CN112630283B - Application of (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene as electrochemical sensor - Google Patents

Application of (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene as electrochemical sensor Download PDF

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CN112630283B
CN112630283B CN202011501277.4A CN202011501277A CN112630283B CN 112630283 B CN112630283 B CN 112630283B CN 202011501277 A CN202011501277 A CN 202011501277A CN 112630283 B CN112630283 B CN 112630283B
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ferrocene
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pyridylvinyl
protonic acid
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CN112630283A (en
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李霞
刘伟
李银峰
赵海鹏
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Henan University of Urban Construction
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Abstract

The invention discloses an electrochemical sensor taking (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene as organic phase protonic acid and application thereof, and specifically comprises the following steps: dissolving (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene and supporting electrolyte (tetra-n-butyl ammonium perchlorate) in an organic solvent according to a proportion to obtain a kit; adding a solution to be detected into the kit, inserting a reference electrode, a working electrode and an auxiliary electrode, and measuring the test system in a voltage range of-0.2-1.3V by using a cyclic voltammetry method, a differential pulse voltammetry method and the like by using an electrochemical workstation under the condition of three electrodes. The test finds that: when (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene is used as an electrochemical sensor for detecting organic phase protonic acid, ca in the organic phase is detected 2+ 、Mg 2+ 、Mn 2+ 、Co 2+ 、Ni 2+ 、Cd 2+ When the interference of cations is small, the electrochemical cell manufactured by the electrochemical sensor is used for detecting the concentration of the organic-phase protonic acid, is simple to manufacture, convenient to use, free of professional operation and particularly suitable for rapidly detecting the content of the protonic acid on site.

Description

Application of (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene as electrochemical sensor
Technical Field
The invention belongs to the technical field of rapid detection and analysis, and particularly relates to application of (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene as a proton electrochemical sensor, in particular to rapid detection of organic phase protonic acid concentration.
Background
Because of the huge potential application of the ferrocene derivatives in the aspects of supramolecular chemistry, electron transport materials, nonlinear optical materials and the like, the design synthesis and property research of the ferrocene derivatives are increasingly prosperous.
In the research of supramolecular chemistry, ferrocene groups are introduced into proper positions of substrate molecules and ion binding fragments, so that the host molecules can utilize the good redox property of ferrocene centers to electrochemically identify specific guest substrates. The conjugated system structure containing ferrocenyl provides possibility for electron transfer between terminal groups, so that the compound shows excellent electron transfer capacity. Although a large number of ferrocenyl host compounds with various functional groups are reported and used for identifying and detecting various metal ions and anions, the host compounds with binding units directly connected with ferrocene fragments through olefinic bonds are still rarely reported.
When the guest is bound to the host molecule, it causes a change in the microenvironment of the host compound molecule, triggering an electrochemical response of the electrochemically responsive group, typically in response to a change in the group potential or current value. Beer et al ([ 1)]Studies of p.d. Beer, p.a. Gale, g.z. Chen, j. Chem. Soc., dalton trans., (1999) 1897.) show that the effect of the bound guest on the redox active center of the host molecule mainly works by: (1) electrostatic perturbation of a space; (2) Through a conjugated group linking the redox active center and the bonding site; (3) Direct interaction between the complexed guest and the metal ion belonging to the redox active center of the ring structure. The binding information can be macroscopically detected by the expression of ferrocenyl by using an electrochemical instrument and a technology, so that the aim of identification is fulfilled. Common electrochemical monitoring methods are Cyclic Voltammetry (CV), differential Pulse Voltammetry (DPV), square Wave Voltammetry (SWV), electrical impedance, and the like. K in the redox process before and after the addition of the guest to the host compound and in the dissociation process of the binding between the host and the guest red Is the binding stability constant between neutral host and guest, K ox Being in an oxidized stateStability constant of complexation between host molecule and guest, E 0 H 、E 0 HG The redox peak potentials of the free host molecule and the host-guest conjugate, respectively. It has the following relations
ΔE 0 = E 0 HG －E 0 H =（RT/nF）×ln（K red /K ox ）
It is anticipated that: when a positively charged guest is added, K is due to steric electrostatic repulsion between the host and the guest ox Should be less than K red That is, the ligand interacts with the cation to cause ferrocenyl ligand Fc + The reason why/Fc couple type potential anode moves; here,. DELTA.E 0 The value directly reflects the change of the binding capacity between the host molecule and the guest molecule before and after the ferrocene center is oxidized, which has important significance for developing molecular switch devices.
