CN102435656A - Sensor array and method for quickly detecting soil nitrate nitrogen - Google Patents
Sensor array and method for quickly detecting soil nitrate nitrogen Download PDFInfo
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- CN102435656A CN102435656A CN2011102699568A CN201110269956A CN102435656A CN 102435656 A CN102435656 A CN 102435656A CN 2011102699568 A CN2011102699568 A CN 2011102699568A CN 201110269956 A CN201110269956 A CN 201110269956A CN 102435656 A CN102435656 A CN 102435656A
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Abstract
The invention relates to the technical field of quick detection of soil nutrient and discloses a sensor array for quickly detecting soil nitrate nitrogen. The sensor array comprises a silver-silver chloride reference electrode and multiple polypyrrole polymer sensitive film sensors; the reference electrode and the multiple sensors are arranged in parallel; and each sensor comprises a substrate and a polypyrrole polymer film which is located on the substrate and is doped with nitrate radical. The invention also provides a method for detecting nitrate nitrogen content by utilizing the sensor array. According to the invention, the problems such as undesirable selectivity and the like in the conventional polyvinyl chloride ion selective electrode for the soil nitrate nitrogen detection sensor can be solved.
Description
Technical field
The present invention relates to the soil nutrient rapid detection technical field, be specifically related to a kind of soil nitrate nitrogen fast detecting sensor array and detection method thereof.
Background technology
Soil and water are human Source of life, are the important prerequisites that ensures social civilization, economic development.Get into 21 century, the Chinese population sustainable growth, the arable land total amount is but successively decreased year by year, is to ensure grain security, improves yield of commercial crops, be that the intensification agricultural production of characteristics is universal thereupon with " high chemical fertilizer input ".Wherein, to cross problems such as executing the soil secondary salinization, surface water and the groundwater azotate pollution that cause, quality of agricultural product decline, greenhouse gas emission particularly severe because of nitrogenous fertilizer.Through test, not only can realize the estimation of crop single cropping amount of application of nitrogen fertilizer and the diagnosis of topdressing of breeding time, and can characterize the pollution level of groundwater azotate to a certain extent soil root layer section nitrate nitrogen content.
Just bibliographical information having been arranged from the seventies in 20th century utilizes ISE directly to measure the method for the nitrate nitrogen content in the soil extracting solution under laboratory condition.But; There is following problem in tradition based on the soil nitrate nitrogen detecting sensor of nitrate ion selective electrode: 1. detecting sensor adopt with season amino-compound be the PVC ion selective membrane of electroactive material, the field is subject to environmental parameter and counter anion serious interference when measuring; 2. amino-compound is on the high side season, in use exists gradually to surface migration and the trend that runs off, and electrode performance is prone to degenerate, and on the high side; 3. must fill the solution of a constant volume in the electrode suppor, be unfavorable for the microminaturization of sensor and integrated.
Conducting polymer is one type of special macromolecule conjugated polymer; Comprise polypyrrole, polyacetylene, polythiophene and polyaniline etc.; Have good physical stability, good electrical conductivity, strong with the base material adhesion, have better organic phase capacitive than metal, show application potential preferably in fields such as fuel cell, chemical sensor, high-energy capacitor device, nano material and electro-catalysis.Through galvanochemistry mediation molecular imprinting; Under the electrochemical conditions of control, make pyrroles's matrix monomer polymerization reaction take place; In the polypyrrole polymers film formation process; Be accompanied by the nitrate ion doping and get into polypyrrole Molecularly Imprinted Polymer conjugated chain, thereby form the polymkeric substance of highly cross-linked structure.
Summary of the invention
The technical matters that (one) will solve
Technical matters to be solved by this invention is the unfavorable problem of selectivity that is used for the conventional PVC ISE existence of soil nitrate nitrogen detecting sensor.
(2) technical scheme
For solving the problems of the technologies described above; The invention provides a kind of soil nitrate nitrogen fast detecting sensor array; Comprise silver-silver chloride contrast electrode and a plurality of polypyrrole polymers sensitive membrane sensor; Said contrast electrode and a plurality of sensor parallel arranged, said sensor comprise substrate and are positioned at said suprabasil, the polypyrrole polymers film that is doped with nitrate radical.
