CN101241105A - Ultra trace aromatic nitro compound electrochemical detection method - Google Patents
Ultra trace aromatic nitro compound electrochemical detection method Download PDFInfo
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- CN101241105A CN101241105A CNA2007100636178A CN200710063617A CN101241105A CN 101241105 A CN101241105 A CN 101241105A CN A2007100636178 A CNA2007100636178 A CN A2007100636178A CN 200710063617 A CN200710063617 A CN 200710063617A CN 101241105 A CN101241105 A CN 101241105A
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Abstract
The present invention relates to detection technique of aromatic nitro compound, especially a method for detecting ultra-trace aromatic nitro compound rapidly by electrochemistry volt-ampere method of solid working electrode decorated by sensitive material fullerene or fullerene derivative. The present invention emphasizes the discovery of electrochemistry sensitive properties of aromatic nitro compound by fullerene or fullerene derivative, and electrochemistry volt-ampere method of solid working electrode decorated by sensitive material applied to rapid detecting technique of ultra-trace aromatic nitro compound. According to the present invention, the detecting device for aromatic nitro compound is simplified, and the detecting process can be finished rapidly by sorption of aromatic nitro compound in gas or electrolyte solution by fullerene or fullerene derivative, and because of the sensitive material applied to electrochemistry volt-ampere detecting technique, the detection sensitivity is improved greatly.
Description
Technical field
The present invention relates to the detection technique of aromatic nitro compound, particularly relate to the method for the aromatic nitro compound of the super trace of galvanochemistry volt-ampere method fast detecting that utilizes sensitive material fullerene or fullerene derivate to modify solid working electrode.
Background technology
Safety problem is the subject matter that countries in the world government is concerned about always, and various terrorist activities are one of the most serious current threats, especially uses various aromatic nitro compounds, as 2,4,6-trinitro-toluene (TNT), 1,3,5-trinitrobenzen (TNB), 2,4-dinitrotoluene (DNT) (DNT), 1,3-dinitro benzene (DNB) etc. carries out the various attacks of terrorism frequently to be taken place all over the world, and serious threat the people's lives and property safety and society stabilize.Follow the raising of countries in the world government antiterrorism awareness, realize the trace detection of aromatic nitro compound fast, also become one of research focus of current sphere of learning.
The detection technique of explosive substance mainly contains at present: canine tooth class animal detects, uses the body phase detection technique of radiation source (for example X ray, gamma-rays, radio frequency or magnetic field), and some trace detection technology based on detection explosive substance steam or particulate that progressively develop, it comprises electron capture detector (ECD), chemiluminescence, thermal oxide reduction, ion mobility spectrum (IMS), the gas chromatography that the surface acoustic wave detecting device is housed, field ion spectrum and mass spectrum or the like.These technology relate to complexity and expensive instrument and equipment mostly, and are difficult to the kind of identification explosive substance molecule, thereby have limited the foundation of effective early warning mechanism and seeking and visiting of explosive source.Another problem that explosive substance detects is that its steam forces down, and TNT is 7ppb.Therefore, set up a kind of trace of explosive substance simply and easily and ultratrace detection technique, and cheap, the portable and Miniaturized explosive substance detecting sensor of development is necessary.And electrochemical detection device is simple, is easy to microminiaturization.The sensitive material modified electrode is used for detecting, and explores and screen the sensitive material of explosive substance molecule, can realize that the trace of explosive substance and ultratrace detect.Help further cheap, the portable and Miniaturized explosive substance detecting sensor of development.
People such as the Wang of the U.S. have done initiative work (Electrochem.Comm.2004,6,176～179) in this respect.2004, they utilized nanometer-material-modified working electrode first, utilized the galvanochemistry voltammetry that TNT compound in the aqueous solution is detected.Utilize the enrichment function of multi-walled carbon nano-tubes, arrive 20S, can reach detection limit 100ug/L by prolonging the enrichment time that detects; Enrichment time extends to 600S, and behind the background baseline of deduction volt-ampere curve, can make detection limit reach 5ug/L.
The people such as Krausa of Germany also utilize the galvanochemistry voltammetry that TNT has been done and detect (J.Electroanal.Chem.1999,461,10～13).They use the Au line of the diameter 25um electrode of working, around it, do electrode around a circle gold thread, working electrode with to dripping the H of 5M in the middle of the electrode
2SO
4Solution is done electrolytic solution, and with its top 10cm place as for solid TNT, the TNT steam of volatilization is dissolved in the electrolytic solution, at-0.3V, records first reduction peak of TNT by constant electrode potential, finishes the detection to TNT.
The inventor is exploring and is screening in the work of the material that helps explosive substance molecule trace detection, found that silica material has very high galvanochemistry sensitivity to explosive aromatic nitro compound, the limit of mesopore silicon oxide MCM-41 modified electrode detection TNT reaches 0.6nM, and (patent No.: 200510086236.2), (TNB, DNT and DNB) also has very low detection polar curve to other aromatic nitro compound.
These initiative work have been opened up new approach for the detection technique of TNT, i.e. galvanochemistry volt-ampere method; For detecting explosive aromatic nitro compound, searching galvanochemistry sensitive material played important facilitation simultaneously.
Fullerene and fullerene derivate are class important functional material, have abundant chemical property, are good electron propagation ducts between tested molecule and the working electrode in Electrochemical Detection, are the good catalyzer in a lot of electrochemical reactions.This class material is because its unique carbon basket structure, and the fundamental research in fields such as chemistry, physics, electronics, optics, material science and bio-science is had than other material with carbon element profound significance more.
