CN101799418B - Material sensitive to sulfide and hydrogen peroxide as well as preparation method and application thereof - Google Patents
Material sensitive to sulfide and hydrogen peroxide as well as preparation method and application thereof Download PDFInfo
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- CN101799418B CN101799418B CN2010103007146A CN201010300714A CN101799418B CN 101799418 B CN101799418 B CN 101799418B CN 2010103007146 A CN2010103007146 A CN 2010103007146A CN 201010300714 A CN201010300714 A CN 201010300714A CN 101799418 B CN101799418 B CN 101799418B
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Abstract
The invention relates to a material sensitive to sulfide and hydrogen peroxide as well as a preparation method and application thereof in detecting sulphions and the hydrogen peroxide in a solution and sulfureted hydrogen in a gas phase, belonging to the field of composite materials. The material has a PbO/SiO2 structure, wherein the mole ratio of Pb and Si is 1:6.67-100. The material sensitive to the sulfide and the hydrogen peroxide can fast and conveniently measure a minute amount of the sulphions and the sulfureted hydrogen and can also carry out oxidation treatment on a specific oxidant and then repeatedly use the specific oxidant or use the specific oxidant to measure the hydrogen peroxide after the measurement, thereby being more economic; and in addition, the invention has the advantages of convenient use in measuring the sulphions and the sulfureted hydrogen, low cost, high sensitivity, fast response and very good market prospect.
Description
Technical field
The invention belongs to field of compound material, be specifically related to a kind of responsive material of sulfide and hydrogen peroxide and preparation method thereof and this material purposes in hydrogen peroxide and sulfide detect.
Background technology
Many types in the sulfide not only are used as a kind of reductive agent usually, and sulfide usually be industry or make as: the accessory substance of processes such as papermaking, medicine and leather industry, so it is present in natural water and the waste water widely.Because the toxicity of sulphur and sulfuretted hydrogen, sulphur are measured the attention that has particularly caused the analysis circle for the mensuration of sulfuretted hydrogen widely.Sulphur is a kind of poisonous nonmetalloid, because the use of coal and sulphur-containing substance, a large amount of sulfide gets into water body and air, and pollution on the environment is more and more serious.Sulfide is one of important indicator of water body quality, and long-term exposure stink damp is known from experience the olfactory nerve system anesthesia that makes the people.Sulphur makes cytotoxic through the passivation of aerobic respiration, and death all is because the generation that suffocates behind the cytotoxic usually.Thereby the sulphur detection method development sensitivity, reliable is very important in clinical, food, pharmacy and environmental area.
So far, Chinese scholars has been carried out big quantity research to the mensuration of sulphion.The method of conventional mensuration sulphion mainly contains titrimetry, photometry, electrochemical method, fluorescence method and chromatography etc.Wherein, titrimetry be the most general a kind of analytical approach that forms of the reductibility according to sulphion (Pawlak, Z.et al.Talanta 1999,48,347-353.).This method is simple to operate; Do not need expensive instrument; But it is more time-consuming when the method is measured; And when measuring authentic sample, receiving sensitivity and optionally restriction, sulfate and salt sulfate are measured the requirement that has very big interference, its sensitivity can not reach trace, determination of trace to sulphion usually.Photometry (Davidson, J.M.et al.Anal.Chem.2009,81; 3669-3675) and fluorescence method (Yang, X.F.et al.Anal.Chim.Acta 2009,631; 91-95.Choi; M.F.Analyst 1998,123, all needs usually when 1631-1634.) measuring sulphion complicated compound reagent and some toxicity more greatly as: the material of mercury class is measured.So just increased and measured the difficulty of process and environment is caused great pollution.Electrochemical techniques (Huang, R.F.et al.Anal.Chim.Acta 2007,582; 267-274.Howard, A.G.et al.Anal.Chem.1998,70; 4868-4872.) be used to measure sulphur; Mainly be silver and the mercury that produces precipitating action with metal and sulphur, sulphur and metal surface reaction produce metal sulfide, can be reduced to metal again through suitable negative potential electrode.But electrochemical process is difficult to keep the accurate serviceable life of functionalized electrode.Chromatographic technique is used for sulphur and is determined at a lot of fields, like soil, and paper-making process water, blood of human body, (Han, K.et al.Anal.Chem.1987,59,1016.) such as Environmental Water and pharmacy procedures.In complicated sample, the introducing of chromatographic separation technology has significant advantage to the mensuration of sulphur, but deficiency is to measure sulphur and all need carry out complicated derivation process to sample usually.And chromatographic apparatus is expensive, and the detecting device that also need depend on other just can be accomplished mensuration.
