CN110554074A - Construction method and application of electrochemical sensor for detecting endogenous H 2 S - Google Patents
Construction method and application of electrochemical sensor for detecting endogenous H 2 S Download PDFInfo
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Abstract
the invention provides a method for constructing an electrochemical sensor for endogenous H 2 S detection, which belongs to the technical field of electrochemical analysis and mainly comprises the steps of preparing a rGO/Fe 3 O 4/Cu 2 O magnetic nano material, reacting the magnetic nano material with H 2 S to generate a sulfur copper compound rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 with a cavity structure, and constructing the electrochemical sensor taking rGO/Fe 3 O 4/Cu 2 O and H 2 S (NaHS) as a system by utilizing the weak electrochemical signal characteristic of rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8.
Description
Technical Field
The invention belongs to the technical field of electrochemical analysis, and particularly relates to a construction method of an electrochemical sensor for detecting endogenous H 2 S.
Background
H 2 S in organisms is mainly produced by three enzymes, cystathionine-beta-synthase (CBS), cystathionine-gamma-lyase (CSE) and fungi/yeast thioglycolic acid-sulfur transferase (3-MST), cystine (Cys). in normal biological systems, the presence of H 2 S contributes to the physiological activities of maintaining a healthy balance, but once the content of H 2 S in the organisms is unbalanced, the occurrence of certain diseases such as cervical cancer, colon cancer and certain lung diseases is marked, and therefore, a great number of researchers use H 2 S as a biological index to measure the healthy state, and thus, the detection of H 2 S is particularly important.
Compared with the detection methods, the electrochemical method has the characteristics of high sensitivity, easiness in operation, simplicity in instrument and the like, and brings great attention to people, for example, ferrocene and Ag NPs are used as electrochemical beacons, and the electrochemical signals are influenced by chemical reaction between sodium hydrosulfide and sodium sulfide as substitutes of H 2 S and the beacons so as to achieve the purpose of detecting H 2 S.
Meanwhile, in order to simplify the collection of materials and the modification process of electrodes, magnetic Fe 3 O 4 and a two-dimensional material rGO capable of improving electron conduction are reflected on sensor materials, and an rGO/Fe 3 O 4/Cu 2 O material is prepared.
disclosure of Invention
aiming at the defects of the prior art, the invention provides a construction method and application of an electrochemical sensor for detecting endogenous H 2 S.
the technical scheme of the invention is as follows:
A construction method of an electrochemical sensor for detecting endogenous H 2 S, comprising the following steps:
(1) synthesis of magnetic reduced graphene oxide (rGO/Fe 3 O 4):
adding reduced graphene oxide into ethylene glycol, mixing and dissolving, adding ferric acetylacetonate, carrying out ultrasonic treatment on the mixed solution for 30-40min, then adding 1.4-1.6g of amine acetate, stirring for 30-50min, transferring the mixed solution obtained by stirring into a reaction kettle, carrying out reaction at the temperature of 190-210 ℃ for 22-26h, cooling to room temperature after the reaction is finished, carrying out solid-liquid separation to obtain a solid phase, cleaning the solid phase with water and ethanol, dissolving and dispersing the obtained solid phase again with water, and fixing the volume to 2-4mg/mL to obtain a magnetic reduced graphene oxide solution, namely an rGO/Fe 3 O 4 solution;
(2) synthesis of rGO/Fe 3 O 4/Cu 2 O solution:
adding the rGO/Fe 3 O 4 solution obtained in the step (1) into 0.01-0.012g/mL of copper nitrate solution, carrying out ultrasonic treatment for 30-40min, uniformly mixing, then adding 80-100 mu L of 0.035-0.04mol/L NaOH solution while stirring, continuously stirring for 30-50min, then adding 400-450mL of 85-90mol/L hydrazine hydrate solution and stirring for 40-50min, then carrying out solid-liquid separation to obtain a solid phase, washing and drying the solid phase with water, and finally dispersing in water again to obtain 2-3mg/mL of rGO/Fe 3 O 4/Cu 2 O solution;
(3) MGCE electrode pretreatment:
MGCE with the diameter of 4-10mm is sequentially polished on alumina powder with the particle size of 0.4-0.6mm and 0.025-0.03mm, then the polished electrode is cleaned by ethanol and water, the cyclic voltammetry curve of the bare electrode is measured, when the potential difference between an oxidation peak and a reduction peak is less than 90mV, the polishing is finished, then the polished electrode is cleaned by ethanol and water, and the cleaned electrode is dried by nitrogen or argon for standby;
(4) construction of the electrochemical sensor:
and (3) adding a certain amount of the rGO/Fe 3 O 4/Cu 2 O dispersion liquid obtained in the step (2) into a series of NaHS with different concentrations and ammonia water with the concentration of 5-7 wt%, reacting for a certain time, adsorbing the reacted magnetic mixed nano material by using a magnet, removing supernatant liquid, separating the magnetic mixed nano material, redissolving and dispersing the magnetic mixed nano material in ultrapure water, then dropwise coating a certain amount of the obtained solution on the surface of the electrode obtained in the step (3), performing electrochemical scanning on the obtained electrode, recording signal change, and establishing a standard curve between the electrochemical signal and the NaHS concentration of the reacted magnetic mixed nano material.
