CN103207225A - Electrochemical transducer probe for detecting chemical oxygen demand and manufacturing method of electrochemical transducer probe - Google Patents
Electrochemical transducer probe for detecting chemical oxygen demand and manufacturing method of electrochemical transducer probe Download PDFInfo
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- CN103207225A CN103207225A CN201310081539XA CN201310081539A CN103207225A CN 103207225 A CN103207225 A CN 103207225A CN 201310081539X A CN201310081539X A CN 201310081539XA CN 201310081539 A CN201310081539 A CN 201310081539A CN 103207225 A CN103207225 A CN 103207225A
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Abstract
The invention provides an electrochemical transducer probe for detecting chemical oxygen demand. The electrochemical transducer probe comprises a platinum disk electrode and a platinum nano sensitive membrane arranged on an exposed surface of a platinum disk of the platinum disk electrode, and the platinum nano sensitive membrane is composed of platinum nano particles and formed by reducing, electroplating and depositing chloroplatinic acid (H2PtCl6) on the exposed surface of the platinum disk (1). Compared with existing potassium dichromate national standard method, the electrochemical transducer probe has the advantages of high sensitivity, fast analysis, high accuracy and practicality, high chloridion interference resistance and the like and overcomes defects of complicated operation, time wasting and certain environmental pollution and the like of the existing potassium dichromate national standard method.
Description
Technical field
The invention belongs to environmental monitoring and electrochemical sensor field, relate to monitoring water environment and nano electrochemical sensor.
Background technology
Chemical oxygen demand (COD) (COD) is to weigh an important indicator of water pollution degree, refers under the certain condition that the reducing substances in the water body is by the concentration of the corresponding oxygen of oxygenant of strong oxidizer oxidation consumption.China's surface water falls into 5 types (GB3838-2002) according to the water environment function by water quality, requires chemical oxygen demand (COD) (COD) value not to be higher than 40 milligrams per liters (mg L-1).The numerical value of chemical oxygen demand (COD) (COD) is more big to show that the pollution level of water body is more high.Therefore monitor water body COD concentration to environmental improvement and guarantee that water safety is most important.Chemical oxygen demand (COD) (COD) assay method often comprises potassium dichromate method (GB11914-89), spectrophotometric method, quick resolution method and electrochemical method at present.Although potassium dichromate method oxidation efficiency height, favorable reproducibility, digestion time is long, the titration process complicated and time consumption.The spectrophotometric method that grows up afterwards and quick resolution method also are improved on traditional potassium dichromate method basis, but these methods all can be used the strong oxidizer potassium dichromate in digestion process, catalyst sulfuric acid silver and chlorion screening agent mercuric sulfate.Strong oxidizer and mercury element all can cause certain contaminative to environment, and the use of silver sulphate reagent also can cause detecting the cost height, and complicated operating process, analysis time long (digestion time is at least 15 minutes fast).Electrochemical method determining chemical oxygen demand (COD) (COD), as measured signal, analysis time is short with the electric current of the electric weight that consumes in the reducing substances oxidizing process in the water body or generation, and operation is simple, highly sensitive fast.Although nano metal or nano-metal-oxide are used for the existing many reports of chemical oxygen demand (COD) (COD) electrochemical sensing as the electrode sensitive material, the exploration of new material is remained a key issue.Therefore, the research high sensitivity, fast, environmental friendliness, new chemical oxygen demand (COD) electrochemical sensor simple to operate, that accuracy is high still be full of challenge and novelty.
Summary of the invention
Task of the present invention provides a kind of electrochemical sensor probe that detects chemical oxygen demand (COD), make its have highly sensitive, analysis speed is fast, accuracy is high, practical, characteristics such as the resisting chloride ion penetration interference performance is strong.
Another task of the present invention provides the preparation method of the electrochemical sensor probe of this detection chemical oxygen demand (COD).
