CN115744961B - Preparation method and device of structure-controllable super-hydrophilic copper-based compound material - Google Patents
Preparation method and device of structure-controllable super-hydrophilic copper-based compound material Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010949 copper Substances 0.000 title claims abstract description 71
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000005751 Copper oxide Substances 0.000 claims abstract description 65
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 150000002978 peroxides Chemical class 0.000 claims abstract description 35
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 85
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000012856 packing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000002135 nanosheet Substances 0.000 claims description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 230000001502 supplementing effect Effects 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- XPLSDXJBKRIVFZ-UHFFFAOYSA-L copper;prop-2-enoate Chemical compound [Cu+2].[O-]C(=O)C=C.[O-]C(=O)C=C XPLSDXJBKRIVFZ-UHFFFAOYSA-L 0.000 claims description 4
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- QGLVEAGMVUQOJP-UHFFFAOYSA-N prop-2-enylboronic acid Chemical compound OB(O)CC=C QGLVEAGMVUQOJP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000906 Bronze Inorganic materials 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000010974 bronze Substances 0.000 description 12
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 12
- BSPSZRDIBCCYNN-UHFFFAOYSA-N phosphanylidynetin Chemical compound [Sn]#P BSPSZRDIBCCYNN-UHFFFAOYSA-N 0.000 description 12
- 239000002060 nanoflake Substances 0.000 description 9
- 229910021642 ultra pure water Inorganic materials 0.000 description 9
- 239000012498 ultrapure water Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention discloses a preparation method of a structure-controllable super-hydrophilic copper-based compound material, which comprises the steps of (1) immersing copper or copper alloy material in deionized water for about 5-30min, (2) immersing the immersed copper or copper alloy material in strong alkali solution completely, then dropwise adding peroxide solution, (3) fully mixing strong alkali and peroxide solution by using a metering pump, and simultaneously carrying out cyclic reaction, (4) rapidly changing the circulating reaction solution in step (3) from colorless solution into blue-black solution, and when the reaction solution is converted into grey solution, adding fresh peroxide solution into the reaction solution to continue the cyclic reaction, (5) repeating the step (4) for 1-3 times, and (6) when the operation in step (5) is completed, washing and drying the obtained copper-based compound material to obtain the copper oxide super-hydrophilic material with a stable nano lamellar structure.
Description
Technical Field
The invention relates to the technical field of functional material preparation, in particular to a preparation method for in-situ growth of nano flaky copper oxide on a copper-based material, and a structure-controllable super-hydrophilic copper-based compound material is prepared by controlling synthesis conditions.
Background
The copper oxide nano material is a natural metal oxide with a monoclinic structure, has a series of unique physical and chemical characteristics, and can be widely applied to the fields of photovoltaics, supercapacitors, catalysis, gas detection, field emission, gas sensing and the like. Copper oxide is a monoclinic material, the space group of which is q6, and four oxygen atoms and four copper atoms constitute a copper oxide unit cell, and is commonly used to make nanostructured materials. Copper or copper alloy materials are subjected to material modification by processing treatment to generate a copper oxide coating on the surface, so that the copper or copper alloy material is applied to different fields. For example, the method can be applied to the rectification process of water, and the strength of a gas-liquid interface is enhanced and the heterogeneous mass transfer process is enhanced by growing a copper oxide super-hydrophilic film on the surface of copper or copper alloy filler in situ. Copper oxide is a P-type multifunctional narrow bandgap semiconductor with excellent performance, has superconducting property, and can be applied to the fields of catalysis, batteries, sensors and the like.
Publication number CN100490940C discloses an application of nano copper oxide and a preparation method thereof, which relates to an application of a compound and a preparation method thereof. As no report of taking single nano copper oxide as a normal temperature desulfurizing agent exists before, the purity of the nano copper oxide prepared by the current nano copper oxide preparation method is low; the invention provides application and a preparation method of nano copper oxide. The nano copper oxide is applied as a normal temperature desulfurizing agent, and is the only component of the normal temperature desulfurizing agent. Preparation of nano copper oxide: sodium hydroxide is added into the copper nitrate solution, and then the copper nitrate solution is filtered, dried and roasted. Or nanometer copper oxide is prepared according to the following steps: adding sodium hydroxide solution into copper nitrate solution, filtering, and drying. The nano copper oxide has high desulfurization precision under normal temperature condition, and the sulfur capacity is as high as 18.3% -28.7%. The purity of the nano copper oxide prepared by the method is higher than 99.9%, the preparation process is simple, the requirements on processing equipment are low, the energy consumption is low, the production cost is low, and the method is easy to popularize and implement.
