CN112378874B - Composite material for detecting organic phenol in seawater and preparation method thereof - Google Patents
Composite material for detecting organic phenol in seawater and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000013535 sea water Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910006648 β-MnO2 Inorganic materials 0.000 claims abstract description 53
- 238000001514 detection method Methods 0.000 claims abstract description 29
- 239000002073 nanorod Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910002521 CoMn Inorganic materials 0.000 claims abstract description 19
- 239000002135 nanosheet Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
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- 238000001035 drying Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 15
- 239000000523 sample Substances 0.000 description 15
- 102000004190 Enzymes Human genes 0.000 description 9
- 108090000790 Enzymes Proteins 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 4
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
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- 230000004044 response Effects 0.000 description 3
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- 239000011572 manganese Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000011540 sensing material Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a composite material for detecting organic phenol in seawater and a preparation method thereof. The composite material comprises beta-MnO2Nanorods and uniformly covered in beta-MnO2CoMn on nanorod surface2O4Nano meterSlicing; the preparation method of the composite material comprises the following steps: firstly, preparing beta-MnO by adopting a hydrothermal method2The nano-rod is then calcined by a hydrothermal method and a beta-MnO method2Nanorod as substrate in beta-MnO2CoMn grown on nanorods2O4Nanosheets. The preparation method has the advantages of simple process, mild reaction conditions, low preparation cost and good stability. The prepared composite material combines the advantages of a p-n junction interface, exerts a synergistic effect, has excellent sensing performance, can be applied to the online detection of organic phenol in seawater, and reduces the detection limit while improving the detection sensitivity.
Description
Technical Field
The invention relates to CoMn2O4/β-MnO2The composite material and the preparation method thereof, and the application of the composite material in the detection of organic phenol in seawater belong to the technical field of novel composite materials.
Background
Hydroquinone (HQ) is an important organic raw material used in the fields of industry, cosmetics, dyes, pesticides, etc. The water body environmental pollutant is identified by the environmental protection agency of European Union and United states because of poor degradability and high toxicity in nature. The ocean is the basic environment and important resources on which human beings live and develop, and hydroquinone entering the ocean can cause great harm to the ocean environment. Since hydroquinone poses a great threat to human health, marine life and the ecosystem, even at low concentrations. Therefore, the development of a novel online sensing mechanism has great significance in detecting hydroquinone under the condition of not being interfered by complex environmental factors of seawater.
Chinese patent application publication No. CN 108956727 a discloses an electrode modification material for detecting hydroquinone in seawater for the first time. However, the method has the disadvantages of high cost, complex equipment and operation, long period, low sensitivity and high detection limit. Chinese patent application publication No. CN 106610372 a also discloses a probe and a method for detecting catechol and/or hydroquinone. However, the method also has the problems of high cost, complex equipment and operation, long period, low sensitivity and relatively high detection limit. The colorimetric sensing method is used for detecting hydroquinone, not only solves the problems, but also has the advantages of visualization and strong practicability. The catalyst used in the colorimetric sensing method can help oxidize the organic substrate to generate color change, and the catalytic efficiency of the catalyst determines the quality of the colorimetric detection performance.
It has been shown that natural enzymes are used as complex biocatalysts for colorimetric biosensing due to their high catalytic activity and substrate specificity. They have the disadvantages of being labile, easily digested by proteases, difficult to purify and transport. Therefore, there is a need to develop enzyme mimetics to overcome the disadvantages of natural enzymes. It has been found that some nanomaterials, e.g. ZnFe2O4@ZnO，Au-C/SiO2And 3DGN @ WO3Etc., have been demonstrated to have enzyme-like activity. However, in the colorimetric detection, the nanomaterial is required to be in H2O2The presence of the enzyme can lead to the display of catalytic activity, which makes the detection process very complicated. Therefore, there is a need to develop an enzyme-like substance that does not require H2O2The catalyst can directly catalyze and oxidize 3,3',5,5' -tetramethyl benzidine (TMB for short).
Meanwhile, the detection of HQ in seawater faces a huge challenge due to the fact that a seawater system is high in salinity, weak in alkalinity and complex in components.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a composite material for online detection of organic phenol in seawater, which improves the detection sensitivity and selectivity and reduces the detection limit.