Realize that technical scheme of the present invention is:
The electrochemical sensor probe of detection chemical oxygen demand (COD) provided by the invention, constituted by platinum disk electrode and the platinum nanometer sensitive membrane that is positioned at platinum dish 1 exposed surface of this platinum disk electrode, described platinum disk electrode is made up of platinum dish 1, electrode jacket 2 and copper rod shape lead 3, platinum dish 1 is packaged in the centre of electrode jacket 2 one ends, a side of platinum dish 1 is exposed to the end face of electrode jacket 2, one end of copper rod shape lead 3 is connected with platinum dish 1 in electrode jacket 2, and the other end of copper rod shape lead 3 extends to outside the electrode jacket 2.The platinum nanometer sensitive membrane that is positioned at platinum dish 1 exposed surface of platinum disk electrode is with chloroplatinic acid (H
2PtCl
6) the platinum nanometer sensitive membrane that is constituted by Pt nanoparticle that forms in platinum dish 1 exposed surface of reduction electroplating deposition.With chloroplatinic acid (H
2PtCl
6) the reduction electroplating deposition in the concrete grammar that platinum dish 1 exposed surface forms the platinum nanometer sensitive membrane that is made of Pt nanoparticle is: will polish to immerse to the platinum dish position of the platinum disk electrode of minute surface and contain every liter of 0.5～10 mM (mmol/L) chloroplatinic acid (H
2PtCl
6) 0.1～2 mole every liter (mol/L) sulfuric acid (H
2SO
4) in, with-0.7～0.1 volt (V), be preferably-0.4～-0.1 volt, more preferably-0.3 volt current potential carries out the constant potential reduction, the potential reduction time is 10-300 second (s), be preferably 60～300 seconds, more preferably 120 seconds, namely the exposed surface at platinum dish 1 formed the platinum nanometer sensitive membrane that is made of Pt nanoparticle.
The preparation method of the electrochemical sensor of this detection chemical oxygen demand (COD) provided by the invention probe is: just polish to immerse to the platinum dish position of the platinum disk electrode of minute surface and contain every liter of chloroplatinic acid (H of 0.5～10 mM
2PtCl
6) 0.1～2 mole of every liter of H
2SO
4In, with-0.7～0.1 volt, be preferably-0.4～-0.1 volt, more preferably-0.3 volt current potential carries out the constant potential reduction, the potential reduction time is 10-300 second (s), be preferably 60～300 seconds, more preferably 120 seconds, namely the exposed surface at platinum dish 1 formed the platinum nanometer sensitive membrane that is made of Pt nanoparticle.
In one embodiment of the invention, platinum disk electrode adopts the Wuhan farsighted Science and Technology Ltd. of Grolsch product sold, and this platinum disk electrode is cylindric, is packaged in the platinum dish 1 in electrode jacket 2 one end centres also for cylindric, and diameter highly is 4 millimeters at 3 millimeters.Its electrode jacket 2 is made of teflon, and electrode jacket 2 also can be made of polychlorotrifluoroethylene or polyetheretherketone.Its copper rod shape lead 3 diameters are 1 millimeter, and an end of copper rod shape lead 3 links to each other with platinum dish 1, and the other end is stretched out by the bottom of electrode jacket 2.
In yet another embodiment of the present invention, platinum dish 1 surface of the electrochemical sensor probe of the detection chemical oxygen demand (COD) that we is provided with scanning electron microscope characterizes, as seen the platinum nanometer sensitive membrane that is made of Pt nanoparticle, its sem photograph as shown in Figures 2 and 3.
Electrochemical sensor probe with detection chemical oxygen demand (COD) provided by the invention is that actual water sample detects to deriving from different lake water or river, relation between systematic study water sample chemical oxygen demand (COD) (COD) current responsing signal and the nanometer platinum pattern, testing result sees Fig. 4, Fig. 5, filtered out the method that the highest the present invention of preparation sensitivity detects the electrochemical sensor probe of chemical oxygen demand (COD).