The detection technique of ultra trace aromatic nitro compound is mainly utilized the suction-operated to aromatic nitro compound in the solution or in the gas phase of fullerene or fullerene derivate, improves the detection sensitivity to aromatic nitro compound.The galvanochemistry voltammetry that this technology utilizes fullerene or fullerene derivate to modify working electrode realizes in the solution or ultra trace aromatic nitro compound fast detecting in the gas phase.
Summary of the invention
The object of the present invention is to provide a kind of simplely, be convenient under the common lab condition to realize fast the electrochemical fast detecting method of ultra trace aromatic nitro compound in solution or the gas.
The electrochemical detection method of ultra trace aromatic nitro compound of the present invention: use the galvanochemistry voltammetry, the electrode that employing is modified the fullerene of aromatic nitro compound sensitivity or fullerene derivate material is as solid working electrode, in three-electrode cell, the aromatic nitro compound of the ultratrace in the electrolyte solution is carried out fast detecting to electrode, contrast electrode and solid working electrode; By the suction-operated of fullerene or fullerene derivate material to the aromatic nitro compound in the electrolyte solution, finish the fast detecting process of the trace aromatic nitro compound in the electrolyte solution, and the position of the feature reduction peak of aromatic nitro compound in the volt-ampere curve that obtains according to detection, qualitatively judge the existence of aromatic nitro compound; Or
Use the galvanochemistry voltammetry, the electrode that employing is modified the fullerene of aromatic nitro compound sensitivity or fullerene derivate material is as solid working electrode, the solid working electrode that will have in the device that electrode, contrast electrode, solid working electrode and solid electrolyte are formed is exposed in the environment that contains aromatic nitro compound gas, and the aromatic nitro compound of the ultratrace in the gas is carried out fast detecting; By the suction-operated of fullerene or fullerene derivate material to the aromatic nitro compound in the gas, finish the fast detecting process of the trace aromatic nitro compound in the gas, and the position of the feature reduction peak of aromatic nitro compound in the volt-ampere curve that obtains according to detection, qualitatively judge the existence of aromatic nitro compound.
The present invention can hang down the level that reaches part per billion (ppb) to the detectability of aromatic nitro compound.
The electrochemical detection method of ultra trace aromatic nitro compound of the present invention, the method for carrying out fast detecting at the aromatic nitro compound to the ultratrace in the electrolyte solution may further comprise the steps:
(1) in electrolytic cell, add the neutral aqueous solution (concentration is not limit) be selected from acidic aqueous solution (the pH value of acid solution does not almost have to influence to detection sensitivity), inorganic salts or and described aromatic nitro compound between chemical reaction does not take place, do not dissolve fullerene or fullerene derivate and the organic solvent that can conduct electricity in one or more potpourri as electrolyte solution; In this electrolyte solution, feed inert gas, to remove the interference gas in the electrolyte solution;
(2) fullerene or fullerene derivate are dissolved in the organic solvent, get on the consubstantiality working electrode that this solution drips to cleaning, treat organic solvent evaporation after, form layer of even fullerene or fullerene derivate material at working electrode surface; Perhaps the nano material of fullerene or fullerene derivate is distributed to water or does not dissolve in the organic solvent of fullerene or fullerene derivate, form uniform suspending liquid, get this hanging drop to the solid working electrode of cleaning, after treating the spreading agent evaporation, form layer of even fullerene or fullerene derivate material on the solid working electrode surface;
(3) will to modify in the electrode, contrast electrode, step (2) good solid working electrode be connected to in the step (1) in the circuit of electrolyte solution that inert gas is handled as the electro-chemical systems of electrolyte solution, 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain the solid working electrode that the partial reduction product of fullerene or fullerene derivate is modified;
(4) aromatic nitro compound is dissolved in it chemical reaction does not take place and do not dissolve wiring solution-forming in the organic solvent of fullerene or fullerene derivate, get this solution and join in the step (3) in the electrolyte solution that inert gas is handled; 0～-the 1.3V scope in, in the three-electrode cell to electrode, contrast electrode and solid working electrode of step (3), the aromatic nitro compound of the ultratrace in the electrolyte solution is carried out fast detecting;
The concentration of described aromatic nitro compound in electrolyte solution detection limit of the concentration of corresponding aromatic nitro compound respectively when modifying solid working electrode with fullerene-based material or fullerene derivate material.
The electrochemical detection method of ultra trace aromatic nitro compound of the present invention, the method for carrying out fast detecting at the aromatic nitro compound to the ultratrace in the gas may further comprise the steps:
(1) fullerene or fullerene derivate are dissolved in the organic solvent, get on the solid working electrode that this solution drips to cleaning, treat organic solvent evaporation after, form layer of even fullerene or fullerene derivate material at working electrode surface; Perhaps the nano material with fullerene or fullerene derivate is distributed in water or the organic solvent, form uniform suspending liquid, get this hanging drop to the solid working electrode of cleaning, after treating the spreading agent evaporation, form layer of even fullerene or fullerene derivate material on the solid working electrode surface;
(2) be connected to make pick-up unit in the circuit of solid electrolyte as electrolyte electrochemical system with the solid working electrode of preparation in the step (1) and to electrode, contrast electrode;
(3) utilize the pick-up unit of step (2), 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain the solid working electrode that the partial reduction product of fullerene or fullerene derivate is modified; Solid working electrode with this device is exposed in the environment that contains aromatic nitro compound gas then, and the aromatic nitro compound of the ultratrace in the gas is carried out fast detecting;
The concentration of described aromatic nitro compound in gas detection limit of the concentration of corresponding aromatic nitro compound respectively when modifying solid working electrode with fullerene-based material or fullerene derivate material.
