CN113702458B - rGO-ZVI nano composite material, application and detection equipment - Google Patents
rGO-ZVI nano composite material, application and detection equipment Download PDFInfo
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- CN113702458B CN113702458B CN202110995249.0A CN202110995249A CN113702458B CN 113702458 B CN113702458 B CN 113702458B CN 202110995249 A CN202110995249 A CN 202110995249A CN 113702458 B CN113702458 B CN 113702458B
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 51
- 238000001514 detection method Methods 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims description 31
- 239000011259 mixed solution Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 29
- 241001122767 Theaceae Species 0.000 claims abstract description 25
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 25
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 5
- 230000004044 response Effects 0.000 claims description 53
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 41
- -1 mercury ions Chemical class 0.000 claims description 40
- 229910052753 mercury Inorganic materials 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005171 square wave anodic stripping voltammetry Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007853 buffer solution Substances 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000013507 mapping Methods 0.000 claims description 5
- 238000005457 optimization Methods 0.000 claims description 5
- 238000010812 external standard method Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000003487 electrochemical reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 3
- 239000008055 phosphate buffer solution Substances 0.000 claims description 2
- 238000007517 polishing process Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 44
- 238000004220 aggregation Methods 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- 238000003911 water pollution Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 description 28
- 150000002500 ions Chemical class 0.000 description 17
- 229910001385 heavy metal Inorganic materials 0.000 description 13
- 239000000872 buffer Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 239000008363 phosphate buffer Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- SPJOZZSIXXJYBT-UHFFFAOYSA-N Fenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=CC=C1 SPJOZZSIXXJYBT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000007979 citrate buffer Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000003950 stripping voltammetry Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention relates to an rGO-ZVI nanocomposite, application and detection equipment. The preparation method of the rGO-ZVI nanocomposite comprises the following steps: dissolving graphene oxide powder in deionized water, and performing ultrasonic dispersion to obtain a first mixed solution; adding tea polyphenol into the first mixed solution and fully stirring to obtain a second mixed solution; adding ferrous sulfate into the mixed solution II, and stirring for a certain time to obtain a mixed solution III; adding tea polyphenol into deionized water, and uniformly stirring to obtain a mixed solution IV; and finally, adding the mixed solution IV into the mixed solution III, stirring for a certain time to obtain a mixed solution V, and sequentially washing and drying the mixed solution V to obtain the rGO-ZVI nanocomposite. The rGO-ZVI nanocomposite is prepared by adopting a green route, and the tea polyphenol is used as a reducing agent and a sealing agent of zero-valent iron, so that nano zero-valent iron with good dispersion performance is prepared on a reduced graphene oxide skeleton, the self-aggregation phenomenon of the zero-valent iron is reduced, and the application of the nano zero-valent iron in water pollution detection is expanded.
Description
Technical Field
The invention relates to water pollution detection, in particular to an rGO-ZVI nanocomposite, application and detection equipment.
Background
With the accelerated development of the social industry, the environmental pollution is increasingly severe, wherein the pollution of heavy metals is particularly prominent, and the industrial wastewater discharged by industries such as electroplating, mining, papermaking and the like is one of the main reasons for the pollution of heavy metal ions. Common heavy metal ions include mercury, lead, cadmium, chromium and the like, which can cause serious damage to human bodies under the condition of low concentration. Because heavy metal ions cannot be naturally degraded by the environment, the generated heavy metal ions are easy to accumulate in fish, algae and plants and finally reach the human body through a food chain to destroy various organs and nerve centers of the human body. Therefore, a rapid, simple and efficient method for detecting the concentration of heavy metal ions in a water body is needed. Traditional detection methods of heavy metal ions comprise a high performance liquid chromatography method, a colorimetric detection method, an atomic absorption spectrometry method and the like, and although the methods can accurately detect the content of the heavy metal ions in the water body, the methods often face the problems of expensive equipment, complex operation and the like and are not suitable for on-site in-situ detection.
The square wave anode stripping voltammetry is used for detecting heavy metal ions (such as mercury ions and the like) in water environment, is a common electrochemical detection method, has the advantages of simple operation, portability, low detection limit, high sensitivity and the like, and is considered as an effective alternative method of the traditional detection method. In the detection of the stripping voltammetry, the electrode surface is firstly required to be subjected to material modification treatment, so that a larger specific surface area and unique surface properties are provided for the electrode surface. Generally, noble metal material modified electrodes perform better because these noble metal materials (including gold, palladium, platinum, etc.) can form a large number of effective active sites on the electrode surface, greatly enhancing the electrochemical response capability of the electrode. However, these noble metal materials often face high cost challenges.
