CN108828047A - A method of detection Mercury in Water Body ion - Google Patents
A method of detection Mercury in Water Body ion Download PDFInfo
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- CN108828047A CN108828047A CN201810704778.9A CN201810704778A CN108828047A CN 108828047 A CN108828047 A CN 108828047A CN 201810704778 A CN201810704778 A CN 201810704778A CN 108828047 A CN108828047 A CN 108828047A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
Abstract
The present invention provides a kind of method for detecting Mercury in Water Body ion, includes the following steps：(1) seed mediated growth method prepares gold nanorods solution；(2) centrifugal purification；(3) it is scattered in 0.1mol/L cetyl trimethylammonium bromide solution, obtains gold nanorods working solution；(4) prepare liquid is added and obtains gold nanorods solution to be etched；(5) etching liquid is added, obtains final solution after constant temperature etching；(6) cooling；(7) λ of spectral measurement final solution and gold nanorods working solutionxAnd λ0；Relative wavelength is displaced λr=(λ0‑λx)/λ0；(8) serial mercury ion standard solution is measured, standard working curve is drawn；(9) λ of sample solutionr, its mercury ion content is calculated by standard working curve.Since measurement mechanism is the protection formed the mercury ion easily restored after amalgam to nanometer rods etching, provided method choice height, strong antijamming capability, the range of linearity are wide.
Description
Technical field
The invention belongs to analytical chemistry fields, are related to a kind of method for detecting Mercury in Water Body.
Background technique
Mercury ion (Hg2+) there is teratogenesis, carcinogenesis, it is accumulative toxicant, it is serious to human health damage.Common mercury
Ion detection method has atomic absorption spectrography (AAS), inductively coupled plasma mass spectrometry, atomic fluorescence spectrometry etc., these methods
The advantages of be that accuracy is relatively high, the disadvantage is that all relying on large-scale instrument, cost is relatively high, needs skilled operator, pre- to locate
The cumbersome time-consuming of reason process, is not able to satisfy the needs of high efficiency, low cost in environmental monitoring.Gold nano-material is due to there is very strong surface
Local plasmon resonance body absorbs, molar extinction coefficient 3~4 orders of magnitude bigger than general dyestuff, and the wave of this absorption
The property of the long size for depending on gold nano-material, shape and the environment locating for it, therefore, based on gold nano-material color
Variation has been used for establishing super sensitivity detection method.
Gold nanorods are the gold nanoparticles of longitudinal elongation, and there are two surface plasmon absorption peaks for tool, right respectively
It should be in horizontal and vertical absorption band.Surfactant hexadecane is usually added into during seed mediated growth method synthesis gold nanorods
Base trimethylammonium bromide (CTAB) is used as shape inducer.Since CTAB has higher accumulation close along the side of gold nanorods
Degree, so that its both ends is relatively exposed.
Schopf et al. report it is a kind of detection based on gold nanorods detection mercury ion method (Carola Schopf,
Alfonso Mart í n, Daniela Iacopino, Science and Technology of Advanced Materials,
2017,18:1,60-67).It is 3.0 gold nanorods that this method, which first synthesizes draw ratio, is then fixed in the sheet glass of silanization
On, when measurement, Hg will be contained2+Sample solution and excessive NaBH4Reaction is allowed to restore, Elemental Mercury and gold nanorods exposed end
Gold on face forms amalgam, causes gold nanorods to shorten, longitudinal local surface plasma resonance absorption peak (L- in spectrum
LSPR blue shift) occurs, it, can be with spectroscopic methodology due in a linear relationship in a certain range between blue shift amount and the concentration of mercury ion
Realize the quantitative analysis of ion concentration of mercury.There are two disadvantages for this method：1. the coexisting ion Cd in sample2+、Pb2+、Ni2+、Mn2+
And Cu2+The detection generation of mercury ion is significantly interfered with.2. the range of linearity is not wide enough, the linearly interval of document report is 10~
100nmol/L, the range of linearity are 10 times.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of strong antijamming capability, the range of linearity wide Mercury in Water Body ion
Concentration measuring method.Inventors have found that a certain concentration mercury ion restores shape by the ascorbic acid of gold nanorods adsorption in situ
The etching liquid being made of hydrogen peroxide, iodide ion and hydrochloric acid can be prevented to the etching of nanometer rods at after gold amalgam, make its L-LSPR