Therefore this area is badly in need of developing fast, and easy qualitative, quantitative is measured the reagent and the device of sulfide.
Summary of the invention
First technical matters to be solved by this invention provides a kind of to sulfide and the responsive material of hydrogen peroxide.
This to the responsive material of sulfide and hydrogen peroxide for having PbO/SiO
2The plumbous Si composite oxide of structure.Wherein, above-mentioned mol ratio to Pb and Si in sulfide and the hydrogen peroxide sensitive material is 1: 6.67～100.Preferably, the mol ratio of Pb and Si is 1: 10～40 in above-mentioned sulfide and the hydrogen peroxide sensitive material.Preferred especially, above-mentioned is 1: 25 to Pb in the material of sulfide and hydrogen peroxide sensitivity and the mol ratio of Si.
Further, above-mentioned to the responsive material of sulfide and hydrogen peroxide after the optical excitation of 290nm wavelength, can produce phosphorescence to the wavelength coverage of 650nm at 400nm.
Further, above-mentioned material to sulfide and hydrogen peroxide sensitivity is prepared from following method:
A, with ethyl orthosilicate and lead acetate add mix in the alcoholic solvent after, add catalyzer HNO while stirring
3Generate with glacial acetic acid to gel; HNO wherein
3Addition press HNO
3: the molar ratio of Si is 1: 10～100; The addition of glacial acetic acid is 1 by the molar ratio of HAC: Si: 0.5-2; Said alcoholic solvent is glycerine, ethanol or monoethylene glycol;
B, with the gel that obtains 450～650 ℃ of down calcinings 1～8 hour, promptly get.
Preferably, the responsive material of above-mentioned sulfide and hydrogen peroxide is prepared from following method:
A, with ethyl orthosilicate and lead acetate add mix in the alcoholic solvent after, add catalyzer HNO while stirring
3Generate with glacial acetic acid to gel; HNO wherein
3Addition press HNO
3: the molar ratio of Si is 1: 50; The addition of glacial acetic acid is 1: 1 by the molar ratio of HAC: Si; Said alcoholic solvent is 20% glycerin solution;
B, with the gel that obtains 500 ℃～600 ℃ down calcinings 1～2 hour, promptly get.
Employed glycerine is a solvent commonly used in the sol-gal process of this area in the said goods and the method, and the consumption of glycerine requires easy to be definite according to the concentration of ethyl orthosilicate and lead acetate with the routine that consumption refers again in the sol-gal process of this area.
Above-mentioned sulfide refers to sodium sulphide, and potassium sulfide, sulfuretted hydrogen, sulphur hydrogen radical ion etc. wherein contain the compound of negative sulfidion.
Second technical matters to be solved by this invention provides the above-mentioned purposes of material in the qualitative or detection by quantitative of solution sulfide or hydrogen peroxide to sulfide and hydrogen peroxide sensitivity.
The 3rd technical matters to be solved by this invention provides a kind of method that detects sulfide and content of hydrogen peroxide in the solution.This method may further comprise the steps:
A. getting above-mentioned sulfide and hydrogen peroxide sensitive material packs in the cuvette of luminoscope;
B. cuvette is put into luminoscope, set instrument parameters such as excitation wavelength (290nm) and emission wavelength ranges;
C. then; Inject pH 11 buffer solution in cuvette, blank as measuring, the concentration that adds same amount respectively again is in 2.67 μ M～596 μ M (concentration M=mol among this paper; Also can represent with mol/L) the interior sodium sulphide standard solution of scope; Measure phosphorescence intensity, the drawing standard curve draws regression equation;
D. in cuvette, inject the solution to be measured of same amount, measure phosphorescence intensity, converse sulphion concentration wherein according to regression equation.
The 4th technical matters to be solved by this invention provides a kind of method that detects content of hydrogen peroxide in the solution.This method may further comprise the steps:
A, with above-mentioned the responsive material of sulfide and hydrogen peroxide is carried out the phosphorescence cancellation with sulfide, in the flow cell of packing into then;
B, flow cell is put into luminoscope, set instrument parameters such as excitation wavelength (290nm) and emission wavelength ranges;
C, then injects distilled water in flow cell, blank as measuring, and adds the H of concentration in 0.5mM～50mM (the M=mol among this paper also can be represented with mol/L) scope of same amount more respectively
2O
2Standard solution is measured phosphorescence intensity, and the drawing standard curve draws regression equation;
D, in flow cell, inject the solution to be measured of same amount, measure phosphorescence intensity, converse H wherein according to regression equation
2O
2Concentration.
The 5th technical matters to be solved by this invention provides a kind of sensor that detects solution sulfide and air cure hydrogen, this sensor be with above-mentioned be that feedstock production forms to sulfide and the responsive material of hydrogen peroxide.
