CN104020203A - Platinum nanocluster and preparation method thereof, as well as platinum nanocluster-modified electrochemical sensor, and preparation method and application thereof - Google Patents
Platinum nanocluster and preparation method thereof, as well as platinum nanocluster-modified electrochemical sensor, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a platinum nanocluster and a preparation method thereof. The platinum nanocluster comprises glutathione, sodium borohydride and chloroplatinic acid, which form an aggregate under the coordination action of a sulphydryl group and platinum. The preparation method comprises the following steps of mixing glutathione, sodium borohydride and chloroplatinic acid in an aqueous solution, adding cetrimonium bromide, performing organic solvent extraction, and transferring a product into an aqueous phase to obtain the platinum nanocluster. The platinum nanocluster has the advantages of high stability, high dispersibility, high purity and the like. The invention also relates to a platinum nanocluster-modified electrochemical sensor, a preparation method and the application of the electrochemical sensor to the detection of hydrazine hydrate. Hydrazine hydrate is catalytically oxidized by the platinum nanocluster to generate an electrical signal, and a linear regression equation is established according to current change and hydrazine hydrate concentration; the electrochemical sensor has the advantages of high sensitivity, quick response, high detection accuracy, high anti-interference capability and the like.
Description
Technical field
The present invention relates to sensor field, be specifically related to a kind of platinum nanoclusters and preparation method, also relate to the electrochemical sensor and the preparation method and application that by platinum nanoclusters, are modified.
Background technology
Hydrazine hydrate has been widely used in the fields such as medicine, chemical industry, military affairs, space flight as a kind of important fine chemical material, and is used in all many-sides such as propellant, water treatment agent, agricultural chemicals, medicine, fuel cell, light stabilizer and Chemical Manufacture auxiliary agent.Because hydrazine hydrate is a kind of neurotoxin, excessive suction can make cell produce mutagenic effect, even carcinogenic; In human body, can generate reactive intermediate with peroxidase reaction, and cause all ill-effects, comprise infringement of DNA etc.Therefore hydrazine hydrate is in use a double-edged sword, sets up sensitive reliably, and fast and simple detection method, provides reliable technical support that tool is of great significance for hydrazine hydrate pollutes to control.
At present the assay method of liquid hydrazine hydrate is had to ultraviolet-spectrophotometric spectra method, fluorescence spectrophotometer spectroscopic methodology, Using Flow Injection Analysis, gas chromatography-each detection means coupling method, chemoluminescence method, chemical titration and electrochemical methods etc.Wherein electrochemical analysis is sensitive with its detection, easy and simple to handle and be more and more subject to people's favor.But on conventional glass-carbon electrode, the oxidation of the Direct Electrochemistry of hydrazine hydrate is subject to superpotential restriction, therefore, how to obtain a kind of simple in structure, workable, highly sensitive, antijamming capability is strong, and the electrochemical sensor of economic and practical detection hydrazine hydrate is assistant officer's problem to be solved.
In recent years, noble metal nano cluster more and more receives researchers' concern, because existing nano platinum particle basic load is in the materials such as nano material, mesoporous carbon, Graphene, carbon nano-tube, because the dispersiveness of nano platinum particle is not strong, easily produce and reunite, limit its application, and nanocluster is with respect to nano particle, its particle diameter is less, has better dispersiveness and stability, is therefore widely used in sensor.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provides a kind of good stability, the platinum nanoclusters that dispersed strong, purity is high, also the corresponding preparation method that a kind of platinum nanoclusters is provided; On this basis, a kind of electrochemical sensor of being modified by aforementioned platinum nanocluster and preparation method thereof is also provided, and the application of this electrochemical sensor in detecting hydrazine hydrate, there is highly sensitive, quick response, high measurement accuracy and compared with advantages such as strong anti-interferences.
In order to solve the problems of the technologies described above, the invention provides a kind of platinum nanoclusters, comprise glutathione, sodium borohydride, chloroplatinic acid, its GSH-PX activity provides ligand, sodium borohydride is as reductive agent, and chloroplatinic acid provides platinum element, and three forms aggregation by the coordination of sulfydryl and platinum.Glutathione is preferably 5～15: 2.24～11.2 with the molal weight ratio of sodium borohydride and chloroplatinic acid: 1.5～3.