Zero-valent iron is a nano material with high catalytic activity, low cost and no toxicity, is commonly used for detecting and adsorbing heavy metal ions in water environment, but is easy to oxidize and agglomerate in external environment, and is faced with a plurality of limitations in practical use. This further limits its application in the field of water pollution detection.
Disclosure of Invention
Based on the above, it is necessary to provide an rGO-ZVI nanocomposite, application and detection equipment aiming at the technical problem that zero-valent iron is easily oxidized and agglomerated in the external environment in the prior art, so that the zero-valent iron is limited in the field of water pollution detection.
The invention provides a rGO-ZVI nanocomposite, and a preparation method thereof comprises the following steps:
(1) According to the mass portion ratio, 5 portions of graphene oxide powder, 10 portions of tea polyphenol, 2000 portions of deionized water and 69.5 portions of ferrous sulfate are respectively prepared.
(2) And adding 5 parts of graphene oxide powder into 1000 parts of deionized water, and performing ultrasonic dispersion for 20min to obtain a first mixed solution for later use.
(3) And 5 parts of tea polyphenol is added into the mixed solution I which is kept to be stirred, and the mixed solution II is obtained after full reaction for standby.
(4) Adding 69.5 parts of ferrous sulfate into the second mixed solution, and stirring for 1h to obtain a third mixed solution for later use.
(5) And 5 parts of tea polyphenol is added into 1000 parts of deionized water, and the mixture is uniformly stirred to obtain a mixed solution IV for later use.
(6) And adding the mixed solution IV into the mixed solution III, and stirring for 24 hours to form a mixed solution V.
(7) And washing and drying the mixed solution five in sequence to obtain the rGO-ZVI nanocomposite.
In one embodiment, in the step (1), graphene oxide is prepared by a Hummers method, and the graphene oxide powder is obtained after vacuum drying treatment.
In one embodiment, in the step (3), whether the tea polyphenol is fully reacted with the first mixed solution is judged by the color change, and when the color change appears from brown yellow to black, the tea polyphenol is fully reacted with the first mixed solution is judged.
In one embodiment, in step (7), the washing treatment process is as follows:
adding a proper amount of ethanol into the mixed solution five, centrifuging the mixed solution five through a centrifugal machine, pouring out supernatant, repeating the steps for three times, adding a proper amount of deionized water into the mixed solution five, centrifuging the mixed solution five through the centrifugal machine, pouring out supernatant, and repeating the steps for three times to fully remove impurities in the mixed solution five.
In one embodiment, the drying process is performed as follows: vacuum drying is carried out for 6 hours at 65 ℃ to obtain the rGO-ZVI solid material.
The invention also provides application of the rGO-ZVI nanocomposite in detecting trace mercury ions in a water environment, wherein the rGO-ZVI nanocomposite is prepared from any one of the rGO-ZVI nanocomposite.
The invention also provides detection equipment for trace mercury ions in the water environment, and the detection equipment adopts square wave anodic stripping voltammetry to detect the concentration of mercury ions in a water sample. The detection device includes:
a three electrode system comprising a glassy carbon electrode, a silver chloride electrode, and a platinum wire electrode. The glassy carbon electrode is used as a working electrode in a three-electrode system and is used for generating corresponding electrochemical response according to the concentration of mercury ions in a water sample under an optimized condition. The glassy carbon electrode is modified by rGO-ZVI nano composite material. The silver chloride electrode serves as a reference electrode in a three electrode system. The platinum wire electrode serves as a counter electrode in a three electrode system.
And the current acquisition module is used for acquiring a response current value of the electrochemical response generated by the glassy carbon electrode.
And the controller is used for inquiring a preset mapping function of the response current and the mercury ion concentration according to the response current value so as to calculate the mercury ion concentration in the water sample corresponding to the response current value.
Wherein, the optimization condition is: the buffer solution of the electrochemical reaction was chosen from phosphate buffer with a concentration of 0.1M and ph=5. The water sample was mixed with the buffer at a ratio of 1:9. The enrichment voltage and time of the first stage are set at-1.2V and 180s, respectively. The rGO-ZVI nanocomposite is prepared by adopting any one of the rGO-ZVI nanocomposite.