The invention also aims to provide the CoMn with simple process, mild reaction conditions, low preparation cost and good stability2O4/β-MnO2A method for preparing a composite material.
The principle of the invention is as follows:
with the development of nanotechnology, metal oxides and A having a spinel structurexB3-xO4The nano structure becomes a promising colorimetric sensing material due to the easy availability, excellent catalytic performance and chemical stability. Wherein, beta-MnO2Is aNarrow bandgap n-type semiconductor material (E)g=1.65eV), has been extensively studied in catalysts and sensors due to their good catalytic and sensing properties. CoMn2O4Is a narrow bandgap p-type semiconductor (E)g=1.55eV), is recognized as an excellent sensing material due to its high stability during catalytic oxidation. beta-MnO2And CoMn2O4The combination can form p-n junction built-in electric field, beta-MnO2And CoMn2O4Both have oxidase-like enzyme activities and are paid much attention to the colorimetric sensing field, however, the two materials alone do not achieve an ideal catalytic effect. At the p-n junction interface, an electron trap is formed by bending the energy band, so that electrons flow from the p-type semiconductor to the n-type semiconductor, holes move reversely, recombination of electron-hole pairs is effectively hindered, and the catalytic efficiency is further improved. When electrons are generated on the surface of the P-type semiconductor, the built-in electric field of the P-n junction provides driving force to enable the electrons to orderly and directionally move, so that the catalytic efficiency is improved, and the high-sensitivity detection signal can be generated. Meanwhile, under the irradiation of visible light, electrons in the P-type semiconductor with narrow forbidden band are excited from valence band to conduction band, and the excited electrons make O2Conversion to superoxide radical (O)2 ·−），O2 ·−Further reaction with water to form H2O2And yet further promote catalysis. To solve the important problem of catalytic efficiency, p-type semiconductor CoMn is used2O4With n-type semiconductor beta-MnO2The combination forms a built-in electric field of a p-n junction, which is helpful for the catalytic substrate to effectively capture electrons of 3,3',5,5' -tetramethyl benzidine (TMB) to generate blue reaction, thereby enhancing pure beta-MnO2And CoMn2O4Intrinsic oxidase-like enzyme activity. The hydroquinone has strong reducibility, and can fade blue, thereby realizing the detection of the hydroquinone with low detection limit, high selectivity and high sensitivity.
The composite material of the invention is prepared by hydrothermal and calcining methods. First hydrothermal growth of beta-MnO2Nano-rod, and then the CoMn is obtained by hydrothermal and calcining method2O4Attachment of Nanoblock to beta-MnO2Nanorod surface, thereby forming CoMn2O4/β-MnO2A composite material. CoMn is used as a material for the present invention2O4And beta-MnO2And a p-n junction potential barrier is formed, so that the catalytic oxidation efficiency is improved, and meanwhile, the detection limit is lower.
The reaction process involved in the present invention is shown in the following equation.
H2NCONH2 +2H2O → 2NH4 + + CO3 2− （1）
1/3Co2+ + 2/3Mn2+ + CO3 2− + nH2O →（Co1/3Mn2/3CO3）· nH2O （2）
（Co1/3Mn2/3）CO3· nH2O + 1/2O2 → CoMn2O4 + 3CO2↑+ nH2O↑ （3）
The specific technical scheme of the invention is as follows:
a composite material for detecting the organic phenol in seawater contains beta-MnO2Nanorods and uniformly covered in beta-MnO2CoMn on nanorod surface2O4Nanosheets.
The CoMn2O4The nano-sheet has uniform thickness of 200 nm.
The beta-MnO2The nanorods were uniform in size, 300 nm in diameter and 13 μm in length.
