CN115739107A - Manganese dioxide nano composite material and preparation method thereof - Google Patents
Manganese dioxide nano composite material and preparation method thereof Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 55
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 72
- 239000002135 nanosheet Substances 0.000 claims abstract description 35
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 11
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 11
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 11
- 239000011565 manganese chloride Substances 0.000 claims abstract description 11
- 239000002064 nanoplatelet Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract 5
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 27
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 12
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- 239000008103 glucose Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
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- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 16
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- -1 p-nitrophenol ions Chemical class 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 230000002588 toxic effect Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910016553 CuOx Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a manganese dioxide nano composite material and a preparation method thereof, relating to the field of nano materials; the method comprises the following steps: 1) Manganese chloride, tetramethyl ammonium hydroxide and oxidant react in a first solvent to obtain MnO 2 A nanosheet; 2) MnO 2 The nanosheet, copper chloride and a reducing agent react in a second solvent in an alkaline environment to obtain Cu 2 O/MnO 2 A nanocomposite material; wherein, mnO is 2 The surface of the nano sheet is provided with active sites, cu 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 A nanoplatelet substrate surface. Cu prepared by the invention 2 O/MnO 2 Nanocomposite material using MnO 2 Cu dispersed on the substrate by using nanosheet as the substrate 2 The O nano particles have a synergistic effect, and have a remarkable degradation effect when being applied to 4-NP degradation.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a manganese dioxide nano composite material and a preparation method thereof.
Background
In recent years, people pay more and more attention to pollution caused by organic matters to water bodies. For example, nitroaromatic compounds are widely used in the pharmaceutical field, and are widely used in pigments, dyes, plastics, insecticides, fungicides, pharmaceuticals, explosives, and the like; nitroaromatics have a certain toxicity, and their volatilization in the atmosphere is very dangerous. Although a number of different treatments are currently proposed for nitroaromatics, including biological and chemical processes; however, these processes not only require a strict operating environment or have a time-consuming production process, but also further produce similar toxic aromatic hydrocarbons, and are therefore completely unsuitable for industrial-scale processing applications.
It is known that industrial wastewater containing p-nitrophenol is an important component of industrial wastewater, and p-aminophenol which can be obtained by treating and converting p-nitrophenol is an important chemical raw material, so that the conversion of p-nitrophenol has important industrial significance. Currently, chemical reduction is the most commonly used method for degrading 4-NP, and the method needs to combine a strong reducing agent and a toxic transition metal for catalysis, such as oxidation reduction by using noble elements such as silver and lead. Recently, researchers have also developed a series of non-noble metal catalysts to inhibit 4-NP contamination, such as Co/SiO 2 、Cu/CuO/C、Ni/SiO 2 And CuFe 2 O 4 . As a novel catalyst, copper is widely used for catalytic hydrogenation reaction due to the characteristics of high reaction activity, good selectivity, many surface active sites, rich raw materials, low cost and the like. Considering that the nano-sized metal particles and/or oxide particles are easy to agglomerate, the activity of the nano-catalyst is low, and therefore the catalytic reduction effect of the copper-based nano-catalyst on 4-NP is temporarily lack of data support. In the prior art, some researchers fix Cu or CuOx nanoparticles on carriers such as carbon, boron nitride, bentonite and graphene to prevent agglomeration, increase active sites of reactants, and find that a supported Cu-based catalyst shows excellent reaction performance in a 4-NP reduction reaction.
At present, most of the synthetic methods for preparing the supported copper-based catalyst are solvent synthesis, and the method has a complicated preparation process, takes long time and causes unnecessary pollution. Therefore, there is a need for a green and simple method for preparing a supported Cu-based catalyst.
Disclosure of Invention
The invention aims to provide a manganese dioxide nano composite material and a preparation method thereof, which firstly adopts the batch preparation of amorphous ultrathin MnO under the mild condition 2 Nanosheet and preparation of Cu-based nanocatalyst, namely Cu, by using nanosheet as carrier 2 O/MnO 2 The nano composite material is applied to the catalytic reduction reaction of 4-NP and researches on Cu 2 O/MnO 2 The relationship between the nanocomposite and the catalytic performance.
In order to achieve the above purpose, the invention provides the following technical scheme: a preparation method of manganese dioxide nano composite material comprises the following steps:
1) Manganese chloride, tetramethyl ammonium hydroxide and an oxidant react in a first solvent to obtain MnO 2 Nanosheets; the MnO 2 The surface of the nano sheet is provided with active sites;
2)MnO 2 the nanosheet, copper chloride and a reducing agent react in a second solvent in an alkaline environment to obtain Cu 2 O/MnO 2 A nanocomposite material;
wherein, cu 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 A nanoplatelet substrate surface.