In one embodiment, the modification method for modifying the glassy carbon electrode by the rGO-ZVI nanocomposite comprises the following steps:
s1, pretreatment of the electrode surface: polishing the glassy carbon electrode to make the surface of the glassy carbon electrode appear a mirror surface, sequentially carrying out continuous ultrasonic treatment on the glassy carbon electrode by using ethanol and deionized water for 2min, and naturally air-drying for later use.
S2, preparing a modification solution: according to the mass ratio, 0.1 part of rGO-ZVI nano composite material is taken and dissolved in 94.5 parts of dimethylformamide solution, and after stirring, the solution is placed in ultrasonic equipment for ultrasonic treatment for 30min, so as to obtain a modification solution, and the modification solution is taken out for standby.
S3, modification of an electrode: and (3) uniformly dripping a proper amount of modification liquid on the surface of the pretreated glassy carbon electrode by using a micropipette, and naturally air-drying to obtain the glassy carbon electrode modified by the rGO-ZVI nano composite material.
In one embodiment, in step S1, the polishing process for the glassy carbon electrode is as follows:
the glassy carbon electrode was polished with alumina powders having particle diameters of 1.0um, 0.3um and 0.05um in this order.
In one embodiment, the response current-mercury ion concentration function is obtained by an external standard method.
Compared with the prior art, the rGO-ZVI nanocomposite, the application and the detection equipment provided by the invention have the following beneficial effects:
1. according to the invention, a green route is adopted to synthesize rGO-ZVI (zero-valent iron-reduced graphite oxide) nano material, and in the preparation process, tea polyphenol is used as a reducing agent and a sealing agent of zero-valent iron at the same time, so that nano zero-valent iron with good dispersion performance is prepared on a reduced graphene oxide skeleton. The green synthesis method not only effectively avoids the pollution of the traditional reducing agent to the environment, but also effectively reduces the aggregation and oxidation of the zero-valent iron. The load of the zero-valent iron forms a large number of effective active sites on the surface of the graphene, and the self-aggregation phenomenon of the zero-valent iron is further reduced by utilizing unique properties of the graphene, such as folds, multiple holes and the like, so that the limitation of the traditional zero-valent iron in actual use is broken through, and the application of the zero-valent iron in the field of water pollution detection can be expanded.
2. According to the invention, the tea polyphenol and the graphene framework are utilized to perform double protection on the zero-valent iron, so that the nano zero-valent iron with good dispersibility can be obtained, and the nano zero-valent iron is not easy to contact with oxygen. The preparation method not only effectively avoids aggregation and oxidization of zero-valent iron, but also prepares the hybrid material with larger specific surface area and a large number of active sites, and the performance is comparable to that of a noble metal material. In addition, the cost of the hybrid material is remarkably reduced relative to noble metals, and the hybrid material is favorable for marketization.
3. The rGO-ZVI nanocomposite prepared by the invention can be modified on the surface of an electrode to detect heavy metal ions in water, and the detection equipment has lower detection limit (1.2 nM) and higher sensitivity (41.422 (nA/mu M)) due to the good synergistic effect of zero-valent iron and graphene, and still has unique affinity for mercury ions under the interference condition of other cations.
4. The electrochemical detection method of the rGO-ZVI modified electrode is optimized, and a series of experiments are carried out on the type of the buffer solution, the pH value of the buffer solution, the enrichment time of the first-stage ions and the enrichment voltage, so that the optimized condition of detecting mercury ions by the rGO-ZVI modified electrode is obtained: the buffer was chosen to be 0.1M phosphate buffer (ph=5), and the enrichment voltage and time in the first stage were set to-1.2V and 180s, respectively.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing rGO-ZVI nanocomposite in example 1 of the invention;
FIG. 2 is a schematic diagram showing typical stripping curves of different electrodes for detecting 0.5. Mu.M mercury ions in example 2 of the present invention;
FIG. 3 is a schematic diagram showing experimental results of rGO-ZVI modified electrodes under certain optimized conditions in example 2 of the present invention; wherein, (a) is the type of buffer solution, (b) is the pH value of the solution, (c) is the enrichment voltage, and (d) is the enrichment time;
FIG. 4 is a schematic diagram showing the detection and analysis of mercury ion solutions of different concentrations under optimized conditions in example 2 of the present invention; wherein, (a) is a SWASV response schematic diagram of the rGO-ZVI modified electrode; (b) is a fitted calibration curve with the response of (a);
FIG. 5 is a plot of SWASV response of rGO-ZVI modified electrodes to a range of concentrations of mercury ions under single or multiple ion interference conditions in example 2 of the present invention;
FIG. 6 is a graph of respective linear fits corresponding to the respective interference conditions of FIG. 5;
FIG. 7 is a SWASV response chart and a linear fitting graph of the rGO-ZVI modified electrode for detecting mercury ions in an actual water sample in example 2 of the present invention;
FIG. 8 shows XPS total spectrum of rGO-ZVI and high resolution spectra of three elements of iron, oxygen and carbon in example 2 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "or/and" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
Referring to fig. 1, the present embodiment provides a rGO-ZVI nanocomposite, and the preparation method of the rGO-ZVI nanocomposite includes the following steps (1) to (7).
