CN102416482B - A kind of nano-Au solution and utilize this nano-Au solution to detect Co 2+method - Google Patents

A kind of nano-Au solution and utilize this nano-Au solution to detect Co 2+method Download PDF

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CN102416482B
CN102416482B CN201110363954.5A CN201110363954A CN102416482B CN 102416482 B CN102416482 B CN 102416482B CN 201110363954 A CN201110363954 A CN 201110363954A CN 102416482 B CN102416482 B CN 102416482B
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冷玉敏
吴爱国
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention discloses a kind of nano-Au solution and utilize this nano-Au solution to detect Co 2+method, this nano-Au solution is for golden nanometer particle is originated with golden salt, take quaternary ammonium salt as surfactant, ion cluster containing element sulphur and carbon oxygen groups (O=C=O) is part, sodium borohydride, potassium borohydride or ascorbic acid are reducing agent, deionized water is synthetic medium, make to modify to nm of gold surface containing the ion cluster of element sulphur and carbon oxygen groups (O=C=O) by golden sulfide linkage (Au-S) effect, the water miscible functionalized nano gold solution obtained, has Co micro-in water solution system 2+detection rapidity, selective, sensitivity and application, therefore, it is possible in conjunction with colorimetric method for detecting micro-Co 2+, it detects solubility can lower than 8.5 × 10 -7m, its detectability even reaches 5 × 10 -10m, and detection speed fast, selective good, with low cost, be easy to carry, be a kind of detection method in environmental science, inspection chemistry and the field such as analytical chemistry with broad prospect of application.

Description

A kind of nano-Au solution and utilize this nano-Au solution to detect Co 2+method
Technical field
The present invention relates to environmental science, inspection chemistry, analytical chemistry and chemistry field, particularly relate to a kind of cobalt ions (Co 2+) extreme quick colorimetric detecting and analysing delicately.
Background technology
Cobalt element is one of basic trace element needed for humans and animals.As Cobastab 12part, Co 2+the formation of hemoglobin cell can be promoted.But, excessive Co 2+enter in human or animal body and will produce toxicity.If human or animal's Long-Time Service is by Co 2+the water polluted, Co 2+will toxic and side effect be produced, make human or animal suffer from various disease, as rubescent in apocleisis, face, blood vessel dilatation, increased heart rate, anaemia, cardiomyopathy etc.Therefore Co in ambient water is measured 2+content seems very important.
At present, Co is measured 2+the instrument and equipment of content has: be electrically coupled plasma emission spectrometer (ICP), Atomic absorption (AAS) and atomic fluorescence and absorb (AFS) etc.But above-mentioned instrument price is expensive, heavy being not easy to of equipment is carried, for measuring Co 2+often there is the defects such as sample preparation steps complexity, other ion interference be serious during content.At present, cash-starved, technology is immature or condition does not possess unit or individuality cannot adopt above-mentioned expensive instrument and equipment to detect Co 2+, cause pollution sources to expand or Co 2+the ambient water of content overproof is drunk.And above-mentioned instrument and equipment heaviness is not easy to carry, can not be used for scene in real time, Co in testing environment water on the spot 2+content.In order to avoid or reduce Co 2+to the pollution that environment water causes, guarantee the health existence of human and animal, must accomplish that unit or individual can in real time and on the spot Co in testing environment water 2+content.
The colorimetric methods of employing reagent is cheap to be easy to carry, and can reach above-mentioned requirements.At present, colorimetric analysis has been applied to detecting the Co in the aqueous solution 2+content.Such as, Central China Normal University Lee sea soldier's teach problem group using function Nano Silver detects and analyzes Co 2+content (see document: Appl.Mater.Interfaces, 2(2010) 684), colorimetric detection limit reaches 7 × 10 -6m(wherein M refers to mol/L), higher than Co in China's regulation drinking water 2+the highest limit 8.5 × 10 of content -7m(is see national standard: National Standards of P.R.China(1993) GB/T14848-93).
Publication number is the detection method that the Chinese patent of CN101881734A discloses a metal ion species, it is disclosed that when metal ion is Co 2+time, detection method comprises the steps (1)-(3):
(1) in tetrachloro alloy aqueous acid, surface protectant is added: softex kw and ethyl thioglycollic acid, and reducing agent, the detection liquid of the obtained Gold nanoparticle containing surface protectant modification, namely the detection liquid of the golden nanometer particle of softex kw and ethyl thioglycollic acid modification is contained, by this detection liquid NaOH adjust ph to 10.0;
(2) two parts of identical and above-mentioned detection liquid of equivalent are provided; Do not add described two parts respectively containing the solution of described metal ion and detected solution detect isopyknic in liquid, form corresponding first mixed solution and the second mixed solution;
(3) if the second mixed solution becomes rufous, then judge in detected solution containing Co 2+; If described second mixed solution color does not change relative to the color of the first mixed solution or described second mixed solution does not change relative to described first mixed solution ultravioletvisible absorption intensity, then judge in detected solution not containing Co 2+.
And disclose and utilize the method to detect Co 2+time its detectability reach 5 × 10 -7m.But this sensitivity still remains on 10 -7the M order of magnitude, higher than Co in international regulations safe drinking water 2+allow the highest limit 6.8 × 10 of content -8m, therefore, as Co in drinking water 2+content is lower than 10 -7during the M order of magnitude, its Detection results is unsatisfactory, and detection sensitivity does not reach the standard of international regulations.
Therefore, research and develop a kind ofly have that detection sensitivity is high, detection speed is fast, Co in selective good and practical testing environment water 2+the method of content, and the method can reach lower than 8.5 × 10 -7the detection limit of M, even lower than Co in international regulations safe drinking water 2+allow the highest limit 6.8 × 10 of content -8m, will in actual applications, especially has important using value in environmental science, inspection chemistry and analytical chemistry field.
Summary of the invention
Technical purpose of the present invention is for micro-Co in above-mentioned detection water solution system 2+the state of the art, a kind of nano-Au solution is provided and utilize this nano-Au solution detect Co 2+method, the method detect Co 2+sensitivity high, its detect solubility can lower than 8.5 × 10 -7m, even reaches 5 × 10- 10m, and detection speed fast, selective good, with low cost, be easy to carry, be a kind of detection method with broad prospect of application.