Larger Δ E in the host-guest interaction Cyclic Voltammetry (CV) curves 0 The values (usually greater than 100 mV) tend to give a duplex wave behaviour of the CV curve, as exemplified by the macrocyclic crown ether ligand containing ferrocene reported in 1986 by Saji (T. Saji, J. Kinoshita, J. Chem. Soc., chem. Commun.,1986, 716.) in the reported example with the cation Na + The interaction between them causes Fc + The anode of the/Fc couple moves with the redox potential and is Na + The addition of (2) a new peak appears in a higher potential area and is accompanied by the regression of the original redox peak; when 1 equivalent of Na is added + Then the original peak disappears, and a new peak in the anode direction is completely developed; at 0.5 equivalent of Na + In the presence of (a), the cyclic voltammetry thereof shows a remarkable duplex wave behavior.
In FIG. 8 of the present application, it can be seen that with the addition of perchloric acid, a new redox peak appears in the higher potential region and is accompanied by a regression of the redox peak of the original host molecule; the new peak appeared at the high potential position with the higher and higher amount of the perchloric acid gradually develops, and the oxidation reduction peak of the original host molecule gradually disappears, when the combination of the host molecule and the guest molecule reaches the saturation state, the new peak in the anode direction completely develops, and the oxidation reduction peak corresponding to the original host molecule completely disappearsAnd (6) losing. This is in contrast to Saji's report of macrocyclic crown ethers on Na + The identified cyclic voltammetry behavior curves were similar. When Δ E of the system 0 When the concentration of the redox peak is more than 100 mV, the redox peaks corresponding to the free host molecules and the host-guest conjugates have better separation degree during electrochemical detection, so that the possibility of respectively and accurately determining the peak current of the corresponding redox peaks is provided, and the system can be used for developing a current amperometric sensor for electrochemical identification and content detection of guest particles.
The application designs that 1,1 '-ferrocene dimethylene triphenyl quaternary phosphonium iodide salt is used as a raw material and reacts with 2-pyridylaldehyde to prepare (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene, in the double-arm ferrocene olefin compound, because a pyridine nitrogen atom in a molecule has good alkalinity and is easy to combine with a proton of organic phase protonic acid to protonate, the change of the whole molecule is caused, and the existence of an olefinic bond can be expected, so that a huge conjugated system is formed by ferrocene groups and pyridine, and the change of the electronic state of a pyridine ring caused by the protonation of the pyridine nitrogen atom is bound to be fed back to a ferrocene center through the electron transfer transmission of the conjugated structure, thereby changing the redox potential of the ferrocene, and further realizing the output of an electrochemical signal in the proton combining process through electrochemical detection. The binding of the proton of the guest protic acid to the host molecule (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene can be monitored by electrochemical methods such as cyclic voltammetry, DPV and the like. The organic phase protonic acid electrochemical sensor is applied to organic phase protonic acid [ H ]] + And (3) recording the corresponding redox peak-to-peak current obtained by electrochemical detection, making a relation curve of acid concentration and peak current to obtain a standard curve of the acid concentration detected by the sensor, mixing the solution to be detected and the prepared kit in proportion, recording the redox peak-to-peak current obtained by electrochemical detection, and calculating the acid value of the solution to be detected through the standard curve. The (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene serving as the proton electrochemical sensor is used for measuring the concentration of the organic-phase protonic acid, has high sensitivity, simple manufacture and convenient use, and solves the problems of great influence on the traditional titration operation man-made factor and operational skill of an operatorLarge error and even no detection when the concentration is high or low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene serving as a proton electrochemical sensor for quickly detecting the concentration of organic-phase protonic acid (such as p-toluenesulfonic acid, perchloric acid and the like), has the advantages of high sensitivity, simplicity in manufacture, convenience in use and the like, and solves the defects of large artificial influence, large error at low concentration and incapability of detection in the traditional titration operation.
In order to achieve the purpose, the invention adopts the following technical scheme:
the application of (E, E) -1,1 '-bis (2-pyridine vinyl) ferrocene as an organic phase protonic acid electrochemical sensor, wherein the structural formula of the (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene is shown as follows:
Figure DEST_PATH_IMAGE001
。
specifically, the (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene is prepared by the following steps:
1) Adding potassium iodide, 1' -ferrocenyl dimethyl alcohol and triphenylphosphine into a round-bottom flask containing water, chloroform and glacial acetic acid, and heating and refluxing for 30-40 h; decompressing and distilling out the organic solvent to obtain yellow solid, washing and drying in vacuum to obtain ferrocene dimethylene triphenyl phosphonium iodide;
2) Weighing ferrocene dimethylene triphenyl phosphonium iodide and potassium tert-butoxide in a round-bottom flask, adding anhydrous THF (tetrahydrofuran) under the conditions of keeping out of the sun and stirring at room temperature in nitrogen atmosphere, adding an anhydrous THF solution containing 2-pyridylaldehyde after 20-40min, reacting at room temperature for 1-3h, then reacting under the reflux condition for 10-14h, distilling off the organic solvent under reduced pressure, adding saturated saline water into the residue, adding CH (CH) into the saturated saline water, and reacting under the reflux condition for 10-14h 2 C1 2 Extracting, and using anhydrous Na for organic phase 2 SO 4 Drying, vacuum evaporating solvent, separating and purifying to obtain the final product.