The present invention also provides the preparation method of aforementioned platinum nanocluster, comprises the following steps:
S1: glutathione, sodium borohydride, chloroplatinic acid are mixed and obtain platinum nanoclusters runic in aqueous solution;
S2: add cetab in aforementioned platinum nanocluster runic, then carry out organic solvent extraction step, make platinum nanoclusters runic transfer in organic phase from water;
S3: separated organic phase, the platinum nanoclusters runic in organic phase is transferred to and in water, obtained platinum nanoclusters.
The concentration that adds cetab in aforementioned S2 step is 100mM.Further, aforementioned organic solvent extraction step for adding toluene and NaOH in platinum nanoclusters runic and cetab potpourri, and stirring, standing, transfers in toluene the platinum nanoclusters runic in water.
Aforementioned S3 step is for to carry out step with centrifugal separation by the platinum nanoclusters in toluene, separated aforementioned organic phase, in organic phase, add successively chloroform, water and tetramethyl-ammonium caprate, stirring, stratification, transfer in water the platinum nanoclusters runic in organic phase.Further, aforementioned tetramethyl-ammonium caprate (TMAD) is to adopt the preparation method comprise the following steps to make: by mass ratio, be that 1～2: 1～2 capric acid and Tetramethylammonium hydroxide are dissolved in and in ethanolic solution, are mixed to get tetramethyl-ammonium caprate.
As a total technical conceive, the present invention also provides a kind of electrochemical sensor, aforementioned electric chemical sensor comprises working electrode, aforementioned working electrode is preferably glass-carbon electrode, the platinum nanoclusters that the test side finishing of glass-carbon electrode has aforementioned platinum nanocluster or aforesaid preparation method to prepare.
Further, aforesaid electrochemical sensor also comprises contrast electrode and to electrode, contrast electrode is preferably saturated calomel electrode, and electrode is preferably to platinum electrode.
As a total technical conceive, the present invention also provides the preparation method of aforementioned electric chemical sensor: by glass-carbon electrode polishing, clean and dry; Then the surface of the glass-carbon electrode after polishing drips platinum nanoclusters, dry under natural conditions, and after rinsing with damping fluid, low tempertaure storage is standby.
As a total technical conceive, the present invention also provides the application in hydrazine hydrate detects of electrochemical sensor that a kind of aforesaid electrochemical sensor or front preparation method prepare, concrete detecting step is: the glass-carbon electrode that the platinum nanoclusters of take is modified is working electrode, saturated calomel electrode is that contrast electrode is, platinum electrode is to electrode, setting up three-electrode system links with electrochemical workstation, hydrazine hydrate solution is added drop-wise in the electrolytic cell of working electrode of electrochemical sensor, by linear sweep voltammetry sweep current change curve, according to hydrazine hydrate concentration and current value, set up equation of linear regression.Further, the equation of linear regression of hydrazine hydrate and current value is:
y＝(78.5996±4.7238)x+(387.6139±19.6222) (1)
In formula (1), y is current average; X is the natural logarithm of hydrazine hydrate concentration, and unit is molL
-1; Related coefficient in formula (1) is 0.9719, under detection, is limited to 5 * 10
-6m (standard deviations of 3 times of blank samples).
Further, the electrolytic solution cell detecting in electrolytic cell is the phosphate buffered solution of pH value 7.17.
Compared with prior art, the invention has the advantages that:
(1) platinum nanoclusters provided by the invention, comprise glutathione, sodium borohydride, chloroplatinic acid, the formation that wherein chloroplatinic acid is platinum nanoclusters provides the initial source of platinum, glutathione provides sulfydryl ligand, suitable glutathione can be stablized platinum nanoclusters, sodium borohydride is as reductive agent, three forms stable aggregation by the coordination of sulfydryl and platinum, there is high, dispersed strong, the stable performance of purity, electronics transmits the advantages such as performance is good, can make the good catalytic oxidation hydrazine hydrate of platinum nanoclusters, improve the detection performance of hydrazine hydrate.