The CoMn2O4/β-MnO2The preparation method of the composite material is characterized by comprising the following steps:
the method comprises the following steps: dissolving manganese sulfate and potassium chlorate in ultrapure water, and violently stirring to obtain a uniform solution; transferring the mixture into a hydrothermal kettle, sealing the hydrothermal kettle, and preserving the heat for 10-15 h at the temperature of 150-; cooling to room temperature, taking out the sample, cleaning and drying to obtain beta-MnO2A nanorod;
step two: dissolving cobalt nitrate, manganese nitrate, ammonium fluoride and urea in ultrapure water, and vigorously stirringStirring to obtain a uniform solution; then the solution and the prepared beta-MnO2Transferring the nano-rod into a hydrothermal kettle in beta-MnO2Method for preparing CoMn on nanorod by hydrothermal method2O4Nanosheets; taking out, cleaning and drying; transferring the obtained powder into a tube furnace, raising the furnace temperature to 350-400 ℃ at a certain speed, preserving the heat for 1.5-2h at the temperature, and naturally cooling to obtain CoMn2O4/β-MnO2A composite material.
Further, in the above-mentioned steps (i) and (ii), the cleaning is performed by using ethanol and deionized water, respectively.
Further, in the above-mentioned steps (i) and (ii), the drying means drying in an oven at 60 ℃ for 12 hours.
Furthermore, in the first step and the second step, the violent stirring means that the rotating speed of the magnetic stirrer is 400r/min, and the time is 10 min.
The above CoMn2O4/β-MnO2The composite material is applied to detection of organic phenol in seawater.
The invention synthesizes beta-MnO by a hydrothermal method2Nanorods of CoMn produced by hydrothermal and calcination methods2O4The nano-sheets are uniformly coated on the beta-MnO2And (4) nanorods. The preparation method is simple, mild in reaction condition, low in preparation cost and good in stability. In the prepared composite material, CoMn2O4And beta-MnO2Can catalyze and oxidize the organic matrix to generate an absorbance response; the p-n junction potential barrier is formed and mainly used for accelerating the electron transfer efficiency and further improving the catalytic performance. The advantage of this structure is that the CoMn is fully utilized2O4And beta-MnO2The performance of the oxidase-like enzyme and the electronic driving action of the built-in electric field of the p-n junction are integrated, the synergistic effect is exerted, the method can be effectively applied to the colorimetric sensing field, and the detection limit is reduced while the detection sensitivity is improved. With CoMn2O4/β-MnO2The composite material is used as a catalytic substrate, hydroquinone in seawater is used as a detection target, and excellent sensing performance is shown.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention.
FIG. 2 is a scanning electron micrograph, a transmission electron micrograph, and a three-dimensional schematic of the material prepared in example 1 of the present invention.
Wherein, a, beta-MnO2Scanning electron microscope image of the nano rod; b. beta-MnO2Transmission electron microscope image of the nano-rod; c. CoMn2O4/β-MnO2Scanning electron microscope images of the composite materials; d-e. CoMn2O4/β-MnO2Transmission electron micrographs of the composite; f. CoMn2O4/β-MnO2Three-dimensional schematic of a composite material.
FIG. 3 shows CoMn prepared in example 1 of the present invention2O4/β-MnO2XRD characterization pattern of the composite.
FIG. 4 is CoMn prepared in example 1 of the present invention2O4/β-MnO2The absorbance of the composite material is plotted as a linear function of the concentration of hydroquinone in seawater.
FIG. 5 is CoMn prepared in example 1 of the present invention2O4/β-MnO2And (3) a graph of the difference in absorbance of the composite material to a common interfering substance.
Detailed Description
The invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings.
Example 1:
the specific preparation process of the invention is shown in figure 1.
(1) 0.338g of manganese sulfate monohydrate and 0.246g of potassium chlorate were weighed out and dissolved in 25 ml of ultrapure water, and after vigorously stirring for 10 minutes, they were transferred to a hydrothermal kettle and sealed, and kept at 200 ℃ for 12 hours. After cooling to room temperature, the sample was taken out, washed with ethanol and deionized water, and oven-dried at 60 ℃ for 12 h.
From FIG. 2a of the scanning electron microscope, it can be seen that beta-MnO2The nanorods are relatively uniform in size, about 13 microns in length, and about 300 nm in diameter as can be seen in transmission electron microscopy, FIG. 2 b.