Wavelength blue shift degree reduces, and in certain concentration range, and the concentration and L-LSPR wavelength blue shift degree of mercury ion are in line
Sexual intercourse.In view of this, including the following steps this application provides a kind of method for detecting Mercury in Water Body ion：
(1) gold nanorods solution is prepared using seed mediated growth method, which is centrifuged, removed water phase, obtain gold nanorods；
(2) it disperses the gold nanorods that step (1) obtains in deionized water, is centrifuged, remove water phase, the dispersion-centrifugation-
Removal step is repeated 2 times, and obtains purifying gold nanorods；
(3) 0.1mol/L cetyl trimethylammonium bromide solution is dispersed by the purifying gold nanorods that step (2) obtains
In, obtain gold nanorods working solution；
(4) solution X is added in the gold nanorods working solution that step (3) obtains, and be vortexed after concussion mixing, obtained
Gold nanorods solution to be etched；The solution X is standard solution or water body example solution；
(5) etching liquid is added into the gold nanorods solution to be etched that step (4) obtains, mixes, is carved at a constant temperature
After erosion reaction, final solution is obtained；
(6) final solution obtained in step (5) is cooling；
(7) spectral measurement：With the L-LSPR wavelength X for the final solution that spectral measurement device measuring process (6) obtainsx；With
The L-LSPR wavelength X for the gold nanorods working solution that spectral measurement device measuring process (3) obtains0；Calculate relative wavelength displacement
λr, λr=(λ0-λx)/λ0；
(8) standard working curve of mercury ion detecting is established：Solution X described in step (4) be containing gradient concentration mercury from
The series standard solution of son, successively executes step (4)~(7) to each solution, obtains corresponding relative wavelength displacement
λr；Using ion concentration of mercury as abscissa, with λrFor ordinate, the standard working curve of mercury ion is drawn；
(9) concentration of mercury ion in water body example solution is measured：Solution X described in step (4) is water body example solution, right
The sample solution successively executes step (4)~(7), obtains the corresponding relative wavelength displacement λ of the sample solutionr, the λ that will obtainr?
It is compared on the standard working curve that step (8) obtains, mercury ion content in water body example solution is calculated.
Wherein, the gold nanorods solution can be prepared by any seed mediated growth method, it is preferred that gold nanorods obtained are molten
Contain ascorbic acid in liquid.
Preferably, the draw ratio of the purifying gold nanorods is 3.5~5.0.
Preferably, the concentration of gold nanorods is 2.0 × 10 in the gold nanorods working solution-9~1.0 × 10-8mol/
L。
Preferably, the incorporation time of vortex concussion described in step (4) is 5~20s.
Gold nanorods surface when ion concentration of mercury is greater than 0 in the solution X, in the gold nanorods solution to be etched
Contain amalgam.
Preferably, the etching liquid include 100~350mmol/L hydrogen peroxide, 0.2~0.7mmol/L sodium iodide, 0.1
~0.6mmol/L hydrochloric acid.
Preferably, the thermostat temperature in step (5) is 30~60 DEG C.
Preferably, the etching reaction time in step (5) is 6~80min.
Preferably, the final solution cooling time in step (6) is 2~4min.
Since method provided by the invention is not required to additionally incorporate excessive reductant in measurement process, but lean on gold nanorods
The ascorbic acid of adsorption is as reducing agent, more because of oxidation-reduction pair Hg2+/Hg0Current potential it is very high, than common interference
Ion is easier that reduction reaction occurs, and therefore, method choice provided by the invention is good, strong antijamming capability.Secondly, of the invention
The measurement method of offer is the inhibition etched based on gold amalgam to gold nanorods, rather than based on the thickness for generating gold amalgam
Degree, because the range of linearity of the method is wide, reaches 100 times, can be simultaneously to the Hg in Drinking Water and army's wartime drinking water2+Contain
Amount is detected.
Detailed description of the invention
The transmission electron microscope figure for the gold nanorods that Fig. 1 embodiment of the present invention 1 provides
The abosrption spectrogram for the gold nanorods that Fig. 2 embodiment of the present invention 1 provides
Influence of the various concentration mercury ion that Fig. 3 embodiment of the present invention 2 provides to etching
The concentration (μm ol/L) of the corresponding mercury ion of spectrum 1~10 in figure:1,0；2,0.01；3,0.05；4,0.2；5,0.4；
6,0.6；7,0.8；8,1.0；9,1.2；10,1.4.