Compared with prior art, namely with respect to consuming time, complicated operation, have the potassium dichromate National Standard Method of certain environment contaminative, the electrochemical sensor probe of detection chemical oxygen demand (COD) provided by the invention has the following advantages:
(1) high sensitivity: by the Pt nanoparticle of control current potential and time in-situ deposition different-shape, find that chemical oxygen demand (COD) (COD) is closely related at the pattern of the response signal on nanometer platinum surface and nanometer platinum; A large amount of testing sieves select the catalytic activity height, to the sensitive material of the significant petal-shaped nano sheets of platinum of chemical oxygen demand (COD) (COD) signal enhancement effect as chemical oxygen demand (COD) (COD) electrochemical sensor, greatly improve detection sensitivity, detect and be limited to 2.29 milligrams every liter (mg L-1); (2) analysis speed is fast: National Standard Method measure chemical oxygen demand (COD) (COD) only water sample just clear up and need 2 hours, this sensor need not to clear up to water sample, can directly measure, whole sample is about 3 minutes analysis time, satisfies on-the-spot fast monitored requirement; (3) accuracy height: with the mensuration of sensor for the separate sources actual water sample, measurement result and GB potassium dichromate method measurement result be identical (relative error is lower than 9%) very; (4) practical: be object with the separate sources water sample directly during sensor optimization, and do not adopt single chemical oxygen demand (COD) (COD) reference material, thereby the more compound actual conditions of research; Many parts of separate sources water body example test results prove that also the sensor of researching and developing has good practical prospect in addition, and are practical; (5) the resisting chloride ion penetration interference performance is strong: when measuring chemical oxygen demand (COD) (COD), chlorion can produce interference, and conventional method is to add poisonous mercury salt to shelter.We are by avoiding the interference of chlorion to measuring the method that adds high concentration chloride in the medium again, and experiment shows that 0.1 mole of every liter of chlorion does not disturb.
Description of drawings
Fig. 1: the structural representation of an embodiment of the electrochemical sensor probe of detection chemical oxygen demand (COD) provided by the invention, toponym shown in the Digital ID is among the figure: 1-platinum dish; The 2-electrode jacket; 3-copper rod shape lead.
Fig. 2: the stereoscan photograph of the Pt nanoparticle sensitive membrane of 4 kinds of nano-sensor probe A that prepare under the different potentials, B, C, D.
Fig. 3: the stereoscan photograph of the Pt nanoparticle sensitive membrane of 6 kinds of nano-sensors probes E, F that the different recovery times prepare down, G, H, I, J.
Fig. 4: graph of a relation between nanometer platinum reduction potential and chemical oxygen demand (COD) (COD) response signal, be different chemical oxygen demand (COD) lake water response current and nanometer platinum reduction potential relation curve, illustration is the ampere curve of actual water sample.
Graph of a relation between Fig. 5 nanometer platinum sedimentation time and chemical oxygen demand (COD) (COD) response signal.Be different chemical oxygen demand (COD) lake water at response current and the sedimentation time relation curve on the nanometer platinum surface of different time deposition, illustration is the ampere curve of separate sources actual water sample.
Embodiment
The preparation of the electrochemical sensor probe of detection chemical oxygen demand (COD) provided by the invention:
To polish to minute surface available from the platinum dish 1 of the platinum disk electrode of the farsighted Science and Technology Ltd. of Wuhan Grolsch, and immerse to platinum dish 1 position of the platinum disk electrode of minute surface polishing and contain every liter of chloroplatinic acid (H of 1 mM
2PtCl
6) 0.1 mole of every liter of H
2SO
4In, carry out the constant potential reduction with-0.3 volt current potential, the potential reduction time is 120 seconds, forms the platinum nanometer sensitive membrane that is made of Pt nanoparticle with the surface at platinum dish (1).Platinum disk electrode available from the farsighted Science and Technology Ltd. of Wuhan Grolsch is cylindric, is packaged in the platinum dish 1 in electrode jacket 2 one end centres also for cylindric, and diameter highly is 4 millimeters at 3 millimeters.Electrode jacket 2 is made of teflon, and copper rod shape lead 3 diameters are 1 millimeter, and an end of copper rod shape lead 3 links to each other with platinum dish 1, and the other end is stretched out by the bottom of electrode jacket 2.
(1) adopts common three-electrode system, pop one's head in as working electrode with the electrochemical sensor that detects chemical oxygen demand (COD), silver/silver chloride electrode is as contrast electrode, platinum post electrode is to electrode, connecting electrochemical workstation and computing machine gathers and record experimental data, with scanning electron microscope platinum dish 1 surface of popping one's head in the electrochemical sensor of the detection chemical oxygen demand (COD) that obtains under the different reduction potentials is characterized, can see the platinum nanometer sensitive membrane that is made of Pt nanoparticle of different-shape, its sem photograph as shown in Figures 2 and 3.