Preferably, said sensor array also comprises support, and said contrast electrode and sensor all are fixed on the said support.
Preferably, said substrate is a graphite carbon rod.
Preferably; Said sensor also comprises glass tube, epoxy resin, sealing cap and the lead of both ends open; Said epoxy resin, graphite carbon rod and the polypyrrole polymers film that is doped with nitrate radical all are positioned at said glass tube; Said sealing cap is positioned at sealing of glass tube one end, and said lead passes said sealing cap and is connected with said graphite carbon rod.
The present invention also provides a kind of method of utilizing described sensor array to detect nitrate nitrogen content, comprises the demarcating steps of sensor array and the determination step of soil nitrate nitrogen;
The demarcating steps of said sensor array comprises:
S11, clean said sensor array, remain unchanged until the difference of the potential measurement value of the potential measurement value of said a plurality of sensors and contrast electrode, promptly said contrast electrode and sensor reach molecular balance;
S12, select for use the nitrate solution of concentration known to feed a plurality of detection cells as volumetric solution; And in each detection cell, insert said a plurality of sensors and contrast electrode; When writing down said contrast electrode and each sensor and reaching molecular balance; The potential measurement value of each sensor, the potential measurement value of this moment is an equilibrium potential;
S13, represent the potential measurement value and the nitrate nitrogen NO of each sensor with following formula (1)
3 -Linear response relationship between the negative logarithm of-N volumetric molar concentration:
E
a＝-S
alog(Mol)+E
0a (1)
In the formula, Mol is nitrate nitrogen NO
3 --N volumetric molar concentration; E
aIt is the potential measurement value that a props up sensor; S
aIt is the electromotive force response slope that a props up sensor; E
0aIt is the standard electrode potential that a props up sensor; The value of a is 1～N, and N is the quantity of sensor;
With the equilibrium potential substitution formula (1) of each sensor, utilize PLS then, calculate the parameter E in the formula (1)
0a, S
aValue, draw sensor array calibrating equation (1) thus;
The computing formula that a props up the Mol value that sensor measures is as shown in the formula (2):
Mol＝10
-(Ea-Eoa)/Sa (2)
The determination step of said soil nitrate nitrogen comprises:
S21, clean said sensor array, remain unchanged until the difference of the potential measurement value of the potential measurement value of each sensor and contrast electrode, promptly said contrast electrode and sensor reach molecular balance;
S22, utilize sensor array parallel detection N to organize the potential measurement value of solution to be measured;
The sensor array detection side formula (2) that S23, utilization have been obtained is measured the nitrate nitrogen NO in the solution to be measured
3 --N volumetric molar concentration.
(3) beneficial effect
(1) sensor array of the present invention comprises many solid-state polypyrrole polymers sensitive membrane sensors and 1 silver-silver chloride contrast electrode; Through the potential measurement method; Can walk abreast and obtain of the electromotive force response of the tested soil extracting solution of multichannel, and then utilize analysis of regression model to draw the nitrate nitrogen content in the pedotheque to be measured at the sensor interface.It is low to have solved conventional soil test experience chamber complicated operation detection efficiency, and has nitrate nitrogen field fast determining method poor accuracy now, is subject to the problem of disturbing effect.
(2) basal electrode of sensor array of the present invention is selected graphite carbon rod for use, and selective membrane material monomer pyrroles material is easy to get, and the cost of two kinds of materials is lower; Film of poly pyrrole is combined in the solid state electrode surface through electropolymerization mode tightening key, fills solution in need not, and is easy to microminaturization, and can pass through activation processing " regeneration "; The integration mode of sensor array is flexible, is easy to expansion.It is few because of detecting the high soil-like given figure that causes of cost to have solved conventional method, the problem of the representative difference of testing result.
(3) because the multiple identification " cavity structure " of inner existence of polypyrrole polymers sensitive membrane (being the polypyrrole polymers film) and nitrate radical space coupling can realize the selectivity identification to nitrate ion.Solved tradition with season amino-compound as the PVC ion selective membrane poor selectivity of electroactive material, the problem that testing result is subject to disturb.