The 6th technical matters to be solved by this invention provides a kind of kit that detects sulfide and hydrogen peroxide.Contain above-mentioned in this kit to sulfide and the responsive material of hydrogen peroxide.
Further, also contain in the kit of above-mentioned detection solution sulfide and air cure hydrogen richness and can make the above-mentioned oxygenant that sulfide and hydrogen peroxide sensitive material phosphorescence are recovered.After measuring sulfide, these specific oxygenants can make this that sulfide and the responsive phosphorescent ability of material of hydrogen peroxide are recovered, and realize reusing.
Preferably, above-mentioned oxygenant is a hydrogen peroxide.
The present invention has by after the optical excitation of 290nm wavelength the responsive material of sulfide and hydrogen peroxide, and to the characteristic that has phosphorescence to generate between the 650nm wavelength coverage, and the phosphorescence intensity of generation is higher at 400nm.
And persulfide of the present invention and hydrogen oxide sensitive material can be used for measuring solution sulphion content.This was based on the phosphorescence quenching that sulphion can make sulfide of the present invention and hydrogen peroxide sensitive material.When the concentration of sulphion at 2.67 μ M in the scope of 596 μ M, the logarithm lgC of its concentration and lg [(P
0-P)/and P] linear.And the present invention also can use oxygenant to carry out oxidation processes to the responsive material of sulfide and hydrogen peroxide after measuring sulphion, after measuring hydrogen peroxide, also can use reductive agent to reduce processings, can the repetitive cycling use.
According to the present invention, can obtain to show the material to sulfide and hydrogen peroxide sensitivity of wide wave spectrum stabilized illumination characteristic, and can be used for qualitative, the quantitative mensuration trace sulfide and the content of hydrogen peroxide.
Beneficial effect of the present invention is: a kind of sulfide and hydrogen peroxide material are provided to the invention property, and its structure is plumbous silicon (PbO/SiO
2) oxide complex, this lead silicon oxidation compound has the phosphorescent characteristics of exciting, simultaneously its it excites the color of phosphorescence and intensity to change with the increase of sulfide concentration in the sulfide solution system.It is a kind of new highly sensitive to use this specific character to make up, both qualitative determination quickly and easily that response speed is fast, method that again can the quantitative measurement trace sulfide.And sulfide of the present invention and hydrogen peroxide sensitive material also can use oxygenant to carry out oxidation processes after mensuration, can reuse more economically and practice thrift.This material can also be measured the compound that hydrogen peroxide etc. has oxidisability after the phosphorescence cancellation simultaneously.Kit and sensor preparation that the present invention detects sulfide and hydrogen peroxide are easy, easy to use, with low cost, have good market outlook.
Description of drawings
Fig. 1 is sulphion of the present invention and the phosphorescence spectrum figure of sulfuretted hydrogen sensitive material in the presence of the variable concentrations sulphion, wherein has concentration to be respectively: (a) 0 μ M, (b) 2.67 μ M, (c) 6.00 μ M; (d) 12.7 μ M, (e) 29.3 μ M, (f) 46.0 μ M; (g) 62.7 μ M, (h) 96.0 μ M, (i) 163 μ M; (j) 263 μ M, (k) 429 μ M, the phosphorescence spectrum figure during (1) 596 μ M..
Fig. 2 is the visual response situation of sulphion and sulfuretted hydrogen sensitive material.Wherein, in Fig. 2-1a, the sulphion concentration of adding is followed successively by: (A) 0 μ M, (B) 50 μ M, (C) 200 μ M, (D) 500 μ M.This figure after the irradiation a period of time with portable uviol lamp, closes uviol lamp with sulphion and sulfuretted hydrogen sensitive material, takes with commercial camera.
In Fig. 2-1b, the sulphion concentration of adding is followed successively by (A) 0 μ M, (B) 50 μ M, (C) 200 μ M, (D) 500 μ M.This figure is under daylight, takes with commercial camera.
In Fig. 2-2a, be sulphion and sulfuretted hydrogen sensitive material indirectly with gas phase in the figure of sulfuretted hydrogen effect, this figure after the irradiation a period of time with portable uviol lamp, closes uviol lamp, with commercial camera shooting with sulphion and sulfuretted hydrogen sensitive material.
In Fig. 2-2b, be sulphion and sulfuretted hydrogen sensitive material indirectly with gas phase in the figure of sulfuretted hydrogen effect, this figure is under daylight, with commercial camera shooting.