Fig. 2 is the stereoscan photograph of the Pt nanoparticle sensitive membrane of 4 kinds of nano-sensor probe A preparing under the different potentials, B, C, D, and the scanning electron microscope model is Quanta200 (Dutch FEI Co.).Figure A among Fig. 2 is the sem photograph in the Pt nanoparticle sensitive membrane of-0.1 volt of reduction potential deposit preparation in 120 seconds; Figure B among Fig. 2 is the sem photograph in the Pt nanoparticle sensitive membrane of-0.2 volt of reduction potential deposit preparation in 120 seconds; Figure C among Fig. 2 is the sem photograph in the Pt nanoparticle sensitive membrane of-0.3 volt of reduction potential deposit preparation in 120 seconds; Figure D among Fig. 2 is the sem photograph in the Pt nanoparticle sensitive membrane of-0.4 volt of reduction potential deposit preparation in 120 seconds;
Different electrode sensitive film preparation parameters are as shown in the table:
From Fig. 2 sem photograph as can be seen, obtained the Pt nanoparticle of different-shape under the different reduction potentials.When sedimentation potential during at-0.1 volt (seeing the figure A among Fig. 2), level and smooth relatively spherical Pt nanoparticle on the platinum disk electrode surface deposition; Current potential changes to-0.2 volt (seeing the figure B among Fig. 2), and the pattern of Pt nanoparticle takes place obviously to change, and becomes diamond shaped; (seeing the figure C among Fig. 2) causes the pattern generation marked change of Pt nanoparticle when continuing to change reduction potential to-0.3 volt, presents the petal shaped nano chip architecture of rule; When sedimentation potential is controlled at-0.4 volt (seeing the figure D among Fig. 2), obtain amorphous nano sheets of platinum, and the heterogeneity that becomes.Clearly, figure C petal-shaped Pt nanoparticle surfaceness is bigger, shows more avtive spot and bigger reaction table area.
Fig. 3 is the stereoscan photograph of the Pt nanoparticle sensitive membrane of following 6 kinds of nano-sensors probes E, F that prepare of different recovery times, G, H, I, J, and the scanning electron microscope model is Quanta200 (Dutch FEI Co.).Figure E among Fig. 3 is the sem photograph in the Pt nanoparticle sensitive membrane of-0.3 volt of reduction potential deposit preparation in 0 second; Figure F among Fig. 3 is the sem photograph in the Pt nanoparticle sensitive membrane of-0.3 volt of reduction potential deposit preparation in 60 seconds; Figure G among Fig. 3 is the sem photograph in the Pt nanoparticle sensitive membrane of-0.3 volt of reduction potential deposit preparation in 120 seconds; Figure H among Fig. 3 is the sem photograph in the Pt nanoparticle sensitive membrane of-0.3 volt of reduction potential deposit preparation in 180 seconds; Figure I among Fig. 3 is the sem photograph in the Pt nanoparticle sensitive membrane of-0.3 volt of reduction potential deposit preparation in 240 seconds; Figure J among Fig. 2 is the sem photograph in the Pt nanoparticle sensitive membrane of-0.3 volt of reduction potential deposit preparation in 300 seconds;
Different electrode sensitive film preparation parameters are as shown in the table:
As seen from Figure 3, when sedimentation time was 0 second (seeing figure E, bare electrode), electrode surface was very smooth; When sedimentation time was brought up to 30 seconds (F) and 60 seconds (G) gradually, the platinum electrode surface major part was covered by nano sheets of platinum; The Pt nanometer amount of surface deposition continue to increase when sedimentation time is 120 seconds, reaches all standing substantially, and the Pt nanometer sheet becomes more regular, and as seen the petal-shaped clear in structure observes petal-like nano-platinum particle, and electrode surface roughness obviously increases; The electrode surface pattern changes then little when surpassing 120 seconds.
(2) with the electrochemical sensor probe of the detection chemical oxygen demand (COD) of the platinum nanometer sensitive membrane with different-shape that obtains under the different reduction potentials, be that actual water sample detects to deriving from different lake water or river, relation between systematic study water sample chemical oxygen demand (COD) (COD) current responsing signal and the nanometer platinum pattern, testing result is seen Fig. 4, Fig. 5, has filtered out the method for the electrochemical sensor probe for preparing the highest detection chemical oxygen demand (COD) of sensitivity.