The application of the (E, E) -1,1 '-bis (2-pyridylvinyl) ferrocene as the organic phase protonic acid electrochemical sensor can specifically dissolve the (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene and the supporting electrolyte tetra-n-butyl ammonium perchlorate in an organic solvent in proportion to obtain the kit.
Further, the concentration of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene in the kit was 2X 10 - 2 mol/L-2×10 -5 The concentration of the supporting electrolyte tetra-n-butyl ammonium perchlorate is 2 multiplied by 10 -1 mol/L. The tetra-n-butyl ammonium perchlorate has the effect that the tetra-n-butyl ammonium perchlorate has good solubility in an organic solvent, provides a conductive medium for electrochemical detection, and can better eliminate the interference of common electrolyte cations and anions on a test system.
More preferably, the organic solvent is one or a mixture of two or more of acetonitrile, dichloromethane, methanol, ethanol, dimethylformamide, and the like. The solvent has the functions of: the solvent is used as a dissolving reagent of (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene, and the solvent is used for determining the organic phase protonic acid solution to be tested by utilizing the better compatibility of the solvent and the sample to be tested. The purity of the solvent is analytically pure.
When the (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene is used as the organic phase protonic acid electrochemical sensor, a sample solution to be detected is mixed with the kit, a reference electrode, a working electrode and an auxiliary electrode are inserted, and a test system is detected in a voltage range of-0.2-1.3V by using a cyclic voltammetry method or a differential pulse voltammetry method and the like by using an electrochemical workstation under the condition of a three-electrode system. And recording oxidation or reduction peak current obtained by electrochemical detection, and calculating the concentration of organic phase protonic acid (such as p-toluenesulfonic acid or perchloric acid) in the sample solution to be detected according to the standard curve.
The standard curve was made as follows: preparing a standard solution of p-toluenesulfonic acid or perchloric acid with accurate concentration, mixing a certain amount of the standard solution with a kit, testing by using a three-electrode system, recording the peak current of an oxidation-reduction peak obtained by electrochemical detection, and making a relation curve of the acid concentration and the peak current to obtain a standard curve of the acid concentration detected by a sensor; and adding the sample solution to be detected into the kit, carrying out determination under the same condition, recording the peak current of the redox peak obtained by electrochemical detection, and substituting the peak current into a standard curve to obtain the concentration of the organic phase protonic acid in the sample solution to be detected.
In the application of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene as an organic-phase protonic acid electrochemical sensor, when a protonic acid is added in a gradual manner, the CV curve shows good duplex wave behavior (see figures 8 and 10); and the larger formula weight potential shift value enables the (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene to be used as a current ampere sensor to realize the quantitative detection of the protonic acid. The application utilizes a DPV method with higher accuracy to carry out a system experiment in the presence of different equivalent amounts of protic acids, and the results are shown in figures 3 and 9. In the DPV curve, the peak current value is plotted against the addition of the protic acid and the ligand stoichiometry, and it can be seen from the plot that the peak current changes with addition of the protic acid in good correlation with the amount added until the peak current reaches a maximum value at which the protic acid and (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene reach 2.
In the invention, (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene is an organic phase protonic acid electrochemical sensor, the combination of the electrochemical sensor and organic phase protonic acid can cause the change of the oxidation-reduction potential and the oxidation-reduction peak current of the ferrocene, and the change of the acid content in the system and the oxidation-reduction peak current form a better linear relation, thereby realizing the determination of the protonic acid content.