In order to realize above-mentioned technical purpose, inventor is on long-term research practice basis, a kind of functionalized nano gold solution is prepared in conjunction with a large amount of experiments, ion cluster containing element sulphur and carbon oxygen groups (O=C=O) for nano Au particle is originated with golden salt, is modified at nm of gold surface by golden sulfide linkage (Au-S) and obtains by this nano-Au solution.Concrete preparation method comprises the steps:
(1) with golden salt for golden nanometer particle is originated, take quaternary ammonium salt as surfactant, sodium borohydride (NaBH 4), potassium borohydride (KBH 4) or ascorbic acid (L-Ascorbic acid) get a certain amount of golden salting liquid for reducing agent, add surfactant, after stirring, add reducing agent, obtained nm of gold mixed solution;
The molecular formula of described quaternary ammonium salt is CH 3(CH 2) mnX (CH 3) n(CH 2) p(C 6h 5) q, wherein m=7 ~ 15, n=2 or 3, p=0 or 1, q=0 or 1, X=Cl, Br, I or F;
(2) in described nm of gold mixed solution, add the compound soluble in water containing sulfydryl (-SH) and carboxyl (-COOH), then the pH value of the mixed solution obtained is adjusted to 5.0 ~ 11.0, the nano-Au solution that the ion cluster that sealing obtains after stirring containing element sulphur and carbon oxygen groups (O=C=O) is modified.
Described golden salt includes but not limited to chlorauride (AuCl 3), aurous chloride (AuCl), gold chloride (HAuCl 4), three hydration gold chloride (HAuCl 43H 2o), four hydration gold chloride (HAuCl 44H 2o), two hydration potassium chloroaurate (KAuCl 42H 2o), two hydration sodium chloraurate (NaAuCl 42H 2o) one or more in.
Described surfactant includes but not limited to softex kw (CH 3(CH 2) 15nBr (CH 3) 3), DTAC (CH 3(CH 2) 11nCl (CH 3) 3) and dodecyl benzyl dimethyl ammonium chloride (CH 3(CH 2) 11nCl (CH 3) 2cH 2c 6h 5) in one or more.
The described compound containing sulfydryl and carboxyl includes but not limited to TGA (HSCH 2cO 2h), 2 mercaptopropionic acid (HSCH 3cHCOOH), 3-mercaptopropionic acid (HSCH 2cH 2cO 2h), Cys (HSCH 2cHNH 2cO 2h, sodium thioglycolate (HSCH 2cOONa), calcium mercaptoacetate ((HSCH 2cOO) 2and thiosalicylic acid (HSC Ca) 6h 4cO 2h) one or more in.
The described ion cluster containing element sulphur and carbon oxygen groups (O=C=O) includes but not limited to [SCH 2cO 2] 2-, [SCH 3cHCO 2] 2-, [SCH 2cH 2cO 2] 2-, [SCH 2cHNH 2cO 2] 2-[SC 6h 4cO 2] 2-.
Functionalized nano gold solution provided by the invention with golden salt for golden nanometer particle is originated, take quaternary ammonium salt as surfactant, ion cluster containing element sulphur and carbon oxygen groups (O=C=O) is part, sodium borohydride, potassium borohydride or ascorbic acid are reducing agent, deionized water is synthetic medium, make to modify to nm of gold surface containing the ion cluster of element sulphur and carbon oxygen groups (O=C=O) by golden sulfide linkage (Au-S) effect, obtain water miscible functionalized nano gold solution.This functionalized nano gold solution has the following advantages:
(1) method of modifying is simple and easy to do, reproducible.Sulphur and gold element mixing, easily form golden sulfide linkage (Au-S), and this experiment and theoretical research data show that wave number corresponding to golden sulfide linkage (Au-S) stretching vibration is 278.5cm -1.The formation of gold sulfide linkage (Au-S) makes to modify to nm of gold surface containing the ion cluster of element sulphur and carbon oxygen groups (O=C=O).Containing the ion cluster of element sulphur and carbon oxygen groups (O=C=O), in the process by golden sulfide linkage (Au-S) modified nano gold, the hydration particle diameter of nm of gold and nm of gold surface Zeta electric potential changed with the modification time.
(2) can with Co 2+rapid complexing, this complex reaction completes in 1min.With ion cluster [SCH 2cO 2] 2-the nm of gold of modifying and Co 2+complexing is example, and the complexing product molecule configuration of the two, the structural stability that theoretical modeling calculates is [3AuSCH 2cO 2+ Co] -.From structural stability, the modification cluster [SCH on nm of gold surface is lured in the formation of cobalt oxygen key (Co-O) into 2cO 2] 2-with Co 2+rapid complexing, causes monodispersed ion cluster [SCH 2cO 2] 2-the nm of gold of modifying is reunited.The formation of cobalt oxygen key (Co-O) obtains the dual confirmation of experimental and theoretical computation infrared spectrum, and the stretching vibration of cobalt oxygen key (Co-O) is presented on 500cm -1about wave number.
(3) to Co 2+selective good, competitive reaction is strong.Other ion or Co relatively 2+during with other ion coexist, the nm of gold prioritizing selection that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) is modified and Co 2+complexing, makes this functional gold nanoparticles solution colour change rapidly.Therefore, this functionalized nano gold solution can be used in detecting Co fast 2+.
The invention allows for and utilize above-mentioned functions nano-Au solution to detect Co 2+method, the method utilize this functional gold nanoparticles can with Co 2+rapid complexing, to Co 2+selective good and Co 2+the RESONANCE ABSORPTION of this functional gold nanoparticles surface plasma is caused to change after complexing, make the characteristic that the color of this functionalized nano gold solution and ultravioletvisible absorption intensity, peak value change, directly by visually observing the change of solution colour or being tested the change of its absorption intensity and peak value by ultraviolet-uisible spectrophotometer, whether can detect fast in solution system containing Co 2+.Concrete detection method comprises the steps:
(1) prepare according to the preparation method of functionalized nano gold solution provided by the invention the nano-Au solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) modifies;
(2) in the nano-Au solution that step (1) is obtained, the identical detection sample of two parts of volumes is measured out; Preparation is identical with detecting aqueous solution volume and do not contain the aqueous solution solution as a comparison of cobalt ions; Portion is detected sample mix mutually with comparative solution, form the first mixed liquor, another part is detected sample and detected aqueous solution, forms the second mixed liquor;
(3) with the first mixed solution for reference, observe the color of the second mixed liquor and the first mixed liquor, if there is color change, then there is Co in the detected aqueous solution 2+if there is not color change, then there is not Co in the detected aqueous solution 2+; Or, contrast ultravioletvisible absorption intensity, the peak value of the second mixed liquor and the first mixed liquor, if its ultravioletvisible absorption intensity, peak value change, then there is Co in the detected aqueous solution 2+if do not change, then there is not Co in the detected aqueous solution 2+.