(2) preparation method of platinum nanoclusters provided by the invention mixes glutathione, sodium borohydride, chloroplatinic acid and obtains initial platinum nanocluster in aqueous solution.Because initial platinum nanoclusters is unstable, easily assemble and form inhomogeneous particle.In order to improve stability and the dispersiveness of platinum nanoclusters, initial nanocluster is added in cetab, then carry out organic solvent extraction, initial platinum nanocluster carboxyl around can with cetab in CTA
+combination in organic solvent, thus initial platinum nanocluster is transferred to organic phase from water.Then again the platinum nanoclusters in organic phase is transferred in water, the tetramethyl-ammonium caprate adding provides D
-can with CTA
+rapidly combination, and staying in organic phase, enters in water with the platinum nanoclusters of carboxyl, thereby reaches separated effect, has the advantages such as easy and simple to handle, workable, equipment requirement is simple.
(3) electrochemical sensor provided by the invention, by Carboplatin electrode is carried out to platinum nanoclusters modification, has improved the sensitivity of electrochemical sensor, has highly sensitive, quick response, high measurement accuracy and compared with advantages such as strong anti-interferences.
(4) preparation method of electrochemical sensor provided by the invention, simple structure, has the wider detection range of linearity and lower detection lower limit.
(5) application of electrochemical sensor provided by the invention in detecting hydrazine hydrate, wherein the platinum nanoclusters in electrochemical sensor amplifies material and nanocatalyst as signal, can catalytic oxidation hydrazine hydrate, can be for the electrochemical signals detecting thereby produce.The present invention is by signal amplification technique and electrochemical analysis means, set up the equation of linear regression of curent change and hydrazine hydrate concentration, according to this regression equation, can carry out efficiently hydrazine hydrate concentration, measure delicately, have operation fast and convenient, be quick on the draw, the advantage such as selectivity is good, low-cost.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage.Below with reference to figure, the present invention is further detailed explanation.
Accompanying drawing explanation
The accompanying drawing that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.
Fig. 1 is the transmission electron microscope picture of the platinum cluster of the embodiment of the present invention 1.
Fig. 2 is the electrochemical sensor scanning electron microscope (SEM) photograph of the embodiment of the present invention 3.
Fig. 3 is pH value optimization figure in electrochemical sensor application.
The LSV curve map that Fig. 4 obtains for detect the hydrazine hydrate of variable concentrations by linear sweep voltammetry.
Fig. 5 is the linear regression graph of hydrazine hydrate concentration and current value.
Fig. 6 is the LSV curve map that three kinds of electrochemical sensors detect hydrazine hydrate.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
The raw material adopting in following examples and instrument are commercially available; Wherein CHI660B electro-chemical systems is purchased from Shanghai Chen Hua instrument company; The CAS of cetyl trimethyl ammonium bromide is numbered: 57-09-0; The CAS of Tetramethylammonium hydroxide is numbered: 75-59-2.
Embodiment 1
A platinum nanoclusters, comprises glutathione (GSH), sodium borohydride (NaBH
4), chloroplatinic acid (H
2ptCl
6).The NaBH that the GSH that is 50mM by 150 μ L concentration, 50 μ L concentration are 112mM
4, H that 125 μ L concentration are 20mM
2ptCl
6in aqueous solution, fully fully mix, the coordination by sulfydryl and platinum forms stable graininess aggregation.
Embodiment 1 is only the preferred embodiments of the present invention, in the present invention, and GSH, NaBH
4, H
2ptCl
6mass ratio can under arbitrary proportion, all can make the platinum nanoclusters of stable performance.In order to obtain dispersed better platinum nanoclusters, the GSH addition of 50mM can be 100～300 μ L; 112mM NaBH
4addition can be 20～100 μ L; 20mMH
2ptCl
6addition can be 75～150 μ L.
Fig. 1 is the transmission electron microscope picture of the platinum nanoclusters of embodiment 1, left figure is the projection Electronic Speculum figure of engineer's scale under 5nm, and right figure is the projection Electronic Speculum figure of engineer's scale under 20nm, and platinum nanoclusters is the graininess aggregation of 3nm left and right as can be known from Fig. 1, particle size distribution is even, good dispersion.