Further, step 1) is adding tetramethylammonium hydroxide and an oxidant into the manganese chloride aqueous solution under the condition of vigorous stirring, and fully stirring the mixed solution at room temperature for reaction to obtain MnO with active sites 2 Nanosheets.
Further, the step 2) is to be alkaline and dispersed with MnO 2 Copper chloride and a reducing agent are sequentially added into a second solvent of the nanosheet, the mixed solution is subjected to reflux reaction for 1-4 h at the temperature of 100-120 ℃, and a fixed product, namely Cu, is collected after the reaction solution is treated 2 O/MnO 2 A nanocomposite material.
Further, the step 2) is a step1) Adding copper chloride and a reducing agent into the reaction solution after fully stirring reaction at room temperature, carrying out reflux reaction on the mixed solution for 1-4 h at 100-120 ℃, collecting a fixed product after the reaction solution is treated, wherein the fixed product is Cu 2 O/MnO 2 A nanocomposite material.
Further, the reducing agent is glucose, and the feeding ratio of copper chloride to glucose in the reactant is (1-2 mmol): 1g.
Further, the alkaline environment in the step 2) is more than 7 and less than pH value and less than 10.
Further, the alkaline environment of the second solvent in the step 2) is formed by adding tetramethylammonium hydroxide, tetrabutylammonium hydroxide or ammonium hydroxide to the second solvent.
Further, the feeding molar ratio of the reactants of manganese chloride and tetramethyl ammonium hydroxide is 1.
Another technical scheme of the invention is to provide a manganese dioxide nanocomposite, which is prepared by the preparation method of the manganese dioxide nanocomposite and is Cu 2 O/MnO 2 A nanocomposite material; the Cu 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 A nanoplatelet substrate surface.
The invention also provides the application of the manganese dioxide nano composite material in the catalytic reduction reaction of p-nitrophenol.
According to the technical scheme, the technical scheme of the invention has the following beneficial effects:
the invention discloses a manganese dioxide nano composite material and a preparation method thereof, wherein the preparation method comprises the following steps: 1) Manganese chloride, tetramethyl ammonium hydroxide and oxidant react in a first solvent to obtain MnO 2 A nanosheet; 2) MnO 2 Reacting the nanosheet, copper chloride and a reducing agent in a second solvent in an alkaline environment to obtain Cu 2 O/MnO 2 A nanocomposite material; wherein, mnO is 2 The surface of the nano sheet is provided with active sites, cu 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nanoparticlesUniformly dispersed in MnO 2 A nanoplatelet substrate surface. Cu prepared by the invention 2 O/MnO 2 Nanocomposite material using MnO 2 Cu dispersed on a substrate by using nanosheet as the substrate 2 The synergistic effect of the O nano particles has obvious degradation effect when being applied to 4-NP degradation.
In specific implementation, the method directly adds copper chloride and a reducing agent into the solution obtained in the step 1), mixes the copper chloride and the reducing agent and fully reacts to prepare the Cu 2 O/MnO 2 Nanocomposite material with reduced MnO 2 Loss generated in the nanosheet collecting process improves the yield of the final product; and the tetramethylammonium hydroxide in the step 1) is directly adopted to provide an alkaline environment for the reaction solution, so that the addition of alkali is not needed, and the preparation process of the final product is further simplified. Cu of the invention 2 O/MnO 2 The nano composite material is simple to prepare, the reaction condition is mild, and the preparation process is environment-friendly and pollution-free; can be applied to the degradation treatment of industrial wastewater containing p-nitrophenol and is environment-friendly.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent.