As preferably, in described step (1), after preparing the nano-Au solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) modifies, this nano-Au solution is dialysed.Experimentally find, can improve by dialysis the nano-Au solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) modifies largely and detect Co 2+sensitivity.
Water solution system Co is detected with existing disclosed 2+method compare, tool of the present invention has the following advantages:
(1) with simple experiment flow, synthesized with the water-soluble nano gold solution modified containing the ion cluster of element sulphur and carbon oxygen groups (O=C=O), and workable, common laboratory has all been had ready conditions;
(2) nm of gold of modifying containing the ion cluster of element sulphur and carbon oxygen groups (O=C=O) can very sensitive, fast, optionally detect the Co of trace in the aqueous solution 2+, there is very strong practicality.
(3) have high sensitivity, the method detects Co 2+sensitivity high, its detection limit can lower than 8.5 × 10 -7m, even reaches 5 × 10 -10m(0.03 μ g/L), lower than the limit of detection 1.7 × 10 being electrically coupled plasma emission spectrometer (ICP) -8m(1 μ g/L).
(4) have detection speed fast, selective good, with low cost, be easy to carry, therefore practicality is very strong, can be used in the fields such as environmental science, inspection chemistry and analytical chemistry, has important using value.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of functionalized nano gold solution of the present invention;
Fig. 2 (a) is the ion cluster [SCH that the present invention contains element sulphur and carbon oxygen groups (O=C=O) 2cO 2] 2-the schematic diagram of modified nano gold, and the stable geometric configuration that theoretical modeling obtains;
Fig. 2 (b) is at 250-700cm -1in wave-number range, modified outcome [AuSCH 2cO 2] -experiment and calculating simulation INFRARED SPECTRUM;
Fig. 3 (a) is that the present invention contains in the ion cluster modified nano gold process of element sulphur and carbon oxygen groups (O=C=O), and the hydration particle diameter of nm of gold is with the change of the time of modification;
Fig. 3 (b) is that the present invention contains in the ion cluster modified nano gold process of element sulphur and carbon oxygen groups (O=C=O), and nm of gold surface Zeta electric potential is with the change of the time of modification;
Fig. 4 is that functionalized nano gold solution of the present invention detects 1 × 10 -6the Co of M 2+time, the variation diagram of corresponding uv-vis spectra before detection in 30min;
Fig. 5 is the ion cluster [SCH that calculating simulation obtains 2cO 2] 2-the nm of gold of modifying and Co 2+structural stability [the 3AuSCH of complexing 2cO 2+ Co] -;
Fig. 6 is that functionalized nano gold solution of the present invention detects different content Co 2+(mass percent is: the infrared spectrum of corresponding complexing product time 0,0.09% and 0.11%), and compares analysis chart with the infrared spectrum of the complexing configuration of calculating simulation;
Fig. 7 is transmission electron microscope and the energy spectrogram that the present invention contains the nm of gold of the ion cluster modification of element sulphur and carbon oxygen groups (O=C=O);
Fig. 8 is functionalized nano gold solution detectable concentration of the present invention is 2 × 10 -5corresponding uv-vis spectra when the alkali metal of M, alkaline-earth metal and transition metal ions;
Fig. 9 is the Co that functional gold nanoparticles of the present invention detects variable concentrations 2+time corresponding colorimetric photo and uv-vis spectra.
Detailed description of the invention
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.
The functionalized nano gold solution that the present embodiment provides is the water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) is modified, its preparation technology's flow process as shown in Figure 1, be specially: get a certain amount of golden salting liquid, add quaternary cationics, such as softex kw, DTAC is or/and dodecyl benzyl dimethyl ammonium chloride, dropwise reducing agent is added after stirring, such as sodium borohydride, potassium borohydride is or/and ascorbic acid, continue to stir, then the compound soluble in water containing sulfydryl (-SH) and carboxyl (-COOH) is added, such as TGA, 2 mercaptopropionic acid, 3-mercaptopropionic acid, Cys, sodium thioglycolate, calcium mercaptoacetate is or/and thiosalicylic acid, use NaOH (NaOH), potassium hydroxide (KOH) is or/and the pH value of solution is adjusted to 5.0 ~ 11.0 by hydrochloric acid (HCl), dialysis, just the obtained nano-Au solution containing the ion cluster modification of element sulphur and carbon oxygen groups (O=C=O).
The functional gold nanoparticles of above-mentioned preparation, it is modified cluster and modifies to nm of gold surface by golden sulfide linkage (Au-S).With ion cluster [SCH 2cO 2] 2-modified nano gold is example, and its modification and corresponding INFRARED SPECTRUM characterize sees Fig. 2 respectively: (a) TGA (HSCH 2cO 2h) hydrolysis ion cluster [SCH in the solution 2cO 2] 2-, the formation of golden sulfide linkage (Au-S), impels ion cluster [SCH 2cO 2] 2-modify to nm of gold surface.(wave-number range is 250-700cm to b far infrared spectrum that the Fourier transform of () modified outcome and theoretical modeling calculate -1), the eigen vibration peak of the two coincide in the extreme.Experimental and theoretical computation analogue data shows: wave number 278.5cm -1the eigen vibration peak at place is golden sulfide linkage (Au-S) stretching vibration peak.