Phosphorescence spectrum figure (a) PbO/SiO of Fig. 3 material of the present invention
2Material phosphorescence spectrum figure, (b) PbO/SiO
2Material and Na
2Phosphorescence spectrum figure after the S effect, (c) PbO/SiO
2The phosphorescence spectrum figure that material is recovered by hydrogen peroxide.
Phosphorescence intensity when recovering after Fig. 4 material cancellation of the present invention detects, and wherein A is by the PbO/SiO of cancellation
2The time dependent restorability phosphorescence spectrum of phosphorescence intensity (a) 0.5mM when adding superoxol, (b) 1mM, (c) 5mM, (d) 15mM, (e) 50mM; B be the phosphorescence intensity recovery value and-relation curve between the lgC.
Fig. 5 material of the present invention recovers the phosphorescence spectrum figure in the presence of the variable concentrations sulphion after 10 times, and sulphion concentration is respectively: (a) 0 μ M, (b) 2.67 μ M, (c) 6.00 μ M; (d) 12.7 μ M, (e) 29.3 μ M, (f) 46.0 μ M; (g) 62.7 μ M, (h) 96.0 μ M, (i) 163 μ M; (j) 263 μ M, (k) 429 μ M, (l) 596 μ M.
Fig. 6 PbO/SiO of the present invention
2Scanning electron microscope sem (a of compound substance
1, b
1, c
1) and X ray energy dispersive spectrum EDS (a
2, a
3, a
4, a
5, b
2, b
3, b
4, b
5, c
2, c
3, c
4, c
5) testing result, (a) be PbO/SiO
2(b) be PbO/SiO
2With Na
2After the S effect; (c) be the PbO/SiO after the regeneration
2
Fig. 7 PbO/SiO of the present invention
2The XRD (X-ray diffraction) of (b) figure after compound substance (a) and this material and the sulphion effect.
Fig. 8 PbO/SiO of the present invention
2Compound substance XPS (x-ray photoelectron power spectrum) spectrogram.A is PbO/SiO of the present invention
2(a) back (b) and by the Pb of hydrogen peroxide regeneration back (c) before compound substance and the sulphion effect
4fXPS spectrum figure.B is PbO/SiO of the present invention
2(a) back (b) and by the Si of hydrogen peroxide regeneration back (c) before compound substance and the sulphion effect
2pXPS spectrum figure.
Embodiment
Key instrument that uses in the instance of the present invention and reagent:
The HITACHI F-4500 of Hitachi luminoscope.
Ethyl orthosilicate (analyze pure, Dihua worker company limited is won in Tianjin) and lead acetate (analyze pure, Chongqing chemical reagent factory).
Methyl alcohol (is analyzed pure; Chengdu chemical reagent factory), ethanol (analyze pure, Chengdu chemical reagent factory), isopropyl alcohol (analyze pure, Chengdu chemical reagent factory), isobutyl alcohol (are analyzed pure; Chengdu chemical reagent factory), monoethylene glycol (is analyzed pure; Chengdu chemical reagent factory), glycerine (analyze pure, Chengdu chemical reagent factory), sodium sulphide (analyze pure, Chengdu chemical reagent factory), HNO
3(analyze pure, Chengdu chemical reagent factory), HAC (analyze pure, Chengdu chemical reagent factory), H
2O
2(30%) (analyze pure, Chengdu chemical reagent factory) etc. also to be commercially available analysis pure.
Embodiment one the present invention is to the preparation of the material of sulfide and hydrogen peroxide sensitivity
A. pour alcohol solution into container, after mixing in ethyl orthosilicate and the lead acetate adding alcoholic solvent, at room temperature add catalyzer HNO while stirring
3Generate with glacial acetic acid to gel;
B. the gel that obtains is calcined certain hour at a certain temperature, promptly get.The condition of material (preparation see table 1) becomes Powderedly with material is levigate, is stored in the exsiccator subsequent use.
With the phosphorescence intensity is index, and to solvent species, the Pb that uses: factors such as the mol ratio of Si, calcining heat, calcination time are investigated, and the result sees table 1.
The various preparation conditions of table 1 are to the influence of phosphorescence intensity.
The more excellent condition of material that is obtained obtaining bigger phosphorescent intensity by above-mentioned previous work is to pour glycerine, ethanol, ethylene glycol solution into container; Molar ratio by Pb: Si is 1: 10～40 adding ethyl orthosilicate and lead acetates; Stirred 30 minutes, and pressed HNO then
3: the molar ratio of Si is to add nitric acid at 1: 50, is to add glacial acetic acid at 1: 1 by the molar ratio of HAC: Si, at room temperature is stirred to the gel generation.And with the gel that obtains 450～600 ℃ of down calcinings 1.5～3.5 hours, promptly get.