At present, researchers report various preparation methods of copper oxide, which are used for preparing nano materials with various microscopic morphologies such as nano sheets, nano wires, nano flowers and the like, and various preparation methods have advantages and disadvantages. The nano material prepared by the solid phase method has the advantages of good filling property, no agglomeration and the like, but has the defects of low efficiency, high energy consumption, low material purity and the like in the preparation process. The liquid phase synthesis method has the advantages of simple synthesis process, mild reaction parts, good dispersibility, high purity and the like, but simultaneously, the process is long in processing time and large in energy consumption. The electrochemical synthesis method can effectively control the microscopic morphology, nano size and structural morphology of the product, the process is complicated, the amount of the added reagent is not clear, waste is easy to cause, and the generated copper oxide is unevenly distributed in structure. Aiming at the problems, the invention provides a method for preparing nano flaky copper oxide by in-situ growth on the surface of a copper or copper alloy material by a liquid phase circulation method, which has the advantages of simple operation, good repeatability, low cost and low energy consumption.
Disclosure of Invention
In order to solve the problems of uneven structural distribution and the like of copper oxide grown on the surface of the copper or copper alloy material, the invention provides a simple and effective preparation method of a structure-controllable super-hydrophilic copper-based compound material.
The invention aims at providing a preparation method of a structure-controllable super-hydrophilic copper-based compound material, which comprises the following steps of:
(1) Soaking copper or copper alloy material in deionized water for about 5-30min;
(2) Completely immersing the soaked copper or copper alloy material in strong alkali solution, and then dropwise adding peroxide solution;
(3) Fully mixing strong alkali and peroxide solution by using a metering pump, and simultaneously carrying out a cyclic reaction;
(4) The reaction solution recycled in the step (3) is changed from a colorless solution into a blue-black solution rapidly, and when the reaction solution is converted into a grey solution, fresh peroxide solution is added into the reaction solution to continue the recycling reaction;
(5) Repeating the step (4) for 1 to 3 times;
(6) And (3) when the operation in the step (5) is completed, washing and drying the obtained copper-based compound material to obtain the copper oxide super-hydrophilic material with the stable nano lamellar structure.
In the above technical solution, the step (6) may further be: when the operation in the step (5) is completed, adding an anti-caking agent, heating to 50-70 ℃, stirring for 10-40 minutes, filtering, and then washing and drying the obtained copper-based compound material to obtain the copper oxide super-hydrophilic material with a stable nano lamellar structure.
In the technical scheme, the addition amount of the anti-caking agent is 0.5-2.5% of the copper-based compound material by mass percent.
In the technical scheme, the preparation method of the anti-caking agent comprises the following steps:
according to parts by weight, 27-35 parts of 2, 3-dimercaptosuccinic acid, 10-20 parts of allylboronic acid pinacol ester, 0.05-0.3 part of copper acrylate, 2-5 parts of potassium tert-butoxide, 200-300 parts of tert-butanol are added into a closed reaction kettle, nitrogen is introduced, stirring is carried out for 1-3 hours at 60-70 ℃, and then the tert-butanol is removed by reduced pressure distillation, thus obtaining the anti-caking agent.
In the technical scheme, the copper or copper alloy material has copper purity of 95-99.99%, and is selected from bulk or structured packing with a large number of different sizes applied industrially, wherein the bulk packing is at least one of a Sita ring, a Raschig ring, a saddle ring, a ladder ring and a pall ring; the regular packing is at least one of silk screen corrugated packing, perforated plate corrugated packing, pore plate corrugated packing and plate net corrugated packing.
In the technical proposal, the strong alkali is alkali metal oxide, can be one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide, and has the concentration of 0.1 to 4.0 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The peroxide can be one or more of hydrogen peroxide, sodium peroxide and potassium peroxide, and the concentration of the peroxide is 0.1-0.95 mol.L < -1 >; the molar concentration ratio of the strong base to the peroxide is preferably (1 to 35): 1. the composition of the reaction solution to which the fresh peroxide solution was added was the same as that of the mixed solution of the initial strong base and peroxide.
In the technical scheme, the ratio of the amount of the copper substance in the copper or copper alloy material to the amount of the peroxide substance in the original mixed solution is 70-400.
In the above technical scheme, in steps (1) to (5), the reaction is carried out at 5-70 ℃.
In the above technical scheme, when the flow rate of the mixed solution and the reaction solution is controlled to be 0.002-0.15 m.s -1 When the nano flake copper oxide structure is obtained, the flow rate of the reaction liquid is preferably controlled to be 0.002-0.05 m.s during the cyclic reaction -1 For example 0.002 mS -1 、0.005m·s -1 、0.01m·s -1 、0.02m·s -1 、0.05m·s -1 Etc.;
in the technical proposal, the highest flow velocity of the generated copper oxide coating is 0.15 m.s -1 At this flow rate copper oxide is formed above 25 c and copper hydroxide is formed at lower temperatures.
In the technical scheme, in the step (3), the cyclic reaction time is 0.5-3h.