The mercury ion linear relationship chart that Fig. 4 embodiment of the present invention 2 provides
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The present invention provides a kind of method for detecting Mercury in Water Body ion, includes the following steps：
(1) gold nanorods solution is prepared using seed mediated growth method, which is centrifuged, removed water phase, obtain gold nanorods；
(2) it disperses the gold nanorods that step (1) obtains in deionized water, is centrifuged, remove water phase, the dispersion-centrifugation-
Removal step is repeated 2 times, and obtains purifying gold nanorods；
(3) 0.1mol/L cetyl trimethylammonium bromide solution is dispersed by the purifying gold nanorods that step (2) obtains
In, obtain gold nanorods working solution；
(4) solution X is added in the gold nanorods working solution that step (3) obtains, and be vortexed after concussion mixing, obtained
Gold nanorods solution to be etched；The solution X is standard solution or water body example solution；
(5) etching liquid is added into the gold nanorods solution to be etched that step (4) obtains, mixes, is carved at a constant temperature
After erosion reaction, final solution is obtained；
(6) final solution obtained in step (5) is cooling；
(7) spectral measurement：With the L-LSPR wavelength X for the final solution that spectral measurement device measuring process (6) obtainsx；With
The L-LSPR wavelength X for the gold nanorods working solution that spectral measurement device measuring process (3) obtains0；Calculate relative wavelength displacement
λr, λr=(λ0-λx)/λ0；
(8) standard working curve of mercury ion detecting is established：Solution X described in step (4) be containing gradient concentration mercury from
The series standard solution of son, successively executes step (4)~(7) to each solution, obtains corresponding relative wavelength displacement
λr；Using ion concentration of mercury as abscissa, with λrFor ordinate, the standard working curve of mercury ion is drawn；
(9) concentration of mercury ion in water body example solution is measured：Solution X described in step (4) is water body example solution, right
The sample solution successively executes step (4)~(7), obtains the corresponding relative wavelength displacement λ of the sample solutionr, the λ that will obtainr?
It is compared on the standard working curve that step (8) obtains, mercury ion content in water body example solution is calculated.
Known to professional and technical personnel in the field, reduction occurs for mercury ion anti-under the effect of excessive reducing agent in solution
Mercury simple substance should be generated, two end faces that mercury simple substance is deposited on gold nanorods generate gold amalgam, so that the length of gold nanorods be made to subtract
It is small, make its L-LSPR that blue shift occur.Establishing standard curve according to the relationship between the concentration and blue shift amount of mercury ion in solution can
The mercury ion content in sample is detected with realizing.
The inventors of the present application found that the gold amalgam that gold nanorods both ends generate is in the etching containing hydrogen peroxide and iodide ion
The etching of gold nanorods can be prevented in liquid, and the concentration of ability and mercury ion is prevented to be positively correlated.Preferably, it makes
When containing ascorbic acid in standby gold nanorods solution, nanorod surfaces will be adsorbed with ascorbic acid, contact when with mercury ion
Afterwards, in-situ reducing reaction occurs to form gold amalgam in nanometer plane rod end.Preferably, when the reaction time is 5-20s
Stable gold amalgam can be formed.Preferably, the etching liquid include 100~350mmol/L hydrogen peroxide, 0.2~
0.7mmol/L sodium iodide when 0.1~0.6mmol/L hydrochloric acid, can etch gold nanorods, and the amalgam on surface can prevent gold
Etching reaction.Preferably, the draw ratio for purifying gold nanorods is 3.5~5.0, and concentration is 2.0 × 10-9~1.0 × 10-8When mol/L, precise measurement can be carried out by central wavelength of the commercialization ultraviolet-visible spectrometer to its peak L-LSPR.
Under room temperature, etching liquid of the present invention does not generate significant etching reaction, temperature higher quarter to gold nanorods
Erosion speed is faster, and required time is also shorter.Preferred etching temperature is 30~60 DEG C；Preferred etch period is 6~80min；
After the completion of etching, preferred cooling scheme is low temperature water-bath, and preferred cooling time is 2~4min.When practical operation, as long as protecting
Demonstrate,proving cooling time is any one definite value in 2~4min, so that it may the result reappeared.