Embodiment 2
The preparation method of platinum nanoclusters:
S1: under the stirring condition that is 500 circles/min in stir speed (S.S.) (stir speed (S.S.) be 400～600 circle/min all can), the NaBH that the GSH that is 50mM by 150 μ L concentration, 50 μ L concentration are 112mM
4, H that 125 μ L concentration are 20mM
2ptCl
6join in 5mL ultrapure water (content of ultrapure water be 4～10mL all can); Stir and within 10 minutes, obtain initial platinum nanocluster (stir 5～20 minutes all can).
S2: the cetab that is 100mM by 5mL concentration (CTAB) joins in initial platinum nanocluster (addition of CTAB be 2～10mL all can), stirs 20s under same stirring condition; Then add the toluene of 5mL and NaOH that 15 μ L concentration are 1M to continue to stir 2min and obtain mixed solution one.By after the standing 5min of mixed solution one minute, solution layering; Originally the initial platinum nanocluster in water is transferred in organic phase.
S3: organic phase is separated from mixed solution one, and then order adds 5mL chloroform, and the tetramethyl-ammonium caprate (TMAD) of 5mL water and 5mL, stirs 2min obtain mixed solution two in stir speed (S.S.) under the stirring condition that is 500 circles/min.By after the standing 5min of mixed solution two, solution layering, the platinum nanoclusters in organic phase will be transferred in water originally, and water is separated and obtained platinum nanoclusters from mixed solution two.
In embodiment 2, tetramethyl-ammonium caprate is to adopt the preparation method who comprises the following steps to make: 1g capric acid and 1g Tetramethylammonium hydroxide are dissolved in 100mL ethanolic solution.
Meanwhile, the preparation method of tetramethyl-ammonium caprate is dissolved in 1～2g capric acid and 1～2g Tetramethylammonium hydroxide in 100～200mL ethanolic solution.
Embodiment 3
An electrochemical sensor, comprises working electrode, contrast electrode and to electrode.Wherein working electrode is glass-carbon electrode, and the test side finishing of this glass-carbon electrode has the platinum nanoclusters of embodiment 1; Contrast electrode is saturated calomel electrode, to electrode, is platinum electrode.
The preparation method of aforementioned electric chemical sensor is:
1, polishing is carried out in the surface of glass-carbon electrode, then water rinses electrode surface, then with nitric acid, acetone, water, carries out ultrasonic cleaning successively, finally with PBS damping fluid, rinses again, naturally dries.
2, the platinum nanoclusters of the embodiment of 20 μ L 1 (concentration is 225 μ M) is directly added drop-wise to processed good glass-carbon electrode surface (platinum nanoclusters addition can also be 10～30 μ L), reacting drying obtains the glass-carbon electrode that platinum nanoclusters is modified for 12 hours at 37 ℃.The glass-carbon electrode phosphate buffered solution clean surface that platinum nanoclusters is modified, dries naturally, is placed in 4 ℃ of refrigerators and saves backup.
Fig. 2 is the scanning electron microscope (SEM) photograph of the electrochemical sensor glass-carbon electrode reactive end of embodiment 3, and platinum nanoclusters is successfully fixed on glass-carbon electrode surface as can be known from Fig. 2.
The application of aforementioned electric chemical sensor in hydrazine hydrate detects:
Hydrazine hydrate solution is added drop-wise in the electrolytic cell of working electrode of electrochemical sensor, by linear sweep voltammetry, according to the content of the equation of linear regression calculated hydration hydrazine of hydrazine hydrate concentration and curent change.
In the control and observation process of above-mentioned three-electrode system, the present invention has fully investigated the hydrazine hydrate of variable concentrations and different assaying reaction conditions.
Investigation to electrolytic solution PH:
Take phosphate buffer as electrolytic solution, is 5.0 * 10 by concentration
-3the hydrazine hydrate solution of M is added drop-wise in electrolytic cell, and regulating the PH of electrolytic solution in electrolytic cell is 4.92,5.91,6.98,7.17,8.34, adopts linear sweep voltammetry to gather CV curve, and sweep speed is 50mVs
-1(CV curve is referring to Fig. 3).As can be known from Fig. 3, when the electrolytic solution PH of electrolytic cell is 7.17, current-responsive is higher.
