CN115739107B - Manganese dioxide nanocomposite and preparation method thereof - Google Patents
Manganese dioxide nanocomposite and preparation method thereof Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 59
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 74
- 239000002135 nanosheet Substances 0.000 claims abstract description 43
- 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 17
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 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
- 239000011565 manganese chloride Substances 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
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 38
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 5
- 238000010531 catalytic reduction reaction Methods 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
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 18
- 239000002131 composite material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 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
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000010842 industrial wastewater Substances 0.000 description 4
- -1 p-nitrophenol ions Chemical class 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
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000002064 nanoplatelet 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
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- 238000001308 synthesis method Methods 0.000 description 2
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- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 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
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
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Abstract
The invention provides a manganese dioxide nanocomposite and a preparation method thereof, relating to the field of nanomaterials; the method comprises the following steps: 1) Reacting manganese chloride, tetramethyl ammonium hydroxide and oxidant in a first solvent to obtain MnO 2 A nanosheet; 2) MnO (MnO) 2 Reacting the nano-sheet, copper chloride and a reducing agent in a second solvent in an alkaline environment to obtain Cu 2 O/MnO 2 A nanocomposite; wherein MnO 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 The surface of the nano-sheet matrix. Cu prepared by the invention 2 O/MnO 2 Nanocomposite utilization of MnO 2 The nano-sheet is used as a matrix to be matched and dispersed with Cu on the matrix 2 The synergistic effect of the O nano particles has 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 increasingly pay attention to pollution of organic matters to water bodies. For example, nitroaromatic compounds are very commonly used in the medical field, and are widely used in pigments, dyes, plastics, pesticides, bactericides, medicines, explosives, and the like; nitroaromatic compounds have a certain toxicity, and their volatilization in the atmosphere is very dangerous. Although many different treatments are currently proposed for para-nitroaromatic compounds, including biological and chemical objectives; however, these methods not only require a strict operating environment or have time consuming production processes, but also further produce similar toxic aromatic hydrocarbons and are thus not suitable for industrial scale processing applications at all.
Industrial wastewater containing p-nitrophenol is known to be 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 common method for degrading 4-NPs, which requires catalysis by combining a strong reducing agent with toxic transition metals, such as redox by noble elements such as silver, lead, etc. Recently, researchers have also developed a range of non-noble metal catalysts to inhibit 4-NP contamination, e.g., co/SiO 2 、Cu/CuO/C、Ni/SiO 2 And CuFe 2 O 4 . Copper is used as a novel catalyst, and is widely used for catalytic hydrogenation reaction due to the characteristics of high reaction activity, good selectivity, multiple surface active sites, abundant raw materials, low cost and the like. Considering that nano-sized metal particles and/or oxide particle catalysts are easily agglomerated, resulting in lower activity of the nanocatalyst, the catalytic reduction effect of copper-based nanocatalyst on 4-NP lacks data support. In the prior art, some researchers fix Cu or CuOx nano particles on carriers such as carbon, boron nitride, bentonite, graphene and the like to prevent agglomeration and increase active sites of reactants, and find that a supported Cu-based catalyst shows excellent reaction performance in 4-NP reduction reaction.
Most of the current synthesis methods for preparing the supported copper-based catalyst are solvent synthesis, and the method has the defects of complicated preparation process, long time consumption and unnecessary pollution. Therefore, there is a need to search for a green, simple method for preparing a supported Cu-based catalyst.
Disclosure of Invention
The invention aims to provide a manganese dioxide nanocomposite and a preparation method thereof, which firstly prepare amorphous ultrathin MnO in batches under mild conditions 2 Nano-sheet and Cu-based nano-catalyst prepared by using nano-sheet as carrier, namely Cu 2 O/MnO 2 Nanocomposite and application to catalytic reduction of 4-NP for Cu studies 2 O/MnO 2 Relationship between nanocomposite and catalytic performance.
In order to achieve the above purpose, the present invention proposes the following technical scheme: a method for preparing manganese dioxide nanocomposite, comprising the following steps:
1) Reacting manganese chloride, tetramethyl ammonium hydroxide and oxidant in a first solvent to obtain MnO 2 A nanosheet; the MnO 2 The surface of the nano-sheet is provided with an active site;
2)MnO 2 reacting the nano-sheet, 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 is 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 The surface of the nano-sheet matrix.
