CN104597010B - A kind of method of Pd in utilization fluorescent probe detection high activity liquid waste - Google Patents
A kind of method of Pd in utilization fluorescent probe detection high activity liquid waste Download PDFInfo
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- CN104597010B CN104597010B CN201410840665.3A CN201410840665A CN104597010B CN 104597010 B CN104597010 B CN 104597010B CN 201410840665 A CN201410840665 A CN 201410840665A CN 104597010 B CN104597010 B CN 104597010B
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Abstract
The present invention relates to a kind of method that utilization fluorescent probe detects Pd in high activity liquid waste, comprises the following steps：Water-soluble CdSe/ZnS quantum dot is adopted for fluorescent probe, spectral conditions and testing conditions that water-soluble CdSe/ZnS quantum dot determines Pd are obtained；The standard solution of Pd is prepared, according to the spectral conditions and testing conditions, the standard curve that water-soluble CdSe/ZnS quantum dot detects Pd is set up；According to the spectral conditions, testing conditions and standard curve, the concentration of Pd in high activity liquid waste is detected.The method that the present invention is provided has the advantages that simple to operate, sensitivity is high, test limit is low, selectivity good, analyze speed is fast, sampling amount is few, and is applied to acid system.
Description
Technical field
The invention belongs to Pd ion detection technical fields, and in particular to Pd in a kind of detection high activity liquid waste using fluorescent probe
Method.
Background technology
Spentnuclear fuel is an important sources of precious metal element Pd, can form its stable isotope such as in fission process104Pd
(17%),105Pd (29%),106Pd (21%),108Pd (12%),110Pd (4%), and radiosiotope107Pd (17%),
Its half-life is 6.5 × 106Year.Palladium is one kind of platinum metal, according to statistics, ends the year two thousand thirty, the platinum produced by nuclear fission
It is that metal is up to 2500～3000 tons, when the time comes, platinum metal present in nature only remains about 7000 tons.With sending out for industry
Exhibition, the demand of Metal Palladium are growing, and people come to realise the value that Metal Palladium is reclaimed from high activity liquid waste；In addition, Pd
Presence can affect the solidification of high activity liquid waste, so the content of Pd is compeled in detection spentnuclear fuel high activity liquid waste (highly active waste)
The eyebrows and eyelashes.
In high activity liquid waste, the detection method of Pd has spectrophotography, atomic absorption spectrography (AAS), ICP-MS and electrochemical method
Deng spectrophotography is simple to operate, economical, but sensitivity and precision is not high；Atomic absorption spectrography (AAS) is a kind of trace
Analytical technology, but interference factor is relatively more, such as spectral interference, chemical interference etc.；ICP-MS detection Pd have the range of linearity
The advantages of wide, precision is high, accuracy is high, but its testing cost is higher；Electrochemical method, such as cyclic voltammetry and dissolution are lied prostrate
Peace method is all applied to the detection of Pd in high activity liquid waste, but detection speed is slower, and repeatability is also undesirable.
Quantum dot is the semiconductor nano that a kind of three-dimensional dimension is limited in nanoscale, is shown as its size is little
Special quantum confined effect, skin effect, Dielectric confinement effect and quantum tunneling effect.Therefore, quantum dot has with tradition
The incomparable fluorescent characteristicss of engine dyeing material, the size Control of such as quantum dot the Absorption and emission spectra of light, with larger this
The advantages of lentor displacement, symmetrical peak shape, excitation wavelength wide ranges, light intensity height, good stability, can be widely applied to
Heavy metal ion such as Hg2+、Cu2+、Zn2+Deng detection by quantitative, but in being also only limitted to partially to the detection of these inorganic metal ions
Property environmental system.There is presently no with regard to the pertinent literature and report using Pd in quantum dots characterization Acidic High-level Liquid Waste.