The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present invention, such as features and/or advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of specific embodiments in accordance with the teachings of the present invention.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 shows pure Cu obtained in accordance with an embodiment of the present invention 2 O、Cu 2 O/MnO 2 XRD spectrogram of the composite material;
FIG. 2 shows pure Cu obtained in example 4 of the present invention 2 SEM image of O;
FIG. 3 shows Cu obtained in example 1 of the present invention 2 O/MnO 2 SEM images of the composite;
FIG. 4 shows Cu obtained in example 1 of the present invention 2 O/MnO 2 TEM images of the composite;
FIG. 5 shows the addition of NaBH in accordance with the present invention 4 Reducing the ultraviolet-visible spectrum of the p-nitrophenol without adding a catalyst;
FIG. 6 shows Cu obtained in example 1 of the present invention 2 O/MnO 2 The ultraviolet-visible spectrum of the p-nitrophenol reduced by the catalyst;
FIG. 7 shows pure Cu produced by the present invention 2 O and Cu 2 O/MnO 2 The conversion rate of catalytic degradation of p-nitrophenol by the composite material is shown as a graph along with the change of reaction time.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention. Unless defined otherwise, technical or 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 use of "first," "second," and similar terms in the description and in the claims of the present application does not denote any order, quantity, or importance, but rather the terms are used to distinguish one element from another. Similarly, the singular forms "a," "an," or "the" do not denote a limitation of quantity, but rather denote the presence of at least one, unless the context clearly dictates otherwise. The terms "comprises," "comprising," or the like, mean that the elements or items listed before "comprises" or "comprising" encompass the features, integers, steps, operations, elements, and/or components listed after "comprising" or "comprising," and do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. "upper", "lower", "left", "right", and the like are used only to indicate relative positional relationships, and when the absolute position of the object to be described is changed, the relative positional relationships may also be changed accordingly.
The Cu-based catalyst shows excellent reaction performance in a 4-NP reduction reaction, but the catalyst is generally synthesized by a solvent synthesis method, so that the preparation process is complicated and time-consuming, and the used solvent causes unnecessary environmental pollution; aiming at the problems, the invention provides a Cu-based catalyst and a preparation method thereof, namely a manganese dioxide nano composite material and a preparation method thereof.
The invention discloses a preparation method of manganese dioxide nano composite material, which comprises the following steps:
1) Manganese chloride, tetramethyl ammonium hydroxide and oxidant react in a first solvent to obtain MnO 2 A nanosheet; the MnO 2 The surface of the nano sheet is provided with active sites;
2)MnO 2 reacting the nanosheet, copper chloride and a reducing agent in a second solvent in an alkaline environment to obtain Cu 2 O/MnO 2 A nanocomposite;
wherein, cu 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 A nanoplatelet substrate surface.
Specifically, in the step 1), tetramethylammonium hydroxide and an oxidant are added into a manganese chloride aqueous solution under the condition of vigorous stirring, and the mixed solution is fully stirred and reacted at room temperature to obtain MnO with active sites 2 Nanosheets; during the reaction, the feeding molar ratio of the reactants of manganese chloride and tetramethyl ammonium hydroxide is1.
Step 2) is alkaline, dispersed MnO 2 Copper chloride and a reducing agent are sequentially added into a second solvent of the nanosheet, the mixed solution is subjected to reflux reaction for 1-4 h at the temperature of 100-120 ℃, and a fixed product, namely Cu, is collected after the reaction solution is treated 2 O/MnO 2 A nanocomposite material; during the reaction, glucose is selected as the reducing agent, and the feeding ratio of copper chloride to glucose in reactants is (1-2 mmol): 1g; the alkaline mixture has a pH range of (7, 10) and is formed from tetramethylammonium hydroxide, tetrabutylammonium hydroxide, or ammonium hydroxide added to the second solvent.
Cu-based catalyst, i.e. Cu, prepared by the above-mentioned preparation method 2 O/MnO 2 The nano composite material can be applied to catalytic degradation of 4-NP, and has excellent degradation efficiency compared with a common Cu-based catalyst; the manganese dioxide nanocomposite and the preparation method thereof disclosed by the present invention will be further described with reference to the following specific examples. In the embodiment, in order to further simplify the preparation process of the material, the step 2) is to directly add copper chloride and a reducing agent into the reaction solution fully stirred and reacted in the step 1) at room temperature in turn, reflux-react the mixed solution at 100-120 ℃ for 1-4 h, and collect a fixed product, namely Cu after the reaction solution is treated 2 O/MnO 2 A nanocomposite material.
The manganese dioxide nanocomposite and the preparation method thereof disclosed by the present invention will be further described with reference to the following specific examples. In the examples, manganese chloride tetrahydrate as a raw material and copper chloride dihydrate as a raw material were commercially available, and the room temperature was 20 to 30 ℃.