Professional and technical personnel in the field know that Concentration Testing limit and the sample solution volume of method are in inverse ratio altogether.The present invention draws
Comparative example document (Carola Schopf, Alfonso Mart í n, Daniela Iacopino, Science and
Technology of Advanced Materials, 2017,18:1,60-67) in, under quantitative when sample volume is 10mL
0.01 μm of ol/L is limited to be defined although comparative example document does not provide detection limit information according to analytical chemistry field, it is quantitative
Lower limit is defined as 10 times of noises, and detection limit is defined as 3 times of noises, and therefore, lower limit of quantitation can reflect detection limit indirectly.This Shen
Lower limit of quantitation when sample volume is 50 μ L in embodiment please is also 0.01 μm of ol/L, it is seen that for side provided by the invention
Method, if detection limit can be further decreased by increasing sample volume.But anti-interference ability (using tolerance as index) and line
Property range is the inwardness of method itself, does not have positive connection with the quality or volume of sample.One analysis method it is practical
Property, it is not only in that whether it is sensitive, it is often more important that it can be applied to actual sample, therefore, in the index of comparative approach
When, anti-interference ability and the range of linearity are evaluated emphatically.
For a further understanding of the present invention, the present invention is described in detail with reference to the accompanying drawings and examples：
The present invention all glasswares used in the following embodiment pass through chloroazotic acid immersion, and thoroughly clear with deionized water
It is dried after washing.
Embodiment 1
The synthesis and characterization of the present embodiment progress gold nanorods.
The synthesis of 1.1 gold medal kinds：A 25mL is added in 5mL 0.1mol/L CTAB and 25 μ L 50mmol/L gold chlorides to burn
In bottle, mixture 5min is stirred, the sodium borohydride solution that 300 μ L 10mmol/L are newly prepared is added into mixture, stirs 25s,
Solution colour switchs to dark brown from brown color, shows to be formed gold kind, golden kind of solution obtained is stored in standby in 27~30 DEG C of environment
With.
The preparation of 1.2 growth-promoting medias：200 μ L 1mol/L hydrochloric acid and 100 μ L 50mmol/L gold chlorides are added to 10mL
In 0.1mol/L CTAB solution, by the silver nitrate solution and 100 μ L of 120 μ L 10mmol/L after stirring 5min mixing
The ascorbic acid of 100mmol/L is added sequentially in said mixture, and growth-promoting media is obtained after mixing.
The preparation of 1.3 gold nanorods：It will be prepared in gold seeds solution-injecting step 1.2 obtained in 24 μ L steps 1.1
Growth-promoting media in, be vigorously stirred be placed within 6~8 seconds under 30 DEG C of constant temperatures stand for 24 hours be made gold nanorods solution.
After the gold nanorods solution prepared in step 1.3 is centrifuged 15min under 10000 revs/min of revolving speed, supernatant is removed
Liquid disperses gold nanorods with deionized water again, and centrifugation removes water phase；This dispersion-centrifugation-removal water phase obtains after being repeated 2 times
Purify gold nanorods；It disperses purifying gold nanorods in 10mL 0.1mmol/L CTAB and obtains gold nanorods working solution, gold
The concentration of nanometer rods is 3.38nmol/L, and solution saves backup at 4 DEG C.
Transmission electron microscope (TF20, FEI Tecnai, Oregon, USA) analyzes the gold in gold nanorods working solution
Nanometer rods show that its length is about 40nm, and diameter is about 10nm, and draw ratio is about 4.0 (Fig. 1).Spectrum analysis (UV-2450,
Shimadzu Corporation, Kyoto, Japan) show that synthesized gold nanorods have one at 520nm and 840nm respectively
Weak absorbing peak and a strong absworption peak (Fig. 2), this two absorption peaks respectively correspond the T-LSPR and L-LSPR of gold nanorods.
Embodiment 2
The present embodiment investigates the range of linearity of institute's providing method measurement mercury ion content.
Gold nanorods working solution in the present embodiment is made for embodiment 1, and the present embodiment etching liquid is by 200mmol/L mistake
Hydrogen oxide, 0.4mmol/L sodium iodide and 0.4mmol/L hydrochloric acid composition.Prepare series of concentrations be 0.01~1.4 μm of ol/L mercury from
The deionized water standard solution of son, the mercury ion standard solution of each concentration measure according to the following steps：
50 μ L standard solution are added in 200 μ L gold nanorods working solutions, is vortexed after concussion 10s, obtains to be etched
Gold nanorods solution；
20 μ L etching liquids are added into gold nanorods solution to be etched, mix, are performed etching in 50 DEG C of waters bath with thermostatic control anti-
After answering 10min, final solution is obtained；
Final solution is put into the cooling 3min of 0 DEG C of ice-water bath；
It is measured with spectral measurement device (UV-2450, Shimadzu Corporation, Kyoto, Japan) after cooling
The L-LSPR wavelength X of final solutionxThe L-LSPR wavelength X of (Fig. 3) and gold nanorods working solution0；Calculate relative wavelength displacement
λr, λr=(λ0-λx)/λ0；
After above-mentioned series standard solution is measured, using ion concentration of mercury as abscissa, with corresponding λrIt is sat to be vertical
Mark, draws the standard working curve (Fig. 4) of mercury ion.Standard working curve Fig. 4 explanation, λr(being indicated in linear relationship with y)
(being equivalent to 0.002~0.2mg/L of mass concentration) between 0.01~1 μm of ol/L with ion concentration of mercury (x, unit μm ol/L) is in
Linear relationship, linear equation y=-0.2436x+0.2419；Coefficient R 2=0.9915.Illustrate measurement provided by the invention
Method has good linear relationship when the range of linearity is 100 times, and wider than the range of linearity of comparative example times.