The content of the invention
For the needs of reality, it is an object of the invention to provide a kind of utilization fluorescent probe detects the side of Pd in high activity liquid waste
Method, the method are simple to operate, and sensitivity is high, and test limit is low, and selectivity is good, and analyze speed is fast, and sampling amount is few, and are applied to acidity
System.
To reach object above, the technical solution used in the present invention is：In a kind of detection high activity liquid waste using fluorescent probe
The method of Pd, comprises the following steps：
Water-soluble CdSe/ZnS quantum dot is adopted for fluorescent probe, the light that water-soluble CdSe/ZnS quantum dot determines Pd is obtained
Spectral condition and testing conditions；
The standard solution of Pd is prepared, according to the spectral conditions and testing conditions, water-soluble CdSe/ZnS quantum dot is set up
The standard curve of detection Pd；
According to the spectral conditions, testing conditions and standard curve, the concentration of Pd in high activity liquid waste is detected.
Further, the spectral conditions refer to that water-soluble CdSe/ZnS quantum dot determines the optimal excitation wavelength of Pd and most
Big wavelength of transmitted light.Optimal excitation wavelength and emission maximum optical wavelength can sweep spectral method acquisition by known, herein no longer
Repeat.
Further, the testing conditions include quantum dot concentration, measurement system pH value and detection time.
Further, in testing conditions, measurement system pH value is 3；Detection time is that fluorescent probe and test sample mix
15-30min after reacting.
Further, the water-soluble CdSe/ZnS quantum dot be surface group be carboxyl CdSe/ZnS quantum dots (hereafter
Referred to as " carboxyl quantum dot ") or surface group for amino CdSe/ZnS quantum dots (hereinafter referred " amino quantum dot ").
Further, when the water-soluble CdSe/ZnS quantum dot is the CdSe/ZnS quantum dots that surface group is carboxyl
When, and when in measurement system, quantum dot concentration is 0.04-0.96mg/L for Pd concentration in 10nmol/L and test sample, add
The logarithm value and Pd of fluorescence intensity F of quantum dot after Pd ions2+Concentration c is linear, and its linear regression equations is logF
=-0.00713c+3.57 (R2=0.996).
Or, when the water-soluble CdSe/ZnS quantum dot is the CdSe/ZnS quantum dots that surface group is amino, and
When quantum dot concentration is 0.2-1.2mg/L for Pd concentration in 10nmol/L and test sample in measurement system, Pd ions are added
Fluorescence intensity F and Pd of quantum dot afterwards2+Concentration c is linear, and its linear regression equations is F=-185.5c+3286 (R2
=0.999).
The present invention has advantages below：
Firstth, this method is simple to operate, and analyze speed is fast, and sensitivity is high, and test limit is low, and lowest detection is limited to 0.04mg/
L。
Secondth, this method selectivity is high.High activity liquid waste complicated component, also has such as in addition to needing the Pd elements of detection
All multielements such as the lanthanide series such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium and copper, ruthenium, ferrum, rubidium, barium, selected by this method
CdSe/ZnS quantum dots have very high selectivity as fluorescent probe detection metal ion, only have response to only a few ion；
In addition, this method has shielding action to partial impurities ion, further improves using citric acid-sodium citrate as buffer solution
The selectivity of method.
3rd, this method suitability is good.As quantum dot is not generally acidproof, in the case of peracid, its fluorescence can occur
It is quenched entirely, therefore was either applied to living things system in the past, is still applied to environmental sample system, all under the conditions of partial neutral,
And the CdSe/ZnS quantum dot acid-proofs adopted by this method, still there is very high fluorescence strong when pH value is equal to 2 or 3
Degree, still has the good suitability in the extremely complex simulated high-level radioactive waste of system.
The method that the present invention is provided is a kind of brand-new method of Pd in detection by quantitative solution, has widened quantum dot in metal
The application in ion quantitative analyses field.