The invention adopts (E, E) -1,1 '-bis (2-pyridine vinyl) ferrocene as an electrochemical sensor, utilizes the positive movement of ferrocene central oxidation-reduction potential caused by protonation of pyridine ring N atom in molecule, the original ferrocene central oxidation-reduction peak current is gradually reduced along with the increase of protonation degree, the peak current of a new peak obtained at a higher potential position is gradually increased until all protonation is completed, at the moment, the upper limit of protonic acid concentration detection is reached, the upper limit of detection is limited by the concentration of the sensor (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene, the higher the concentration of the sensor is, the higher the upper limit of detection is, and the lower the concentration of the sensor is, the higher the detection sensitivity is. In use, can be configured (E, E)-1,1' -bis (2-pyridylvinyl) ferrocene 10 -2 mol/L-10 - 5 And (3) mixing the sample liquid to be tested with the low-concentration sensor solution to test by mol/L gradient solution, if only the oxidation reduction peak at the potential position corresponding to the protonation is observed, indicating that the concentration detection upper limit is reached, further replacing the higher-concentration sensor kit until double waves appear, and recording the new peak current and the old peak current at the low potential position. At the moment, a standard curve of the relation between the standard acid concentration and the peak current under the concentration is made, and the concentration of the protonic acid in the sample liquid to be detected can be obtained by drawing. Compared with the prior art, the invention has the following beneficial effects:
the detection kit has the advantages of simple manufacture, convenient use, wide test range and no need of professional operation, and is particularly suitable for the determination of the content of the protic acid of the organic phase system. In the given examples, the lower limit of the concentration of the protonic acid detected is 2.4X 10 -6 mol/L, can be well used for the determination of the concentration of organic phase protonic acid. K at 50 times of acid concentration under measuring environment + 、Ca 2+ 、Mg 2+ And Mn of 10 times the acid concentration 2+ 、Co 2+ 、Ni 2+ 、Cd 2+ The acid concentration is measured without interference. The method solves the problems that the traditional titration operation has large artificial influence, high operation skill of operators, large error and even no detection at low concentration, and has important application value in the application field of rapidly detecting the content of organic phase protonic acid.
Drawings
FIG. 1 is a NMR chart of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig);
FIG. 2 is a graph comparing the results of Cyclic Voltammetry (CV) measurements of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig) at 4 equivalents of different metal ions, p-toluenesulfonic acid and perchloric acid;
FIG. 3 shows the results of Differential Pulse Voltammetry (DPV) measurements of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig) with different equivalents of perchloric acid;
FIG. 4 is a graph of peak current versus HClO for a Differential Pulse Voltammetry (DPV) (lig) peak 4 A concentration relation curve;
FIG. 5 is a differentialPulsed Voltammetry (DPV) (lig + HClO) 4 ) Peak current of peak and HClO 4 A concentration relation scatter diagram;
FIG. 6 is Differential Pulse Voltammetry (DPV) (lig + HClO) 4 ) Peak current of peak and HClO 4 A concentration relation curve;
FIG. 7 shows (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene at a concentration of 3.2X 10 relative to 5ml -3 mol/L HClO 4 Results of Differential Pulse Voltammetry (DPV) measurements in solution;
FIG. 8 shows the results of Cyclic Voltammetry (CV) measurements of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig) under different equivalents of perchloric acid;
FIG. 9 is a graph of the Differential Pulse Voltammetry (DPV) measurements of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig) at different equivalents of p-toluenesulfonic acid (TSOH);
FIG. 10 shows the results of Cyclic Voltammetry (CV) measurements of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig) at different equivalents of p-toluenesulfonic acid (TSOH).
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the following examples, (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene was prepared by the following method:
16.6 g of potassium iodide, 4.92 g of 1,1' -ferrocenyl dimethyl alcohol and 17.6 g of triphenylphosphine are added into a 250 mL round-bottom flask containing 20 mL of water, 60 mL of chloroform and 30 mL of glacial acetic acid, the mixture is heated and refluxed for 36 h, a large amount of yellow crystals are separated out from a reaction bottle, an organic solvent is evaporated under reduced pressure to obtain a large amount of yellow solid, the yellow solid is filtered by suction, a filter cake is washed by 3X 20 mL of secondary water, 3X 10 mL of absolute ethyl alcohol and 3X 10 mL of absolute ethyl ether in sequence, and the yellow crystals are dried in vacuum to obtain 19.2 g of ferrocene dimethylene triphenyl phosphonium iodide yellow crystals (the yield is 97%).
6.0 g of ferrocene dimethylene triphenyl phosphonium iodide and 1.5 g of potassium tert-butoxide are weighed in a glove box at room temperature in a 100 mL round-bottom flask, and added into the system under the conditions of light shielding and vigorous stirring at room temperature in a nitrogen atmosphereAdding 40 mL of anhydrous THF (the reaction solution is dark red), dropwise adding an anhydrous THF solution containing 13.5 mmol of 2-pyridylaldehyde into the reaction system after 30 min, reacting for 2h at room temperature after dropwise adding, and reacting overnight (12 h) under reflux. The reaction mixture was evaporated under reduced pressure to remove the organic solvent, and the residue was added with saturated brine and CH 2 C1 2 Extracting, and using anhydrous Na as organic phase 2 SO 4 Drying overnight, evaporating the solvent under reduced pressure to give a dark red viscous mass, adding CH 2 Cl 2 /CH 3 COOC 2 H 5 (V/V = 5) performing silica gel column chromatographic separation by using a mixed solvent as an eluent to obtain a target product; dark red powdery crystals 0.823g, yield 35%; 160-162 ℃ in M.p. and Cacld for C in HRMS 24 H 21 FeN 2 [M + H] + 393.1054, found 393.1052; IR ν max (KBr): 1632, 1582, 1469, 1427, 963, 768 cm -1 ; 1 H NMR (400 MHz): 4.32(t, J=1.7 Hz, 4H, Cp-H), 4.50(t, J=1.7 Hz, 4H, Cp-H), 6.65(d, J=16.0 Hz, 2H, olefinic H), 7.01-7.07(m, 4H, Ar-H), 7.21(d, J=16.2 Hz, 2H, olefinic H), , 7.42-7.46 (m, 2H, Ar-H), 8.45(d, 2H, J= 4.4 Hz, Ar-H); 13 C NMR (100 MHz): 68.60, 70.75, 83.15, 120.98, 120.99, 126.06, 130.75, 136.35, 149.26, 155.82; ESI-MS: [M + H] + : 393.1, [M + Na] + : 415.0. The NMR spectrum is shown in FIG. 1.