The concentration of the ethylene glycol solution for reducing the graphene oxide in the step (1) is 1-2 w/v%, wherein the mass ratio of the reduced graphene oxide, the ferric acetylacetonate and the amine acetate is 30-60:15-35: 100-.
in the step (2), the volume usage ratio of the reduced graphene oxide dispersion liquid, the copper nitrate solution, the NaOH solution and the hydrazine hydrate solution is 0.2-1.2:5-15:0.04-0.16: 200-.
the voltage range of the electrochemical scanning in the step (3) is-0.5 v-0.3 v.
and (4) the construction of the electrochemical sensor in the step (4) comprises the following specific steps of parallelly taking 5-12 parts of 20-30 mu L of rGO/Fe 3 O 4/Cu 2 O dispersion liquid obtained in the step (2), respectively adding 100-150 mu L of NaHS solutions with different concentrations, simultaneously adding 20-30 mu L of ammonia water with the concentration of 5-7 wt%, reacting for 50-70min, respectively separating out the magnetic mixed nano material after reaction, taking out, respectively re-dispersing in 20-30 mu L of ultrapure water, then taking 8-12 mu L of the obtained dispersion liquid to drop and coat on the surface of the electrode obtained in the step (3), performing electrochemical scanning, recording signal change, and establishing a standard curve between the electrochemical signal and the NaHS concentration of the magnetic mixed nano material.
The concentration range of the NaHS solution is 0.5-100000 nM.
The magnetic mixed nano material is a mixture of rGO/Fe 3 O 4/Cu 2 O and rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 nano materials.
an electrochemical sensor for detecting endogenous H 2 S, which is applied to the detection of endogenous H 2 S.
the beneficial technical effects of the invention are as follows:
1. in the constructed electrochemical sensor, the used nano material has low cost and is simple and easy to obtain.
2. the principle of the invention is that an electroactive material rGO/Fe 3 O 4/Cu 2 O and NaHS are subjected to redox reaction to generate a sulfur copper compound rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 with a cavity structure, the electrochemical signal of the sulfur copper compound is weaker than that of rGO/Fe 3 O 4/Cu 2 O, the amount of rGO/Fe 3 O 4/Cu 2 O is reduced along with the increase of rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 in the reaction process, so that the electrochemical signal of the integral magnetic mixed nano material is weakened, and finally the purpose of detecting H 2 S is achieved by establishing a standard curve between the electrochemical signal of the integral magnetic mixed nano material and the concentration of NaHS, and the experimental principle is simple.
3. The existing method for detecting H 2 S is mainly a methylene blue method (the detection limit is about 8 mu M, and the detection range is 25 mu M-1000 mu M), and compared with the methylene blue method, the detection limit of the electrochemical sensor is 230pM, and the detection range is 500pM-500 mu M, so that the detection limit of the electrochemical sensor is lower, the detection range is wide, and the sensitivity is high.