Described acid is selected from one or more any mixture in perchloric acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hyperbromic acid, the carbonic acid etc.
Described inorganic salts be selected from sodium halogen salt, halogenation sylvite, and other soluble inorganic salt in one or more any mixture etc.Halogen is Br, I or Cl.
When the aromatic nitro compound to the ultratrace in the electrolyte solution carries out fast detecting, organic solvent described in step (1) and the step (4) comprises acetonitrile, absolute ethyl alcohol, N, and dinethylformamide, tetrahydrofuran etc. can dissolve aromatic nitro compound, not dissolve the single organic solvent of fullerene and fullerene derivate or their any mixed organic solvents.
The organic solvent of described dissolving fullerene or fullerene derivate is benzene, toluene, carbon disulphide, methyl phenyl ethers anisole, chlorobenzene, o-dichlorobenzene etc. or their any mixture.
The organic solvent of described dispersion fullerene or fullerene derivate nano material is n-pentane, normal hexane, cyclohexane, n-decane etc. or their any mixture.
Described electrode is selected from a kind of in the inert metal that oxidation/reduction reaction does not take place platinum, gold or tungsten etc. in testing circuit; Described contrast electrode is selected from saturated calomel electrode or silver/silver chloride electrode.
Will carry out cleaning surfaces before described solid working electrode uses handles.Solid working electrode can be various solid electrodes, as glassy carbon electrode, gold electrode, platinum electrode or graphite electrode etc.
Described solid electrolyte is the solid electrolyte that can conduct electricity under the normal temperature, as sulphur silver iodide (Ag
3SI) or silver iodide rubidium (RbAg
4I
5), and some other contains the complex compound of a large amount of silver iodide etc.
Described inert gas can be nitrogen, helium or argon gas etc.
Described fullerene or fullerene derivate are modified solid working electrode, be meant and pass through to select different organic solvents, adjustment fullerene or the fullerene derivate concentration in organic solution, the consumption of the solution when reaching the modification solid working electrode, to reach the purpose of different size (molecular dimension, nano-scale or micron-scale) fullerene or fullerene derivate modification solid working electrode; Fullerene or fullerene derivate are fullerene or the fullerene derivates that is in the partial reduction state in the detection.
Described fullerene or fullerene derivate are the fullerene or the fullerene derivate materials of molecular dimension, nano-scale or micron-scale (less than 10um).The fullerene of described molecular dimension or fullerene derivate comprise the fullerene or the fullerene derivate of self assembled monolayer and unimolecule state; The fullerene of described nanometer or micron-scale or fullerene derivate comprise various materials with nanometer and micron-scale, various patterns, as fullerene and fullerene derivate materials such as spherical, bar-shaped or tubuloses.
Described fullerene is selected from C
60, C
70, C
76, C
78, C
82, C
84And the fullerene of other carbon number etc. or their any mixture.
Described fullerene derivate is that various embed fullerenes (are embedded one or more metals (this metal is: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, Sc, Y, La or Ti) or various external fullerene (being the derivant (this organic group is: pyrrolidino group, alkyl azide group, methylene amine groups or tolyl group etc.) that fullerene cage is externally connected with various organic groups) in the fullerene cage.
Described aromatic nitro compound comprises the aromatics that contains one or more nitryl groups on the aromatic rings.
Described aromatic nitro compound comprises 2,4,6-trinitro-toluene (TNT), 1,3,5-trinitrobenzen (TNB), 2,4-dinitrotoluene (DNT) (DNT) or 1,3-dinitro benzene (DNB) etc.
Described TNT, TNB, DNT or the DNB concentration in electrolyte solution should be when modifying solid working electrode with different fullerenes or fullerene derivate material the detection limit of corresponding concentration respectively.
The present invention adopts galvanochemistry volt-ampere method, and the galvanochemistry volt-ampere method of particularly utilizing sensitive material fullerene and fullerene derivate to modify solid working electrode detects the method for ultra trace aromatic nitro compound.The present invention focuses on the discovery to aromatic nitro compound galvanochemistry sensitive property of fullerene and derivant thereof, and the galvanochemistry volt-ampere method that sensitive material is modified solid working electrode is applied to the ultra trace aromatic nitro compound Fast Detection Technique.Utilize the present invention not only can make the pick-up unit summary of aromatic nitro compound, and can finish testing process apace to the suction-operated of the aromatic nitro compound in the electrolyte solution or in the gas by fullerene and derivant material thereof, and because sensitive material is applied to galvanochemistry volt-ampere detection technique, the combination of the two has improved detection sensitivity dramatically.
The present invention and other prior art relatively have following characteristics:
1. the applied material of the present invention is the fullerene or the fullerene derivate of micron-scale (less than 10 microns), nano-scale or molecular dimension.
2. the present invention focuses on the discovery to the aromatic nitro compound sensitive property of fullerene or fullerene derivate material.Utilize susceptibility fullerene or fullerene derivate material to modify the galvanochemistry volt-ampere method of solid working electrode, by of the suction-operated of this material to aromatic nitro compound, make the aromatic nitro compound of the trace in the electrolyte solution or in the gas arrive electrode surface fast, and in electrode surface generation reduction reaction, thereby has fast, low, easy to operate, the simple advantage of technology of energy consumption of response.