Prepare in the process of functionalized nano gold solution above-mentioned, use dynamic light scattering (DLS) to characterize the change with the modification reaction time of nm of gold hydration particle diameter and surperficial Zeta electric potential.Dynamic light scattering (DLS) has been proved and can have characterized the hydration particle diameter of nano particle in solution and the minor variations of Zeta electric potential well, during interaction between molecular detection and nm of gold, very responsive (Nano Lett.3(2003) 935, J.Am.Chem.Soc.130(2008) 2780, Angew.Chem.Int.Ed.48(2009) 1, Chem.Commun.47(2011) 4192, J.Immunol.Methods349(2009) 38).Containing in the ion cluster modified nano gold process of element sulphur and carbon oxygen groups (O=C=O), nm of gold hydration particle diameter and surperficial Zeta electric potential are with the change of modification reaction time, see Fig. 3 (a) and (b) respectively, can find out: nm of gold hydration particle diameter increases with the modification reaction time and increases; Electronegative because modifying cluster, make adorned nm of gold surface Zeta electric potential increase with the modification reaction time and reduce.The modification reaction time is approximately 40min, and the particle diameter of nm of gold hydration subsequently and surperficial Zeta electric potential increase with the modification reaction time and no longer change, and reach dynamic equilibrium.This DLS characterization data shows: containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O), reaching dynamic equilibrium approximately needs 40min.
Experiment one:
By the water-soluble nano gold solution containing the ion cluster modification of element sulphur and carbon oxygen groups (O=C=O) of above-mentioned preparation and containing Co 2+concentration is 1 × 10 -6the water-soluble liquid phase mixing of M, uses ultraviolet-visual spectrometer (Uv-vis) to detect the change of corresponding uv-vis spectra before detection in 30min, sees Fig. 4.Find from Fig. 4: detect in 1min, the ultraviolet and visible absorption peak of this functionalized nano gold solution obviously reduces.Ratio (the A of the absorption value that the illustration from Fig. 4: characteristic absorption wavelength 462nm and 527nm is corresponding 462/ A 527) with the change of detection time, can find out that the water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) is modified can detect Co fast 2+, detection time only needs 1min.
The water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) of above-mentioned preparation is modified can detect Co fast 2+principle Exploration, employ theoretical modeling and calculate and the mode of Experimental Characterization binding analysis.With ion cluster [SCH 2cO 2] 2-the nm of gold of modifying, is used to detect Co 2+research is example, and calculate from theoretical modeling, inventor have found the modification cluster [SCH on nm of gold surface 2cO 2] 2-, by cobalt oxygen key (Co-O) and Co 2+structural stability [the 3AuSCH of complexing 2cO 2+ Co] -, as Fig. 5.Inventor uses Gauss's software simulation to calculate structural stability [3AuSCH 2cO 2+ Co] -vibration frequency, corresponding infrared vibration spectrum is shown in Fig. 6.It is reported from theory calculate frequency number: cobalt oxygen key (Co-O) stretching vibration is presented on 500cm -1about wave number.Meanwhile, the water-soluble nano gold solution that inventor uses the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) to modify detects the Co of variable concentrations 2+(mass percent is: 0,0.09% and 0.11%), by mixed liquor freeze drying powdered, uses Fourier transformation infrared spectrometer (FT-IR) to characterize its infrared vibration spectrum, sees Fig. 5.Know from experimental data: with detected Co 2+the increase of concentration, 500cm -1cobalt oxygen key (Co-O) stretching vibration peak has been there is about wave number.Theoretical modeling calculates and the coincideing of experimental data, and the water-soluble nano gold solution described containing the ion cluster modification of element sulphur and carbon oxygen groups (O=C=O) can detect cobalt ions (Co fast 2+) reason be: the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) of nm of gold finishing, identifies Co fast by cobalt oxygen complex bonds (Co-O) 2+, cause monodispersed functional gold nanoparticles to reunite, as shown in Figure 7.Fig. 7 is transmission electron microscope and energy spectrogram: the dispersed nano gold that (a) modifies for the ion cluster that the present invention contains element sulphur and carbon oxygen groups (O=C=O); B () is Co 2+lure that (a) functional gold nanoparticles is reunited into.The color of this functionalized nano gold solution and uv-vis spectra there occurs change simultaneously, see Fig. 9.
Above-mentioned experiment and analysis show: the water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) is modified is to Co 2+metachromasia can be played fast, i.e. Co 2+can by nm of gold surface ligand, such as: [SCH 2cO 2] 2-, [SCH 3cHCO 2] 2-, [SCH 2cH 2cO 2] 2-, [SCH 2cHNH 2cO 2] 2-[SC 6h 4cO 2] 2-in carbon oxygen groups (O=C=O) identify fast, this effect causes nm of gold to reunite and variable color, and (colorimetric detection is limit and reached 5 × 10 to have very strong selective and very high sensitivity -10m), therefore this functional nano gold solution can be used in on-the-spot actual detection Co 2+.Such as, can be used for scene micro-Co in colorimetric detection ambient water fast in real time and on the spot 2+.
Experiment two:
The water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) prepared by the present embodiment is modified is for detecting 2 × 10 -5the Co of M 2+time, the change of its color and the alkali metal ion (Li detected with concentration +, Na +, K +), alkaline-earth metal ions (Mg 2+, Ca 2+, Sr 2+, Ba 2+), transition metal ions (Co 2+, Mn 2+, Fe 2+, Fe 3+, Al 3+, Ni 2+, Cu 2+, Zn 2+, Cd 2+, Cr 3+, Hg 2+, Pb 2+), do not comprise Co 2+the hybrid ionic (M of above-mentioned 18 metal ion species x-1 +=Li ++ Na ++ K ++ Mg 2++ Ca 2++ Sr 2++ Ba 2++ Mn 2++ Fe 2++ Fe 3++ Al 3++ Ni 2++ Cu 2++ Zn 2++ Cd 2++ Cr 3++ Hg 2++ Pb 2+) and comprise Co 2+at the hybrid ionic (M of interior above-mentioned 19 metal ion species x +=M x-1 ++ Co 2+) compare discovery: the color of pure function nano-Au solution relatively, only have and detect containing Co 2+functional gold nanoparticles solution colour there occurs change.
Meanwhile, use ultraviolet-visual spectrometer (Uv-vis) to characterize this functionalized nano gold solution and detect the uv-vis spectra of above-mentioned metal ion and the uv-vis spectra of pure function nano-Au solution, and obtain the ratio (A/A of corresponding ultraviolet and visible absorption peak value 0), as shown in Figure 8.Show shown in Fig. 8: detect containing 2 × 10 -5m Co 2+(comprise hybrid ionic M x +) the ultraviolet-visible absorption spectra of functionalized nano gold solution and the ratio (A/A of absorption value 0) be obviously different from the ultraviolet-visible absorption spectra of pure function nano-Au solution and the ratio (A of absorption value 0/ A 0); Detect and contain with the ultraviolet-visible absorption spectra of the functionalized nano gold solution of concentration other ion above-mentioned and the ratio (A/A of absorption value 0), the ultraviolet-visible absorption spectra of relative pure function nano-Au solution and the ratio (A of absorption value 0/ A 0), change is little.