Advantages such as in a word, the present invention has selectivity, accuracy and good stability, and cost is low, extensibility good, and applicability is wide.
Description of drawings
Fig. 1 is the polypyrrole polymers sensitive membrane sensor construction synoptic diagram of doping nitrate radical;
Fig. 2 is a sensor array structural representation of the present invention;
Fig. 3 is the structural representation of support;
Fig. 4 is a sensor array calibrating curve of the present invention;
Fig. 5 is the testing result of sensor array.
Embodiment
Regard to a kind of soil nitrate nitrogen fast detecting sensor array and detection method thereof proposed by the invention down, specify in conjunction with accompanying drawing and embodiment.
The present invention makes up solid-state polypyrrole polymers sensitive membrane sensor (the Nitrate doped Polypyrrole (PPy (NO of doping nitrate radical
3 -)) Solid-State Sensor), and with this as basic perception unit; Sensor array is made up of 4 solid-state polypyrrole polymers sensitive membrane sensors and 1 silver-colored silver chloride contrast electrode; Polypyrrole polymers sensitive membrane 1 is aggregated in graphite carbon rod basal electrode surface through electrochemical method; Based on the potential measurement principle; After with the known low concentrations nitrate solution sensor array being carried out activation; Utilize the washed with de-ionized water array surface, and then utilize the concentration known nitrate solution that sensor array is demarcated, measure the nitrate nitrogen content in the soil extracting solution.The present invention can be used for applications such as soil nutrient management and fertilization compositions based on earth measurement engineering.
The preparation method of soil nitrate nitrogen sensor array of the present invention may further comprise the steps:
The preparation of A1, graphite carbon rod substrate and pre-service
The base material of polypyrrole polymers sensitive membrane sensor is selected graphite carbon rod 2 for use, and its preparation process is: at first graphite carbon rod is put into glass tube 3, with epoxy resin 4 cans.Be the effecting reaction area of control sensor, the epoxy resin filling process should slowly at the uniform velocity prevent that as far as possible bubble from producing; After the encapsulation, this sensor ventilated dried 3-5 days, treat the epoxy resin full solidification after, again sensor surface is handled.
The sensor surface pre-treatment step is following: at first, use the sand papering sensor surface of 30 μ m, 3 μ m and 0.3 μ m successively, polishing is washed with absolute ethyl alcohol after accomplishing; Then, sensor is immersed in the deionized water, utilize ultrasound wave to clean, remove the sand paper particle of electrode surface absorption.Through assay optimization, the ultrasonic cleaning time is 5 minutes among the present invention.
A2, sensor plated film
Polymeric solution is by 0.5mol/L pyrrole monomer (purifying in advance) and 1mol/L NaNO
3Mixed solution is formed.Before polyreaction, fed nitrogen 10 minutes, to remove the oxygen in the electrolyte solution; In the electropolymerization process, above electrolyte solution, constantly feed nitrogen,, prevent the pyrrole monomer oxidation to get rid of the air in the reaction environment.The electropolymerization process adopts galvanostat, in the WS, carries out the polypyrrole preparation.
In two electrode systems, working electrode adopts the self-control carbon electrode, and auxiliary electrode is selected the platinized platinum electrode for use, between working electrode and auxiliary electrode, feeds the constant polymerization electric current of 80 μ A.After being 40 minutes conduction time, the polypyrrole conducting polymer thin film of the doping nitrate radical of brownish black is deposited on the basal electrode surface.Behind the electropolymerization, need slowly to wash sensor surface with deionized water, then it is positioned over activation in the nitrate solution, activated solution concentration is 1 * 10
-3Mol/LNaNO
3, soak time is 24 hours.
Among the present invention, basal electrode is selected graphite carbon rod for use, and the carbon-point diameter of section is 2mm, and length is 100mm; Sensor sealing cap 5 adopts plastic material, utilizes epoxy resin to stick in the glass tube surface; Utilize epoxy resin to fill between glass tube and the graphite carbon rod, the polypyrrole polymers sensitive membrane of doping nitrate radical adopts the electropolymerization mode to be deposited on the carbon-point surface.The structure of single sensor is as shown in Figure 1, wherein 6 expression leads.