3. the present invention is in conjunction with the sensitive property of fullerene or fullerene derivate material and the sensitive performance of galvanochemistry voltammetry, utilize fullerene or fullerene derivate sensitive material to modify solid working electrode, improved detection sensitivity to a great extent, be up to 0.2ppb as the detection sensitivity of TNT.
4. the present invention can at room temperature operate and finish, and does not need airtight or experimental situation harshly such as high temperature, is convenient to be used in practice.
5. detection method of the present invention can be expanded easily in the fast detecting to other Trace Organic Compounds.
Description of drawings
Fig. 1. fullerene C in the embodiment of the invention 1
60The AFM photo of nano material (A figure yardstick is 1 μ m, and B figure yardstick is 300nm).
Fig. 2. the embodiment of the invention 1 detects the volt-ampere curve of variable concentrations aromatic nitro compound: A, TNT; B, TNB; C, DNT; D, DNB.
Fig. 3. fullerene Gd@C in the embodiment of the invention 3
82The AFM photo of nano material (A figure yardstick is 1 μ m, and B figure yardstick is 300nm).
Fig. 4. the embodiment of the invention 3 detects the volt-ampere curve of variable concentrations aromatic nitro compound: A, TNT; B, TNB; C, DNT; D, DNB.
Fig. 5. fullerene derivate PCBM is the molecular structure (Me is a methyl) of 1-(3-methoxy carboxyl) propyl group-1-phenyl-[6,6]-methyl fullerene in the embodiment of the invention 4.
Fig. 6. the embodiment of the invention 4 detects the volt-ampere curve of variable concentrations aromatic nitro compound: A, TNT; B, TNB; C, DNT; D, DNB.
Fig. 7. the embodiment of the invention 7 detects the volt-ampere curve of variable concentrations TNT.
Fig. 8. the embodiment of the invention 8 detects the volt-ampere curve of variable concentrations TNT.
Embodiment
Further describe the present invention below in conjunction with embodiment and accompanying drawing.
Embodiment 1.
(1) fullerene C
60The preparation of nanometer material modified electrode:
To carry out cleaning surfaces before the solid working electrode glassy carbon electrode uses and handle, earlier with α-Al
2O
3Polishing uses distilled water ultrasonic again.Be put in then in the baking oven and dry electrode surface about 45 ℃.
Under the room temperature with fullerene C
60Be dissolved in the toluene solvant, get an amount of this solution and drip to above-mentioned electrode surface, after the toluene solvant spontaneous evaporation, generate C equably under the room temperature on the glassy carbon electrode surface
60Nano material, as shown in Figure 1.
(2) utilize fullerene C
60Nanometer-material-modified working electrode, the electrochemical process of ultra trace aromatic nitro compound in the detection electrolyte solution:
(I) the simple three-electrode electro Chemical of employing system, and comprise working electrode (C
60Nanometer-material-modified working electrode), to electrode (Pt silk) and contrast electrode (saturated calomel electrode).At first in electrolytic cell, add the 1mM perchloric acid solution as electrolyte solution, in this solution, feed high pure nitrogen, to get rid of interference gas in the solution.Modify good solid working electrode in will step (1), and electrode and contrast electrode are connected in the circuit of electro-chemical systems, utilize the galvanochemistry voltammetry, 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain C
60The electrode that the partial reduction product is modified.
(II) TNT is dissolved in is configured to lean solution in the absolute ethyl alcohol, get in the electrolyte solution that this solution joins step (I), the concentration that makes TNT is 20ppb.
(III) utilize the galvanochemistry voltammetry, be provided with working electrode voltage 0～-detect under the 1.3V scope, obtain the virgin curve of going back of TNT.
Volt-ampere curve when being respectively 40ppb, 80ppb and 120ppb by changing the concentration of TNT in the step (III), obtaining concentration.
The C that utilizes this method to obtain
60Nanometer-material-modified electrode detects other aromatic nitro compound such as TNB, DNT, DNB, and only needing TNT in the step (2) is changed is other aromatic nitro compound (comprising TNB, DNT, DNB); The concentration that detects TNB then is respectively 4.5ppb, 30ppb, 60ppb and 120ppb, detects concentration difference 2.5ppb, 5ppb, 10ppb and the 15ppb of DNT, and the concentration that detects DNB is respectively 5ppb, 10ppb, 20ppb and 30ppb.The result is shown in Fig. 2 A, B, C, D.
Embodiment 2.
(1) fullerene C
70The preparation of nanometer material modified electrode:
To carry out cleaning surfaces before the solid working electrode graphite electrode uses and handle, earlier with α-Al
2O
3Polishing uses distilled water ultrasonic again.Be put in then in the baking oven and dry electrode surface about 45 ℃.
Under the room temperature with fullerene C
70Be dissolved in the carbon disulphide solvent, get an amount of this solution and drip to above-mentioned electrode surface, after the spontaneous evaporation of carbon disulphide solvent, be formed uniformly C under the room temperature at graphite electrode surface
70Nano material.
(2) utilize fullerene C
70Nanometer-material-modified working electrode, the electrochemical process of ultra trace aromatic nitro compound in the detection electrolyte solution:
(I) the simple three-electrode electro Chemical of employing system, and comprise working electrode (C
70Nanometer-material-modified glassy carbon electrode), to electrode (spun gold) and contrast electrode (saturated calomel electrode).At first in electrolytic cell, add 0.5M NaCl solution as electrolyte solution, in this solution, feed high pure nitrogen, to get rid of interference gas in the solution.Modify good working electrode in will step (1), and electrode and contrast electrode are connected in the circuit of electro-chemical systems, utilize the galvanochemistry voltammetry, 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain C
70The electrode that the partial reduction product is modified.