In the above-mentioned embodiments, the mass ratio of the addition amount of the fresh peroxide solution in the step (4) to the addition amount of the peroxide solution in the step (2) is 0.5 to 4, and may be, for example, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, etc.
In the above technical scheme, in step (6), the drying conditions are as follows: vacuum degree is 0.09-0.095 MPa, temperature is 40-70 ℃, and drying is carried out for 2-8 h.
In the technical scheme, before the step (1), the copper or copper alloy material can be pretreated, and the copper or copper alloy material is respectively ultrasonically cleaned in concentrated hydrochloric acid, absolute ethyl alcohol and ultrapure water for 5-30min and is dried by nitrogen. Wherein the concentration of the hydrochloric acid can be 0.5-5 mol.L -1 Preferably 1 to 3 mol.L -1 。
According to a preferred embodiment of the present invention, the preparation method may comprise:
(1) Soaking the cleaned copper or copper alloy material in deionized water at the temperature of 5-70 ℃, fully wetting, immersing the wetted copper or copper alloy material in a reactor filled with strong alkali solution, and dripping peroxide solution. Fully mixing the alkali and peroxide solution by using a metering pump, and then circulating the mixed solution in a reactor by using the metering pump, wherein the circulating reaction flow rate of the mixed solution in the reactor is 0.002-0.15 m.s -1 Circularly reacting for 0.5-3h, changing the reaction solution from colorless solution to blue-black transparent solution, and finally changing the reaction solution into grey transparent solution;
(2) Delivering fresh peroxide solution into a reactor by a metering pump, wherein the ratio of the addition amount of the fresh solution to the addition amount of the first time is 0.2-1, performing cyclic reaction for 0.5-3h, and converting colorless transparent reaction solution into blue-black transparent solution and then into grey transparent solution;
(3) Delivering fresh peroxide solution into the reactor by a metering pump, wherein the ratio of the addition amount of the fresh solution to the addition amount of the first time is 0.2-1, and performing cyclic reaction for 0.5-2 h;
(4) And (3) reacting until the solution is changed into a grey transparent solution, and then washing and drying the obtained sample to obtain the nano flaky copper oxide material.
The second purpose of the invention is to provide the super-hydrophilic copper-based compound material with controllable structure obtained by the preparation method.
The super-hydrophilic copper-based compound material has a controllable nano sheet structure, wherein the thickness of the nano sheet is 5-50 nm, the width of the root is about 50-500 nm, and the height is about 0.5-4 mu m.
The third object of the present invention is to provide a device for preparing a structure-controllable superhydrophilic copper-based compound material, for performing the above preparation method, comprising:
the reactor is used for carrying out the reaction between the mixed solution of strong alkali and peroxide and copper or copper alloy materials, the upper part of the reactor is provided with a first inlet, an outlet and a temperature measuring port, and the lower part of the reactor is provided with a second inlet;
the upper part of the liquid storage tank is provided with an inlet, the lower part of the liquid storage tank is provided with an outlet, and the outlet of the liquid storage tank is connected with the inlet of the reactor through a pipeline;
the first metering pump is arranged on a pipeline between the outlet of the liquid storage tank and the second inlet of the reactor so as to ensure the stability of the liquid flow;
and the second metering pump is arranged on a pipeline between the outlet and the first inlet of the reactor so as to ensure the stability of the liquid flow.
Preferably, the lower part of the reactor is provided with a liquid second inlet and a temperature measuring port, and the upper part of the reactor is provided with a liquid outlet.
The preparation device may further include:
a first liquid flow controller mounted on a line between the first metering pump and the second inlet of the reactor;
and the second liquid flow controller is arranged on a pipeline between the second metering pump and the first inlet of the reactor.
The nano flaky copper oxide prepared by the invention is prepared by the co-oxidation of strong alkali and peroxide. According to the invention, the circulating flow rate and the reaction temperature of different alkali and peroxide mixed reaction solutions are regulated and controlled, so that the structural morphology of the copper oxide is regulated and controlled, and finally, a simple and easy-to-operate method for preparing the nano flaky copper oxide with a controllable structure is explored. The method can grow nano flaky copper oxide on the surface of complex copper or copper alloy material in situ, and the surface of the copper or copper alloy material is observed to have a uniform nano flaky structure through a Scanning Electron Microscope (SEM), and a contact angle test shows that the contact angle between the copper or copper alloy material and water is about 0, so that the copper or copper alloy material has good super-hydrophilic performance. The invention also provides a circulating reaction system which has the advantages of simple process, short time consumption and easiness in industrialized preparation of the structure-controllable super-hydrophilic copper-based compound material.