Equation of linear regression to hydrazine hydrate concentration and curent change is investigated:
The phosphate buffered solution that the pH value of take is 7.17 is electrolytic solution, and the working electrode of the electrochemical sensor of embodiment 3 is respectively to 8 * 10 with concentration successively
-6m～5 * 10
-3the hydrazine hydrate solution reaction of M, (LSV curve is referring to Fig. 4, and the concentration that in Fig. 4, A～F represents is respectively: 0M, 5.0 * 10 to adopt linear sweep voltammetry to draw respectively the LSV curve of the hydrazine hydrate solution of each group
-5m, 1.0 * 10
-4m, 5.0 * 10
-4m, 1.0 * 10
-3m, 5.0 * 10
-3m; The concentration that G～L represents is respectively: 0M, 8.0 * 10
-6m, 1.0 * 10
-5m, 2 * 10
-5m, 3.0 * 10
-5m, 4.0 * 10
-5m).And according to the concentration of all differential pulse voltammetry curves (LSV curve) and hydrazine hydrate solution, calculate the natural logarithm relation curve of curent change and hydrazine hydrate concentration.
As can be seen from Figure 5, the equation of linear regression of hydrazine hydrate concentration and curent change is:
y＝(78.5996±4.7238)x+(387.6139±19.6222) (1)
In formula (1), y is current average; X is the natural logarithm of aimed concn, and unit is molL
-1; Related coefficient in formula (1) is 0.9719, under detection, is limited to 5 * 10
-6m (detecting lower limit according to the standard deviation calculation of 3 times of blank samples).
Platinum nanoclusters is modified to the investigation of performance of electrochemical sensors:
A: the electrochemical sensor of platinum carbon electrode not being modified;
B: the electrochemical sensor that adopts nano platinum particle to modify glass-carbon electrode reactive end;
C: the electrochemical sensor (being the electrochemical sensor of embodiment 3) that the platinum nanoclusters of employing embodiment 1 is modified glass-carbon electrode reactive end.
By the electrochemical sensor detectable concentration of a, b, c, be 5.0 * 10 respectively
-3the hydrazine hydrate solution of M, the phosphate buffered solution that the pH value of take is 7.17 is electrolytic solution, adopts linear sweep voltammetry with 50mVs
-1sweep speed is drawn respectively the LSV curve (LSV curve is referring to Fig. 6) of a, b, c, and as can be known from Fig. 6, the current-responsive of curve c is the highest, and the current-responsive of curve b takes second place, and the good catalytic activity of platinum nanoclusters to hydrazine hydrate is described.
Experimental example
In order further to verify, the electrochemical sensor of the present embodiment and the detection effect of detection method thereof now three groups of hydrazine hydrate concentration are respectively to 1 * 10
-4molL
-1, 5 * 10
-5molL-
1, 7 * 10
-5molL-
1solution to be measured splash into respectively in the electrolytic cell of working electrode, in electrolytic cell, electrolyte solution is that pH value is 7.17 phosphate buffered solution, then with the electrochemical sensor of embodiment 3, measures, and carries out recovery experiment.
Detecting step: by the three-electrode system of the electrochemical sensor access 50mL electrolytic cell of embodiment 3, and carry out Electrochemical Detection as working electrode, wherein saturated calomel electrode is as contrast electrode, platinum plate electrode is as to electrode.Adopt CHI660B electro-chemical systems to be connected with the three-electrode system in electrolytic cell simultaneously, adopt linear sweep voltammetry, according to hydrazine hydrate concentration in response current change detection testing sample.Testing result is as shown in table 1.
Table 1: the recovery the result of three groups of environmental samples
| Testing sample molL -1 | aMeasure concentration molL -1 | Recovery % |
| 1×10 -4 | 1.09×10 -4 | 109.0 |
| 5×10 -5 | 5.12×10 -5 | 103.7 |
| 7×10 -5 | 6.8×10 -5 | 97.1 |
Note: a represents the mean concentration of measuring three times.