4. According to the invention, by introducing Fe 3 O 4 and utilizing the magnetism of the material to be adsorbed on the surface of the magnetic electrode, the steps of electrode modification are greatly simplified, the cost of electrode modification is reduced, and errors caused by the traditional electrode modification process are reduced.
5. The reduced graphene oxide improves the electronic conduction capability of the sensor, so that the result is more accurate.
Drawings
FIG. 1 is the XRD patterns of the magnetic composite nano-materials of the intermediate product rGO/Fe 3 O 4/Cu 2 O, the final reaction mixture rGO/Fe 3 O 4/Cu 2 O and rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 prepared in example 1;
FIG. 2 is an XPS spectrum of the intermediate product rGO/Fe 3 O 4/Cu 2 O prepared in example 1, the final reaction mixture rGO/Fe 3 O 4/Cu 2 O and rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 magnetic composite nano-materials;
FIG. 3 is an AC impedance graph and a Cyclic Voltammetry (CV) graph of the electrochemical sensor prepared in example 1;
FIG. 4 is a DPV spectrum and validation UV spectrum of an electrochemical sensor;
FIG. 5 is a DPV graph of the electrochemical signals of reacted rGO/Fe 3 O 4/Cu 2 O and rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 magnetic hybrid nanomaterials, as measured by the electrochemical sensor prepared in example 1, as a function of NaHS concentration, and a standard graph established between a peak current value and a NaHS concentration logarithm value.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
example 1:
(1) Synthesis of magnetic reduced graphene oxide (rGO/Fe 3 O 4):
Adding 0.45g of reduced graphene oxide into ethylene glycol, mixing and dissolving, adding 0.23g of ferric acetylacetonate, carrying out ultrasonic treatment on the mixed solution for 30min, then adding 1.49g of ammonium acetate, stirring for 30min, transferring the mixed solution obtained by stirring into a reaction kettle, reacting for 24h at 200 ℃, cooling to room temperature after the reaction is finished, carrying out solid-liquid separation to obtain a solid phase, cleaning the solid phase with water and ethanol, dissolving and dispersing the obtained solid phase with water again, and fixing the volume to 3mg/mL to obtain a magnetic reduced graphene oxide (rGO/Fe 3 O 4) solution;
(2) Synthesis of rGO/Fe 3 O 4/Cu 2 O solution:
Adding 1mL of rGO/Fe 3 O 4 solution prepared in the step (1) into 10mL of copper nitrate solution with the concentration of 0.01g/mL, performing ultrasonic treatment at room temperature for 30min to fully and uniformly mix the solution, finishing the ultrasonic treatment, adding 80 muL of NaOH solution with the concentration of 0.035M into a mixing system under the action of stirring, continuously stirring for 30min, then adding 400mL of hydrazine hydrate with the concentration of 85mM into the solution, stirring at room temperature for 40min, then performing solid-liquid separation to obtain a solid phase, washing and drying the solid phase with water, finally re-dispersing the solid phase in water to obtain 2mg/mL of rGO/Fe 3 O 4/Cu 2 O solution, and performing structural characterization on the rGO/Fe 3 O 4/Cu 2 O product by using an XRD scanner, wherein the result is shown in a step (1).
(3) MGCE electrode pretreatment:
MGCE with the diameter of 4mm is sequentially polished on alumina powder with the particle size of 0.5mm and 0.03mm, then the polished electrode is cleaned by ethanol and water, the CV curve of the bare electrode is measured, when the potential difference between an oxidation peak and a reduction peak is 85mV, the polished electrode is cleaned by ethanol and water, and the cleaned electrode is dried by nitrogen or argon for standby;
(4) construction of the electrochemical sensor:
In a constructed electrochemical sensor system, 20 μ L of rGO/Fe 3 O 4/Cu 2 O solution obtained in step (2) is added, a series of NaHS with different concentrations (0.5nM, 1nM, 10nM, 100nM, 1000nM, 10000nM, 100000nM) and ammonia water with a concentration of 5 wt% are added, the reaction is performed for 50min, the reacted rGO/Fe 3 O/Cu 2 O and rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 magnetic composite nanomaterial is adsorbed and separated by using magnetism, the obtained mixed nanomaterial is redispersed in ultrapure water, 10 μ L of the obtained dispersed liquid is taken to coat the obtained electrode surface in step (3), the obtained electrode is subjected to electrochemical scanning, signal changes are recorded, blank signal changes are established, a blank signal concentration curve of rGO/Fe 3 O 4/Cu 2 O and rGO 3 O 4/Cu 367O-Cu 9 O is established, and a linear signal detection curve obtained by multiplying a NaHS 72-hs concentration curve of a standard curve of a mgo concentration curve 8 with a relatively high pmhs 72H 8 H, a linear detection curve is obtained by using a linear detection curve of a linear detection curve 8, wherein the electrochemical detection curve of a correlation curve of a linear detection result is obtained by a linear detection curve of a linear detection peak concentration of a linear detection peak of rGO 8, a standard mg- 8, a linear detection curve of a linear detection method disclosed in a standard mg- 8, a standard substance with a standard curve of a detection method disclosed in a standard substance with a detection method disclosed in the invention, wherein the invention is obtained by a detection method disclosed in the invention, wherein the invention.