(2) 0.2911g of cobalt nitrate hexahydrate, 0.5021g of manganese nitrate tetrahydrate, 0.0741g of ammonium fluoride and 0.3002g of manganese nitrate tetrahydrate are weighedThe urea was dissolved in 35 ml of ultrapure water and stirred vigorously for 10 minutes. 0.0590g of prepared beta-MnO was weighed2The mixture was placed in the above solution, stirred vigorously for 10 minutes, transferred to an autoclave and sealed, and kept at 200 ℃ for 6 hours. After taking out the sample, washing the sample by using ethanol and deionized water, and drying the sample in an oven at the temperature of 60 ℃ for 12 hours. Putting the obtained powder into a tube furnace, calcining in air, setting the furnace temperature to 400 ℃ within 375min, keeping the temperature for 2h, taking out a sample after the furnace temperature is gradually cooled, and showing that the surface becomes black to obtain CoMn2O4/β-MnO2A composite material.
From FIGS. 2c-d, the beta-MnO can be seen2The surface of the nano-rod is covered with CoMn2O4The nanosheets, as can be seen in fig. 2c, are uniform in thickness, being about 200nm in thickness.
FIG. 3 shows CoMn2O4/β-MnO2The XRD pattern of the composite material can show obvious beta-MnO2(211) Characteristic peak and CoMn2O4(111)、CoMn2O4(202)、CoMn2O4(220)、CoMn2O4(113)、CoMn2O4(311)、CoMn2O4(004)、CoMn2O4(400)、CoMn2O4(332)、CoMn2O4(205)、CoMn2O4(511)、CoMn2O4(404)、CoMn2O4(440) Characteristic peaks, and no impurity peaks appear.
The colorimetric detection test is carried out on an ultraviolet spectrophotometer, TMB is taken as a catalytic substrate, and prepared CoMn2O4/β-MnO2The composite material is an oxidase-like enzyme catalyst, and the pH value of the composite material is Na of 3.02HPO4-CA buffer is used as reaction environment.
As can be seen from FIG. 4, CoMn2O4/β-MnO2The detection range of the composite material on hydroquinone in seawater is 0-24 mu M, and the lowest detection limit is 0.21 mu M. The detection limit disclosed in the Chinese patent application with publication No. CN 108956727A is 5.6 μ M, while that disclosed in the Chinese patent application with publication No. CN 106610372AThe detection limit of (2) is 1.6 mu M, and compared with the detection limit, the invention has lower detection limit and higher sensitivity.
Table 1 shows CoMn prepared in example 1 of the present invention2O4/β-MnO2And (3) determining the recovery rate of the hydroquinone standard solution in the seawater by a composite material colorimetric method.
TABLE 1 colorimetric method for determining recovery rate of hydroquinone standard solution in seawater
As can be seen from table 1, the relative standard deviation of the test conducted on parallel samples of hydroquinone in seawater was below 5.08%, and the calculated recovery was between 97.23% and 101.37%. The above results show that CoMn is used2O4/β-MnO2The composite material has excellent performance for detecting hydroquinone in seawater.
As can be seen from FIG. 5, when the concentrations of hydroquinone, catechol and resorcinol are all 20 μ M, and the concentrations of other metal ions are 100 μ M, CoMn is present2O4/β-MnO2The composite material has the highest response to hydroquinone and has lower response to other interfering substances except the hydroquinone, which indicates that the composite material has the capacity of resisting disturbance to common interfering substances.
Example 2:
(1) 0.338g of manganese sulfate monohydrate and 0.246g of potassium chlorate were weighed out and dissolved in 25 ml of ultrapure water, and after vigorously stirring for 10 minutes, they were transferred to an autoclave and sealed, and held at 200 ℃ for 10 hours. After cooling to room temperature, the sample was taken out, washed with ethanol and deionized water, and oven-dried at 60 ℃ for 12 h.
