography (HPLC)And (4) measuring accuracy. 5mL of the pretreated lake water was added to 5mL of 3 mg/mL -1 2, 4-dinitrophenylhydrazine solution, and incubating for 1h at 60 ℃. Then, the mixture was passed through a 0.22 μm microporous membrane and the filtrate was subjected to HPLC. The HPLC apparatus was equipped with a diode array detector (Shimadzu corporation, Japan) having a detection wavelength of 360nm, and the column selected was a Diamonsil C18 column (250 mm. times.4.6 mm, 5 μm). The mobile phase adopts 0.1 percent trifluoroacetic acid (A) -acetonitrile (B) and adopts gradient elution, and the elution conditions are as follows: 0-5 min: mobile phase B rose from 30% to 70%; 5-10 min: mobile phase B rose from 70% to 80%; 10-12 min: mobile phase B decreased from 80% to 30%; 12-17 min: mobile phase B was maintained at 30%; the flow rate was 1.0mL/min and the amount of sample was 20. mu.L. HPLC detection shows that the concentration of formaldehyde in the lake water sample is 209.1 (+ -0.4) mu g.L -1 The relative deviation from the SERS analysis method is 4.9%, which proves the reliability of the quantitative analysis method of the invention.
In order to verify that the solid surface enhanced Raman scattering substrate has specific selection and anti-interference performance on formaldehyde, the method provided by the invention is adopted for substances with similar formaldehyde structures: acetone, methanol, ethanol, acetonitrile, acetaldehyde, acetic acid, and ethyl acetate, and the SERS spectrogram thereof is shown in FIG. 6. As can be seen from fig. 6, when the solid surface-enhanced raman scattering substrate of the present invention is used to detect the above eight substances, SERS responses of acetone, methanol, ethanol, acetonitrile, acetaldehyde, acetic acid, and ethyl acetate are all weak. In addition, fig. 7 is a graph showing SERS responses of the series of formaldehyde structural analogs coexisting with formaldehyde, and it can be seen from fig. 7 that the SERS responses are hardly changed when formaldehyde coexists with the above interferents, and thus it can be seen that the method of the present invention can accurately determine the content of formaldehyde.
In order to verify that the solid-state surface-enhanced Raman scattering substrate has better repeatability and reproducibility for formaldehyde detection, 11 times of SERS tests, 11 random point SERS tests, 11 batches of solid-state surface-enhanced Raman scattering substrate SERS tests and 11 days of continuous solid-state surface-enhanced Raman scattering substrate SERS tests are respectively carried out on the solid-state surface-enhanced Raman scattering substrate, and the results are shown in FIGS. 8a-8 d. From fig. 8, the solid-state surface enhanced raman scattering substrate of the present invention has good repeatability and reproducibility for formaldehyde detection, and can be used for testing formaldehyde content in water environment.
Example 2
A quantitative analysis method for formaldehyde in a water environment comprises the following steps:
1) preparing a solid surface enhanced Raman scattering substrate;
1.5mmol of lead nitrate and 1.5mmol of bismuth nitrate are respectively added into a 50mL round-bottom flask, 30mL of ethylene glycol and 1.5mmol of ionic liquid 1-hexadecyl-3-methylimidazolium bromide are added and stirred for 40min, and the mixture is randomly transferred to a 50mL polytetrafluoroethylene reaction kettle and reacted for 22h at 150 ℃. Finally, respectively cleaning the perovskite nano material with the diameter of about 800nm by using absolute ethyl alcohol and ultrapure water for 3 times, and drying the washed perovskite nano material.
80mg of perovskite is dispersed in 58mL of ultrapure water, ultrasonic dispersion is carried out for 40min, then heating is carried out until boiling, and 2mL of 15 mmol.L is added -1 Heating chloroauric acid and silver nitrate for 15min, adding 8mL of 30 mmol.L -1 And (3) keeping the sodium citrate solution in a boiling state for 25min, randomly cooling to room temperature, cleaning for 3 times by using ultrapure water, and drying to obtain the gold-silver nano alloy modified perovskite-like composite material. The perovskite-like composite material modified by the gold-silver nano alloy is prepared by adopting a transmission electron microscope.
Preparation of 2 mg/mL -1 The perovskite-like composite material modified by the gold-silver nano alloy is prepared by taking 3mL of the solution by using an injector, and loading the perovskite-like composite material modified by the gold-silver nano alloy on 13mm qualitative filter paper in a filtering mode to obtain the solid surface enhanced Raman scattering substrate.
2) And (3) drawing a formaldehyde standard curve:
respectively prepared at a concentration of 20. mu.g.L -1 、50μg·L -1 、100μg·L -1 、200μg·L -1 、400μg·L -1 、500μg·L -1 Formaldehyde standard solution. In addition, the formaldehyde derivatization step is as follows: 0.2mL of 10 mg. L was added to 0.5mL of the formaldehyde standard solution -1 4-amino-5-hydrazino-3-mercapto-1, 2, 4-triazole and 0.2mL of 1 mol. L -1 Sodium hydroxide, followed by incubation for 20 min. Sucking 5-10 μ L of the derivatized solution, and straightening with a Delta Nu Raman instrumentDetecting, with excitation intensity of 48mV and integration time of 5s, continuously detecting each concentration solution for 3 times, taking average value and relative deviation, and drawing 840cm -1 The peak value-formaldehyde concentration standard curve at the Raman shift position takes the lowest concentration capable of detecting 3 times of signal-to-noise ratio as the detection limit, and the detection limit is 2.6 mu g.L -1 (S/N is 3), the linear range and detection limit of the method can meet the requirement of practical sample analysis.