The optimum condition of material that is obtained obtaining maximum phosphorescent intensity by above-mentioned previous work is to pour 20% glycerin solution into container, is 1: 25 adding ethyl orthosilicate and lead acetate by the molar ratio of Pb: Si, stirs 30 minutes, presses HNO then
3: the molar ratio of Si is to add nitric acid at 1: 50, is to add glacial acetic acid at 1: 1 by the molar ratio of HAC: Si, at room temperature is stirred to the gel generation.And with the gel that obtains 550 ℃ of down calcinings 2 hours, become Powderedly with material is levigate, be stored in the exsiccator subsequent use.
Morphology research and element distribution to subsequent use material characterize and analyze (SEM and EDS result see that Fig. 6, XRD result see that Fig. 7, XPS result see Fig. 8) through SEM (ESEM), EDS, XPS and XRD.The result of SEM test shows PbO/SiO
2Nano-complex, PbO/SiO
2With nano-complex after the Na2S effect and the PbO/SiO that is reproduced
2The Size Distribution broad of nano-complex particle is greatly between 50 to 100nm.Be clear that very some big particles are to be formed by some little particle aggregations, so difficulty is known average particle diameter.The result of EDS test shows that each element all is evenly distributed in the material, and only at PbO/SiO
2With Na
2There is element sulphur to appear in the material uniformly in the nano-complex after the S effect.In the XRD spectra, visible PbO/SiO of the present invention
2Obtain.And after PbO/SiO2 compound substance of the present invention and sulphion react, the diffraction peak of tangible PbS in XRD spectra, occurred, PbO/SiO of the present invention has been described
2Change into PbS/SiO after compound substance and the sulfide effect
2Structure.XPS spectrum figure characterizes explanation PbO/SiO
2There is Pb in the compound substance
2+, and sign illustrative material structure is PbO/SiO more than further combining
2Oxide complex.And material with the sulphur effect after its bond energy change, explain that its chemical environment changes.After material is reproduced, Pb
4fAnd Si
2pBond energy return to original PbO/SiO again
2The bond energy value of compound substance, structure that shows the material regeneration material and original PbO/SiO
2Material structure is identical.
Embodiment two the present invention detect the preparation of the sensor of sulfide and hydrogen peroxide
Instance one the of the present invention of preparation promptly got sensor of the present invention to sulfide and hydrogen peroxide sensitive material powder compacting flakiness, put into cuvette and just can directly use.Obviously, under the condition of different mensuration environment and determining instrument, can be with the sheet that sulfide and hydrogen peroxide sensitive material is pressed into different size or block to use as sensor.
Embodiment three the present invention detect the preparation of the kit of sulfide and hydrogen peroxide
With PbO/SiO of the present invention
2Plumbous Si composite oxide sensor is put into the packing box of packing into colorimetric card, promptly gets the kit of the qualitative and semiquantitative determination solution sulfide concentration of the present invention.
With PbO/SiO of the present invention
2The sodium sulphide of plumbous silicon compound sensor and independent lucifuge packing is packed in the packing box together, promptly get the kit of detection by quantitative solution sulfide concentration of the present invention and the kit of typing detection solution hydrogen peroxide.The a plurality of gradient standard cure sodium solutions that again sodium persulfide are mixed with between 2.67 μ M～596 μ M in use are subsequent use.Use the conventional instrument in this area such as luminoscope to detect during test.
With PbO/SiO of the present invention
2The oxidants hydrogen peroxide solution of plumbous silicon compound and independent lucifuge inner wrapping sodium sulphide and independent lucifuge inner wrapping is placed on packing box, promptly gets the kit of the reusable detection by quantitative solution of the present invention concentration of hydrogen peroxide.It is subsequent use again hydrogen peroxide to be mixed with the hydrogen peroxide titer of 0.5mM～50mM in use.And use the sodium sulfide solution processes sensor to make it the phosphorescence cancellation, detect with the conventional instrument in this areas such as luminoscope then.
Test Example one is used material of the present invention qualitative or semiquantitative determination sulphion and hydrogen sulfide content
The phosphorescence intensity of phosphorescence sensor changes, and not only can note accurately with luminoscope, but also can with the naked eye carry out Direct observation.Shown in Figure 2 is the sulphion solution that adds variable concentrations, the phosphorescence intensity of sensor and change in color.Can see after irradiation a period of time by Fig. 2 (1a), close uviol lamp with portable uviol lamp.Can see that the concentration of the sulphion solution of adding is high more, phosphorescence quenching obvious more.When the sulphion solution concentration that adds was 200 μ M, sensor can only send faint phosphorescence.And when the concentration of sulphion solution increased to 500 μ M, the phosphorescence intensity of biology sensor had not with the naked eye observed tangible phosphorescence almost completely by quencher.In addition, obvious variation has also taken place in the surface color of sensor under normal daylight, like Fig. 2 (1b).The priming color of sensor is a white, and when the sulphion solution that adds, the color of sensor surface gradually becomes brown from white.Based on the sensor surface change in color, we can become a kind of simple with this sensor production, the visual sensor of portable sulphion and sulfuretted hydrogen.