Embodiment 3
The present embodiment investigates the selectivity of institute's providing method, i.e. anti-interference ability.
Gold nanorods working solution in the present embodiment is made for embodiment 1, and the present embodiment etching liquid is by 350mmol/L mistake
Hydrogen oxide, 0.7mmol/L sodium iodide and 0.6mmol/L hydrochloric acid composition.
In this experiment, Hg2+Concentration is 50nmol/L, chooses transition metal ions and heavy metal ion common in water and makees
For interfering ion, including：Zn2+,Cd2+,Co2+,Ni2+,Mn2+,Pb2+,Fe2+,Cr3+And Cu2+, the concentration of every kind of interfering ion is
Hg2+100 times of concentration, i.e. 5 μm of ol/L；Above-mentioned every kind of ion individually prepares a solution.It is every portion solion all in accordance with
Lower step measurement：
50 μ L solions are added in 200 μ L gold nanorods working solutions, are vortexed after concussion 5s, metal@gold is obtained
The solution of nanometer rods；
20 μ L etching liquids are added into metal@gold nanorods solution, mixes, performs etching reaction in 30 DEG C of waters bath with thermostatic control
After 70min, final solution is obtained；
Final solution is put into the cooling 2min of 0 DEG C of ice-water bath；
It is measured with spectral measurement device (UV-2450, Shimadzu Corporation, Kyoto, Japan) after cooling
The L-LSPR wavelength X of final solutionxWith the L-LSPR wavelength X of gold nanorods working solution0；It calculates relative wavelength and is displaced λr, λr=
(λ0-λx)/λ0；Above-mentioned every kind of solion is measured in parallel 3 times.
Tolerance (tolerance ratio) of the method to disturbance ion of the measurement mercury ion is calculated, herein, is held
Degree of bearing is defined as fixed ion concentration of mercury, when the presence of interfering ion makes mercury ion measurement result generate 10% relative deviation, does
Disturb the concentration of ion and the ratio of ion concentration of mercury.Acquired results such as following table：
The tolerance of 1 method of table assesses (n=3)
As can be seen from Table 1, method provided by the invention is than comparative example (Carola Schopf, Alfonso Mart
í n, Daniela Iacopino, Science and Technology of Advanced Materials, 2017,18:1,
60-67) have higher tolerance to interfering ion, for comparative example report ion, the tolerance of this method be its 24.7~
297.3 times, it is meant that this method has better choice.
Embodiment 4
The feasibility of method measurement Mercury in Water Body ion provided by the invention is investigated, and is compared to each other with comparative example.Herein
Water body example solution is mark-on tap water.
About the content of Mercury in Drinking Water ion, the mark-on sample that the application prepares is referring to two standards.(a) referring to the U.S.
Suggestion (U.S.Environmental Protection Agency, the 2016.National Primary of environmental protection association
Drinking Water Regulations), the Hg in drinking water2+、Pb2+And Cd2+Concentration be respectively be no more than 0.002,
0.015 and 0.005mg/L；(b) reference《HYGIENIC STANDARD OF DRINKING WATER FOR ARMY IN WARTIME》(People's Republic of China's National Military Standard,
GJB651-89), in 7 days drinking water heavy metals ion Limited Doses, Hg2+、Pb2+And Cd2+Concentration is respectively to be no more than
0.1,2 and 1mg/L, the Limited Doses of heavy metals ion, Hg in 90 days drinking water2+、Pb2+And Cd2+Concentration is respectively to be no more than
0.01,0.2 and 0.1mg/L.