(1) 0.5g of graphene oxide powder, 1g of tea polyphenol, 200mL of deionized water, and 6.95g of ferrous sulfate were prepared, respectively. In this embodiment, graphene oxide may be prepared by a Hummers method, and the prepared graphene oxide may be subjected to vacuum drying treatment to obtain graphene oxide powder.
Graphene is a common two-dimensional nanomaterial, and is paid attention to because of a large specific surface area and excellent heat conduction and electric conduction properties, and is commonly used in the fields of supercapacitors, sensors and the like. However, the electrochemical response of the electrode cannot be greatly improved by modifying the graphene material on the surface of the electrode, because the limited number of active sites on the surface of the graphene material limits the capture of heavy metal ions in the water environment, and the difficulty can be well solved by performing corresponding modification treatment on the graphene material.
(2) Adding 0.5g of graphene oxide powder into 100mL of deionized water, and performing ultrasonic dispersion for 20min to obtain a first mixed solution for later use. Due to the ultrasonic dispersion treatment, the graphene oxide powder can be uniformly dispersed in deionized water, and the first mixed solution is in a suspension state.
(3) Adding 0.5g of tea polyphenol into the mixed solution I kept stirring, and fully reacting to obtain mixed solution II for later use. In this embodiment, whether the tea polyphenol is sufficiently reacted with the first mixed solution can be determined according to the color change mode, and when the color change is changed from brown yellow to black, it can be determined that the tea polyphenol is sufficiently reacted with the first mixed solution.
(4) And adding 6.95g of ferrous sulfate into the second mixed solution, and stirring for 1h to obtain a third mixed solution for later use.
(5) Adding 0.5g of tea polyphenol into 100mL of deionized water, and uniformly stirring to obtain a mixed solution IV for later use.
(6) And adding the mixed solution IV into the mixed solution III, and stirring for 24 hours to form a mixed solution V.
(7) And washing and drying the mixed solution five in sequence to obtain the rGO-ZVI nanocomposite.
In this embodiment, the washing treatment process may be as follows: adding a proper amount of ethanol into the mixed solution five, centrifuging the mixed solution five through a centrifugal machine, pouring out supernatant, repeating the steps for three times, adding a proper amount of deionized water into the mixed solution five, centrifuging the mixed solution five through the centrifugal machine, pouring out supernatant, and repeating the steps for three times to fully remove impurities in the mixed solution five. The centrifugal treatment in the step (7) is to remove impurities in the mixed liquor five, so that relatively pure solid substances are obtained.
The drying process may be as follows: vacuum drying at 65 deg.c for 6 hr to obtain rGO-ZVI solid material. In this example, drying may be performed by a vacuum oven.
In the embodiment, the rGO-ZVI (zero-valent iron-reduced graphene oxide) nanomaterial is synthesized by adopting a green route, and in the preparation process, tea polyphenol is used as a reducing agent and a sealing agent of zero-valent iron at the same time, so that nano zero-valent iron with good dispersion performance is prepared on a reduced graphene oxide skeleton. The green synthesis method not only effectively avoids the pollution of the traditional reducing agent to the environment, but also effectively reduces the aggregation and oxidation of the zero-valent iron. The load of the zero-valent iron forms a large number of effective active sites on the surface of the graphene, and the self-aggregation phenomenon of the zero-valent iron is further reduced by utilizing unique properties of the graphene, such as folds, multiple holes and the like, so that the limitation of the traditional zero-valent iron in actual use is broken through, and the application of the zero-valent iron in the field of water pollution detection can be expanded.