Metal ion identification and competition experiments:
adding prepared acetonitrile solution (1X 10) of (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene into an electrolytic cell -3 M), acetonitrile solution (0.2M) of metal ions (in the form of their perchlorate salt) was added by a microsyringe in an amount of 4 equivalents of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene; the electrochemical test is carried out by using a CHI-650A type comprehensive electrochemical workstation (Shanghai Chenghua company) for determination, wherein a three-electrode system is adopted, a working electrode is a phi 3 mm glassy carbon electrode, an auxiliary electrode is a platinum wire, and a reference electrode is a 232 type calomel electrode; the working electrode was first passed through 0.05 μm A1 before use 2 O 3 Grinding and polishing the polishing powder to a mirror surface, and then sequentially using 0.1M NaOH and concentrated HNO with the volume l:1 3 And water, absolute ethyl alcoholUltrasonically cleaning the secondary distilled water; the measurement was carried out by cyclic voltammetry at a potential sweep rate of 100 mV/s in the range of 0.00 to 0.90V.
The results show that: remove Ca 2+ 、Mg 2+ In addition to almost no response, when Mn is added 2+ 、Co 2+ 、Zn 2+ 、Cd 2+ In acetonitrile solution of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene, the selected transition metal ions all changed the redox properties of the ferrocene center (see FIG. 2), resulting in ferrocene Fc/Fc + The anode generated by the electric pair type quantum potential moves, and the electric pair still shows better reversibility. Despite Mn 2+ 、Co 2+ 、Zn 2+ 、Cd 2+ Has a certain electrochemical response, but Fc/Fc thereof + The change value of the electric pair type quantum potential is obviously less than that of the proton acid perchloric acid and p-toluenesulfonic acid to Fc/Fc + The influence of electricity on the equation-magnitude potential. When (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene 2 equivalents of perchloric acid and 100 equivalents of Ca are added simultaneously 2+ Or Mg 2+ The redox peak profile still appeared the same as in the presence of 2 equivalents of perchloric acid. When 2 equivalents of perchloric acid and 20 equivalents of Mn are added simultaneously to (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene 2+ 、 Co 2+ 、Zn 2+ Or Cd 2+ The redox-type peak profile still appeared identical to that of 2 equivalents of perchloric acid, indicating that (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene selectively recognizes protic acids in the presence of these metal ions tested.
The identification and detection results of perchloric acid and p-toluenesulfonic acid in acetonitrile solution are shown in the following examples.
Example 1:
an organic phase protonic acid electrochemical sensor and a detection method thereof are disclosed:
sensor (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig) solution preparation: using acetonitrile as solvent, preparing a solution containing 2X 10 of acetonitrile -1 mol/L tetra-n-butyl ammonium perchlorate and 2X 10 -3 A solution of mol/L lig; 5mL of the prepared solution is bottled to be used as a kit for detection;
preparing acetonitrile standard solution of perchloric acid: 0 mol/L, 5X 10 -4 mol/L、1×10 -3 mol/L、1.5×10 - 3 mol/L、2×10 -3 mol/L、2.5×10 -3 mol/L、3×10 -3 mol/L、3.5×10 -3 mol/L、4×10 -3 mol/L、4.5×10 -3 mol/L、5×10 -3 Respectively bottling 5mL of the obtained product for a calibration standard curve in mol/L;
the electrochemical test is carried out by using a CHI-650A type comprehensive electrochemical workstation (Shanghai Chenghua company) for determination, wherein a three-electrode system is adopted, a working electrode is a phi 3 mm glassy carbon electrode, an auxiliary electrode is a platinum wire, and a reference electrode is a 232 type calomel electrode; the working electrode is first processed through 0.05 μm A1 before use 2 O 3 Grinding and polishing the polishing powder to a mirror surface, and then sequentially using 0.1M NaOH and concentrated HNO with the volume l:1 3 And ultrasonically cleaning with water, absolute ethyl alcohol and secondary distilled water.