Further, the step 1) is to add tetramethyl ammonium hydroxide and oxidant into manganese chloride water solution under the condition of intense stirring, and the mixed solution is fully stirred at room temperature for reaction to obtain MnO with active site 2 A nano-sheet.
Further, the step 2) is to make the MnO dispersed in the mixture alkaline 2 Sequentially adding copper chloride and a reducing agent into a second solvent of the nano-sheet, carrying out reflux reaction on the mixed solution at 100-120 ℃ for 1-4 h, and collecting a fixed product after the treatment of the reaction solution to obtain Cu 2 O/MnO 2 A nanocomposite.
Further, the step 2) is to add copper chloride and a reducing agent into the reaction solution after fully stirring and reacting at room temperature in the step 1), reflux-react the mixed solution for 1-4 hours at 100-120 ℃, collect and fix the reaction solution after treatmentThe product is Cu 2 O/MnO 2 A nanocomposite.
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 7 < pH < 10.
Further, the alkaline environment of the second solvent in the step 2) is formed by tetramethylammonium hydroxide, tetrabutylammonium hydroxide, or ammonium hydroxide added to the second solvent.
Further, the feeding mole ratio of the reactants of manganese chloride and tetramethylammonium hydroxide is 1:2.
The invention also provides a manganese dioxide nanocomposite material which is prepared by the preparation method of the manganese dioxide nanocomposite material and is Cu 2 O/MnO 2 A nanocomposite; the Cu is 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 The surface of the nano-sheet matrix.
The invention also provides application of the manganese dioxide nanocomposite in p-nitrophenol catalytic reduction reaction.
According to the technical scheme, the following beneficial effects are achieved:
the invention discloses a manganese dioxide nanocomposite and a preparation method thereof, wherein the preparation method comprises the following steps: 1) Reacting manganese chloride, tetramethyl ammonium hydroxide and oxidant in a first solvent to obtain MnO 2 A nanosheet; 2) MnO (MnO) 2 Reacting the nano-sheet, copper chloride and a reducing agent in a second solvent in an alkaline environment to obtain Cu 2 O/MnO 2 A nanocomposite; wherein MnO 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 The surface of the nano-sheet matrix. Cu prepared by the invention 2 O/MnO 2 Nanocomposite utilization of MnO 2 Nano sheet as matrixCu dispersed on matrix 2 The synergistic effect of the O nano particles has remarkable degradation effect when being applied to 4-NP degradation.
In the concrete implementation, the method adopts the steps that copper chloride and a reducing agent are directly added into the solution after the reaction in the step 1), and the mixture is fully reacted to prepare Cu 2 O/MnO 2 Nanocomposite material, reduction of MnO 2 Loss generated in the process of collecting the nanosheets, and improving the yield of the final product; and the tetramethylammonium hydroxide in the step 1) is directly adopted to provide the alkaline environment of 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 green and pollution-free to the environment; 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, as well as additional concepts described in more detail below, may be considered a part of the inventive subject matter of the present disclosure as long as such concepts are not mutually inconsistent.
The foregoing and other aspects, embodiments, and features of the present teachings will be more fully understood from the following description, taken together with the accompanying drawings. Other additional aspects of the invention, such as features and/or advantages of the exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of the embodiments according to the teachings of the 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 invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 shows pure Cu obtained by the example of the present invention 2 O、Cu 2 O/MnO 2 XRD spectra 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 image of the composite material;
FIG. 5 shows the addition of NaBH according to the present invention 4 An ultraviolet visible spectrum of the p-nitrophenol is reduced 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 is reduced by the catalyst;
FIG. 7 shows pure Cu obtained by the example of the present invention 2 O and Cu 2 O/MnO 2 The conversion rate of the composite material catalytic degradation of the p-nitrophenol is shown as the change of the reaction time.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention. Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The terms "first," "second," and the like in the description and in the claims, are not used for any order, quantity, or importance, but are used for distinguishing between different elements. Also, unless the context clearly indicates otherwise, singular forms "a," "an," or "the" and similar terms do not denote a limitation of quantity, but rather denote the presence of at least one. The terms "comprises," "comprising," or the like are intended to cover a feature, integer, step, operation, element, and/or component recited as being present in the element or article that "comprises" or "comprising" does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. "up", "down", "left", "right" and the like are used only to indicate a relative positional relationship, and when the absolute position of the object to be described is changed, the relative positional relationship may be changed accordingly.