Example 2
(1) Synthesis of magnetic reduced graphene oxide (rGO/Fe 3 O 4):
Adding 0.3g of reduced graphene oxide into ethylene glycol, mixing and dissolving, adding 0.15g of ferric acetylacetonate, carrying out ultrasonic treatment on the mixed solution for 40min, then adding 1.6g of ammonium acetate, stirring for 50min, transferring the mixed solution obtained by stirring into a reaction kettle, and reacting for 26h at 210 ℃; after the reaction is finished, cooling to room temperature, then carrying out solid-liquid separation, taking a solid phase, washing the solid phase by using water and ethanol, then dissolving the solid by using water again, and fixing the volume of the solution to 4 mg/mL;
(2) Synthesis of rGO/Fe 3 O 4/Cu 2 O solution:
Adding 1mL of the magnetic reduced graphene oxide (rGO/Fe 3 O 4) dispersion obtained in the step (1) into 0.012g/mL of copper nitrate solution, carrying out ultrasonic treatment for 40min, uniformly mixing, then adding 100 mu L of 0.04mol/L NaOH solution while stirring, continuously stirring for 50min, then adding 450mL of 90mol/L hydrazine hydrate solution and stirring for 50min, then carrying out solid-liquid separation to obtain a solid phase, washing and drying the solid phase with water, and finally re-dispersing in water to obtain 3mg/mL of rGO/Fe 3 O 4/Cu 2 O solution;
(3) MGCE electrode pretreatment:
MGCE with the diameter of 10mm is polished on alumina powder with the diameter of 0.6mm and 0.025mm in sequence, then the polished electrode is cleaned by ethanol and water, the CV curve of the bare electrode is measured, and polishing is finished when the potential difference between the oxidation peak and the reduction peak is 83 mV. Then cleaning the polished electrode with ethanol and water, and blow-drying the cleaned electrode with nitrogen or argon for later use;
(4) Construction of the electrochemical sensor:
in a constructed electrochemical sensor system, 15 mu L of rGO/Fe 3 O 4/Cu 2 O solution obtained in the step (2) is added with a series of NaHS with different concentrations (0.5nM, 1nM, 10nM, 100nM, 1000nM, 10000nM, 100000nM) and ammonia water with the concentration of 7 wt% to react for 60min, the magnetic composite nano material after the reaction is absorbed and separated by utilizing magnetism, the obtained magnetic composite nano material is redispersed in ultrapure water, 8 mu L of the obtained dispersion liquid is coated on the surface of an electrode obtained in the step (3), the obtained electrode is electrochemically scanned, the signal change is recorded, and a standard curve between the magnetic signal concentration of the reacted rGO/Fe 3 O 4/Cu 2 O and rGO/Fe 3 O 4/Cu 2 O-68692S nano material and the NaHS standard curve between the magnetic signal concentrations of the magnetic composite nano material after the reaction is established.