Example 1
First, 0.593g (3 mmol) of MnCl is weighed 2 ·4H 2 Dissolving O in 10ml of water, adding 2.175g of tetramethylammonium hydroxide (TMA. OH) and 2ml of an aqueous solution of hydrogen peroxide to the solution under vigorous stirring, fully reacting at room temperature, and stirring overnight; after overnight, 2mmol of CuCl was added to the overnight solution 2 ·2H 2 O(0.34g) And 1g of glucose, refluxing the mixed solution for 3 hours at the temperature of 110 ℃ in a sand bath, centrifuging the reaction solution, collecting a fixed product, washing, and drying to obtain Cu 2 O/MnO 2 A nanocomposite material. Wherein TMA. OH is excessive and part of TMA. OH is used for reacting with MnCl 2 ·4H 2 O reacts to form nano sheets, and part of the nano sheets are used for providing an alkaline environment required by subsequent reaction; if the solid product of the reaction solution after the overnight is directly centrifuged and washed, and then dried, mnO can be obtained 2 Nanosheets.
Example 2
Example 2 differs from example 1 in that 1mmol of CuCl was added to the overnight solution in succession 2 ·2H 2 O (0.17 g) and 1g glucose, refluxing the mixed solution at 110 ℃ for 3h, centrifuging the reaction solution, collecting the fixed product, washing, and drying to obtain MnO 2 A nanocomposite material.
Example 3
Example 3 differs from example 1 in that 2mmol of CuCl was added to the overnight solution in succession 2 ·2H 2 O (0.34 g) and 1g glucose, refluxing the mixed solution at 120 ℃ for 3h, centrifuging the reaction solution, collecting the fixed product, washing and drying to obtain MnO 2 A nanocomposite material.
Example 4
Example 4 differs from example 1 in that MnO was not prepared 2 Nanosheets, 1g of glucose was added directly to 100ml of a solution containing 2g of TMA. OH and 1mmol of CuCl 2 ·2H 2 Stirring in water solution of O, refluxing the mixed solution at 110 deg.C for 3 hr, centrifugally washing the solid product, drying, and purifying Cu 2 And O material.
XRD and microscopic electron microscopy were performed on the products of examples 1-4, respectively. In the MnO direction 2 When the nanosheets support Cu groups, the products of example 2 and example 3 are both Cu 2 O/MnO 2 A nanocomposite material. As shown in FIG. 2, pure Cu is directly prepared 2 O particles other than MnO 2 Pure Cu prepared in similar reaction system under nanosheet loading scheme 2 The O particles are large and non-uniform in particle size. Cu obtained in example 1, as shown in the electron micrographs of FIGS. 3 and 4 2 O/MnO 2 Nanometer compositeThe material is mixed, and micro Cu is obtained on the microstructure 2 O nanoparticles having a particle diameter of about 3nm and uniformly dispersed in MnO 2 A nanoplatelet substrate. Example 2 and example 3, respectively, by adjusting the reactants CuCl 2 ·2H 2 The molar ratio of O and the reaction temperature and time are determined for the product Cu 2 O/MnO 2 The effect of the nanocomposite, the results show that the reactant CuCl is reduced under example 2 2 ·2H 2 The amount of O does not affect the composition of the product, but on the microstructure, cu 2 In MnO with O nanoparticles 2 The nanoplatelets substrate cannot be uniformly distributed; reaction temperature substantially to Cu 2 O/MnO 2 The microstructure of the composite material is not influenced, the reaction time is too long, and Cu can occur 2 The phenomenon of O nano particle agglomeration can cause Cu when the reaction time is too short 2 In MnO with O nanoparticles 2 The phenomenon of uneven distribution of the nanosheet substrate due to Cu generated in the reaction solution 2 Few O nano particles and MnO can not be matched with the O nano particles 2 The active sites on the nanoplatelets are well matched.
Example 5
Cu prepared in the above examples 1 and 4 2 O/MnO 2 Nanocomposite and pure Cu 2 The O materials are respectively used as Cu-based catalysts for catalytically reducing p-nitrophenol into corresponding aminophenol; taking 10mgCu 2 O/MnO 2 Adding the composite material into 100mL of water, performing ultrasonic dispersion, taking 1mL of the liquid after 20min, adding 10mg/L of 1.5mL of p-nitrophenol solution into 10mL of distilled water, adding 0.114g of sodium borohydride, taking 2mL of reaction solution at a UV-Vis 200-600 nm position according to a set time interval, determining, recording the change of absorbance of the p-nitrophenol at the position of 400nm of an absorption peak, and recording the catalytic reaction rate of the p-nitrophenol.
Example 6
Example 6 differs from example 1 only in 10mL of distilled water, only 10mg/L of 1.5mL of p-nitrophenol solution and 0.114g of sodium borohydride were added, and no ultrasonically dispersed Cu was added 2 O/MnO 2 The composite material has consistent other reaction test conditions.