Above-mentioned experiment shows that the water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) prepared by the present embodiment is modified detects Co 2+have well selective.
Experiment three:
What configure same volume comprises Co 2+the aqueous solution to be measured, wherein Co 2+concentration is respectively: 10 -4m, 10 -5m, 10 -6m, 10 -7m, 5 × 10 -8m, 10 -8m, 5 × 10 -9m, 10 -9m, 5 × 10 -10m and 0M; The water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) prepared by the present embodiment measuring many parts of equivalent is modified is as detection sample, detect sample by every part to mix with each water-soluble liquid phase to be measured respectively, the color change of each mixed solution as shown in Figure 9.As can be seen from Figure 9, relative Co 2+concentration is the color of the mixed solution of 0M, containing Co 2+concentration is equal to or greater than 5 × 10 -10the color of the mixed solution of M all changes.Meanwhile, ultraviolet-visual spectrometer (Uv-vis) is used to characterize the different Co of above-mentioned detection 2+the uv-vis spectra of the functionalized nano gold solution of concentration, finds the increase with detected concentration of cobalt ions, and the characteristic absorption peak of corresponding uv-vis spectra there occurs blue shift.
Above-mentioned experiment shows: the water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) prepared by the present embodiment is modified detects Co 2+there is very strong sensitivity.
Experiment four:
The application of the water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) prepared to investigate the present embodiment is modified, inventor gathers environmental water sample from Ningbo Jinhe New Materials Co., Ltd.'s blowdown, use is electrically coupled plasma emission spectrometer (ICP) and detects analysis, testing result: the environmental water sample of collection is containing Co 2+concentration is 2 × 10 -7m.
Meanwhile, deionized water preparation Co is used 2+concentration is 2 × 10 -7the standard water sample of M.The functionalized nano gold solution of the equivalent prepared by the present embodiment is respectively with the above-mentioned environmental water sample of equivalent, the standard water sample of preparation and do not comprise Co 2+deionized water press the mixing of 3:1 volume ratio, namely detected Co 2+concentration is diluted 4 times, and the concentration after dilution is 5 × 10 -8m.Find after colorimetric: relative to not comprising Co 2+mixed solution, containing identical Co 2+the environmental water sample of concentration and the color of standard liquid change, and the change of this color closely.
Above-mentioned experiment shows: the water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) prepared by the present embodiment is modified can be used in Co in colorimetric detection ambient water 2+content, has very strong application.
Below in conjunction with specific embodiment to the preparation of the water-soluble nano gold solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) is modified and to Co 2+colorimetric detection further illustrates.
Embodiment 1:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the four hydration gold chloride (HAuCl of 5mL5mM 44H 2o) solution, adds the deionized water of 95mL and the softex kw (CH of 1.5mL2M respectively 3(CH 2) 15nBr (CH 3) 3) solution, stir 20min; Then sodium borohydride (the NaBH of 1.5mL0.1M is dropwise added 4), continue to stir 20min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 50mL above-mentioned steps (1) prepares, stir, add the TGA (HSCH of 40 μ L simultaneously 2cO 2h), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 5.0, then about 40min is stirred in sealing, the nano-Au solution that the ion cluster obtaining containing element sulphur and carbon oxygen groups (O=C=O) is modified.
Adopt following methods to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and application test, specific as follows:
(1) to dialyse the above-mentioned functionalized nano gold solution prepared
Bag filter is cut into suitable length (10 ~ 20cm), is placed on containing 0.24M sodium acid carbonate (NaHCO 3) and 1M ethylenediamine tetra-acetic acid (EDTA) mixed solution in boil 10min.Naturally thoroughly clean bag filter by deionized water after cooling, be placed in 1mM ethylenediamine tetra-acetic acid (EDTA), bag filter is boiled 10min.Guarantee that bag filter is immersed in 1mM ethylenediamine tetra-acetic acid (EDTA) all the time, naturally cool.
Thoroughly bag filter is cleaned by deionized water, load the functionalized nano gold solution of above-mentioned preparation, then put it in the beaker filling deionized water and dialyse, in dialysis procedure, pass into nitrogen, obtained pure function nano-Au solution, is placed in 4 ° of C refrigerators for subsequent use after sealing.
(2) functionalized nano gold solution is to Co 2+the rapidity test detected:
Measure dialysing the functionalized nano gold solution obtained through step (1) of two parts of 3mL; 4 × 10 of a copy of it and 1mL -6m standard C o 2+solution mixes, and obtains the first mixed solution, the Co in the first mixed solution 2+by dilution 4 times, concentration is 1 × 10 -6m; Another part mixes with the deionized water of 1mL, obtains the second mixed solution.
With the second mixed solution for reference, carry out colorimetric, find that the color of two parts of mixed solutions is different;
After mixing in 30min, use UV, visible light spectrometer (Uv-vis) to test 11 UV, visible light spectrums, see Fig. 4, be the ratio (A of absorption value corresponding to absorbing wavelength 462nm and 527nm 462/ A 527) with the curve that detection time changes, see Fig. 4 illustration, find that this functionalized nano gold solution is to Co 2+detection time only need 1min.
(3) functionalized nano gold solution is to Co 2+selectivity test:
Take alkali metal containing ion (Li +, Na +, K +), alkaline-earth metal ions (Mg 2+, Ca 2+, Sr 2+, Ba 2+), transition metal ions (Co 2+, Mn 2+, Fe 2+, Fe 3+, Al 3+, Ni 2+, Cu 2+, Zn 2+, Cd 2+, Cr 3+, Hg 2+, Pb 2+) chloride, be dissolved in deionized water, compound concentration is 8 × 10 -5above-mentioned 19 metal ion species of M, the hybrid ionic (M of 18 metal ion species x-1 +, not containing Co 2+) and the hybrid ionic (M of 19 metal ion species x +=M x-1 ++ Co 2+) standard liquid.
Measure dialysing the functionalized nano gold solution obtained through step (1) of two parts of 3mL; 8 × 10 of the above-mentioned preparation of a copy of it and 1mL -5the standard metal solion mixing of M, obtain the first mixed solution, the metal ion in the first mixed solution is diluted 4 times, and concentration is 2 × 10 -6m; Another part mixes with the deionized water of 1mL, obtains the second mixed solution.