Example 3
(1) Synthesis of magnetic reduced graphene oxide (rGO/Fe 3 O 4):
adding 0.6g of reduced graphene oxide into ethylene glycol, mixing and dissolving, adding 0.35g of ferric acetylacetonate, carrying out ultrasonic treatment on the mixed solution for 35min, then adding 1.4g of ammonium acetate, stirring for 40min, transferring the mixed solution obtained by stirring into a reaction kettle, and reacting for 22h at 190 ℃; cooling to room temperature after the reaction is finished, then carrying out solid-liquid separation, taking a solid phase, washing the solid phase by using water and ethanol, then dissolving the solid by using water again, fixing the volume of the solution to 2mg/ml of dispersion liquid, and then refrigerating for later use;
(2) Synthesis of rGO/Fe 3 O 4/Cu 2 O solution:
adding 1mL of the magnetic reduced graphene oxide (rGO/Fe 3 O 4) dispersion obtained in the step (1) into 0.011g/mL of copper nitrate solution, carrying out ultrasonic treatment for 35min, uniformly mixing, then adding 90 muL of 0.037mol/L NaOH solution while stirring, continuously stirring for 40min, then adding 430mL of 87mol/L hydrazine hydrate solution, stirring for 45min, then carrying out solid-liquid separation to obtain a solid phase, washing and drying the solid phase with water, and finally re-dispersing in water to obtain 2.5mg/mL of rGO/Fe 3 O 4/Cu 2 O solution;
(3) MGCE electrode pretreatment:
Grinding MGCE with the diameter of 6mm on 0.4mm and 0.027mm of alumina powder in sequence, then cleaning the ground electrode with ethanol and water, measuring the CV curve of the bare electrode, finishing grinding when the potential difference between an oxidation peak and a reduction peak is 82mV, then cleaning the ground electrode with ethanol and water, and blowing the cleaned electrode with nitrogen or argon for later use;
(4) Construction of the electrochemical sensor:
In a constructed electrochemical sensor system, 25 mu L of rGO/Fe 3 O 4/Cu 2 O solution obtained in the step (2) is added with a series of NaHS with different concentrations (0.5nM, 1nM, 10nM, 100nM, 1000nM, 10000nM, 100000nM) and ammonia water with the concentration of 6 wt% to react for 40 minutes, the magnetic composite nano material after the reaction is absorbed and separated by utilizing magnetism, the obtained magnetic composite nano material is redispersed in ultrapure water, 13 mu L of the obtained dispersion liquid is coated on the surface of an electrode obtained in the step (3), the obtained electrode is electrochemically scanned, the signal change is recorded, and a standard curve between the magnetic signal concentration of the reacted rGO/Fe 3 O 4/Cu 2 O and rGO/Fe 3 O 4/Cu 2 O-Cu 9 S nano material and the NaHS standard curve between the magnetic signal concentrations of the magnetic composite nano material after the reaction is established.
Test example
characterization of the intermediate product rGO/Fe 3 O 4/Cu 2 O, the final reaction mixture rGO/Fe 3 O 4/Cu 2 O and rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 magnetic composite nanomaterials prepared in example 1
a, an XRD scanner is used for carrying out structural characterization on the rGO/Fe 3 O 4/Cu 2 O product prepared in example 1, and the result is shown in figure 1(1), wherein in an X-ray diffraction pattern, a Cu 2 O peak in the obtained rGO/Fe 3 O 4/Cu 2 O is found to be well matched with Cu 2 O of a standard cube, and the result is preliminarily shown to be rGO/Fe 3 O 4/Cu 2 O after the reaction, meanwhile, an XRD scanner is used for carrying out structural characterization on a reaction product obtained after the reaction of the rGO/Fe 3 O 4/Cu 2 O and NaHS in step (4) of example 1, and the obtained result is shown in figure 1(2), wherein the X-ray diffraction peak of the product obtained by the reaction is compared with the standard Cu 9 S 8, the peak in the obtained reaction product is found to be matched with the peak, and the sample obtained after the reaction is preliminarily shown to be rGO/Fe 3 O 4/Cu 2 O-Cu 39 9 S 8.