The Cu-based catalyst shows excellent reaction performance in 4-NP reduction reaction, but the synthesis of the catalyst generally adopts a solvent synthesis method, so that the preparation process is tedious and time-consuming, and the used solvent can cause unnecessary environmental pollution; aiming at the problems, the invention provides a Cu-based catalyst and a preparation method thereof, namely a manganese dioxide nanocomposite and a preparation method thereof, wherein the preparation method is simple in preparation process and short in time consumption, can be used for catalytic degradation of industrial wastewater containing 4-NP, and is environment-friendly.
The preparation method of the manganese dioxide nanocomposite disclosed by the invention comprises the following steps:
1) Reacting manganese chloride, tetramethyl ammonium hydroxide and oxidant in a first solvent to obtain MnO 2 A nanosheet; the MnO 2 The surface of the nano-sheet is provided with an active site;
2)MnO 2 reacting the nano-sheet, 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 is 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 The surface of the nano-sheet matrix.
Specifically, the step 1) is to add tetramethyl ammonium hydroxide and oxidant into manganese chloride water solution under the condition of intense stirring, and fully stir the mixed solution at room temperature for reaction to obtain MnO with active site 2 A nanosheet; in the reaction, the feeding mole ratio of the reactants of manganese chloride and tetramethylammonium hydroxide is 1:2, and hydrogen peroxide is taken as an oxidant in the examples in consideration of pollution generated in the preparation process.
Step 2) is to alkaline with MnO dispersed therein 2 Sequentially adding copper chloride and a reducing agent into a second solvent of the nano-sheet, carrying out reflux reaction on the mixed solution at 100-120 ℃ for 1-4 h, and collecting a fixed product after the treatment of the reaction solution to obtain Cu 2 O/MnO 2 A nanocomposite; during the reaction, the reducing agent is glucose, and the feeding ratio of copper chloride to glucose in the reactant is (1-2 mmol): 1g; the alkaline mixture has a pH in the range of (7, 10) and the alkaline environment is formed by tetramethylammonium hydroxide, tetrabutylammonium hydroxide, or ammonium hydroxide added to the second solvent.
The Cu-based catalyst prepared by the preparation method is Cu 2 O/MnO 2 The nanocomposite 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 disclosed in the invention and the preparation method thereof are further specifically described below with reference to specific examples. In the embodiment, in order to further simplify the preparation process of the material, step 2) is to directly add copper chloride and a reducing agent into the reaction solution obtained by fully stirring the reaction in step 1) at room temperature, reflux-react the mixed solution at 100-120 ℃ for 1-4 h, treat the reaction solution, and collect the fixed product, namely Cu 2 O/MnO 2 A nanocomposite.
The manganese dioxide nanocomposite disclosed in the invention and the preparation method thereof are further specifically described below with reference to specific examples. In the examples, manganese chloride tetrahydrate and cupric chloride dihydrate are commercially available as raw materials, and the room temperature is 20-30deg.C.
Example 1
Firstly, weighing 0.593g (3 mmol) of MnCl 2 ·4H 2 O was dissolved in 10ml of water, and an aqueous solution of 2.175g of tetramethylammonium hydroxide (TMA. OH) and 2ml of hydrogen peroxide was added to the above solution under vigorous stirring, and the reaction was allowed to proceed well at room temperature, and stirred overnight; after overnight, 2 mmole of CuCl was added to the overnight post-solution in sequence 2 ·2H 2 Reflux the mixture of O (0.34 g) and 1g glucose at 110deg.C for 3h, centrifuging the reaction solution, collecting the fixed product, washing, and drying to obtain Cu 2 O/MnO 2 Nanocomposite(s)A material. Wherein TMA.OH is excessive, partly for use with MnCl 2 ·4H 2 O reacts to form nano-sheets, and part of the nano-sheets are used for providing alkaline environment required by subsequent reaction; if the solid product of the reaction liquid after overnight is directly centrifugally washed and then dried, mnO can be obtained 2 A nano-sheet.