A3, composition sensor array
Sensor array is by 4 solid-state polypyrrole polymers sensitive membrane sensors, and 1 silver-silver chloride contrast electrode and support are formed: microminiature silver-silver chloride contrast electrode can provide stable and reappearance reference potential preferably in the array; But the nitrate nitrogen content in perception array parallel detection 4 road soil extracting solutions that 4 solid-state polypyrrole polymers sensitive membrane sensors are formed, and convert the nitrate ion concentration in the solution into the potential measurement value; Sensor and electrode are fixed by support, use bolt between support.The sensor array array structure is as shown in Figure 2, and supporting structure is as shown in Figure 3.
Discuss 5 courses of work of the present invention below;
The present invention is based on and this special principle to be measured by the nitrate nitrogen in the pedotheque extracting solution; Utilize the method for potential measurement; Write down the potential difference (PD) between 4 sensors and the contrast electrode respectively; According to the sensor array calibrating curve that obtains in advance, to calculate and learn the nitrate nitrogen content in the soil extracting solution to be measured, the concrete course of work is following;
The demarcation of S1, sensor array
S11, utilize the washed with de-ionized water sensor array, remain unchanged until the difference of the potential measurement value of the potential measurement value of each road sensor and contrast electrode, promptly said contrast electrode and sensor reach molecular balance;
S12, select for use the concentration known nitrate solution to feed each detection cell, as 10
-5, 10
-4, 10
-3, 10
-2, 10
-1Mol/L NaNO
3, insert sensor array, between record contrast electrode and each sensor reach molecular balance the time, the potential measurement value of each sensor, potential measurement value at this moment is an equilibrium potential;
S13, represent the potential measurement value and the NO of each sensor with following formula (1)
3 -Linear response relationship between the negative logarithm of-N volumetric molar concentration (ol representes with symbol M)
E
a-S
alog(Mol)+E
0a (1)
In the regression model of following formula, E
aBe the potential measurement value that a props up sensor, unit is mV; S
aBe the electromotive force response slope that a props up sensor, unit is mV/decade; E
0aBe the standard electrode potential that a props up sensor, unit is mV; The value of a is 1 to 4.With the equilibrium potential substitution formula (1) of each sensor, utilize PLS then, calculate the parameter E in the formula (1)
0a, S
aValue, draw sensor array calibrating equation (1) thus; Hence one can see that:
A props up the Mol=10 that sensor goes out
-(Ea-Eoa)/Sa(2)
According to above-mentioned experimental technique, can draw sensor array calibrating equation, and can draw the nitrate nitrogen content in the solution according to formula (2) derivation suc as formula (1) form.
The mensuration of S2, soil nitrate nitrogen
S21, utilize the washed with de-ionized water sensor array, remain unchanged until the difference of the potential measurement value of the potential measurement value of each road sensor and contrast electrode, promptly said contrast electrode and sensor reach molecular balance;
S22, utilize the nitrate nitrogen content of sensor array parallel detection 4 road pedotheque extracting solutions, obtain respectively to organize the sense potential of solution;
The sensor array detection side formula (2) that S23, utilization have been obtained can be measured the nitrate nitrogen content in the testing sample.
The present invention's continuous coverage that can walk abreast, repeating step S21 during continuous coverage.
Embodiment
The 100 groups of pedotheques in spring wheat experimental plot are gathered in experiment base in Xiao Tang mountain from Beijing.The collection soil sample is all 55 ℃ of following low temperature dryings 8 hours, utilizes the soil comminutor back of milling to cross 40 order analyses sieve.In the leaching process, get the 10g pedotheque and add 25ml digestion agent vibration 30 minutes, make it to homogenize.After soil lixiviate suspension after will vibrating again leaves standstill 2 hours,, obtain the soil extraction of clarification with middling speed quantitative test filter paper filtering.