B, the change of the chemical composition and chemical state of the elements in the rGO/Fe 3 O 4/Cu 2 O prepared in example 1 and the nano-material rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 9 obtained by the reaction in step (4) of example 1 are studied by XPS measurement, as shown in FIGS. 2(1) and (2), the study of the XPS spectra confirms the coexistence of Cu element and O element in the composite material before the reaction with NaHS, from the Cu 9 XPS spectra, we can see that the XPS spectra of the composite material show two peaks at 365 eV and 951 931, and the binding energies respectively belonging to Cu 9 and Cu 9, 2p orbitals substantially match Cu 9, in addition, a broad peak appears at 530, and the 1S orbital binding energy of O matches, after the reaction of the material with NaHS, the XPS spectra further study of the composite material show that the binding energies of the elements in the XPS 9 eV and Cu 9 eV are found in the XRD peak at 9 eV, the peak of the Cu 9 eV and the Cu 9 eV, the peaks of the Cu 9 eV, the XPS 9 are found in the XRD spectra of the Cu 9 eV, and the Cu 9 eV.
2, in order to achieve the purpose of electrochemical detection, the electrochemical properties of the material before and after the reaction are studied, and an equivalent circuit in software is used for processing alternating current impedance data to obtain an electron transfer kinetic spectrum of the sensor in a 0.1M [ Fe (cn) 6 ] 3-/4- solution, as shown in fig. 3(1), a naked MGCE presents a nearly smooth straight line, however, a half arc shape can be observed by MGCE/rGO/Fe 3 O 4/Cu 2 O, which indicates that the presence of rGO/Fe 3 O 4/Cu 2 O hinders the conduction of electrons, further, after the reaction with NaHS, the material is modified on the electrode surface to find that the arc radius is larger than rGO/Fe 3 O 4/Cu 9O, which indicates that the mobility of the surface charge of rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 is lower than that of the surface charge of rGO/Fe 4/Cu 2 O, as shown in fig. 3, the electrochemical detection shows that the change of the cycle of the electrode (i.g/g) is not corresponding to the rGO 2, and the eio 2/Cu 2, and 2/2 is not observed according to the electrochemical change of the eio 2, 2.
3, verification of ultraviolet spectrum and DPV spectrum of electrochemical sensor
For more accurate detection of endogenous hydrogen sulfide, changes of ultraviolet absorption before and after reaction of rGO/Fe 3 O 4/Cu 2 O with NaHS are recorded, and as a result, as shown in fig. 4, it is found that an electrode modified by rGO/Fe 3 O 4/Cu 2 O has a significant DPV current response at a voltage of-0.1 v after reaction of rGO/Fe 3 O 4/Cu 2 O with 500 μ M NaHS, unreacted S 2- is removed by using a magnetic separation material and a material washed with super water, and volume is re-determined, changes of optical properties before and after reaction of rGO/Fe 3 O 4/Cu 2 O nanomaterial with NaHS on the surface of the electrode are modified in a scanning range of-0.5 v to 0.3v after scanning DPV, and a significant decrease of an electrochemical signal is found, and at the same time, as shown in fig. 4(2), changes of optical properties before and after reaction of rGO/Fe 3 O 4/Cu 2 O nanomaterial and NaHS react with NaHS are studied by using ultraviolet absorption spectroscopy, as compared with a near infrared absorption curve of increasing near infrared absorption at 500nm and increasing absorbance at a wavelength of 500nm after reaction of 500 nm.