With the second mixed solution for reference, carry out colorimetric, meanwhile, use ultraviolet-visual spectrometer (Uv-vis) to characterize the uv-vis spectra of this first mixed solution and the second mixed solution, obtain the ratio (A/A of corresponding ultraviolet and visible absorption peak value 0), as shown in Figure 8, show that the obtained functionalized nano gold solution of the present embodiment is to Co 2+have well selective.
(4) functionalized nano gold solution is to Co 2+sensitivity test:
Take CoCL2 6H2O (CoCl 26H 2o), deionized water preparation Co is used 2+concentration is respectively 10 -4m, 10 -5m, 10 -6m, 10 -7m, 5 × 10 -8m, 10 -8m, 5 × 10 -9m, 10 -9m, 5 × 10 -10the standard C o of M and 0M 2+solution.
With Co 2+concentration is the mixed solution of 0M is reference, carries out colorimetric, meanwhile, uses ultraviolet-visual spectrometer (Uv-vis) to characterize functionalized nano gold solution and detects variable concentrations Co 2+uv-vis spectra, as shown in Figure 9, result shows that the obtained functional gold nanoparticles of the present embodiment detects Co 2+have fabulous sensitivity, colorimetric detection limit can reach 5 × 10 -10m.
(5) functionalized nano gold solution detects Co 2+application test:
Obtain Ningbo Jinhe New Materials Co., Ltd.'s blowdown actual environment water sample from environment measuring center, Ningbo City, use is electrically coupled plasma emission spectrometer (ICP) and carries out detection analysis, and testing result is: containing 2 × 10 in environmental water sample -7the Co of M 2+.
Use deionized water preparation containing 2 × 10 -7the Co of M 2+standard water sample.
Measure dialysing the functionalized nano gold solution obtained through step (1) of two parts of 3mL; A copy of it mixes with the above-mentioned environmental water sample of 1mL, obtains the first mixed solution; Portion mixes with the above-mentioned standard water sample of 1mL, obtains the second mixed solution; Portion mixes with the deionized water of 1mL in addition, obtains the 3rd mixed solution.Co in first mixed solution and the second mixed solution 2+concentration is diluted, and is 5 × 10 -8m.
With the 3rd mixed solution for reference, carry out colorimetric, find: containing identical cobalt ions (Co 2+) after the environmental water sample of concentration and standard water sample detected by the functionalized nano gold solution that the present embodiment obtains, color change closely, illustrates that the functional gold nanoparticles that the present embodiment obtains can be applied to micro-Co in testing environment water 2+content.
Embodiment 2:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the three hydration gold chloride (HAuCl of 5mL5mM 43H 2o) solution, adds the deionized water of 95mL and the softex kw (CH of 5mL0.04M respectively 3(CH 2) 15nBr (CH 3) 3) solution, stir 15min; Then potassium borohydride (the KBH of 2mL0.1M is dropwise added 4), continue to stir 20min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the 3-mercaptopropionic acid (HSCH of 100 μ L simultaneously 2cH 2cO 2h), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 6.0, then about 45min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 3:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the gold chloride (HAuCl of 5mL5mM 4) solution, add the deionized water of 95mL and the softex kw (CH of 1mL0.5M respectively 3(CH 2) 15nBr (CH 3) 3) solution, stir 10min; Oil bath is heated to 80 ° of C, then dropwise adds the ascorbic acid (L-Ascorbic acid) of 50mL1M, continues to add thermal agitation 5min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the Cys (HSCH of 10mL92mM simultaneously 2cHNH 2cO 2h), after being uniformly mixed, use the potassium hydroxide (KOH) of 0.2M and hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 6.68, then about 40min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 4:
In the present embodiment, functional gold nanoparticles mixed solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the chlorauride (AuCl of 5mL5mM 3) solution, add the deionized water of 95mL and the DTAC (CH of 3mL0.05M respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 5min; Then sodium borohydride (the NaBH of 1mL0.2M is dropwise added 4), continue to stir 10min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the sodium thioglycolate (HSCH of 40mL80mM simultaneously 2cOONa), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 7.4, then about 50min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 5:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the chlorauride (AuCl of 5mL5mM 3) solution, add the deionized water of 95mL and the DTAC (CH of 15mL5mM respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 25min; Then potassium borohydride (the KBH of 5mL0.1M is dropwise added 4), continue to stir 20min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the calcium mercaptoacetate ((HSCH of 10mL94mM simultaneously 2cOO) 2ca), after being uniformly mixed, use the potassium hydroxide (KOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 8.0, then about 38min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 6:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the chlorauride (AuCl of 5mL5mM 3) solution, add the deionized water of 95mL and the DTAC (CH of 8mL0.1M respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 10min; Oil bath is heated to 90 ° of C, then dropwise adds the ascorbic acid (L-Ascorbicacid) of 60mL0.8M, continues to stir 35min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the thiosalicylic acid (HSC of 10mL50mM simultaneously 6h 4cO 2h), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 8.68, then about 60min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 7:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get aurous chloride (AuCl) solution of 5mL5mM, add the deionized water of 95mL and the DTAC (CH of 10mL0.08M respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 26min; Oil bath is heated to 100 ° of C, then dropwise adds the ascorbic acid (L-Ascorbic acid) of 70mL0.65M, continues to add thermal agitation 30min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 80mL above-mentioned steps (1) prepares, stir, add the sodium thioglycolate (HSCH of 8mL15mM simultaneously 2cOONa), after being uniformly mixed, use the potassium hydroxide (KOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 9.6, then about 35min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 8:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the gold chloride (HAuCl of 5mL5mM 4) solution, add the deionized water of 95mL and the softex kw (CH of 6mL0.3M respectively 3(CH 2) 15nBr (CH 3) 3) solution, stir 3min; Oil bath is heated to 80 ° of C, then dropwise adds the ascorbic acid (L-Ascorbic acid) of 5mL10M, continues heating and stirs 35min, naturally cool, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 60mL above-mentioned steps (1) prepares, stir, add the Cys (HSCH of 20mL1.5mM simultaneously 2cHNH 2cO 2h), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 9.4, then about 40min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 9:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL5mM 42H 2o) solution, adds the deionized water of 95mL and the dodecyl benzyl dimethyl ammonium chloride (CH of 15mL5mM respectively 3(CH 2) 11nCl (CH 3) 2cH 2c 6h 5) solution, stir 4min; Then potassium borohydride (the KBH of 5mL0.06M is dropwise added 4), continue to stir 2min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the calcium mercaptoacetate ((HSCH of 50mL1.5mM simultaneously 2cOO) 2ca), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 7.5, then about 42min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 10:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the two hydration sodium chloraurate (NaAuCl of 5mL5mM 42H 2o) solution, adds the deionized water of 95mL and the dodecyl benzyl dimethyl ammonium chloride (CH of 15mL5mM respectively 3(CH 2) 11nCl (CH 3) 2cH 2c 6h 5) solution, stir 2min; Then sodium borohydride (the NaBH of 2mL0.3M is dropwise added 4), continue to stir 10min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the 3-mercaptopropionic acid (HSCH of 100 μ L simultaneously 2cH 2cO 2h), after being uniformly mixed, use the potassium hydroxide (KOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 10.8, then about 45min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 11:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL5mM 42H 2o) solution, adds the deionized water of 95mL and the