(II) TNT is dissolved in is configured to lean solution in the acetonitrile, get this solution of part in the electrolyte solution of step (I), the concentration that makes TNT is 20ppb.
(III) utilize the galvanochemistry voltammetry, be provided with working electrode voltage 0～-detect under the 1.3V scope, obtain the virgin curve of going back of TNT.
Volt-ampere curve when being respectively 80ppb, 120ppb and 160ppb by changing the concentration of TNT in the step (III), obtaining concentration.
The C that utilizes this method to obtain
70Nanometer-material-modified electrode detects other aromatic nitro compound such as TNB, DNT, DNB, and only needing TNT in the step (2) is changed is other aromatic nitro compound (comprising TNB, DNT, DNB); The concentration that detects TNB then is respectively 4.5ppb, 13.5ppb, 27ppb and 54ppb, detects concentration difference 2.5ppb, 5ppb, 15ppb and the 30ppb of DNT, and the concentration that detects DNB is respectively 5ppb, 10ppb, 20ppb and 40ppb.
Embodiment 3.
(1) fullerene Gd@C
82The preparation of nanometer material modified electrode:
To carry out cleaning surfaces before the solid working electrode glassy carbon electrode uses and handle, earlier with α-Al
2O
3Polishing uses distilled water ultrasonic again.Be put in then in the baking oven and dry electrode surface about 45 ℃.
To synthesize good Gd@C under the room temperature
82Nano material is distributed in the cyclohexane solvent, gets an amount of this solution and drips to above-mentioned electrode surface, makes the cyclohexane spontaneous evaporation under the room temperature, is formed uniformly Gd@C on the glassy carbon electrode surface
82Nano material, as shown in Figure 3.
(2) utilize fullerene Gd@C
82Nanometer-material-modified working electrode, the electrochemical process of ultra trace aromatic nitro compound in the detection electrolyte solution:
(I) the simple three-electrode electro Chemical of employing system, and comprise working electrode (Gd@C
82Nanometer-material-modified glassy carbon electrode), to electrode (Pt silk) and contrast electrode (silver/silver chloride electrode).At first in electrolytic cell, add the 1mM sulfuric acid solution as electrolyte solution, in this solution, feed high pure nitrogen, to get rid of interference gas in the solution.Modify good working electrode in will step (1), and electrode and contrast electrode are connected in the circuit of electro-chemical systems, utilize the galvanochemistry voltammetry, 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain Gd@C
82The electrode that the partial reduction product is modified.
(II) TNT is dissolved in is configured to lean solution in the absolute ethyl alcohol, get this solution in the electrolyte solution of step (I), the concentration that makes TNT is 20ppb.
(III) utilize the galvanochemistry voltammetry, be provided with working electrode voltage 0～-detect under the 1.3V scope, obtain the virgin curve of going back of TNT.
Volt-ampere curve when being respectively 40ppb, 80ppb and 120ppb by changing the concentration of TNT in the step (III), obtaining concentration.
The Gd@C that utilizes this method to obtain
82Nanometer-material-modified electrode detects other aromatic nitro compound such as TNB, DNT, DNB, and only needing TNT in the step (2) is changed is other aromatic nitro compound (comprising TNB, DNT, DNB); The concentration that detects TNB then is respectively 4.5ppb, 13.5ppb, 54ppb and 108ppb, detects concentration difference 5ppb, 10ppb, 20ppb and the 30ppb of DNT, and the concentration that detects DNB is respectively 5ppb, 10ppb, 20ppb and 30ppb.The result is shown in Fig. 4 A, B, C, D.
Embodiment 4.
(1) preparation of fullerene derivate PCBM self assembled monolayer modified electrode:
To carry out cleaning surfaces before the solid working electrode glassy carbon electrode uses and handle, earlier with α-Al
2O
3Polishing uses distilled water ultrasonic again.Be put in then in the baking oven and dry electrode surface about 45 ℃.
Under the room temperature PCBM is dissolved in the toluene solvant, above-mentioned electrode was soaked in time solution about 10 minutes, be formed uniformly the PCBM self assembled monolayer on the glassy carbon electrode surface.
(2) utilize fullerene PCBM to modify working electrode, detect the electrochemical process of ultra trace aromatic nitro compound in the electrolyte solution:
(I) adopt simple three-electrode electro Chemical system, and comprise working electrode (glassy carbon electrode that PCBM modifies), to electrode (Pt silk) and contrast electrode (saturated calomel electrode).At first in electrolytic cell, add the 1mM perchloric acid solution as electrolyte solution, in this solution, feed high pure nitrogen, to get rid of interference gas in the solution.Good working electrode will be modified in the step (1), and electrode and contrast electrode are connected in the circuit of electro-chemical systems, utilize the galvanochemistry voltammetry, 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain the electrode that PCBM partial reduction product is modified.
(II) TNT is dissolved in is configured to lean solution in the absolute ethyl alcohol, get this solution in the electrolyte solution of step (I), the concentration that makes TNT is 1ppb.
(III) utilize the galvanochemistry voltammetry, be provided with working electrode voltage 0～-detect under the 1.3V scope, obtain the virgin curve of going back of TNT.
Volt-ampere curve when being respectively 5ppb, 10ppb and 20ppb by changing the concentration of TNT in the step (III), obtaining concentration.