5ml of the prepared kit and 5ml of acetonitrile standard solution of perchloric acid are mixed in equal volume in a potential range of 0.00-0.90V, and the response of the sensor to different concentrations of perchloric acid is measured by differential pulse voltammetry (DPV, operating parameters are shown in the right column of figure 3). The results are shown in FIG. 3. As can be seen from fig. 3, in the DPV curve, as the amount of perchloric acid increases, the protonation degree increases, the oxidation-reduction peak current of the ferrocene center of the pro-ligand gradually decreases, and the peak current of the new peak obtained at a higher potential position gradually increases until the protonation is completely completed when the acid is equivalent to 1 of ligand 2, at which time the oxidation-reduction peak of the ferrocene center corresponding to the pro-ligand completely disappears, and the upper limit of the detection of the protonic acid concentration is reached.
Further, the obtained DPV test results are processed at HClO 4 The concentration is 0-1.5 × 10 -3 In the mol/L range, the peak current corresponding to the (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig) peak (peak at low potential) is taken as the ordinate, and HClO is taken as 4 The concentrations are plotted on the abscissa, resulting in FIG. 4, from which it can be seen that: in the concentration interval, the peak current of the peak corresponding to lig and the perchloric acid concentration present a better linear relationship.
In HClO 4 Concentration 2X 10 -3 -5×10 -3 In the mol/L range corresponding to (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene and HClO 4 Adduct (lig + HClO) 4 ) Peak Current (Peak at high potential) as ordinate with HClO 4 The concentration is plotted on the abscissa to obtain a scatter plot-FIG. 5. As can be seen from FIG. 5, when the perchloric acid concentration reached 4X 10 -3 After mol/L, (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig) and perchloric acid completely form a stable adduct in this state and reach the upper test limit, and higher acid concentration can not enable the peak current to be further obviously improved.
In HClO 4 Concentration of 0-4X 10 -3 In mol/L range of (lig + HClO) 4 ) Peak Current (Peak at high potential) as ordinate with HClO 4 The concentrations are plotted on the abscissa to obtain FIG. 6. As can be seen in fig. 6: in this concentration range, corresponds to (lig + HClO) 4 ) The peak current of the peak and the perchloric acid concentration present a better linear relationship.
Further, the present application prepared 5ml of 3.2X 10 -3 mol/L HClO 4 The solution was mixed with a 5ml kit in equal volume, and the response of the sensor to the perchloric acid concentration was measured by Differential Pulse Voltammetry (DPV), the results of which are shown in fig. 7; the peak current 2.647E-05 was recorded and substituted into the linear relation (y =0.0091 x-3E-06) of the standard curve shown in FIG. 6 to calculate, and the detected concentration result was 3.24 × 10 -3 The deviation was 1.25% in mol/L, and the results were satisfactory.
Example 2:
an organic phase protonic acid electrochemical sensor and a detection method thereof are disclosed:
sensor (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig) solution preparation: using acetonitrile as solvent, preparing a solution containing 2X 10 of acetonitrile -1 mol/L tetra-n-butyl ammonium perchlorate and 2X 10 -3 A solution of mol/L lig; 5mL of the prepared solution is bottled to be used as a kit for detection;
0 mol/L and 5X 10 acetonitrile standard solution for preparing perchloric acid -4 mol/L、1×10 -3 mol/L、1.5×10 -3 mol/L、2×10 -3 mol/L、2.5×10 -3 mol/L、3×10 -3 mol/L、3.5×10 -3 mol/L、4×10 -3 mol/L, respectively taking 5mL of the solution and bottling the solution for use in a calibration standard curve;
the electrochemical test is carried out by a CHI-650A type comprehensive electrochemical workstation (Shanghai Chenhua company), and the three-electrode system comprises a working electrode, an auxiliary electrode and a reference electrode, wherein the working electrode is a phi 3 mm glassy carbon electrode, the auxiliary electrode is a platinum wire, and the reference electrode is a 232 type calomel electrode; the working electrode is first processed through 0.05 μm A1 before use 2 O 3 Grinding and polishing the polishing powder to a mirror surface, and then sequentially using 0.1M NaOH and concentrated HNO with the volume l:1 3 And ultrasonically cleaning with water, absolute ethyl alcohol and secondary distilled water.