Example 2
Example 2 differs from example 1 in that 1 mmole of CuCl was added to the overnight post-solution in sequence 2 ·2H 2 Reflux of mixed solution of O (0.17 g) and 1g glucose at 110 ℃ for 3h, centrifuging the reaction solution, collecting the fixed product, washing, drying to obtain MnO 2 A nanocomposite.
Example 3
Example 3 differs from example 1 in that 2 mmole of CuCl was added to the overnight post-solution in sequence 2 ·2H 2 Reflux of mixed solution of O (0.34 g) and 1g glucose at 120 ℃ for 3h, centrifuging the reaction solution, collecting the fixed product, washing, drying to obtain MnO 2 A nanocomposite.
Example 4
Example 4 differs from example 1 in that no MnO was prepared 2 The nano-sheet is prepared by directly adding 1g of glucose into 100ml of nano-sheet containing 2g of TMA.OH and 1 mmole of CuCl 2 ·2H 2 Stirring the mixture in O aqueous solution, refluxing the mixed solution for 3 hours at 110 ℃, centrifugally washing a solid product, and drying to obtain pure Cu 2 And O material.
XRD and microscopic electron microscopy were performed on the products of examples 1-4, respectively. In the direction of MnO 2 When the nanosheets are loaded with Cu groups, the products of example 2 and example 3 are both found to be Cu 2 O/MnO 2 A nanocomposite. As shown in FIG. 2, pure Cu is directly prepared 2 O particles, not in MnO 2 Under the scheme of nano-sheet loading, pure Cu prepared in a similar reaction system 2 The O particles are large and the particle size is not uniform. As shown in the electron microscope diagrams of FIGS. 3 and 4, cu obtained in example 1 2 O/MnO 2 Nanocomposite, in microstructure, is obtained with micro Cu 2 O nanoparticles, about 3nm in particle size, uniformly dispersed in MnO 2 On the nanoplatelet matrix. Example 2 and examplesIn example 3, the reaction CuCl was prepared by the reaction mixture 2 ·2H 2 O molar ratio and 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 in microstructure, cu 2 O nanoparticle at MnO 2 The nanosheet matrix cannot be uniformly distributed; the reaction temperature is basically equal 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 agglomeration of O nano particles can cause Cu even if the reaction time is too short 2 O nanoparticle at MnO 2 The non-uniform distribution of the nanosheet matrix is due to Cu generated in the reaction solution 2 O nano particles are small and cannot be matched with MnO 2 The active sites on the nanoplatelets are sufficiently matched.
Example 5
Cu prepared in example 1 and example 4 was prepared as described above 2 O/MnO 2 Nanocomposite and pure Cu 2 O materials are respectively used as Cu-based catalysts for catalyzing and 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 into 10mL of distilled water after 20min, adding 10mg/L of 1.5mL of p-nitrophenol solution, adding 0.114g of sodium borohydride, taking 2mL of reaction solution at a set time interval to measure at 200-600 nm of UV-Vis, recording the change of absorbance at the 400nm position of the absorption peak of the p-nitrophenol, and recording the catalytic reaction rate of the p-nitrophenol.
Example 6
Example 6 differs from example 1 in that only 10mg/L of 1.5mL of p-nitrophenol solution and 0.114g of sodium borohydride were added to only 10mL of distilled water, and no ultrasonically dispersed Cu was added 2 O/MnO 2 The composite material and other reaction test conditions are consistent.