Before the analysis to measure, at first carry out the demarcation of sensor array: utilize the washed with de-ionized water sensor array, reach stable until the potential measurement value of No. 4 sensors and the sense potential value between the contrast electrode; Then, select 10 for use
-5, 10
-4, 10
-3, 10
-2, 10
-1Mol/L NaNO
3, successively through sensor array, when record contrast electrode and each sensor reach molecular balance, the equilibrium potential of sensor.With NO in the solution
3 -The negative logarithm of-N concentration is a transverse axis, is the longitudinal axis with the sense potential of each sensor, and the transducer calibration curve is as shown in Figure 4.
According to testing result, draw the equilibrium potential and the NO of each sensor
3 -Linear response relationship between the negative logarithm of-N volumetric molar concentration Mol utilizes partial least-square regression method according to the equilibrium potential value of measured sensor then, draws the parameter E in the regression model formula (1)
0a, S
aValue, can draw the calibration equation of four sensor arraies in the detection arrays, respectively suc as formula shown in (3), (4), (5), (6):
E
1＝-47.3×log(Mol)+37.2 (3)
E
2＝-47.6×log(Mol)+43.3 (4)
E
3＝-47.3×log(Mol)+42.8 (5)
E
4＝-47.7×log(Mol)+40.2 (6)
E in formula (3)-(6)
1-E
4Be respectively the 1st equilibrium potential to the 4th sensor, unit is mV;-log (Mol) represents NO
3 -The negative logarithm of-N volumetric molar concentration.
According to above-mentioned formula, the detection equation that conversion draws sensor array is suc as formula (7)～formula (10), shown in:
The 1st
(7) that sensor goes out
The 2nd
(8) that sensor goes out
The 3rd
(9) that sensor goes out
The 4th
(10) that sensor goes out
According to above formula (7)～(10), the sense potential E of substitution extracting solution to be measured
a, can obtain the nitrate nitrogen content Mol in the solution to be measured.
The mensuration of soil nitrate nitrogen:
Utilize the washed with de-ionized water sensor array, reach stable until the potential measurement value of each road sensor and the sense potential value between the contrast electrode;
Utilize the nitrate nitrogen content of sensor array parallel detection 4 road pedotheque extracting solutions, obtain respectively to organize the sense potential of solution;
Utilize the electrod-array examination criteria equation (1) that has obtained, can measure the nitrate nitrogen content in the testing sample.This sample collecting amount is 100, but the present invention's real-time parallel detects 4 groups, and then the sensor array continuous coverage is 25 times.The nitrate nitrogen testing result of 100 representative soil samples is as shown in Figure 5.
In Fig. 5, black dispersion point is represented the testing result (C of sensor
1Sample～C
4Sample).According to testing result, between the measurement of concetration result of all measurement points concentrates on 3～5 (seeing transverse axis), because transverse axis unit is the NO of solution to be measured
3 -The negative logarithm of-N volumetric molar concentration is so the nitrate nitrogen content that should organize soil sample is 10
-510
-3Mol/L, parallel detection efficient is higher, and it is better to detect stability, reliability and accuracy, and system cost is lower.
Can find out by above embodiment; The present invention with low-cost graphite carbon rod as basal electrode; Prepare all solid state polypyrrole ISE senser element based on galvanostatic method, and electrode surface pre-service and ion selectivity film preparation procedure parameter are optimized; Utilize 4 solid-state polypyrrole polymers sensitive membrane sensors and 1 microminiature silver silver chloride contrast electrode to form nitrate nitrogen sensor array; Through the potential measurement method; Walk abreast and obtain the sense potential of 4 road tested soil extracting solutions, utilize the detection model analysis to draw the nitrate nitrogen content in the pedotheque to be measured at the sensor interface; Through detecting, the parallel detection efficient of detection arrays is higher, and it is better to detect stability, reliability and accuracy, and system cost is lower.
Can find out by above embodiment; With tradition with season amino-compound compare as the PVC ion selective membrane of electroactive material; The multiple identification " cavity structure " of inner existence of polypyrrole polymerization sensitive membrane and nitrate radical space coupling can realize the selectivity identification to nitrate ion; Matrix monomer pyrroles material is easy to get, and cost is lower, can be combined in the solid state electrode surface through electropolymerization mode tightening key, has improved " ion transition " potential barrier influence that the PVC sensitive membrane exists, and can pass through activation processing " regeneration ", improves electrode life; Fill solution in solid-state polypyrrole polymers sensitive membrane sensor need not, be easier to microminaturization and integrated.