According to above-mentioned standard, the present embodiment prepares 4 kinds of water body example solution, respectively：(1) laboratory tap water；(2) add
Mark Hg2+、Pb2+And Cd2+Concentration is respectively the laboratory tap water of 0.002,0.015 and 0.005mg/L；(3) mark-on Hg2+、Pb2+
And Cd2+Concentration is respectively the laboratory tap water of 0.01,0.2 and 0.1mg/L；(4) mark-on Hg2+、Pb2+And Cd2+Concentration is respectively
0.1, the laboratory tap water of 2 and 1mg/L.
4.1 using mercury ion content in the method measurement water body example of comparative example
It is carried out according to the experimental procedure of comparative example, for the reagent and equipment of several brands involved in its experiment, if state
It is interior to buy, it is substituted using the reagent or equipment of the same race or higher quality that professional and technical personnel in the field approve.
4.1.1 gold nanorods are synthesized
The nanometer rods for being 3.0 according to the synthesis draw ratio of method described in comparative example, are scattered in the CTAB of 0.1mmol/L.
4.1.2 gold nanorods are fixed on glass slide
By glass slide (sailing boat, Taizhou Min Jian medical equipment Co., Ltd, Jiangsu Province) respectively in acetone and deionized water
Be cleaned by ultrasonic 10min, be dried with nitrogen after being washed with deionized water, then with the oxygen gas plasma of 50W (Shanghai pavilion instrument instrument,
Shanghai City) processing 5min, then immerse 3%3- aminopropyltriethoxywerene werene (APTES):It is reacted in methanol (MeOH) solution
30min.Glass slide is cleaned 2 times with methanol and deionized water after removing unreacted silylating reagent APTES respectively, is put into baking
Make the crosslinked with silicane on glass slide in case at 120 DEG C.By the nanometer rods solution coating synthesized in 100 μ L step 4.1.1 in silicon
On the glass slide of alkanisation, glass slide is rinsed to remove extra ctab surface activating agent with 40 DEG C of deionized waters.
4.1.3 standard curve is established
Prepare the deionized water standard solution for the mercury ion that series of concentrations is 0.002~0.2 μm of ol/L, each described
The mercury ion standard solution of concentration measures according to the following steps：
The glass slide for being attached with gold nanorods is immersed into 10mL 0.01mol/L NaBH410min in solution takes out and carries glass
Piece is dried with nitrogen after being rinsed 2 times with deionized water, and the absorption light of gold nanorods on glass slide is measured on ultraviolet-visual spectrometer
Spectrum, obtains the wavelength X at the peak L-LSPR0；Then, NaBH is added in the standard solution for taking 10mL to be configured4It, will be attached to 0.01mol/L
There is the glass slide of gold nanorods to immerse 10min in this solution, take out glass slide, be dried with nitrogen after being rinsed 2 times with deionized water,
With the absorption spectrum of the gold nanorods on ultraviolet-visual spectrometer measurement glass slide with gold amalgam, the wavelength at the peak L-LSPR is obtained
λ1, calculate wavelength blue shift value the Δ λ, Δ λ=λ at the corresponding peak L-LSPR of sample solution0–λ1。
After above-mentioned series standard solution is measured, using ion concentration of mercury as abscissa (x, unit nmol/L), with
Corresponding Δ λ be ordinate (y, unit nm), the method for comparative example (is equivalent to mass concentration between 5~100nmol/L
0.001~0.02mg/L) in a linear relationship, linear equation y=-0.3221x+0.2020；Coefficient R2=0.9807.This
The experimental result at place and the result in comparative example document are coincide, and the 10~100nmol/L slightly offered better than original text illustrates that the application adopts
The validity of reagent, equipment and instrument.
4.1.4 the content of mercury ion in sample is measured
The glass slide for being attached with gold nanorods is immersed into 10mL 0.01mol/L NaBH410min in solution takes out and carries glass
Piece is dried with nitrogen after being rinsed 2 times with deionized water, and the absorption light of gold nanorods on glass slide is measured on ultraviolet-visual spectrometer
Spectrum, obtains the wavelength X at the peak L-LSPR0；Then, 10mL sample solution is taken, NaBH is added4To 0.01mol/L, Jenner will be attached with
The glass slide of rice stick immerses 10min in this solution, takes out glass slide, is dried with nitrogen after being rinsed 2 times with deionized water, with it is ultraviolet can
The absorption spectrum for seeing the gold nanorods on spectrometer measurement glass slide with gold amalgam, obtains the wavelength X at the peak L-LSPR1, calculate
Wavelength blue shift value the Δ λ, Δ λ=λ at the corresponding peak L-LSPR of sample solution0–λ1.The regression equation calculation sample obtained by 4.1.3
The concentration of mercury ion in product, the result for measuring mercury ion content in 4 kinds of sample solutions are included in table 2.