5ml of the prepared kit and 5ml of acetonitrile standard solution of perchloric acid are mixed in equal volume in a potential range of 0.00-0.90V, and the response of the sensor to different perchloric acid concentrations is measured by cyclic voltammetry (CV, operating parameters are shown in the right column of FIG. 8). The results are shown in FIG. 8. As can be seen from fig. 8, in the CV curve, as the amount of perchloric acid increases, the peak current of the ferrocene central redox peak of the pro-ligand gradually decreases, and the peak current of the new redox peak obtained at a higher potential position gradually increases until protonation is completely completed when the acid is equivalent to 1 of ligand 2, at which time the ferrocene central redox peak of the corresponding pro-ligand completely disappears, reaching the upper limit of the detection of the protonic acid concentration.
Further, the present application prepared 5ml of 3.0X 10 -3 mol/L HClO 4 Mixing the solution with 5ml of kit in equal volume, performing sensor response determination on perchloric acid concentration by using cyclic voltammetry, and recording the corresponding [ lig + HClO ] at high potential 4 ]The peak current of the oxidation peak of the redox couple is calculated by using a linear relation of a standard curve, and the detected concentration result is 2.92 multiplied by 10 -3 The mol/L deviation was 2.67%, and the results were as follows.
Example 3:
an organic phase protonic acid electrochemical sensor and a detection method thereof are disclosed:
sensor (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig)Solution preparation: using acetonitrile as solvent, preparing a solution containing 2X 10 of acetonitrile -1 mol/L tetra-n-butyl ammonium perchlorate and 2X 10 -3 A solution of mol/L lig; 5mL of the prepared solution is bottled to be used as a kit for detection;
preparing acetonitrile standard solution of p-toluenesulfonic acid (TSOH): 0 x 10 -3 mol/L、2×10 -3 mol/L、2.5×10 - 4 mol/L、3×10 -3 mol/L、3.5×10 -3 mol/L、4×10 -3 mol/L, respectively taking 5mL of the solution and bottling the solution for use in a calibration standard curve;
the electrochemical test is carried out by a CHI-650A type comprehensive electrochemical workstation (Shanghai Chenhua company), and the three-electrode system comprises a working electrode, an auxiliary electrode and a reference electrode, wherein the working electrode is a phi 3 mm glassy carbon electrode, the auxiliary electrode is a platinum wire, and the reference electrode is a 232 type calomel electrode; the working electrode was first passed through 0.05 μm A1 before use 2 O 3 Grinding and polishing the polishing powder to a mirror surface, and then sequentially using 0.1M NaOH and concentrated HNO with the volume l:1 3 And ultrasonically cleaning with water, absolute ethyl alcohol and secondary distilled water.
5ml of the prepared kit and 5ml of acetonitrile standard solution of p-toluenesulfonic acid are mixed in equal volume within the potential range of 0.00-0.90V, and the response of the sensor to different concentrations of p-toluenesulfonic acid (TSOH) is measured by using differential pulse voltammetry (the operating parameters are shown in the right column of FIG. 9). The results are shown in FIG. 9. As can be seen from fig. 9, in the DPV curve, as the amount of acid increases, the oxidation-reduction peak current of the ferrocene center of the pro-ligand gradually decreases, and the peak current of the new peak obtained at a higher potential position gradually increases until protonation is completely completed when the acid is equivalent to 1 of ligand 2, at which time the oxidation-reduction peak of the ferrocene center corresponding to the pro-ligand completely disappears, reaching the upper limit of the detection of the protonic acid concentration.
Example 4:
an organic phase protonic acid electrochemical sensor and a detection method thereof are disclosed:
sensor (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene (lig) solution preparation: using acetonitrile as solvent, preparing into a solution containing 2 × 10 -1 mol/L tetra-n-butyl ammonium perchlorate and 2X 10 -3 A solution of mol/L lig; the prepared solution is mixed with water5mL of the solution is bottled for detection;
preparing acetonitrile standard solution of p-toluenesulfonic acid (TSOH) with the concentration of 0 mol/L and the concentration of 2 multiplied by 10 -3 mol/L、2.5×10 -4 mol/L、3×10 -3 mol/L、3.5×10 -3 mol/L、4×10 -3 Respectively bottling 5mL of the obtained product for a calibration standard curve in mol/L;
the electrochemical test is carried out by using a CHI-650A type comprehensive electrochemical workstation (Shanghai Chenghua company) for determination, wherein a three-electrode system is adopted, a working electrode is a phi 3 mm glassy carbon electrode, an auxiliary electrode is a platinum wire, and a reference electrode is a 232 type calomel electrode; the working electrode was first passed through 0.05 μm A1 before use 2 O 3 Grinding and polishing the polishing powder to a mirror surface, and then sequentially using 0.1M NaOH and concentrated HNO with the volume l:1 3 And ultrasonically cleaning with water, absolute ethyl alcohol and secondary distilled water.