FIG. 5 shows that p-nitrophenol in neutral aqueous solution and p-nitrophenol in NaBH containing 4 In the ultraviolet-visible spectrum of the aqueous solution of p-nitrophenol, wherein the neutral aqueous solution of p-nitrophenol is at 317nmPeak at NaBH addition 4 After that, the absorption peak was shifted from 317nm to 400nm, because p-nitrophenol and NaBH were reacted under alkaline conditions 4 Forming p-nitrophenol ions; although NaBH 4 Can be used as an electron donor and a hydrogen source, but cannot reduce p-nitrophenol ions in the absence of a catalyst. Cu (Cu) 2 O/MnO 2 The composite material has excellent p-nitrophenol ionization performance, and after the catalyst is added, mnO is used for preparing the catalyst 2 The nano-sheet is used as an active site for adsorbing and ionizing p-nitrophenol ions, and is used for adsorbing the p-nitrophenol ions, borohydride ions and Cu in the composite material 2 O component reacts and transfers hydrogen species and electrons on the surface to the O component, so that along with the extension of the catalytic time, the-NO of the p-nitrophenol can be quickly and effectively realized 2 Efficient reduction of the-NH group 2 A group. As shown in FIGS. 6 and 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 Nanoplatelets and Cu 2 The synergistic effect of the O nano particles promotes the degradation of the p-nitrophenol, and the absorption peak height of the p-nitrophenol rapidly drops in a short time; in FIG. 7, cu was found to be the reaction rate 2 O/MnO 2 The composite material is compared with pure Cu 2 The O material can rapidly degrade the p-nitrophenol in a short time, has a rapid degradation efficiency, and can completely degrade the p-nitrophenol in a short time.
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (10)
1. The preparation method of the manganese dioxide nanocomposite is characterized by comprising the following steps:
1) Reacting manganese chloride, tetramethyl ammonium hydroxide and oxidant in a first solvent to obtain MnO 2 A nanosheet; the MnO 2 The surface of the nano-sheet is provided with an active site; wherein the oxidant is hydrogen peroxide;
2)MnO 2 reacting the nano-sheet, 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 is 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 The surface of the nano-sheet matrix.
2. The method for preparing manganese dioxide nanocomposite according to claim 1, wherein step 1) comprises adding tetramethylammonium hydroxide and an oxidant to an aqueous solution of manganese chloride under vigorous stirring, and reacting the mixed solution under stirring at room temperature to obtain MnO with active site 2 A nano-sheet.
3. The method of preparing manganese dioxide nanocomposite according to claim 1, wherein step 2) is alkaline, dispersed with MnO 2 Sequentially adding copper chloride and a reducing agent into a second solvent of the nano-sheet, carrying out reflux reaction on the mixed solution at 100-120 ℃ for 1-4 h, and collecting a fixed product after the treatment of the reaction solution to obtain Cu 2 O/MnO 2 A nanocomposite.
4. The method for preparing manganese dioxide nanocomposite according to claim 2, wherein step 2) comprises sequentially adding copper chloride and a reducing agent into the reaction solution obtained by sufficiently stirring at room temperature in step 1), reflux-reacting the mixture at 100-120 ℃ for 1-4 hours, treating the reaction solution, and collecting the immobilized product to obtain Cu 2 O/MnO 2 A nanocomposite.
5. The method for preparing manganese dioxide nanocomposite according to claim 3, wherein the reducing agent is glucose, and the ratio of copper chloride to glucose in the reactant is (1-2 mmol): 1g.
6. The method of preparing manganese dioxide nanocomposite according to claim 1, wherein the alkaline environment in step 2) is 7 < pH < 10.
7. The method of preparing manganese dioxide nanocomposite according to claim 1, wherein the alkaline environment of the second solvent in step 2) is formed by tetramethylammonium hydroxide, tetrabutylammonium hydroxide or ammonium hydroxide added to the second solvent.
8. The method of preparing manganese dioxide nanocomposite according to claim 2, wherein the reactants manganese chloride and tetramethylammonium hydroxide are fed in a molar ratio of 1:2.
9. A manganese dioxide nanocomposite obtained by the method for producing a manganese dioxide nanocomposite according to any one of claims 1 to 8, which is Cu 2 O/MnO 2 A nanocomposite; the Cu is 2 O/MnO 2 The microstructure of the nanocomposite is Cu with uniform size 2 O nano particles are uniformly dispersed in MnO 2 The surface of the nano-sheet matrix.
10. The use of the manganese dioxide nanocomposite of claim 9 in a catalytic reduction reaction of p-nitrophenol.
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