Above embodiment only is used to explain the present invention; And be not limitation of the present invention; The those of ordinary skill in relevant technologies field under the situation that does not break away from the spirit and scope of the present invention, can also be made various variations and modification; Therefore all technical schemes that are equal to also belong to category of the present invention, and scope of patent protection of the present invention should be defined by the claims.
Claims (5)
1. soil nitrate nitrogen fast detecting sensor array; It is characterized in that; Comprise silver-silver chloride contrast electrode and a plurality of polypyrrole polymers sensitive membrane sensor; Said contrast electrode and a plurality of sensor parallel arranged, said sensor comprise substrate and are positioned at said suprabasil, the polypyrrole polymers film that is doped with nitrate radical.
2. sensor array as claimed in claim 1 is characterized in that said sensor array also comprises support, and said contrast electrode and sensor all are fixed on the said support.
3. sensor array as claimed in claim 1 is characterized in that, said substrate is a graphite carbon rod.
4. sensor array as claimed in claim 3; It is characterized in that; Said sensor also comprises glass tube, epoxy resin, sealing cap and the lead of both ends open; Said epoxy resin, graphite carbon rod and the polypyrrole polymers film that is doped with nitrate radical all are positioned at said glass tube, and said sealing cap is positioned at sealing of glass tube one end, and said lead passes said sealing cap and is connected with said graphite carbon rod.
5. a method of utilizing each described sensor array detection nitrate nitrogen content in the claim 1～4 is characterized in that, comprises the demarcating steps of sensor array and the determination step of soil nitrate nitrogen;
The demarcating steps of said sensor array comprises:
S11, clean said sensor array, remain unchanged until the difference of the potential measurement value of the potential measurement value of said a plurality of sensors and contrast electrode, promptly said contrast electrode and sensor reach molecular balance;
S12, select for use the nitrate solution of concentration known to feed a plurality of detection cells as volumetric solution; And in each detection cell, insert said a plurality of sensors and contrast electrode; When writing down said contrast electrode and each sensor and reaching molecular balance; The potential measurement value of each sensor, the potential measurement value of this moment is an equilibrium potential;
S13, represent the potential measurement value and the nitrate nitrogen NO of each sensor with following formula (1)
3 -Linear response relationship between the negative logarithm of-N volumetric molar concentration:
E
a-S
alog(Mol)+E
0a (1)
In the formula, Mol is nitrate nitrogen NO
3 --N volumetric molar concentration; E
aIt is the potential measurement value that a props up sensor; S
aIt is the electromotive force response slope that a props up sensor; E
0aIt is the standard electrode potential that a props up sensor; The value of a is 1～N, and N is the quantity of sensor;
With the equilibrium potential substitution formula (1) of each sensor, utilize PLS then, calculate the parameter E in the formula (1)
0a, S
aValue, draw sensor array calibrating equation (1) thus;
The computing formula that a props up the Mol value that sensor measures is as shown in the formula (2):
Mol＝10
-(Ea-Eoa)/Sa (2)
The determination step of said soil nitrate nitrogen comprises:
S21, clean said sensor array, remain unchanged until the difference of the potential measurement value of the potential measurement value of each sensor and contrast electrode, promptly said contrast electrode and sensor reach molecular balance;
S22, utilize sensor array parallel detection N to organize the potential measurement value of solution to be measured;
The sensor array detection side formula (2) that S23, utilization have been obtained is measured the nitrate nitrogen NO in the solution to be measured
3 --N volumetric molar concentration.
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| CN103499984A (en) * | 2013-09-26 | 2014-01-08 | 北京农业智能装备技术研究中心 | Nutrient solution ion concentration control method and system |
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| CN104897731A (en) * | 2015-06-17 | 2015-09-09 | 江苏大学 | Portable device for detecting nutrition level of plant |
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