The electrode that the PCBM that utilizes this method to obtain modifies detects other aromatic nitro compound such as TNB, DNT, DNB, only needs TNT change in the step (2) is other aromatic nitro compound (comprising TNB, DNT, DNB); The concentration that detects TNB then is respectively 1.8ppb, 5.4ppb, 10.8ppb and 14.4ppb, detects concentration difference 1.5ppb, 5ppb, 10ppb and the 15ppb of DNT, and the concentration that detects DNB is respectively 1.5ppb, 5ppb, 20ppb and 30ppb.The result is shown in Fig. 6 A, B, C, D.
Fullerene derivate PNA is N-(n-dodecyl)-2-(p-hydroxyphenyl) [60] pyrrole radicals fullerene, modifies working electrode, when doing electrolyte with solid electrolyte, detects the electrochemical process of the explosive nitro compound of ultra trace aromatic:
(1) with solid electrolyte (sulphur silver iodide) compacting (5 * 5mm is wide, 0.3mm thickness) in flakes, descend the two sides to fix a little Au sheet, two Au silks respectively thereon with conductive silver glue, respectively as working electrode, to electrode and contrast electrode.
(2) with the PNA dispersion of materials of micron-scale in n-pentane, get this dispersant liquid drop of part to working electrode surface, treat that n-pentane evaporates after, be formed uniformly the PNA film at working electrode surface.
(3) with working electrode (PNA modify Au electrode), electrode (Au silk) and contrast electrode (Au silk) are connected in the circuit of electro-chemical systems, and working electrode is placed a container, in this container, feed high pure nitrogen, with interference gas in the deaeration.Utilize the galvanochemistry voltammetry, 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain the electrode that PNA partial reduction product is modified.
(4) and will be equipped with in the container of working electrode and put into solid TNT, treat that solid TNT volatilizes gas TNT after, be arranged on 0 in operating voltage～-detect under the 1.2V scope.
The electrode that the PNA that utilizes this method to obtain modifies detects other aromatic nitro compound such as TNB, DNT, DNB, only needs TNT change in the step (4) is other aromatic nitro compound (comprising TNB, DNT, DNB).
Embodiment 6.
(1) fullerene C
60Film (the C of nanoscale
60Material) preparation of modified electrode:
To carry out cleaning surfaces before the solid working electrode glassy carbon electrode uses and handle, earlier with α-Al
2O
3Polishing uses distilled water ultrasonic again.Be put in then in the baking oven and dry electrode surface about 45 ℃.
Under the room temperature with fullerene C
60Be dissolved in the toluene solvant, get an amount of this solution and drip to above-mentioned electrode surface, after the toluene solvant spontaneous evaporation, form uniform C outwardly under the room temperature at glassy carbon electrode
60Film.
(2) utilize fullerene C
60Film modified working electrode, the electrochemical process of ultratrace TNT in the detection electrolyte solution:
(I) the simple three-electrode electro Chemical of employing system, and comprise working electrode (C
60Film modified glassy carbon electrode), to electrode (Pt silk) and contrast electrode (saturated calomel electrode).At first in electrolytic cell, add the 1mM perchloric acid solution as electrolyte solution, in this solution, feed high pure nitrogen, to get rid of interference gas in the solution.Modify good working electrode in will step (1), and electrode and contrast electrode are connected in the circuit of electro-chemical systems, utilize the galvanochemistry voltammetry, 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain C
60The electrode that the membrane portions reduzate is modified.
(II) TNT is dissolved in is configured to lean solution in the absolute ethyl alcohol, get in the electrolyte solution that this solution joins step (I), the concentration that makes TNT is 0.4ppb.
(III) utilize the galvanochemistry voltammetry, be provided with working electrode voltage 0～-detect under the 1.3V scope, obtain the virgin curve of going back of TNT.
By changing the concentration of TNT in the step (III), the volt-ampere curve when obtaining concentration and being respectively 0.8ppb, 1.2ppb, 2ppb etc.
Embodiment 7.
(1) fullerene C
70Film (the C of nanoscale
70Material) preparation of modified electrode:
To carry out cleaning surfaces before the solid working electrode glassy carbon electrode uses and handle, earlier with α-Al
2O
3Polishing uses distilled water ultrasonic again.Be put in then in the baking oven and dry electrode surface about 45 ℃.
Under the room temperature with fullerene C
70Be dissolved in the methyl phenyl ethers anisole solvent, get an amount of this solution and drip to above-mentioned electrode surface, after the spontaneous evaporation of methyl phenyl ethers anisole solvent, form uniform fullerene film outwardly under the room temperature at glassy carbon electrode.
(2) utilize fullerene C
70Film modified working electrode, the electrochemical process of TNT in the detection electrolyte solution:
(I) the simple three-electrode electro Chemical of employing system, and comprise working electrode (C
70Film modified glassy carbon electrode), to electrode (Pt silk) and contrast electrode (saturated calomel electrode).At first in electrolytic cell, add the 1mM perchloric acid solution as electrolyte solution, in this solution, feed high pure nitrogen, to get rid of interference gas in the solution.Modify good working electrode in will step (1), and electrode and contrast electrode are connected in the circuit of electro-chemical systems, utilize the galvanochemistry voltammetry, 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain C
70The electrode that the membrane portions reduzate is modified.
(II) TNT is dissolved in is configured to lean solution in the absolute ethyl alcohol, get in the electrolyte solution that this solution joins step (1), the concentration that makes TNT is 0.2ppb.
(III) utilize the galvanochemistry voltammetry, be provided with working electrode voltage 0～-detect under the 1.3V scope, obtain the virgin curve of going back of TNT.