dodecyl benzyl dimethyl ammonium chloride (CH of 0.5mL5M respectively 3(CH 2) 11nCl (CH 3) 2cH 2c 6h 5) solution, stir 1min; Oil bath is heated to 70 ° of C, then dropwise adds the ascorbic acid (L-Ascorbic acid) of 10mL5M, continues to add thermal agitation 30min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the 2 mercaptopropionic acid (HSCH of 90 μ L simultaneously 3cHCOOH), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 11.0, then about 40min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 12:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the gold chloride (HAuCl of 5mL5mM 4) solution, add the deionized water of 95mL and the softex kw (CH of 1mL0.2M respectively 3(CH 2) 15nBr (CH 3) 3) solution, stir 5min; Then potassium borohydride (the KBH of 1.5mL0.1M is dropwise added 4), continue to stir 2min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the calcium mercaptoacetate ((HSCH of 10mL5.0mM simultaneously 2cOO) 2ca), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 7.0, then about 42min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 13:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get aurous chloride (AuCl) solution of 5mL5mM, add the deionized water of 95mL and the DTAC (CH of 2mL0.1M respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 5min; Oil bath is heated to 85 ° of C, then dropwise adds the ascorbic acid (L-Ascorbic acid) of 50mL0.4M, continues to add thermal agitation 3min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the 2 mercaptopropionic acid (HSCH of 90 μ L simultaneously 3cHCOOH), after being uniformly mixed, use the potassium hydroxide (KOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 8.2, then about 37min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 14:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL5mM 42H 2o) solution, adds the deionized water of 95mL and the dodecyl benzyl dimethyl ammonium chloride (CH of 1mL0.2M respectively 3(CH 2) 11nCl (CH 3) 2cH 2c 6h 5) solution, stir 5min; Then potassium borohydride (the KBH of 10mL0.02M is dropwise added 4), continue to stir 2min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the 3-mercaptopropionic acid (HSCH simultaneously adding 100 μ L simultaneously 2cH 2cO 2h), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 10.25, then about 40min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 15:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the two hydration sodium chloraurate (NaAuCl of 5mL5mM 42H 2o) solution, adds the deionized water of 95mL and the DTAC (CH of 2mL0.1M respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 5min; Oil bath is heated to 88 ° of C, then dropwise adds the ascorbic acid (L-Ascorbic acid) of 10mL5M, continues to add thermal agitation 10min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the 2 mercaptopropionic acid (HSCH of 90 μ L simultaneously 3cHCOOH), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 8.5, then about 41min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 16:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the gold chloride (HAuCl of 5mL5mM 4) solution, add the deionized water of 95mL and the softex kw (CH of 1mL0.5M respectively 3(CH 2) 15nBr (CH 3) 3) solution, stir 2min; Then sodium borohydride (the NaBH of 500 μ L0.5M is dropwise added 4), continue to stir 40min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the 3-mercaptopropionic acid (HSCH of 90 μ L simultaneously 2cH 2cO 2h), after being uniformly mixed, use the potassium hydroxide (KOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 10.4, then about 50min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 17:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL5mM 42H 2o) solution, adds the deionized water of 95mL and the DTAC (CH of 90 μ L2M respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 1min; Oil bath is heated to 78 ° of C, then dropwise adds the ascorbic acid (L-Ascorbic acid) of 1mL1M, continues to add thermal agitation 12min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the Cys (HSCH of 15mL1mM simultaneously 2cHNH 2cO 2h), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 10.82, then about 39min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 18:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the gold chloride (HAuCl of 5mL5mM 4) solution, add the deionized water of 95mL and the DTAC (CH of 5mL0.03M respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 8min; Then potassium borohydride (the KBH of 3mL0.08M is dropwise added 4), continue to stir 10min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the calcium mercaptoacetate ((HSCH of 40mL0.5mM simultaneously 2cOO) 2ca), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 7.6, then about 60min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 19:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get aurous chloride (AuCl) solution of 5mL5mM, add the deionized water of 95mL and the softex kw (CH of 2mL0.1M respectively 3(CH 2) 15nBr (CH 3) 3) solution, stir 5min; Oil bath is heated to 87 ° of C, then dropwise adds the ascorbic acid (L-Ascorbic acid) of 50mL0.6M, continues to add thermal agitation 10min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the Cys (HSCH of 30mL0.15mM simultaneously 2cHNH 2cO 2h), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 6.6, then about 41min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 20:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL5mM 42H 2o) solution, adds the deionized water of 95mL and the DTAC (CH of 1mL0.2M respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 60min; Then potassium borohydride (the KBH of 10mL0.02M is dropwise added 4), continue to stir 15min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 60mL above-mentioned steps (1) prepares, stir, add the 2 mercaptopropionic acid (HSCH simultaneously adding 60 μ L simultaneously 3cHCOOH), after being uniformly mixed, use the potassium hydroxide (KOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 10.5, then about 40min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 21:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get aurous chloride (AuCl) solution of 5mL5mM, add the deionized water of 95mL and the DTAC (CH of 10mL0.01M respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 9min; Oil bath is heated to 86 ° of C, then dropwise adds the ascorbic acid (L-Ascorbicacid) of 100mL0.05M, continues to add thermal agitation 3min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 200mL above-mentioned steps (1) prepares, stir, add 200 μ L TGA (HSCH simultaneously 2cO 2h), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 9.9, then about 40min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 22:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get aurous chloride (AuCl) solution of 5mL5mM, add the deionized water of 95mL and the softex kw (CH of 10mL0.06M respectively 3(CH 2) 15nBr (CH 3) 3) solution, stir 15min; Oil bath is heated to 83 ° of C, then dropwise adds the ascorbic acid (L-Ascorbic acid) of 10mL0.9M, continues to add thermal agitation 13min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 120mL above-mentioned steps (1) prepares, stir, add the Cys (HSCH of 100mL0.1mM simultaneously 2cHNH 2cO 2h), after being uniformly mixed, use the potassium hydroxide (KOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 6.25, then about 60min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 23:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get aurous chloride (AuCl) solution of 5mL5mM, add the deionized water of 95mL and the DTAC (CH of 3mL0.08M respectively 3(CH 2) 11nCl (CH 3) 3) solution, stir 5min; Oil bath is heated to 89 ° of C, then dropwise adds the ascorbic acid (L-Ascorbic acid) of 100mL0.1M, continues to add thermal agitation 3min, naturally cools, and obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 150mL above-mentioned steps (1) prepares, stir, add the sodium thioglycolate (HSCH of 50mL2mM simultaneously 2cOONa), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 5.5, then about 47min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Embodiment 24:
In the present embodiment, functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL5mM 42H 2o) solution, adds the deionized water of 95mL and the softex kw (CH of 7mL0.3M respectively 3(CH 2) 15nBr (CH 3) 3) solution, stir 10min; Then potassium borohydride (the KBH of 10mL0.07M is dropwise added 4), continue to stir 6min, obtained nm of gold mixed solution, is placed in 4 DEG C of refrigerators for subsequent use.