And mixing the prepared 5ml kit and a standard 5ml acetonitrile standard solution of p-toluenesulfonic acid in equal volumes within a potential range of 0.00-0.90V, and measuring the response of the sensor to different concentrations of the p-toluenesulfonic acid (TSOH) by using cyclic voltammetry (operation parameters are shown in the right column of FIG. 10). The results are shown in FIG. 10. As can be seen from fig. 10, in the CV curve, as the amount of acid increases, the protonation degree increases, the oxidation-reduction peak current of the ferrocene center of the pro-ligand gradually decreases, and the peak current of a new peak obtained at a higher potential position gradually increases until the protonation is completely completed when the acid is equivalent to 1 of the ligand 2, at which time the oxidation-reduction peak of the ferrocene center corresponding to the pro-ligand completely disappears, and the detection upper limit of the protonic acid concentration is reached.
In the invention, (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene is an organic phase protonic acid electrochemical sensor, the protonation degree is increased along with the increase of the proton concentration of a system to be detected in the detection upper limit concentration range during the determination of the concentration of the organic phase protonic acid, the oxidation-reduction peak current of the original ferrocene center is gradually reduced, the peak current of a new peak obtained at a higher potential position is gradually increased until the protonation is completely finished, and the unknown sample protonic acid concentration can be obtained by recording a standard curve of the relation between the standard acid concentration and the peak current under different concentrations and through detection and drawing. The invention has high sensitivity, simple manufacture and convenient use, and solves the problems of great artificial influence, high operating skill of operators, great error at low concentration and even incapability of detection in the traditional titration operation.
The foregoing detailed description is given by way of example only, to better enable a person skilled in the art to understand the patent, and is not to be construed as limiting the scope of protection of the patent; any equivalent alterations or modifications made according to the spirit of the disclosure of this patent are intended to be included in the scope of this patent.

Claims (6)

1. The application of (E, E) -1,1 '-bis (2-pyridine vinyl) ferrocene as an organic phase protonic acid electrochemical sensor is characterized in that the structural formula of the (E, E) -1,1' -bis (2-pyridine vinyl) ferrocene is shown as follows:
Figure 691738DEST_PATH_IMAGE001
。
2. the use of (E, E) -1,1 '-bis (2-pyridylvinyl) ferrocene as an organic phase protonic acid electrochemical sensor according to claim 1, wherein the (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene is prepared by the following steps:
1) Adding potassium iodide, 1' -ferrocenyl dimethyl alcohol and triphenylphosphine into a round-bottom flask containing water, chloroform and glacial acetic acid, and heating and refluxing for 30-40 h; decompressing and distilling out the organic solvent to obtain yellow solid, washing and drying in vacuum to obtain ferrocene dimethylene triphenyl phosphonium iodide;
2) Weighing ferrocene dimethylene triphenyl phosphonium iodide and potassium tert-butoxide in a round-bottom flask, adding anhydrous THF under the conditions of keeping out of the sun and stirring at room temperature in nitrogen atmosphere, adding an anhydrous THF solution containing 2-pyridylaldehyde after 20-40min, reacting at room temperature for 1-3h, then reacting under the reflux condition for 10-14h, distilling off the organic solvent under reduced pressure, adding saturated saline water into the residue, and reacting with CH 2 C1 2 Extracting, and using anhydrous Na for organic phase 2 SO 4 Drying, vacuum evaporating solvent, and separating pureAnd (5) dissolving to obtain the product.
3. The use of (E, E) -1,1 '-bis (2-pyridylvinyl) ferrocene as an organic phase protonic acid electrochemical sensor according to claim 2, wherein the kit is obtained by dissolving (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene and a supporting electrolyte tetra-n-butyl ammonium perchlorate in an organic solvent in proportion.
4. Use of (E, E) -1,1 '-bis (2-pyridylvinyl) ferrocene as an organic-phase protonic acid electrochemical sensor according to claim 3, wherein the concentration of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene in the kit is 2X 10 -2 mol/L-2×10 -5 The concentration of the supporting electrolyte tetra-n-butyl ammonium perchlorate is 2 multiplied by 10 -1 mol/L。
5. Use of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene as an organic phase protonic acid electrochemical sensor according to claim 3 or 4, wherein the organic solvent is one or a mixture of two or more of acetonitrile, dichloromethane, methanol, ethanol and dimethylformamide.
6. The use of (E, E) -1,1' -bis (2-pyridylvinyl) ferrocene as an organic phase protonic acid electrochemical sensor according to claim 5, wherein a sample solution to be measured is mixed with the reagent kit, and a reference electrode, a working electrode and an auxiliary electrode are inserted, and the measurement is performed by cyclic voltammetry or differential pulse voltammetry at an electrochemical workstation under a three-electrode system condition at a voltage ranging from-0.2V to 1.3V.
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