By changing the concentration of TNT in the step (III), the volt-ampere curve (as shown in Figure 7) when obtaining concentration and being respectively 0.8ppb, 2ppb, 4ppb etc.
Embodiment 8.
(1) fullerene Gd@C
82Film (the Gd@C of nanoscale
82Material) preparation of modified electrode:
To carry out cleaning surfaces before the solid working electrode glassy carbon electrode uses and handle, earlier with α-Al
2O
3Polishing uses distilled water ultrasonic again.Be put in then in the baking oven and dry electrode surface about 45 ℃.
Under the room temperature with Gd@C
82Be dissolved in the chlorobenzene solvent, get an amount of this solution and drip to above-mentioned electrode surface, after the chlorobenzene solvent spontaneous evaporation, form uniform fullerene film outwardly under the room temperature at glassy carbon electrode.
(2) utilize fullerene Gd@C
82Film modified working electrode, the electrochemical process of TNT in the detection electrolyte solution:
(I) the simple three-electrode electro Chemical of employing system, and comprise working electrode (Gd@C
82Film modified glassy carbon electrode), to electrode (Pt silk) and contrast electrode (saturated calomel electrode).At first in electrolytic cell, add the 1mM perchloric acid solution as electrolyte solution, in this solution, feed high pure nitrogen, to get rid of interference gas in the solution.Modify good working electrode in will step (1), and electrode and contrast electrode are connected in the circuit of electro-chemical systems, utilize the galvanochemistry voltammetry, 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain Gd@C
82The electrode that the membrane portions reduzate is modified.
(II) TNT is dissolved in is configured to lean solution in the absolute ethyl alcohol, get an amount of this solution and join in the electrolyte solution of step (I), the concentration that makes TNT is 0.4ppb.
(III) utilize the galvanochemistry voltammetry, be provided with working electrode voltage 0～-detect under the 1.3V scope, obtain the virgin curve of going back of TNT.
By changing the concentration of TNT in the step (III), the volt-ampere curve (as shown in Figure 8) when obtaining concentration and being respectively 1.2ppb, 2ppb, 4ppb etc.
Need to prove, the foregoing description just is used for illustrating technical characterictic of the present invention, not being used for limiting patent claim of the present invention, can be the fullerene of various molecular dimensions, nano-scale, micron-scale such as fullerene that relates in the present embodiment or fullerene derivate material.The method of modified electrode also can be the suspending liquid of fullerene or fullerene derivate material.The preparation of these materials also can be prepared with other prior art.But modify working electrode with fullerene and fullerene derivate material, detect this technology of aromatic nitro compound with galvanochemistry volt-ampere method and still belong to patented claim category of the present invention.
Claims (10)
1. the electrochemical detection method of a ultra trace aromatic nitro compound, it is characterized in that: use the galvanochemistry voltammetry, the electrode that employing is modified the fullerene of aromatic nitro compound sensitivity or fullerene derivate material is as solid working electrode, in three-electrode cell, the aromatic nitro compound of the ultratrace in the electrolyte solution is carried out fast detecting to electrode, contrast electrode and solid working electrode; By the suction-operated of fullerene or fullerene derivate material to the aromatic nitro compound in the electrolyte solution, finish the fast detecting process of the trace aromatic nitro compound in the electrolyte solution, and the position of the feature reduction peak of aromatic nitro compound in the volt-ampere curve that obtains according to detection, qualitatively judge the existence of aromatic nitro compound; Or
Use the galvanochemistry voltammetry, the electrode that employing is modified the fullerene of aromatic nitro compound sensitivity or fullerene derivate material is as solid working electrode, the solid working electrode that will have in the device that electrode, contrast electrode, solid working electrode and solid electrolyte are formed is exposed in the environment that contains aromatic nitro compound gas, and the aromatic nitro compound of the ultratrace in the gas is carried out fast detecting; By the suction-operated of fullerene or fullerene derivate material to the aromatic nitro compound in the gas, finish the fast detecting process of the trace aromatic nitro compound in the gas, and the position of the feature reduction peak of aromatic nitro compound in the volt-ampere curve that obtains according to detection, qualitatively judge the existence of aromatic nitro compound.
2. method according to claim 1 is characterized in that: the method that described aromatic nitro compound to the ultratrace in the electrolyte solution carries out fast detecting may further comprise the steps:
(1) in electrolytic cell, add the neutral aqueous solution be selected from acidic aqueous solution, inorganic salts or and described aromatic nitro compound between chemical reaction does not take place, do not dissolve fullerene or fullerene derivate and the organic solvent that can conduct electricity in one or more potpourri as electrolyte solution; In this electrolyte solution, feed inert gas, to remove the interference gas in the electrolyte solution;
(2) fullerene or fullerene derivate are dissolved in the organic solvent, get on the solid working electrode that this solution drips to cleaning, treat organic solvent evaporation after, form layer of even fullerene or fullerene derivate material at working electrode surface; Perhaps the nano material of fullerene or fullerene derivate is distributed to water or does not dissolve in the organic solvent of fullerene or fullerene derivate, form uniform suspending liquid, get this hanging drop to the solid working electrode of cleaning, after treating the spreading agent evaporation, form layer of even fullerene or fullerene derivate material on the solid working electrode surface;
(3) will to modify in the electrode, contrast electrode, step (2) good solid working electrode be connected to in the step (1) in the circuit of electrolyte solution that inert gas is handled as the electro-chemical systems of electrolyte solution, 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain the solid working electrode that the partial reduction product of fullerene or fullerene derivate is modified;
(4) aromatic nitro compound is dissolved in it chemical reaction does not take place and do not dissolve wiring solution-forming in the organic solvent of fullerene or fullerene derivate, get this solution and join in the step (3) in the electrolyte solution that inert gas is handled; 0～-the 1.3V scope in, in the three-electrode cell to electrode, contrast electrode and solid working electrode of step (3), the aromatic nitro compound of the ultratrace in the electrolyte solution is carried out fast detecting;
The organic solvent of described dissolving fullerene or fullerene derivate is benzene, toluene, carbon disulphide, methyl phenyl ethers anisole, chlorobenzene, o-dichlorobenzene or their any mixture;
The organic solvent of described dispersion fullerene or fullerene derivate nano material is n-pentane, normal hexane, cyclohexane, n-decane or their any mixture.