(2) 0.2911g of cobalt nitrate hexahydrate, 0.5021g of manganese nitrate tetrahydrate, 0.0741g of ammonium fluoride and 0.3002g of urea were weighed out and dissolved in 35 ml of ultrapure water, and vigorously stirred for 10 minutes. Prepared 0.0590g beta-MnO was weighed2Adding into the above solution, stirring for 10min, transferring into hydrothermal kettle, sealing, and maintaining at 200 deg.C for 4 hr. Taking out the sample, removing with ethanolWashing with water, and oven drying at 60 deg.C for 12 hr. Putting the obtained powder into a tube furnace, calcining in air, setting the furnace temperature to 400 ℃ within 375min, keeping the temperature for 1.5h, taking out a sample after the furnace temperature is gradually cooled, and showing that the surface becomes black to obtain CoMn2O4/β-MnO2A composite material.
Example 3:
(1) 0.338g of manganese sulfate monohydrate and 0.246g of potassium chlorate were weighed out and dissolved in 25 ml of ultrapure water, and after vigorous stirring for 10 minutes, they were transferred to a hydrothermal kettle and sealed, and kept at 150 ℃ for 15 hours. After cooling to room temperature, the sample was taken out, washed with ethanol and deionized water, and oven-dried at 60 ℃ for 12 h.
(2) 0.2911g of cobalt nitrate hexahydrate, 0.5021g of manganese nitrate tetrahydrate, 0.0741g of ammonium fluoride and 0.3002g of urea were weighed out and dissolved in 35 ml of ultrapure water, and vigorously stirred for 10 minutes. Prepared 0.0590g beta-MnO was weighed2The mixture was placed in the above solution, stirred vigorously for 10 minutes, transferred to an autoclave and sealed, and kept at 150 ℃ for 6 hours. After taking out the sample, washing the sample by using ethanol and deionized water, and drying the sample in an oven at the temperature of 60 ℃ for 12 hours. Putting the obtained powder into a tube furnace, calcining in air, setting the furnace temperature to 350 ℃ within 325min, keeping the temperature for 2h, taking out a sample after the furnace temperature is gradually cooled, and showing that the surface is black to obtain CoMn2O4/β-MnO2A composite material.
Those skilled in the art will appreciate that modifications, additions and substitutions are possible, without departing from the scope of the invention as disclosed in the accompanying claims.
Claims (8)
1. The composite material for detecting hydroquinone in seawater is characterized by comprising beta-MnO2Nanorods and uniformly covered in beta-MnO2CoMn on nanorod surface2O4Nanosheets, said CoMn2O4And beta-MnO2Forming a p-n junction barrier.
2. According to the rightThe composite material of claim 1, wherein the CoMn is2O4The nano-sheet has uniform thickness of 200 nm.
3. The composite material of claim 1, wherein said beta-MnO is2The nanorods were uniform in size, 300 nm in diameter and 13 μm in length.
4. The preparation method of the composite material for detecting hydroquinone in seawater as claimed in claim 1, characterized by comprising the following steps:
the method comprises the following steps: dissolving manganese sulfate and potassium chlorate in ultrapure water, and violently stirring to obtain a uniform solution; transferring the mixture into a hydrothermal kettle, sealing the hydrothermal kettle, and preserving the heat for 10-15 h at the temperature of 150-; cooling to room temperature, taking out, cleaning and drying to obtain beta-MnO2A nanorod;
step two: dissolving cobalt nitrate, manganese nitrate, ammonium fluoride and urea in ultrapure water, and violently stirring to obtain a uniform solution; then the solution and the prepared beta-MnO2Transferring the nano-rod into a hydrothermal kettle in beta-MnO2Method for preparing CoMn on nanorod by hydrothermal method2O4Nanosheets; taking out, cleaning and drying; transferring the obtained powder into a tubular furnace, heating the furnace to 350-400 ℃, preserving the heat for 1.5-2h at the temperature, and naturally cooling to obtain CoMn2O4/β-MnO2A composite material.
5. The method according to claim 4, wherein the cleaning in steps (i) and (ii) is performed with ethanol and deionized water, respectively.
6. The method according to claim 4, wherein the drying in steps (i) and (ii) is performed in an oven at 60 ℃ for 12 hours.
7. The preparation method according to claim 4, wherein in the first step and the second step, the vigorous stirring means that the rotating speed of a magnetic stirrer is 400r/min and the time is 10 min.
8. Use of the composite material according to any one of claims 1 to 3 for the detection of hydroquinone in seawater.
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