From the testing result of table 1, can find out, the detection method of embodiment 1 is highly sensitive, and selectivity is good, can efficient, low-cost on-line measurement hydrazine hydrate concentration.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, to those skilled in the art, the present invention can have various modifications and variations.Within every the spirit and principles in the present invention, any modification of doing, be equal to replacement, improvement etc., within protection scope of the present invention all should be included in.
Claims (10)
1. a platinum nanoclusters, is characterized in that, comprises glutathione, sodium borohydride, chloroplatinic acid, and described glutathione, sodium borohydride and chloroplatinic acid form aggregation by coordination.
2. platinum nanoclusters according to claim 1, is characterized in that, described glutathione is 5～15: 2.24～11.2 with the molal weight ratio of sodium borohydride and chloroplatinic acid: 1.5～3.
3. a preparation method for platinum nanoclusters described in any one in claim 1 to 2, is characterized in that, comprises the following steps:
S1: glutathione, sodium borohydride, chloroplatinic acid are mixed and obtain platinum nanoclusters runic in aqueous solution;
S2: add cetab in described platinum nanoclusters runic, then carry out organic solvent extraction step, described platinum nanoclusters runic is transferred to organic phase from water;
S3: separated described organic phase, the platinum nanoclusters runic in organic phase is transferred to and in water, obtained platinum nanoclusters.
4. preparation method according to claim 3, is characterized in that, the concentration that adds described cetab in described S2 step is 100mM.
5. preparation method according to claim 3, it is characterized in that, described in described S2 step, organic solvent extraction step is: in described platinum nanoclusters runic and cetab potpourri, add toluene and NaOH, stirring, standing, transfers in toluene the platinum nanoclusters runic in water.
6. preparation method according to claim 3, it is characterized in that, described S3 step is specially: separated described organic phase adds successively chloroform, water and tetramethyl-ammonium caprate in described organic phase, stirring, stratification, transfer in water the platinum nanoclusters runic in organic phase.
7. preparation method according to claim 6, is characterized in that, described tetramethyl-ammonium caprate is to adopt the preparation method who comprises the following steps to make: the capric acid and the Tetramethylammonium hydroxide that by mass ratio, are 1～2: 1～2 are dissolved in ethanolic solution.
8. an electrochemical sensor, comprise that one can be used as the glass-carbon electrode of working electrode in three-electrode system, it is characterized in that the test side finishing of the described glass-carbon electrode platinum nanoclusters that the preparation method described in any one prepares in platinum nanoclusters described in any one or claim 3 to 7 of having the right in requirement 1 to 2.
9. a preparation method for electrochemical sensor in claim 8, is characterized in that: comprise the following steps: glass-carbon electrode is carried out to polishing; Then on the glass-carbon electrode surface of polishing, drip platinum nanoclusters, dry rear low tempertaure storage.
10. the application of the electrochemical sensor that described in the electrochemical sensor described in a claim 8 or a kind of claim 9, preparation method prepares in hydrazine hydrate detects, it is characterized in that, hydrazine hydrate solution is added drop-wise in the electrolytic cell of working electrode of electrochemical sensor, by linear sweep voltammetry sweep current change curve, according to hydrazine hydrate concentration and current value, set up equation of linear regression; Electrolytic solution cell in described electrolytic cell is the phosphate buffered solution of pH value 7.17; The equation of linear regression of described hydrazine hydrate concentration and current value is:
y＝(78.5996±4.7238)x+(387.6139±19.6222) (1)
In formula (1), y is current average; X is the natural logarithm of hydrazine hydrate concentration, and unit is molL
-1; Related coefficient in formula (1) is 0.9719, under detection, is limited to 5 * 10
-6m.
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| CN110082329B (en) * | 2019-01-24 | 2022-03-15 | 安徽师范大学 | Bromelain-coated fluorescent platinum nanocluster and preparation method and application thereof |
| CN114740062A (en) * | 2022-02-16 | 2022-07-12 | 陕西化工研究院有限公司 | Method for detecting hydrazine by electrochemistry |
| CN114740062B (en) * | 2022-02-16 | 2024-05-14 | 陕西化工研究院有限公司 | Method for detecting hydrazine by adopting electrochemistry |
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