3. method according to claim 2 is characterized in that: the concentration of described step (4) aromatic nitro compound in electrolyte solution detection limit of the concentration of corresponding aromatic nitro compound respectively when modifying solid working electrode with fullerene-based material or fullerene derivate material.
4. method according to claim 1 is characterized in that: described method of carrying out fast detecting at the aromatic nitro compound to the ultratrace in the gas may further comprise the steps:
(1) fullerene or fullerene derivate are dissolved in the organic solvent, get on the solid working electrode that this solution drips to cleaning, treat organic solvent evaporation after, form layer of even fullerene or fullerene derivate material at working electrode surface; Perhaps the nano material with fullerene or fullerene derivate is distributed in water or the organic solvent, form uniform suspending liquid, get this hanging drop to the solid working electrode of cleaning, after treating the spreading agent evaporation, form layer of even fullerene or fullerene derivate material on the solid working electrode surface;
(2) be connected to make pick-up unit in the circuit of solid electrolyte as electrolyte electrochemical system with the solid working electrode of preparation in the step (1) and to electrode, contrast electrode;
(3) utilize the pick-up unit of step (2), 0～-1.3V scope build-in test cyclic voltammetry curve 1～10 time, obtain the solid working electrode that the partial reduction product of fullerene or fullerene derivate is modified; Solid working electrode with this device is exposed in the environment that contains aromatic nitro compound gas then, and the aromatic nitro compound of the ultratrace in the gas is carried out fast detecting;
Described solid electrolyte is sulphur silver iodide or silver iodide rubidium;
The organic solvent of described dissolving fullerene or fullerene derivate is benzene, toluene, carbon disulphide, methyl phenyl ethers anisole, chlorobenzene, o-dichlorobenzene or their any mixture;
The organic solvent of described dispersion fullerene or fullerene derivate nano material is n-pentane, normal hexane, cyclohexane, n-decane or their any mixture.
5. method according to claim 4 is characterized in that: the concentration of described step (3) aromatic nitro compound in gas detection limit of the concentration of corresponding aromatic nitro compound respectively when modifying solid working electrode with fullerene-based material or fullerene derivate material.
6. method according to claim 2 is characterized in that: described acid is selected from one or more any mixture in perchloric acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hyperbromic acid, the carbonic acid;
Described inorganic salts are selected from one or more any mixture in sodium halogen salt, the halogenation sylvite, and halogen is Br, I or Cl.
7. method according to claim 2 is characterized in that: the organic solvent described in step (1) and the step (4) comprises acetonitrile, absolute ethyl alcohol, N, dinethylformamide, tetrahydrofuran single organic solvent or their any mixed organic solvents.
8. according to claim 1,2 or 4 described methods, it is characterized in that: described electrode is selected from a kind of in the inert metal that oxidation/reduction reaction does not take place platinum, gold or tungsten in testing circuit; Described contrast electrode is selected from saturated calomel electrode or silver/silver chloride electrode;
Described solid working electrode is glassy carbon electrode, gold electrode, platinum electrode or graphite electrode.
9. according to claim 1,2,3,4 or 5 described methods, it is characterized in that: described fullerene or fullerene derivate are the fullerene or the fullerene derivate materials of molecular dimension, nano-scale or micron-scale;
Described aromatic nitro compound comprises the aromatics that contains one or more nitryl groups on the aromatic rings.
10. method according to claim 9 is characterized in that: described fullerene is selected from C
60, C
70, C
76, C
78, C
82, C
84Fullerene or their any mixture;
Described fullerene derivate is the derivant that interior embedded one or more metals of fullerene cage or fullerene cage are externally connected with organic group;
Described metal is: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, Sc, Y, La or Ti;
Described organic group is: pyrrolidino group, alkyl azide group, methylene amine groups or methyl group;
Described aromatic nitro compound comprises 2,4,6-trinitro-toluene, 1,3,5-trinitrobenzen, 2,4-dinitrotoluene (DNT) or 1,3-dinitro benzene.
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| SU1217087A1 (en) * | 1983-12-29 | 1995-08-27 | Отделение Института химической физики АН СССР | Method of voltametric determination of aromatic nitrocompounds and products of its reduction |
| RU2159424C2 (en) * | 1998-12-23 | 2000-11-20 | Государственный научный центр Российской Федерации "НИОПИК" | Procedure determining aromatic nitrocompounds and products for their reduction |
| CN1195103C (en) * | 2002-04-15 | 2005-03-30 | 中国科学院化学研究所 | Process for electrochemically preparing nanoline array of Fullerenes |
| JP2007026708A (en) * | 2005-07-12 | 2007-02-01 | Jsr Corp | Electrode catalyst layer |
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