Can judge whether there is sulphion in the solution through this fast and convenient observational measurement method, and can compare, with the order of magnitude of approximate evaluation sulphion concentration with standard color comparison card.
Test Example two uses sensor determination of the present invention to add the content of sulphion in water and the leather-making waste water
The present invention adopts sol-gal process to synthesize a kind of novel sulphion and the hydrogen peroxide sensitive material of sulfuretted hydrogen, and its structure is PbO/SiO
2Plumbous silicon compound, and can use in its quantitative measurement solution the content of sulfuretted hydrogen in the sulphion and gas phase.
Take from the waste water of process hides testing laboratory of Sichuan University; Before mensuration, it is carried out the pre-treatment that acidifying is blown; To handle 1000 times and 333 times of back sulfur-containing waste water dilutions with redistilled water then; Join them respectively then and be equipped with in the cuvette that the present invention detects sulfide ion sensor, put into luminoscope and measure its phosphorescence intensity.
Concrete operations are following:
1, the demarcation of sulphion standard solution:, it is demarcated with iodimetric titration by the sodium sulfide solution dilution preparation of 0.1M.The sodium sulphide standard solution of compound concentration in 2.67～596 μ M scopes.
2, get a certain amount of PbO/SiO
2After plumbous silicon compound grinds, be pressed into sheet with sheeter.Then pack into behind the cuvette, put into luminoscope.With the optical excitation of 290nm wavelength, detect 400nm to the phosphorescence between the 650nm.Then, in cuvette, add a certain amount of buffer solution, blank as measuring.Add the sodium sulphide standard solution in 2.67 μ M～596 μ M scopes successively.Visible by Fig. 1, phosphorescence intensity reduces successively.
Wherein, work as PbO/SiO
2Plumbous silicon compound is respectively (a) 0 μ M in sodium sulphide concentration, (b) 2.67 μ M, and (c) 6.00 μ M, (d) 12.7 μ M, (e) 29.3 μ M, (f) 46.0 μ M, (g) 62.7 μ M, (h) 96.0 μ M, (i) 163 μ M, (j) 263 μ M, (k) 429 μ M are (l) during 596 μ M, promptly
When sulphion concentration is increased to 596 μ M from 2.67 μ M, the logarithm lgC of its concentration and lg [(P
0-P)/and P] linear.Its regression equation y=1.4938x-6.8627, correlation coefficient r
2=0.9941, detecting lower limit (signal/noise=3) is 0.138 μ M.Can find out PbO/SiO
2Plumbous silicon compound can be used in the sulphion of trace in the quantitative measurement solution and the sulfuretted hydrogen in the gas phase.
3, above-mentioned system is added water and leather wastewater sample and join respectively in the cuvette that the sensor that the present invention detects sulphion and sulfuretted hydrogen is housed, put into luminoscope and measure its phosphorescence intensity, go out the concentration of sulphion according to above-mentioned regression equation calculation.
Simultaneously, these several kinds of samples are also used conventional methylene blue spectrphotometric method for measuring sulphion concentration wherein.Two kinds of assay method comparative results and recovery experimental result are seen table 2.
Table 2 is measured and is added sulphion content results and recovery experimental result in water and the leather-making waste water
A representes the mean value of measuring eight times; Leather-making waste water
1And leather-making waste water
2Be identical waste water, leather-making waste water
1In contained sulphion use sensor determination of the present invention, leather-making waste water
2The sensor determination of the present invention that institute's sulfur-containing anion usefulness recovery regeneration is 10 times.
Visible by table, the relative deviation of every kind of sample is less than 8%.Show with sulphion of the present invention and sulfuretted hydrogen sensitive material and can measure the sulphion content in the actual sample preferably.And after this material recovers with hydrogen peroxide, can carry out quantitative measurement, the result has shown that the material of regeneration can precision measure sulphion accurately.
The present invention to interfering ion to sensor of the present invention influence when measuring 10 μ M sulphions study.Acceptable ratio (chaff interference is as shown in table 3) in 5% concentration.Most negative ion can not influence sensor of the present invention to be measured sulphion, but because metallic ion will can form insoluble salt with sulphion, so the part metals ion can disturb measuring to produce.But these interference can be eliminated through the pre-treatment of the sulfur-containing anion sample being carried out the acidifying air blowing.