Mercury ion content in 4.2 method measurement water body examples provided by the invention
The gold nanorods working solution obtained using embodiment 1；The standard curve obtained using embodiment 2；Using implementation
Method, step and the parameter of example 2 carry out the detection of mercury ion in sample solution, specifically：
For etching liquid by 200mmol/L hydrogen peroxide, 0.4mmol/L sodium iodide and 0.4mmol/L hydrochloric acid composition, described is every
One sample solution measures according to the following steps：
50 μ L sample solution are added in 200 μ L gold nanorods working solutions, is vortexed after concussion 10s, obtains to be etched
Gold nanorods solution；
20 μ L etching liquids are added into gold nanorods solution to be etched, mix, are performed etching in 50 DEG C of waters bath with thermostatic control anti-
After answering 10min, final solution is obtained；
Final solution is put into the cooling 3min of 0 DEG C of ice-water bath；
It is measured with spectral measurement device (UV-2450, Shimadzu Corporation, Kyoto, Japan) after cooling
The L-LSPR wavelength X of final solutionxWith the L-LSPR wavelength X of gold nanorods working solution0；It calculates relative wavelength and is displaced λr, λr=
(λ0-λx)/λ0.Mercury ion content in 4 kinds of water body example solution is calculated according to linear equation provided by embodiment 2, is as a result included in
Table 2.
The measurement result comparison of mercury ion in 2 actual sample solution of table
The result of table 2 illustrates that method provided by the invention may be implemented to mercury ion in water body example solution (1)~(4)
The measurement of content, the rate of recovery are 97%~110%, meet the requirement of quantitative analysis.And the method for comparative example may be implemented to water
The measurement of mercury ion content in body sample solution (1) and (2)；Due to Pb in sample (3)2+And Cd2+Concentration be respectively Hg2+It is dense
20 times and 10 times of degree, the concentration of chaff interferent alreadys exceed the tolerance of method (referring to table 1), measures relative error up to 76%；
The concentration of mercury ion is 0.1mg/L in sample solution (4), has exceeded the range of linearity of method, is unable to measure.Result above is said
Bright, the method range of linearity provided by the invention is wide, strong antijamming capability, can satisfy the Mercury in Drinking Water ion of various criterion
Detection.
Above embodiments purpose is to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that for this skill
For the professional technician in art field, without departing from the principle of the present invention, several change can also be carried out to the present invention
Into and modification, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of method for detecting Mercury in Water Body ion, includes the following steps：
(1) gold nanorods solution is prepared using seed mediated growth method, which is centrifuged, removed water phase, obtain gold nanorods；
(2) it disperses the gold nanorods that step (1) obtains in deionized water, is centrifuged, remove water phase, repeat the above steps 2 times,
Obtain purifying gold nanorods；
(3) it disperses the purifying gold nanorods that step (2) obtains in 0.1mol/L cetyl trimethylammonium bromide solution, obtains
To gold nanorods working solution；
(4) solution X is added in the gold nanorods working solution that step (3) obtains, and be vortexed after concussion mixing, obtained to be etched
Lose gold nanorods solution；The solution X is standard solution or water body example solution；
(5) etching liquid is added into the gold nanorods solution to be etched that step (4) obtains, mixes, perform etching at a constant temperature anti-
Ying Hou obtains final solution；
(6) final solution obtained in step (5) is cooling；
(7) spectral measurement：With the longitudinal local surface plasma for the final solution that spectral measurement device measuring process (6) obtains
Resonant absorption wavelengths λx；With the longitudinal local surface for the gold nanorods working solution that spectral measurement device measuring process (3) obtains
Plasmon absorption wavelength X0；It calculates relative wavelength and is displaced λr, λr=(λ0-λx)/λ0；
(8) standard working curve of mercury ion detecting is established：Solution X described in step (4) is to contain gradient concentration mercury ion
Series standard solution successively executes step (4)~(7) to each solution, obtains corresponding relative wavelength displacement λr；With
Ion concentration of mercury is abscissa, with λrFor ordinate, the standard working curve of mercury ion is drawn；
(9) concentration of mercury ion in water body example solution is measured：Solution X described in step (4) is water body example solution, to the sample
Product solution successively executes step (4)~(7), obtains the corresponding relative wavelength displacement λ of the sample solutionr, the λ that will obtainrIn step
(8) it is compared on the standard working curve obtained, mercury ion content in water body example solution is calculated.