The traditional preparation method of the zero-valent iron is often faced with the fact that the zero-valent iron is easy to oxidize and agglomerate, and the tea polyphenol and the graphene framework are utilized to perform double protection on the zero-valent iron, so that nano iron ions with good activity and dispersibility can be moved, and oxygen contact is not easy to occur. According to the embodiment, tea polyphenol is used as a reducing agent, a green route is adopted to prepare zero-valent iron nano particles on a reduced graphene oxide skeleton, and rGO-ZVI nano materials are successfully synthesized. In addition, the cost of the hybrid material is remarkably reduced relative to noble metals, and the hybrid material is favorable for marketization.
Example 2
The rGO-ZVI nanocomposite in the embodiment 1 can be applied to detection of trace mercury ions in a water environment, and can effectively adsorb mercury ions in the water environment in the process of detecting trace mercury ions in the water environment due to the large specific surface area and a large number of active sites of the rGO-ZVI nanocomposite, so that the detection of the mercury ion concentration in the water environment is facilitated.
The embodiment provides detection equipment for trace mercury ions in a water environment, and the detection equipment detects the concentration of mercury ions in a water sample by adopting square wave anodic stripping voltammetry. The detection device includes:
a three electrode system comprising a glassy carbon electrode, a silver chloride electrode, and a platinum wire electrode. The glassy carbon electrode is used as a working electrode in a three-electrode system and is used for generating corresponding electrochemical response according to the concentration of mercury ions in a water sample under an optimized condition. The glassy carbon electrode is modified by rGO-ZVI nano composite material. The silver chloride electrode serves as a reference electrode in a three electrode system. The platinum wire electrode serves as a counter electrode in a three electrode system.
And the current acquisition module is used for acquiring a response current value of the electrochemical response generated by the glassy carbon electrode.
And the controller is used for inquiring a preset response current-mercury ion concentration function according to the response current value and calculating the mercury ion concentration in the water sample corresponding to the response current value. It should be noted that, the mapping function of the response current and the mercury ion concentration can be obtained by an external standard method, before the detection device in this embodiment detects the mercury ion concentration in the water sample, detection and analysis can be performed on mercury ion solutions with different concentrations under an optimized condition, and the sensitivity of the working electrode can be obtained through linear fitting analysis and a linear fitting coefficient can be calculated, so as to obtain the foregoing mapping function of the response current and the mercury ion concentration.
Wherein, the optimization condition is: the buffer solution of the electrochemical reaction was selected to be phosphate buffer solution with a concentration of 0.1M and ph=5, and the enrichment voltage and time of the first stage were set at-1.2V and 180s, respectively. The rGO-ZVI nanocomposite was prepared as described in example 1.
In this embodiment, the modification method for modifying the glassy carbon electrode by the rGO-ZVI nanocomposite material may include the following steps:
s1, pretreatment of the electrode surface: sequentially polishing the glassy carbon electrode by using alumina powder with particle sizes of 1.0um, 0.3um and 0.05um to enable the surface of the glassy carbon electrode to be mirror surface, sequentially carrying out continuous ultrasonic treatment on the glassy carbon electrode by using ethanol and deionized water for 2min, and naturally air-drying for later use.
S2, preparing a modification solution: according to the mass part ratio, 10mg of rGO-ZVI nano composite material is taken and dissolved in 10mL of dimethylformamide solution, the solution is placed in ultrasonic equipment for ultrasonic treatment for 30min after stirring, and the modified liquid is obtained and taken out for standby.
S3, modification of an electrode: and (3) uniformly dripping 6 mu L of the modification liquid on the surface of the pretreated glassy carbon electrode by using a micropipette, and naturally air-drying to obtain the glassy carbon electrode modified by the rGO-ZVI nano composite material.
In order to verify the effectiveness of the detection apparatus of this embodiment, this embodiment also performs multiple sets of experiments.
Experiment one:
under the condition of the same other variables, working electrodes in a three-electrode system of the detection device are respectively set into a glassy carbon electrode (unmodified), a glassy carbon electrode modified by graphene materials and a glassy carbon electrode modified by the rGO-ZVI nanocomposite in the embodiment 1 under the optimized condition, and the three glassy carbon electrodes are used as three working electrodes to respectively detect Hg with the concentration of 0.5 mu M 2+ Different electrochemical response values.