Fig. 4 is different chemical oxygen demand (COD) lake water response current and nanometer platinum reduction potential relation curve, and illustration is the ampere curve of actual water sample.The response condition of separate sources actual water sample on nanometer platinum surface that the ampere experimental study has been adopted in this experiment.Two kinds of used water samples are taken from different lakes, Wuhan, and chemical oxygen demand (COD) (COD) value that the potassium dichromate National Standard Method is measured is respectively 30.17 and 20.28mgL
-1As shown in Figure 4, after adding actual water sample, observe a current step that significantly, makes progress, this be since in the water body oxidation of reducing substances cause.Detecting medium is pH6.5PBS buffer solution, and detecting current potential is 0.46 volt.When reduction potential changed to-0.3 volt from-0.1 volt, water sample increased gradually in chemical oxygen demand (COD) (COD) response signal on nanometer platinum surface; When reduction potential continues negatively when moving on to-0.4 volt, chemical oxygen demand (COD) (COD) current signal obviously reduces on the contrary.Clearly, the petal-shaped nano sheets of platinum that obtains-0.3 volt of current potential deposition is the strongest to the signal enhancement effect of chemical oxygen demand (COD) (COD).From sem photograph as can be known, petal-shaped nano sheets of platinum (0.3 volt, 120 seconds) has bigger surface area and more avtive spot.Undoubtedly, water sample is in its surperficial chemical oxygen demand (COD) (COD) response current maximum.So selecting-0.3 volt is best reduction potential.
Fig. 5 is different chemical oxygen demand (COD) lake water at response current and the sedimentation time relation curve on the nanometer platinum surface of different time deposition, and illustration is ampere curve of separate sources actual water sample.Detecting medium is pH6.5PBS buffer solution, and detecting current potential is 0.46 volt.When the sedimentation time of nanometer platinum was increased to 120 seconds by 0, the response current of COD obviously strengthened, and this is owing to the high catalytic activity of nano-platinum particle.When further increasing recovery time to 4 minute, the current signal increase of COD is very slow, and this moment, background current obviously increased.In order to improve detection sensitivity, take all factors into consideration, 120 seconds is the sensor probe sensitive membrane optimal deposition time.
Above experimental data shows: in containing 0.1 mole of every liter of sulfuric acid of every liter of chloroplatinic acid of 1 mM, prepare the Pt nanoparticle of different-shapes such as sphere, rhombus, petal sheet at the platinum disk electrode surface in situ by the constant potential reduction.Compare with the diamond shaped nano-platinum particle with spherical, 120 seconds prepared petal-shaped nano sheets of platinum of-0.3 volt of reduction are stronger to the current responsing signal enhancement effect of chemical oxygen demand (COD) (COD).Therefore be chosen in the 0.1 mole of every liter of sulfuric acid solution that contains every liter of chloroplatinic acid of 1 mM, reduction is 120 seconds under-0.3 volt of potential condition, in the mensuration of platinum disk electrode surface preparation petal shaped nano platinum grain sensitive membrane for actual lake water or river water sample chemical oxygen demand (COD) (COD), it is the highest that it measures sensitivity.
With the electrochemical sensor probe of the detection chemical oxygen demand (COD) of pressing embodiment 1 method preparation, the big or small COD water sample of difference to be measured, water sample COD size adopts potassium dichromate National Standard Method (GB11914-89) to demarcate and obtains.Adopt common three-electrode system, with the electrochemical sensor probe of the detection chemical oxygen demand (COD) of pressing embodiment 1 method preparation as working electrode, silver/silver chloride electrode is as contrast electrode, platinum post electrode is to electrode, connects electrochemical workstation and computing machine experimental data is gathered and record.
Under well-beaten situation, study chemical oxygen demand (COD) (COD) response signal of actual water sample with the ampere method.Detecting current potential is 0.45 volt, and medium is 9.00 milliliters, the phosphate buffered solution of 0.1 mole every liter pH6.5.For avoiding the interference of chlorion, add 0.1 mole every liter potassium chloride in the medium.After i-t curve background current is stable, add 1.00 milliliters water sample rapidly, measure the added value of electric current as the current responsing signal of water sample chemical oxygen demand (COD) (COD).