When table 3. is 10 μ M in sulphion concentration, the influence of interfering ion to measuring
The recovery of Test Example three material phosphorescence of the present invention reaches the detection to hydrogen peroxide
1, the performance recovery of cancellation material
Because the reductibility of sulphion is by the PbO/SiO of sulphion and sulfuretted hydrogen cancellation
2Thaumatropy is PbS/SiO
2, oxygenant can make above-mentioned sulphion and sulfuretted hydrogen material phosphorescence recover.Experimental result shows that the peroxidating Hydrogen Energy is recovered material phosphorescence.
(1) concrete rejuvenation is:
A, will be by the photophor PbS/SiO of cancellation
2Put into the aqueous hydrogen peroxide solution 5min of 0.1M, photophor is taken out with distilled water flushing.
B puts into the cuvette of F-4500 luminoscope with photophor, and (instrument parameters such as 400～650nm) are measured phosphorescence intensity, about PbO/SiO more than 95% to set excitation wavelength (290nm) and emission wavelength ranges
2The phosphorescence intensity of nano-complex can be resumed.(as shown in Figure 2)
2, by cancellation material PbS/SiO
2Quantitative measurement to hydrogen peroxide:
Hydrogen peroxide is when recovering material phosphorescence and PbS/SiO
2Quantitative reaction takes place, thereby can measure the amount of hydrogen peroxide.
Detailed process is following:
A. get the most preferably material of condition preparation of embodiment one, with its phosphorescence cancellation, again it being pressed into about diameter with sheeter is the thick photophor of the about 1mm of 12mm with sulphion, and photophor is packed in the cuvette of luminoscope;
B. cuvette is put into luminoscope, set excitation wavelength (290nm) and emission wavelength ranges (parameters together such as 400～650nm);
C. then, distilled water in cuvette adds, blank as measuring, distinguish the hydrogen peroxide standard solution of concentration in 0.5mM～50mM scope that adds same amount successively again, measure phosphorescence intensity, the drawing standard curve draws regression equation; When the concentration of sulphion in 0.5mM～50mM scope, the logarithm-lgC of its concentration and its phosphorescence intensity P that in the time of the 5th minute, is resumed are linear, its regression equation y=-144.67x+545.71, correlation coefficient r
2=0.9924.
D. in cuvette, inject the solution to be measured of same amount, measure phosphorescence intensity, converse the concentration of hydrogen peroxide wherein according to regression equation.(the response performance figure when Fig. 4 is sulphion and sulfuretted hydrogen sensitive material test hydrogen peroxide)
3, the material after will recovering is used for the mensuration of sulphion
A, get most preferred sulphion and sulfuretted hydrogen sensitive material, carry out cancellation 10 times, and after it was recovered, it is pressed into about diameter with sheeter was the thick photophor of the about 1mm of 12mm, the photophor powder is packed in the cuvette of luminoscope;
B, cuvette is put into luminoscope, set excitation wavelength (290nm) and emission wavelength ranges (parameters together such as 400～650nm);
C, then injects pH=11 buffer solution (PBS) in cuvette, and is blank as measuring; The sodium sulphide standard solution of concentration in 2.67 μ M～596 μ M scopes that adds same amount more respectively successively; Measure phosphorescence intensity, the drawing standard curve draws regression equation; When the concentration of sulphion in 2.67 μ M～596 μ M scopes, the logarithm-lgC of its concentration and lg [(P0-P)/P] are linear, its regression equation y=1.3124x-5.726, correlation coefficient r
2=0.9965.
D, in cuvette, inject the solution to be measured of same amount, measure phosphorescence intensity, converse sulphion concentration wherein according to regression equation.(the response performance figure when Fig. 6 is sulphion and sulfuretted hydrogen sensitive material test sulphion)
Find out that from above result this sulphion and sulfuretted hydrogen sensitive material are resumed after 10 times, the responding range that material is measured sulphion does not change, and linear relationship is good, explains that it has good recyclability.
Can know by above-mentioned instance, utilize sulphion of the present invention and the qualitative determination quickly and easily of sulfuretted hydrogen sensitive material, again can quantitative measurement solution in the content in the sulfuretted hydrogen in sulphion and the gas phase, can also measure the content of hydrogen peroxide.The present invention detect in the solution in the sulphion and hydrogen peroxide and gas phase the sensor of sulfuretted hydrogen prepare simple, easy to use, with low cost, highly sensitive, selectivity is good, the range of linearity is wide, the response time is fast, has good market outlook.