Description of the drawings
Fig. 1 is the emission spectrum schematic diagram that Pd is quenched carboxyl quantum dot fluorescence；
Fig. 2 is working curve of the present invention using carboxyl quantum dots characterization Pd；
Fig. 3 is the emission spectrum schematic diagram that Pd is quenched amino quantum dot fluorescence；
Fig. 4 is working curve of the present invention using amino quantum dots characterization Pd.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and detailed description.
Reagent in following examples can be buied from market.
Embodiment 1
The embodiment is used for method of the explanation using Pd in carboxyl quantum dots characterization simulated high-level radioactive waste.
1. the foundation of working curve
The standard solution of compound concentration 0.002g/L Pd；(quantum dot concentration is 0.25 to take 10 μ L carboxyl quantum dots of several pieces
μm ol/L), it is separately added into the 100 μ L of citric acid-sodium citrate buffer of pH=3；It is separately added into the 0.002g/ of different volumes
The standard solution of L Pd, with the nitric acid constant volume of 0.001mol/L to 250 μ L；After 15min, difference fluorescence intensity.
From from Fig. 1, the concentration of Pd is higher, then carboxyl quantum dot fluorescence intensity is lower, that is, degree is quenched bigger.
Testing result finds that Pd concentration is in the range of 0.04-0.96mg/L, and carboxyl quantum dot concentration is in measurement system
During 10nmol/L, the concentration c of the logarithm value and Pd of quantum dot fluorescence intensity F for measuring is linear.
It is bent with the standard that the concentration c mapping of the logarithm value and Pd of quantum dot fluorescence intensity F obtains carboxyl quantum dots characterization Pd
Line, its linear regression equations are logF=-0.00713c+3.57 (R2=0.996), as shown in Figure 2.
The precision and relative deviation of method are investigated again, as shown in table 1.
Table 1
2. the detection of Pd and add-back yield experiment again in simulated high-level radioactive waste
According to the concentration of coexisting ion in high activity liquid waste, 100 times are diluted, configure simulated high-level radioactive waste, each ion concentration is such as
Shown in table 2 below.
Table 2
Take 50 μ L of above-mentioned simulated high-level radioactive waste, according to testing conditions (see detection method when setting up standard curve) and obtain
Standard curve, detect simulated high-level radioactive waste in Pd concentration, parallel six times；The experiment of add-back yield, detection knot are carried out again simultaneously
Fruit is as shown in table 3
Table 3
In the present embodiment, measure Pd concentration meansigma methodss be 1.76mg/L, relative standard deviation 4%；Known analog is high
In radioactive waste liquid, the concentration of Pd is 1.918mg/L, then relative deviation is -8%；Add-back yield is 97.8%～109.1% again, explanation
In carboxyl quantum dots characterization simulated high-level radioactive waste, the accuracy of Pd is higher.
Embodiment 2
1. the foundation of working curve
The standard solution of compound concentration 0.01g/L Pd；
10 μ L amino quantum dots (quantum dot concentration is 0.25 μm of ol/L) are taken, adds the citric acid-sodium citrate of pH=3 to delay
Rush 100 μ L of solution, then be separately added into the standard solution of different volumes 0.01g/L Pd, arrived with the nitric acid constant volume of 0.001mol/L
250μL.After 15min, difference fluorescence intensity.
From from Fig. 3, the concentration of Pd is higher, and amino quantum dot fluorescence intensity is lower, that is, degree is quenched bigger.
Testing result finds that Pd concentration is in the range of 0.2～1.2mg/L, and carboxyl quantum dot concentration is in measurement system
During 10nmol/L, quantum dot fluorescence intensity F for measuring and the concentration c of Pd are linear.
The working curve of amino quantum dots characterization Pd is obtained with concentration c mapping of quantum dot fluorescence intensity F to Pd, which is linear
Regression equation is F=-185.5c+3286 (R2=0.999), as shown in Figure 4.