Referring to fig. 2, fig. 2 shows that 0.5 μm Hg is detected by three electrodes, namely, a glassy carbon electrode modified by graphene material, and a glassy carbon electrode modified by graphene material loaded with zero-valent iron 2+ Is a typical peeling curve of (2). The effect of detecting mercury ions by the graphene material loaded with zero-valent iron is obviously better than that of the graphene material without zero-valent iron, and is more better than that of a glassy carbon electrode without material modification. The zero-valent iron can provide a large number of effective active sites for the graphene material, the graphene material enables the surface of the electrode to have a larger specific surface area, and the electrode modified by the hybrid material shows a stronger response current peak to mercury ions due to the synergistic effect of the zero-valent iron and the graphene material.
In this embodiment, when the detection device detects the concentration of mercury ions in the solution, the conditions such as the type of buffer solution, the pH value of the solution, the enrichment voltage, and the enrichment time may also be determined by experiments to determine the optimal conditions. Thus, a set of experiments is provided below to explore the determination of the optimization conditions.
Experiment II:
the experiment can be divided into a plurality of groups of experiments, and the variables in each group of experiments are controlled by adopting a variable control mode. They are respectively: (1) buffer type experiments, (2) solution pH experiments, (3) enrichment voltage experiments, and (4) enrichment time experiments.
(1) Buffer type experiments:
and respectively selecting 0.1M acetic Acid Buffer (ABS), 0.1M phosphoric acid buffer (PBS) and 0.1M citrate buffer (CPBS) as buffers of three control groups, and observing the influence of different buffer types on the response current of the working electrode under the same mercury ion concentration under the same conditions. Referring to fig. 3, fig. 3 (a) shows the effect of different buffer types on the response current of the working electrode. As can be seen from the graph, in this experiment, the working electrode showed the strongest response current peak to mercury ions when phosphate buffer was selected. ( And (3) injection: 0.1M acetic Acid Buffer (ABS) is prepared by mixing 0.1M acetic acid and sodium acetate solution; the 0.1M Phosphate Buffer (PBS) is prepared by mixing 0.1M disodium hydrogen phosphate and potassium dihydrogen phosphate solution; the 0.1M citrate buffer (CPBS) was prepared from 0.1M citric acid and sodium citrate solution. All solutions were prepared from deionized water )
(2) Solution pH value experiment
The pH of the buffer solution was set to 3, 4, 5 and 6, respectively, and the other conditions were unchanged, and the influence of different pH on the response current of the working electrode (rGO-ZVI modified electrode) was observed.
With continued reference to fig. 3, fig. 3 (b) illustrates the effect of different pH on the response current of the working electrode. As can be seen from the graph, the response current of the working electrode peaks when the pH is at 5.
(3) Enrichment Voltage experiment
The magnitude of the enrichment voltage of the control groups is respectively-1.5V, -1.4V, -1.3V, -1.2V, -1.1V and-1.0, other conditions are unchanged, and the influence of different enrichment voltages on the response current is observed.
With continued reference to FIG. 3, FIG. 3 (c) shows the effect of different enrichment voltages on the response current, as can be seen, the response current of the working electrode is maximum when the enrichment voltage is at-1.2V.
(4) Enrichment time experiment
The enrichment time of the control groups is respectively set at 90s, 120s, 150s, 180s, 210s and 240s under the same conditions, and the influence of the enrichment time with different lengths on the response current of the working electrode is observed.
With continued reference to fig. 3, fig. 3 (d) illustrates the effect of different lengths of enrichment time on the working electrode response current. As can be seen from the graph, the response current of the working electrode is relatively high when the enrichment time is set at 180s-240 s.
In summary, each optimized condition of the rGO-ZVI modified electrode can be judged by a plurality of groups of experiments of the experiment II.
In this embodiment, after the optimization conditions are determined, the aforementioned current-mercury ion concentration function can be obtained through experiments. The following set of experiments is provided for verification:
experiment III:
under the optimized condition, the square wave anodic stripping voltammetry is adopted to detect mercury ions in the water environment, and a certain amount of mercury ions are added into a water sample from low concentration in an equivalent way through an external standard method. In this example, the concentration of mercury ions can be gradually increased from 0.05. Mu.M to 0.6. Mu.M, and after each addition of a fixed amount of mercury ions, the response current of the working electrode is recorded and the voltammogram of the response is plotted therefrom.