Claims (10)
1. to sulfide and the responsive material of hydrogen peroxide, it is characterized in that: be PbO/SiO
2Plumbous Si composite oxide, Pb wherein and the molar ratio of Si are 1: 6～100;
Said material to sulfide and hydrogen peroxide sensitivity is made by following method:
A, with ethyl orthosilicate and lead acetate add mix in the alcoholic solvent after, add catalyzer HNO while stirring
3Generate with glacial acetic acid to gel; HNO wherein
3Addition press HNO
3: the molar ratio of Si is 1: 10～100; The addition of glacial acetic acid is 1 by the molar ratio of HAC: Si: 0.5-2; Said alcoholic solvent is glycerine, ethanol or monoethylene glycol; B, with the gel that obtains 450～650 ℃ of down calcinings 1～8 hour, promptly get.
2. according to claim 1 to sulfide and the responsive material of hydrogen peroxide, it is characterized in that: the molar ratio of described Pb and Si is 1: 10～40.
3. according to claim 2 to sulfide and the responsive material of hydrogen peroxide, it is characterized in that: the molar ratio of described Pb and Si is 1: 25.
4. the material responsive to sulfide and hydrogen peroxide according to claim 1 is characterized in that: said to the responsive material of sulfide and hydrogen peroxide after the optical excitation of 290nm wavelength, can produce phosphorescence to the wavelength coverage of 650nm at 400nm.
5. according to claim 1 to sulfide and the responsive material of hydrogen peroxide, it is characterized in that: said material to sulfide and hydrogen peroxide sensitivity is prepared from following method:
A, with ethyl orthosilicate and lead acetate add mix in the alcoholic solvent after, add catalyzer HNO while stirring
3Generate with glacial acetic acid to gel; HNO wherein
3Addition press HNO
3: the molar ratio of Si is 1: 50; The addition of glacial acetic acid is 1: 1 by the molar ratio of HAC: Si; Said alcoholic solvent is 20% glycerin solution;
B, with the gel that obtains 500 ℃～600 ℃ down calcinings 1～2 hour, promptly get.
6. each described material purposes in the qualitative or quantitative phosphorescence of sulfide or hydrogen peroxide detect responsive of claim 1～5 to sulfide and hydrogen peroxide.
7. detect the phosphorescence sensor of sulfide or hydrogen peroxide, it is characterized in that be by claim 1～5 each described be that feedstock production forms to sulfide and the responsive material of hydrogen peroxide.
8. detect the kit of sulfide and hydrogen peroxide, each is described to sulfide and the responsive material of hydrogen peroxide to it is characterized in that containing claim 1～5.
9. detect the method for sulfide content, it is characterized in that may further comprise the steps:
A, weighting profit require 1～5 each described the responsive material of sulfide and hydrogen peroxide is packed in the cuvette of luminoscope;
B, cuvette is put into luminoscope, set instrument parameter excitation wavelength and emission wavelength ranges, excitation wavelength is made as 290nm;
C, then, it is blank as measuring in cuvette, to inject pH 11 buffer solution, adds the sodium sulphide standard solution of concentration in 2.67 μ M～596 μ M scopes more respectively, measures phosphorescence intensity, and the drawing standard curve draws regression equation;
D, in cuvette, inject solution to be measured, measure phosphorescence intensity, converse sulphion concentration wherein according to regression equation.
10. the method for content of hydrogen peroxide in the detection solution is characterized in that this method may further comprise the steps:
A, each describedly carries out the phosphorescence cancellation to the responsive material of sulfide and hydrogen peroxide with sulfide with claim 1～5, in the cuvette of packing into then;
B, cuvette is put into luminoscope, set instrument parameter excitation wavelength and emission wavelength ranges, excitation wavelength is made as 290nm;
C, in cuvette, inject pH 11 buffer solution then, blank as measuring, add the H of concentration in 0.5mM～50mM scope more respectively
2O
2Standard solution is measured phosphorescence intensity, and the drawing standard curve draws regression equation;
D, the solution to be measured that in flow cell, injects are measured phosphorescence intensity, converse H wherein according to regression equation
2O
2Concentration.
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| CN2010103007146A CN101799418B (en) | 2010-01-26 | 2010-01-26 | Material sensitive to sulfide and hydrogen peroxide as well as preparation method and application thereof |
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| CN2010103007146A CN101799418B (en) | 2010-01-26 | 2010-01-26 | Material sensitive to sulfide and hydrogen peroxide as well as preparation method and application thereof |
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| CN101799418B true CN101799418B (en) | 2012-05-23 |
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| CN106442448B (en) * | 2016-09-28 | 2019-01-22 | 安徽师范大学 | A kind of method of quick detection sulphion |
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