The precision and relative deviation of method are investigated again, it is as shown in table 4 below：
Table 4
2. add-back yield experiment again
Take the 70 μ L of simulated high-level radioactive waste for having prepared, according to testing conditions (see detection method when setting up standard curve)
And the standard curve for obtaining, detect the concentration of Pd in simulated high-level radioactive waste；The experiment of add-back yield is carried out again simultaneously, and measurement result is such as
Shown in table 5.
Table 5
In the present embodiment, measure Pd concentration be 2.075mg/L, relative standard deviation 8%；In known analog high activity liquid waste
The concentration of Pd is 1.918mg/L, then relative deviation is 8%；Add-back yield is 89%～107.8% again, illustrates amino quantum dot
Detection Pd accuracys are higher.
Above-described embodiment illustration simply to the present invention, the present invention can also be with other ad hoc fashions or other
Particular form is implemented, without departing from idea of the invention or substitutive characteristics.Therefore, from the point of view of the embodiment of description is in terms of any
It is regarded as illustrative rather than determinate.The scope of the present invention should be illustrated by appended claims, any and claim
Intention and the equivalent change of scope also should be within the scope of the present invention.
Claims (7)
1. a kind of method that utilization fluorescent probe detects Pd in high activity liquid waste, comprises the following steps：
Water-soluble CdSe/ZnS quantum dot is adopted for fluorescent probe, the spectrum bar that water-soluble CdSe/ZnS quantum dot determines Pd is obtained
Part and testing conditions, in described testing conditions, measurement system pH value is 3；
The standard solution of Pd is prepared, according to the spectral conditions and testing conditions, water-soluble CdSe/ZnS quantum dot detection is set up
The standard curve of Pd；
According to the spectral conditions, testing conditions and standard curve, the concentration of Pd in high activity liquid waste is detected.
2. the method that a kind of utilization fluorescent probe according to claim 1 detects Pd in high activity liquid waste, it is characterised in that institute
State spectral conditions and refer to that water-soluble CdSe/ZnS quantum dot determines the optimal excitation wavelength and emission maximum optical wavelength of Pd.
3. the method that a kind of utilization fluorescent probe according to claim 1 detects Pd in high activity liquid waste, it is characterised in that institute
Stating testing conditions also includes quantum dot concentration and detection time.
4. the method that a kind of utilization fluorescent probe according to claim 3 detects Pd in high activity liquid waste, it is characterised in that inspection
In survey condition, detection time be fluorescent probe and test sample mixing react after 15-30min.
5. the method for Pd in high activity liquid waste being detected according to a kind of arbitrary described utilization fluorescent probe of claim 1-4, its feature
It is that it is amino that the water-soluble CdSe/ZnS quantum dot is the CdSe/ZnS quantum dot or surface group that surface group is carboxyl
CdSe/ZnS quantum dots.
6. the method that a kind of utilization fluorescent probe according to claim 5 detects Pd in high activity liquid waste, it is characterised in that when
When water-soluble CdSe/the ZnS quantum dot is the CdSe/ZnS quantum dots that surface group is carboxyl, and quantum dot in measurement system
Concentration is Pd in 10nmol/L and test sample2+When concentration is 0.04-0.96mg/L, Pd is added2+The fluorescence of quantum dot is strong afterwards
The logarithm value and Pd of degree F2+Concentration c is linear, and its linear regression equations is logF=-0.00713c+3.57, linear to return
Return coefficient square for 0.996.
7. the method that a kind of utilization fluorescent probe according to claim 5 detects Pd in high activity liquid waste, it is characterised in that when
When water-soluble CdSe/the ZnS quantum dot is the CdSe/ZnS quantum dots that surface group is amino, and quantum dot in measurement system
Concentration is Pd in 10nmol/L and test sample2+When concentration is 0.2-1.2mg/L, Pd is added2+The fluorescence intensity of quantum dot afterwards
F and Pd2+Concentration c is linear, its linear regression equations is F=-185.5c+3286, and linear regression coeffficient square is
0.999。
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