Referring to fig. 4, fig. 4 (a) shows the change in response current of the working electrode at different mercury ion concentrations. Fig. 4 (b) represents a fitted calibration curve of response current as a function of concentration. From the graph, the modified electrode modified by rGO-ZVI can show electrochemical response at the mercury ion concentration of only 0.05 mu M, and the sensitivity of the electrode is 41.422 (nA/mu M) through linear fitting analysis, and the linear fitting coefficient is 0.999.
In this embodiment, in order to verify the anti-interference capability of the detection device provided in this embodiment in practical application under the interference condition of multiple heavy metal ions, this embodiment further provides a set of experiments.
Experiment IV:
four control groups were each set, each of which initially contained the same detection base fluid. Quantitative cadmium ions were added in the first control group, quantitative copper ions were added in the second control group, quantitative lead ions were added in the third control group, and equal amounts of cadmium ions, copper ions and lead ions were added simultaneously in the fourth control group. An equal amount of mercury ions can be added to the four control groups simultaneously starting from a low concentration after the start of the experiment.
Referring to fig. 5, fig. 5 shows SWASV response of the rGO-ZVI modified electrode of this embodiment to a series of mercury ions under single-ion or multi-ion interference conditions, where (a), (b), (c), and (d) in fig. 5 correspond to the four control groups described above in this experiment, respectively. It can be seen from the graph that the peak value of the response current of the rGO-ZVI modified electrode provided by the embodiment can play a relatively high level and has high response sensitivity under both single-ion interference and multi-ion interference conditions.
Referring to fig. 6, fig. 6 shows a corresponding linear fitting curve under a plurality of anti-interference condition control groups in the experiment, and fig. 6 corresponds to fig. 5. As can be obtained by combining fig. 5 and fig. 6, the rGO-ZVI modified electrode still shows a higher response current peak and a good linear fit (R 2 =0.999), which indicates that the rGO-ZVI modified electrode has excellent anti-interference ability, and still exhibits unique affinity for mercury ions even in the presence of other ions.
In order to further verify the effectiveness of the detection device provided by the embodiment in practical application, the embodiment also takes a water sample of south river in the city of combined fertilizer to detect an actual water sample, and a sampling point of the actual water sample is one of domestic water sources of local residents. In this example, an actual water sample was mixed with ABS (ph=5.0) at a ratio of 1:9, and square wave anodic stripping voltammetry was used to detect mercury ions in aqueous environments.
Referring to fig. 7, fig. 7 shows a SWASV response plot of an rGO-ZVI modified electrode for detection of mercury ions in an actual water sample. As can be seen from the graph, since the original mercury ion concentration in the actual water sample is relatively low, after a series of equivalent mercury ions are added into the solution, the hybridization material modified electrode shows electrochemical response similar to the optimized condition (as shown in fig. 4), and the sensitivity of the detection of the working electrode in the actual water sample is 40.956 (nA/μM), and the linear fitting coefficient is 0.999. Therefore, the detection device provided in this embodiment can still exert better detection sensitivity in practical application.
Referring to fig. 8, fig. 8 (a) shows the XPS total spectrum of the rGO-ZVI nanocomposite of the present embodiment; (b) is a high resolution spectrum of the corresponding Fe2 p; (c) is the corresponding high resolution spectrum of O1 s; (d) high resolution spectrum for C1 s. The graph shows that the rGO-ZVI nanocomposite material is respectively composed of three elements of iron, oxygen, carbon and the like, wherein the two elements of carbon and oxygen are from tea polyphenol and graphene, and the iron element is from zero-valent iron reduced by the tea polyphenol.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
Claims (10)
1. The rGO-ZVI nanocomposite is characterized in that the preparation method of the rGO-ZVI nanocomposite comprises the following steps:
(1) According to the mass portion ratio, respectively preparing 5 portions of graphene oxide powder, 10 portions of tea polyphenol, 2000 portions of deionized water and 69.5 portions of ferrous sulfate;
(2) Adding 5 parts of graphene oxide powder into 1000 parts of deionized water, and performing ultrasonic dispersion for 20min to obtain a first mixed solution for later use;
(3) Adding 5 parts of tea polyphenol into the first mixed solution which is kept to be stirred, and fully reacting to obtain a second mixed solution for later use;
(4) Adding 69.5 parts of ferrous sulfate into the second mixed solution, and stirring for 1h to obtain a third mixed solution for later use;
(5) Adding 5 parts of tea polyphenol into 1000 parts of deionized water, and uniformly stirring to obtain a mixed solution IV;
(6) Adding the mixed solution IV into the mixed solution III, and stirring for 24 hours to form mixed solution V;
(7) And washing and drying the mixed solution five in sequence to obtain the rGO-ZVI nanocomposite.