2. the method for detection Mercury in Water Body ion according to claim 1, which is characterized in that the seed mediated growth method preparation
Gold nanorods solution in contain ascorbic acid.
3. the method for detection Mercury in Water Body ion according to claim 1, which is characterized in that the purifying gold nanorods
Draw ratio is 3.5~5.0.
4. the method for detection Mercury in Water Body ion according to claim 1, which is characterized in that the gold nanorods work is molten
The concentration of gold nanorods is 2.0 × 10 in liquid-9~1.0 × 10-8mol/L。
5. the method for detection Mercury in Water Body ion according to claim 1, it is characterised in that be vortexed shake described in step (4)
Swinging incorporation time is 5~20s.
6. it is according to claim 1 detection Mercury in Water Body ion method, which is characterized in that when in the solution X mercury from
When sub- concentration is greater than 0, amalgam is contained on the gold nanorods surface in the gold nanorods solution to be etched.
7. the method for detection Mercury in Water Body ion according to claim 1, which is characterized in that the etching liquid includes 100
~350mmol/L hydrogen peroxide, 0.2~0.7mmol/L sodium iodide, 0.1~0.6mmol/L hydrochloric acid.
8. the method for detection Mercury in Water Body ion according to claim 1, it is characterised in that the constant temperature in step (5)
Temperature is 30~60 DEG C.
9. the method for detection Mercury in Water Body ion according to claim 1, it is characterised in that the etching in step (5)
Reaction time is 6~80min.
10. it is according to claim 1 detection Mercury in Water Body ion method, it is characterised in that in step (6) it is described most
Whole solution cooling time is 2~4min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575915A (en) * | 2018-12-17 | 2019-04-05 | 鲁东大学 | A kind of method of amphiphilic polymer modified AuNPs colorimetric detection organic mercury |
| CN110044885A (en) * | 2019-04-18 | 2019-07-23 | 桂林理工大学 | One kind exempting from instrument Hg2+Quantitative detecting method |
| CN110220869A (en) * | 2019-07-17 | 2019-09-10 | 北京师范大学 | A kind of method of mercury ion in detection water |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102253006A (en) * | 2011-04-21 | 2011-11-23 | 湖南科技大学 | Rapid mercury detection method based on self-assembly of gold nanorods |
| CN107966416A (en) * | 2017-11-21 | 2018-04-27 | 中南林业科技大学 | A kind of compound gold nanorods and preparation method thereof, application |
-
2018
- 2018-07-02 CN CN201810704778.9A patent/CN108828047B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102253006A (en) * | 2011-04-21 | 2011-11-23 | 湖南科技大学 | Rapid mercury detection method based on self-assembly of gold nanorods |
| CN107966416A (en) * | 2017-11-21 | 2018-04-27 | 中南林业科技大学 | A kind of compound gold nanorods and preparation method thereof, application |
Non-Patent Citations (4)
| Title |
|---|
| CAROLA SCHOPF ET.AL: "Plasmonic detection of mercury via amalgam formation on surface-immobilized single Au nanorods", 《SCIENCE AND TECHNOLOGY OF ADVANCED MATERIALS》 * |
| LI DENG ET.AL: "Exploiting the Higher Specificity of Silver Amalgamation: Selective Detection of Mercury(II) by Forming Ag/Hg Amalgam", 《ANAL. CHEM.》 * |
| LU CHEN ET.AL: "Valence States Modulation Strategy for Picomole Level Assay of Hg2+ in Drinking and Environmental Water by Directional Self-Assembly of Gold Nanorods", 《ACS SENSORS》 * |
| MATTHEW REX ET.AL: "Pushing the Limits of Mercury Sensors with Gold Nanorods", 《ANAL. CHEM.》 * |
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| CN109575915B (en) * | 2018-12-17 | 2021-08-24 | 鲁东大学 | Method for colorimetric detection of organic mercury by using amphiphilic polymer modified AuNPs |
| CN110044885A (en) * | 2019-04-18 | 2019-07-23 | 桂林理工大学 | One kind exempting from instrument Hg2+Quantitative detecting method |
| CN110220869A (en) * | 2019-07-17 | 2019-09-10 | 北京师范大学 | A kind of method of mercury ion in detection water |
| CN113567398A (en) * | 2020-04-28 | 2021-10-29 | 南开大学 | Lead ion concentration detection method based on dark field spectrum detection technology |
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