3) Detecting formaldehyde in a water sample:
taking 10mL reservoir water, naturally settling for 24h, centrifuging for 7min at 6000 r/min, and filtering with 0.22 μm nylon membrane to obtain 0.5mL and 0.2mL 10 mg.L -1 4-amino-5-hydrazino-3-mercapto-1, 2, 4-triazole and 0.2mL of 1 mol. L -1 And (5) incubating with sodium hydroxide for 20min, and finally carrying out SERS detection. The SERS signal was measured as shown in FIG. 5, and measured 3 times in succession, and 840cm of 3 data was calculated -1 Substituting the average value and the relative standard deviation of the peak values into the standard curve shows that the concentration of the formaldehyde in the lake water sample is 181.9 mu g.L -1 。
Subsequently, the sample was subjected to a labeling treatment in which 20. mu.g.L of the sample was added to the migration solution -1 、50μg·L -1 And 200. mu.g.L -1 Measuring standard formaldehyde solution, performing SERS detection, continuously measuring for 3 times, and calculating 840cm of 3 data -1 And substituting the average value and the relative deviation of the peak values into a standard curve to obtain the concentration of the formaldehyde in the standard sample, and calculating to obtain the standard recovery rate of the sample of 93.3-100.3% and the relative standard deviation of 3.3-5.7%.
The detection accuracy of the established SERS analysis method is verified by High Performance Liquid Chromatography (HPLC). 5mL of pretreated reservoir water was added to 5mL of 3 mg/mL -1 2, 4-dinitrophenylhydrazine solution, and incubating for 1h at 60 ℃. Then, the mixture was passed through a 0.22 μm microporous membrane and the filtrate was subjected to HPLC. The HPLC apparatus was equipped with a diode array detector (Shimadzu corporation, Japan) having a detection wavelength of 360nm, and the column selected was a Diamonsil C18 column (250 mm. times.4.6 mm, 5 μm). The mobile phase adopts 0.1 percent trifluoroacetic acid (A) -acetonitrile (B) and adopts gradient elution, and the elution conditions are as follows: 0-5 min: mobile phase B from 30% literTo 70%; 5-10 min: mobile phase B rose from 70% to 80%; 10-12 min: mobile phase B decreased from 80% to 30%; 12-17 min: mobile phase B was maintained at 30%; the flow rate was 1.0mL/min and the amount of sample was 20. mu.L. HPLC detection shows that the concentration of formaldehyde in the lake water sample is 186.4 (+ -1.7) mu g.L -1 The relative deviation from the SERS analysis method is 6.9%, and the reliability of the analysis method is proved.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A method of making a solid state surface enhanced raman scattering substrate, the method comprising:
(1) preparing a perovskite-like nano material: mixing a lead nitrate solution and a bismuth nitrate solution, adding ethylene glycol and ionic liquid 1-hexadecyl-3-methylimidazolium bromide, uniformly mixing, reacting at the temperature of 120-160 ℃ for 18-30h, washing, and drying to obtain the perovskite-like nano material;
(2) preparing a gold-silver nano alloy modified perovskite-like composite material: dispersing the perovskite-like nano material prepared in the step (1) into water, performing ultrasonic dispersion, heating to boil, adding chloroauric acid and silver nitrate solution, continuing heating for 5-20min, adding sodium citrate solution, keeping the boiling state for 15-30min, cooling, washing and drying to obtain the gold-silver nano alloy modified perovskite-like composite material;
(3) preparing a solid surface enhanced Raman scattering substrate: preparing the gold-silver nano alloy modified perovskite-like composite material prepared in the step (2) into the perovskite-like composite material with the concentration of 1.0-3.0mg mL -1 The dispersion liquid is filtered on the surface of qualitative filter paper, and then the solid surface enhanced Raman scattering substrate can be obtained.
2. The preparation method according to claim 1, wherein in the step (1), the molar ratio of the lead nitrate to the bismuth nitrate is 1-2: 1 to 2.
3. The method according to claim 1, wherein in the step (1), the molar ratio of the lead nitrate to the 1-hexadecyl-3-methylimidazolium bromide is: 1-2: 1 to 2.
4. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the chloroauric acid to the silver nitrate is 1-2: 1, the mass ratio of silver nitrate to the perovskite-like nano material is 1: 8-16.
5. The preparation method according to claim 4, wherein in the step (2), the mass ratio of the sodium citrate to the perovskite-like nanomaterial is 1.24:1 to 1.24: 2.
6. The solid surface-enhanced Raman scattering substrate prepared by the preparation method according to any one of claims 1 to 5.
7. A quantitative detection method for formaldehyde in a water environment is characterized by comprising the following steps:
step S01: preparing formaldehyde standard solutions with different concentrations, detecting by using the solid surface enhanced Raman scattering substrate of claim 6, and drawing a standard curve according to the peak value of the characteristic Raman shift position of the obtained formaldehyde with different concentrations and the concentration of the formaldehyde standard solution;
step S02: the solid-state surface-enhanced Raman scattering substrate of claim 6 is adopted to detect a pretreated water sample, and the peak value of the obtained characteristic Raman shift position is compared with the standard curve to obtain the concentration of formaldehyde in the water sample.
8. The quantitative determination method of claim 7, wherein the pretreatment of the water sample comprises natural sedimentation, centrifugation, and membrane filtration.
9. The quantitative determination method according to claim 8, wherein the standard formaldehyde solution or water sample is subjected to derivatization before the detection on the solid-state surface enhanced Raman scattering substrate, and specifically comprises: adding a 4-amino-5-hydrazino-3-mercapto-1, 2, 4-triazole solution and a sodium hydroxide solution into a formaldehyde-containing solution, and then incubating for 10-60 min.
10. The application of the quantitative detection method according to any one of claims 7 to 9 in the environmental field.
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