2. The rGO-ZVI nanocomposite according to claim 1, wherein in step (1), graphene oxide is prepared by a Hummers method, and the graphene oxide powder is obtained after vacuum drying treatment.
3. The rGO-ZVI nanocomposite according to claim 1, wherein in step (3), whether the tea polyphenol is sufficiently reacted with the first mixed solution is determined by a color change, and when the color change appears to change from brown to black, the tea polyphenol is determined to be sufficiently reacted with the first mixed solution.
4. The rGO-ZVI nanocomposite of claim 1 wherein in step (7), the washing treatment process is as follows:
adding a proper amount of ethanol into the mixed solution five, centrifuging the mixed solution five through a centrifugal machine, pouring out supernatant, repeating the steps for three times, adding a proper amount of deionized water into the mixed solution five, centrifuging the mixed solution five through the centrifugal machine, pouring out supernatant, and repeating the steps for three times to fully remove impurities in the mixed solution five.
5. The rGO-ZVI nanocomposite of claim 1 wherein in step (7), the drying process is performed as follows:
vacuum drying is carried out for 6 hours at 65 ℃ to obtain the rGO-ZVI solid material.
6. An application of an rGO-ZVI nanocomposite in detecting trace mercury ions in an aqueous environment, wherein the rGO-ZVI nanocomposite is the rGO-ZVI nanocomposite according to any one of claims 1 to 5.
7. The detection equipment for trace mercury ions in water environment is characterized by detecting the concentration of mercury ions in a water sample by adopting square wave anodic stripping voltammetry; the detection apparatus includes:
a three electrode system comprising a glassy carbon electrode, a silver chloride electrode, and a platinum wire electrode; the glassy carbon electrode is used as a working electrode in the three-electrode system and is used for generating corresponding electrochemical response according to the concentration of mercury ions in the water sample under an optimized condition; the glassy carbon electrode is modified by an rGO-ZVI nanocomposite; the silver chloride electrode is used as a reference electrode in the three-electrode system; the platinum wire electrode is used as a counter electrode in the three-electrode system;
the current acquisition module is used for acquiring a response current value of the glassy carbon electrode for generating an electrochemical response;
a controller for querying a preset mapping function of response current to mercury ion concentration according to the response current value to calculate the mercury ion concentration in the water sample corresponding to the response current value;
wherein the optimization conditions are as follows: the buffer solution of the electrochemical reaction is selected from phosphate buffer solution with the concentration of 0.1M and the pH=5; the water sample and the buffer solution are mixed in a ratio of 1:9; the enrichment voltage and time of the first stage are respectively set at-1.2V and 180s; the rGO-ZVI nanocomposite is prepared by adopting the rGO-ZVI nanocomposite as claimed in any one of claims 1 to 5.
8. The apparatus for detecting trace mercury ions in an aqueous environment according to claim 7, wherein the method for modifying the glassy carbon electrode with the rGO-ZVI nanocomposite comprises the steps of:
s1, pretreatment of the electrode surface: polishing the glassy carbon electrode to enable the surface of the glassy carbon electrode to be a mirror surface, sequentially carrying out continuous ultrasonic treatment on the glassy carbon electrode by using ethanol and deionized water for 2min, and naturally air-drying for later use;
s2, preparing a modification solution: according to the mass ratio, 0.1 part of rGO-ZVI nano composite material is taken and dissolved in 94.5 parts of dimethylformamide solution, and after stirring, the solution is placed in ultrasonic equipment for ultrasonic treatment for 30min, so as to obtain a modification solution and taken out for standby;
s3, modification of an electrode: and (3) uniformly dripping a proper amount of modification liquid on the surface of the pretreated glassy carbon electrode by using a micropipette, and naturally air-drying to obtain the glassy carbon electrode modified by the rGO-ZVI nanocomposite.
9. The device for detecting trace mercury ions in an aqueous environment according to claim 8, wherein in step S1, the polishing process for the glassy carbon electrode comprises the following steps:
the glassy carbon electrode was subjected to polishing treatment using alumina powder having particle diameters of 1.0 μm, 0.3 μm and 0.05 μm in this order.
10. The apparatus for detecting trace amounts of mercury ions in an aqueous environment of claim 7, wherein the mapping function of response current to mercury ion concentration is obtained by an external standard method.
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