FIG. 5 shows MirabilitumNeutral aqueous solution of phenylphenol and NaBH in the presence of nitrophenol 4 The ultraviolet-visible spectrum of the aqueous solution of (1), wherein the neutral aqueous solution of p-nitrophenol shows a peak at 317nm when NaBH is added 4 The absorption peak then shifts from 317nm to 400nm, since p-nitrophenol reacts with NaBH under alkaline conditions 4 Forming p-nitrophenol ions; although NaBH 4 Can be used as an electron donor and a hydrogen source, but can not reduce p-nitrophenol ions without a catalyst. Cu 2 O/MnO 2 The composite material has excellent p-nitrophenol ionization performance, and after the catalyst is added, due to MnO 2 The nano sheet is used as an active site for adsorbing and ionizing p-nitrophenol ions, and adsorbing the p-nitrophenol ions, borohydride ions and Cu in the composite material 2 The O component reacts and transfers hydrogen species and electrons on the surface to the O component, and then the-NO of the p-nitrophenol can be quickly and effectively realized along with the prolonging of the catalytic time 2 Effective reduction of the radical-NH 2 A group. As shown in FIG. 6 and FIG. 7, cu 2 O/MnO 2 When the composite material is used as a catalyst to degrade p-nitrophenol, mnO can be fully exerted 2 Nanosheet and Cu 2 The synergistic effect of the O nano particles mutually promotes and degrades the p-nitrophenol, and the absorption peak height of the p-nitrophenol rapidly falls in a short time; in FIG. 7, cu is shown by the reaction rate 2 O/MnO 2 Composite material compared to pure Cu 2 The O material can rapidly degrade the p-nitrophenol in a short time, has high degradation efficiency, and can completely degrade the p-nitrophenol in a short time.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (10)
1. The preparation method of the manganese dioxide nanocomposite is characterized by comprising the following steps of:
1) Manganese chloride, tetramethyl ammonium hydroxide and oxidant react in a first solvent to obtain MnO 2 A nanosheet; the MnO 2 The surface of the nano sheet is provided with active sites;
2)MnO 2 the nanosheet, copper chloride and a reducing agent react in a second solvent in an alkaline environment to obtain Cu 2 O/MnO 2 A nanocomposite material;
wherein, cu 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 A nanoplatelet substrate surface.
2. The method for preparing manganese dioxide nanocomposite according to claim 1, wherein the step 1) comprises adding tetramethylammonium hydroxide and an oxidant to an aqueous solution of manganese chloride under vigorous stirring, and reacting the resulting mixture with stirring at room temperature to obtain MnO with active sites 2 Nanosheets.
3. The method of claim 1, wherein the step 2) is performed to make the manganese dioxide nanocomposite alkaline and dispersed with MnO 2 Copper chloride and a reducing agent are sequentially added into a second solvent of the nanosheet, the mixed solution is subjected to reflux reaction for 1-4 h at the temperature of 100-120 ℃, and a fixed product, namely Cu, is collected after the reaction solution is treated 2 O/MnO 2 A nanocomposite material.
4. The method for preparing manganese dioxide nanocomposite according to claim 2, wherein in the step 2), copper chloride and a reducing agent are sequentially added to the reaction solution obtained in the step 1) after the reaction is fully stirred at room temperature, the mixed solution is refluxed at 100-120 ℃ for 1-4 h, and after the reaction solution is treated, a fixed product, namely Cu, is collected 2 O/MnO 2 A nanocomposite material.
5. The method of claim 3, wherein the reducing agent is glucose, and the ratio of copper chloride to glucose in the reactants is (1-2 mmol): 1g of the total weight of the composition.
6. The method of claim 1, wherein the alkaline environment in step 2) is 7 < pH < 10.
7. The method for preparing manganese dioxide nanocomposite according to claim 1, wherein the alkaline environment of the second solvent in step 2) is formed by adding tetramethylammonium hydroxide, tetrabutylammonium hydroxide or ammonium hydroxide to the second solvent.
8. The method of claim 2, wherein the molar ratio of the reactants manganese chloride and tetramethylammonium hydroxide is 1.
9. Manganese dioxide nanocomposite, characterized in that said composite is obtained by a process for the preparation of a manganese dioxide nanocomposite according to any one of claims 1 to 8, being Cu 2 O/MnO 2 A nanocomposite material; the Cu 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 A nanoplatelet substrate surface.
10. Use of manganese dioxide nanocomposite according to claim 9 in catalytic reduction of p-nitrophenol.
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