Claims (8)
1. A construction method of an electrochemical sensor for detecting endogenous H 2 S is characterized by comprising the following steps:
(1) synthesizing magnetic reduced graphene oxide:
Adding reduced graphene oxide into ethylene glycol, mixing and dissolving, adding ferric acetylacetonate, carrying out ultrasonic treatment on the mixed solution for 30-40min, then adding 1.4-1.6g of amine acetate, stirring for 30-50min, transferring the mixed solution obtained by stirring into a reaction kettle, carrying out reaction at the temperature of 190-210 ℃ for 22-26h, cooling to room temperature after the reaction is finished, carrying out solid-liquid separation to obtain a solid phase, cleaning the solid phase with water and ethanol, dissolving and dispersing the obtained solid phase again with water, and fixing the volume to 2-4mg/mL to obtain a magnetic reduced graphene oxide solution, namely an rGO/Fe 3 O 4 solution;
(2) Synthesis of rGO/Fe 3 O 4/Cu 2 O solution:
adding the rGO/Fe 3 O 4 solution obtained in the step (1) into 0.01-0.012g/mL of copper nitrate solution, carrying out ultrasonic treatment for 30-40min, uniformly mixing, then adding 80-100 mu L of 0.035-0.04mol/L NaOH solution while stirring, continuously stirring for 30-50min, then adding 400-450mL of 85-90mol/L hydrazine hydrate solution and stirring for 40-50min, then carrying out solid-liquid separation to obtain a solid phase, washing and drying the solid phase with water, and finally dispersing in water again to obtain 2-3mg/mL of rGO/Fe 3 O 4/Cu 2 O solution;
(3) MGCE electrode pretreatment:
MGCE with the diameter of 4-10mm is sequentially polished on alumina powder with the particle size of 0.4-0.6mm and 0.025-0.03mm, then the polished electrode is cleaned by ethanol and water, the cyclic voltammetry curve of the bare electrode is measured, when the potential difference between an oxidation peak and a reduction peak is less than 90mV, the polishing is finished, then the polished electrode is cleaned by ethanol and water, and the cleaned electrode is dried by nitrogen or argon for standby;
(4) Construction of the electrochemical sensor:
adding a certain amount of rGO/Fe 3 O 4/Cu 2 O solution obtained in the step (2) into a series of NaHS with different concentrations and ammonia water with the concentration of 5-7 wt%, reacting for a certain time, adsorbing the reacted magnetic mixed nano material by using a magnet, removing supernatant liquid, separating the magnetic mixed nano material, re-dissolving and dispersing the magnetic mixed nano material in ultrapure water, then dropwise coating a certain amount of the obtained solution on the surface of the electrode obtained in the step (3), performing electrochemical scanning on the obtained electrode, recording signal change, and establishing a standard curve between an electrochemical signal and the NaHS concentration of the reacted magnetic mixed nano material.
2. the construction method according to claim 1, wherein the concentration of the ethylene glycol solution for reducing graphene oxide in step (1) is 1-2 w/v%, and the mass ratio of reduced graphene oxide, ferric acetylacetonate and amine acetate is 30-60:15-35: 100-.
3. The construction method according to claim 1, wherein the volume usage ratio of the reduced graphene oxide dispersion liquid, the copper nitrate solution, the NaOH solution and the hydrazine hydrate solution in step (2) is 0.2-1.2:5-15:0.04-0.16: 200-.
4. the method of claim 1, wherein the electrochemical scanning in step (3) is performed at a voltage ranging from-0.5 v to 0.3 v.
5. the construction method of claim 1, wherein the electrochemical sensor in step (4) is constructed by placing 5-12 parts of 20-30 μ L of the rGO/Fe 3 O 4/Cu 2 O dispersion obtained in step (2) into a centrifuge tube, adding 100-150 μ L of NaHS solutions with different concentrations, adding 20-30 μ L of 5-7 wt% ammonia water, reacting for 50-70min, separating the reacted magnetic mixed nano-materials, re-dispersing the separated magnetic mixed nano-materials into 20-30 μ L of ultrapure water, applying 8-12 μ L of the dispersed liquid onto the surface of the electrode obtained in step (3), performing electrochemical scanning, recording signal changes, and establishing a standard curve between the electrochemical signal and the NaHS concentration of the magnetic mixed nano-materials.
6. the method of claim 5, wherein the NaHS solution is used at a concentration ranging from 0.5 to 100000 nM.
7. The construction method according to claim 1 or 5, wherein the magnetic mixed nanomaterial is a mixture of rGO/Fe 3 O 4/Cu 2 O and rGO/Fe 3 O 4/Cu 2 O-Cu 9 S 8 nanomaterials.
8. an electrochemical sensor for detecting endogenous H 2 S, which is prepared by the construction method of claim 1, and is applied to the detection of endogenous H 2 S.
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| CN110615693A (en) * | 2019-09-19 | 2019-12-27 | 中国科学院合肥物质科学研究院 | Hydrogen sulfide gas sensing material, sensor, preparation method and use method |
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