Will be with the detection to 8 parts of actual lake water of separate sources or river water sample of the electrochemical sensor probe of the detection chemical oxygen demand (COD) of pressing embodiment 1 method preparation, the water sample sequence number is remembered work 1,2,3,4,5,6,7,8 respectively, and actual water sample chemical oxygen demand (COD) (COD) value obtains by the ampere experiment and in conjunction with linear regression equation calculation.Each water sample replicate determination three times, relative standard deviation (RSD) is lower than 5%, and the favorable reproducibility of this sensor is described.In order to verify the accuracy of the method, contrast with potassium dichromate National Standard Method (GB11914-89) mensuration, the results are shown in Table 1.National Standard Method (GB11914-89) measurement result and sensor measurement result are coincide very much, and (relative error is lower than 9%, this deviation is generally in tolerance interval), the electrochemical sensor probe accuracy of measurement height of the detection chemical oxygen demand (COD) of pressing embodiment 1 method preparation is described.
The chemical oxygen demand (COD) of table 1 actual water sample (COD) pH-value determination pH
Claims (9)
1. an electrochemical sensor that detects chemical oxygen demand (COD) is popped one's head in, by the platinum nanometer sensitive membrane formation of platinum disk electrode and platinum dish (1) exposed surface that is positioned at this platinum disk electrode.
2. the electrochemical sensor of detection chemical oxygen demand (COD) according to claim 1 is popped one's head in, it is characterized in that, described platinum disk electrode is made up of platinum dish (1), electrode jacket (2) and copper rod shape lead (3), platinum dish (1) is packaged in the centre of electrode jacket (2) one ends, a side of platinum dish (1) is exposed to the end face of electrode jacket (2), one end of copper rod shape lead (3) is connected with platinum dish (1) in electrode jacket (2), and the other end of copper rod shape lead (3) extends to outside the electrode jacket (2).
3. the electrochemical sensor of detection chemical oxygen demand (COD) according to claim 1 probe is characterized in that the platinum nanometer sensitive membrane that is positioned at platinum dish (1) exposed surface of platinum disk electrode is with chloroplatinic acid (H
2PtCl
6) the platinum nanometer sensitive membrane that is constituted by Pt nanoparticle that forms in platinum dish (1) exposed surface of reduction electroplating deposition.
4. the electrochemical sensor of detection chemical oxygen demand (COD) according to claim 3 probe is characterized in that, with chloroplatinic acid (H
2PtCl
6) the reduction electroplating deposition in the concrete grammar that platinum dish (1) exposed surface forms the platinum nanometer sensitive membrane that is made of Pt nanoparticle is: will polish to immerse to the platinum dish position of the platinum disk electrode of minute surface and contain every liter of 0.5～10 mM (mmol/L) chloroplatinic acid (H
2PtCl
6) 0.1～2 mole every liter (mol/L) sulfuric acid (H
2SO
4) in, carry out the constant potential reduction with the current potential of-0.7～0.1 volt (V), the potential reduction time is 10-300 second (s), namely the exposed surface at platinum dish (1) forms the platinum nanometer sensitive membrane that is made of Pt nanoparticle.
5. the electrochemical sensor of detection chemical oxygen demand (COD) according to claim 4 probe is characterized in that the constant potential reduction potential is-0.4～-0.1 volt, and the potential reduction time is 60～300 seconds.
6. according to the electrochemical sensor probe of claim 4 or 5 described detection chemical oxygen demand (COD), it is characterized in that the constant potential reduction potential is-0.3 volt, the potential reduction time is 120 seconds.
7. the preparation method of an electrochemical sensor probe that detects chemical oxygen demand (COD) may further comprise the steps: just polish to immerse to the platinum dish position of the platinum disk electrode of minute surface and contain every liter of chloroplatinic acid (H of 0.5～10 mM
2PtCl
6) 0.1～2 mole of every liter of H
2SO
4In, carry out the constant potential reduction with-0.7～0.1 volt current potential, the potential reduction time is 10～300 seconds, namely forms the platinum nanometer sensitive membrane that is made of Pt nanoparticle on the surface of platinum dish (1).
8. the method for the electrochemical sensor of detection chemical oxygen demand (COD) according to claim 7 probe is characterized in that the constant potential reduction potential is-0.4～-0.1 volt, and the potential reduction time is 60～300 seconds.
9. the method for popping one's head in according to the electrochemical sensor of claim 7 or 8 described detection chemical oxygen demand (COD) is characterized in that the constant potential reduction potential is-0.3 volt, and the potential reduction time is 120 seconds.
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Application publication date: 20130717 |