(2) containing the ion cluster modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 20mL above-mentioned steps (1) prepares, stir, add the TGA (HSCH simultaneously adding 20 μ L simultaneously 2cO 2h), after being uniformly mixed, use the NaOH (NaOH) of 0.2M or hydrochloric acid (HCl) that the pH value of mixed liquor is adjusted to 6.83, then about 40min is stirred in sealing, obtains functionalized nano gold solution.
Adopt method of testing in the same manner as in Example 1 to the above-mentioned functionalized nano gold solution prepared to Co micro-in water solution system 2+detection rapidity, selective, sensitivity and practicality etc. test, obtain and embodiment identical result, show that the obtained functionalized nano gold solution of the present embodiment can detect micro-Co in water solution system 2+, and have and detect rapidity, selective, sensitivity and practicality, in environmental science, inspection chemistry and analytical chemistry field, there is important using value.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any amendments and improvement etc. made in spirit of the present invention, all should be included within protection scope of the present invention.

Claims (4)

1. one kind utilizes nano-Au solution to detect Co 2+method, it is characterized in that: comprise the steps:
Be detect sample with nano-Au solution, described nano-Au solution is prepared by following steps (1)-(3):
(1) with golden salt for golden nanometer particle is originated, take quaternary ammonium salt as surfactant, sodium borohydride, potassium borohydride or ascorbic acid are reducing agent; Get a certain amount of golden salting liquid, add surfactant, after stirring, add reducing agent, obtained nm of gold mixed solution;
The molecular formula of described quaternary ammonium salt is CH 3(CH 2) mnX (CH 3) n(CH 2) p(C 6h 5) q, wherein m=7 ~ 15, n=2 or 3, p=0 or 1, q=0 or 1, X=Cl, Br, I or F;
(2) in described nm of gold mixed solution, add the compound soluble in water containing sulfydryl (-SH) and carboxyl (-COOH), then the pH value of the mixed solution obtained is adjusted to 5.0 ~ 11.0, sealing obtains nano-Au solution after stirring, comprise surfactant in described nano-Au solution, and be modified at nm of gold surface containing the ion cluster of element sulphur and carbon oxygen groups (O=C=O);
The described ion cluster containing element sulphur and carbon oxygen groups (O=C=O) comprises [SCH 2cO 2] 2-, [SCH 3cHCO 2] 2-, [SCH 2cH 2cO 2] 2-, [SCH 2cHNH 2cO 2] 2-or [SC 6h 4cO 2] 2-;
(3) described nano-Au solution is loaded in bag filter, then bag filter is put into the beaker filling deionized water and dialyse, to remove surfactant and other impurity, in dialysis procedure, pass into nitrogen; This nano-Au solution is dialysed; Experimentally find, can improve by dialysis the nano-Au solution that the ion cluster containing element sulphur and carbon oxygen groups (O=C=O) modifies largely and detect Co 2+sensitivity;
Measure the detection sample that two parts of volumes are identical; Preparation is identical with detecting aqueous solution volume and do not contain the aqueous solution solution as a comparison of cobalt ions; Portion is detected sample mix with comparative solution, form the first mixed liquor, another part is detected sample and detected aqueous solution, forms the second mixed liquor;
With the first mixed solution for reference, observe the color of the second mixed liquor and the first mixed liquor, if there is color change, then there is Co in the detected aqueous solution 2+if there is not color change, then there is not Co in the detected aqueous solution 2+; Or, contrast ultravioletvisible absorption intensity, the peak value of the second mixed liquor and the first mixed liquor, if its ultravioletvisible absorption intensity, peak value change, then there is Co in the detected aqueous solution 2+if do not change, then there is not Co in the detected aqueous solution 2+.
2. the nano-Au solution that utilizes according to claim 1 detects Co 2+method, it is characterized in that: described golden salt comprise in chlorauride, aurous chloride, gold chloride, three hydration gold chlorides, four hydration gold chlorides, two hydration potassium chloroaurates, two hydration sodium chloraurates one or more.
3. the nano-Au solution that utilizes according to claim 1 detects Co 2+method, it is characterized in that: described surfactant comprise in softex kw, DTAC and dodecyl benzyl dimethyl ammonium chloride one or more.
4. the nano-Au solution that utilizes according to claim 1 detects Co 2+method, it is characterized in that: the described compound containing sulfydryl and carboxyl comprise in TGA, 2 mercaptopropionic acid, 3-mercaptopropionic acid, Cys, sodium thioglycolate, calcium mercaptoacetate and thiosalicylic acid one or more.
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