The thickness of the copper oxide with the nano sheet structure prepared by the novel method is 5-50 nm, the width of the root is about 50-500 nm, the height is about 0.5-4 mu m, and the size is uniform. The copper oxide with the nano-sheet structure prepared by the invention has excellent hydrophilic effect, has a contact angle of about 0 with water, and can be further applied as a base material of a structural functional material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a method for preparing a copper oxide material with a nano sheet structure by a strong alkali oxidation method, which has the advantages of simple process, short time consumption and easy amplification, and can be applied to processing copper or copper alloy materials with complex geometric structures.
(2) The nano flaky copper oxide prepared by the method provided by the invention has excellent hydrophilic performance, has a contact angle of about 0, and can be applied to a substrate of a structural functional material.
(3) The nano sheet structure prepared by the method provided by the invention increases the specific surface area of the copper oxide, and can be applied to the chemical engineering fields of catalysis, reaction, rectification and the like.
Drawings
FIG. 1 is a flow chart of a preparation method according to the present invention;
fig. 1 identifies an illustration:
1-liquid storage tank, 2-first metering pump, 3-first liquid flow controller, 4-kettle reactor, 5-thermoscope, 6-second liquid flow controller, 7-second metering pump.
In fig. 1, the fully wetted copper or copper alloy material is placed in a kettle-type reactor 4 filled with a strong alkali solution, the peroxide solution in a liquid storage tank 1 is conveyed into the reactor by a first metering pump 2, the reaction is carried out at the temperature of 5-70 ℃, and the total reaction time is 1.5-8 h. The method comprises the steps of adding fresh hydrogen peroxide solution twice in the reaction process, adding fresh hydrogen peroxide solution for the first time when the color of the reaction solution is changed from colorless transparent solution to blue-black transparent solution and then to grey solution after the reaction is carried out for 0.5-3h, and conveying the fresh reaction solution in a liquid storage tank into a reactor by a first metering pump by the hydrogen peroxide solution, wherein the ratio of the adding amount to the first adding amount is 0.2-1. When the reaction time is 3 to 6 hours, the colorless transparent reaction solution is changed into blue-black transparent solution and then is changed into a grey solution, and then the second fresh hydrogen peroxide solution is supplemented, wherein the mass ratio of the supplementing amount of the fresh hydrogen peroxide solution to the adding amount of the first reaction solution is 0.2 to 1. And when the reaction is carried out for 6 to 8 hours, after the reaction solution is changed into a grey solution, taking out and washing with water, and drying with nitrogen or drying in vacuum to obtain the copper oxide with the nano sheet structure.
FIG. 2 is an SEM image of nano-flake copper oxide prepared in example 1;
FIG. 3 is a graph showing the static contact angle of the nano-flake copper oxide prepared in example 1 with respect to water in air;
FIG. 4 is an SEM image of nano-flake copper oxide prepared in example 2;
FIG. 5 is a graph showing the static contact angle of nano-flake copper oxide prepared in example 2 with respect to water in air;
FIG. 6 is an SEM image of nano-flake copper oxide prepared in example 3;
FIG. 7 is a graph showing the static contact angle of the nano-flake copper oxide prepared in example 3 with respect to water in air;
FIG. 8 is an SEM image of nano-flake copper oxide prepared in example 4;
fig. 9 is a graph showing the static contact angle of nano-flake copper oxide prepared in example 4 with respect to water in air.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Example 1
The preparation method of the nano flaky copper oxide comprises the following specific steps:
(1) Bulk packing of xita ringTin phosphor bronze with 97% copper purity) is copper-based material, and is respectively ultrasonically cleaned in concentrated hydrochloric acid, absolute ethyl alcohol and ultrapure water for 30min, and then dried by nitrogen for standby.
(2) Immersing the tin-phosphor bronze bulk filling material treated in the step (1) in deionized water for 20min for full wetting at 25 ℃, immersing the wetted tin-phosphor bronze bulk filling material in a kettle-type reactor 4 filled with a strong alkali solution, wherein the reactor 4 is a kettle-type reactor with the length of 400mm and the inner diameter of 50mm, both ends of a filling layer are covered by copper meshes, a hydrogen peroxide solution is conveyed into the reactor by a first metering pump 3 for mixing, the molar concentration ratio of sodium hydroxide and hydrogen peroxide in the mixed solution is 15, the concentration of sodium hydroxide is 1.5mol.L < -1 >, the concentration of hydrogen peroxide is 0.1mol.L < -1 >, the ratio of the molar amount of copper to the molar amount of hydrogen peroxide in the mixed solution is 150, and the flow rate of the mixed solution in the reactor is 0.003 m.s < -1 >. The reaction solution is conveyed to the kettle type reactor for circulation through a second metering pump.
(3) And (3) circularly reacting for 2 hours, wherein the reaction solution is changed from a colorless transparent solution into a grey transparent solution, and the first metering pump 2 is used for conveying fresh hydrogen peroxide solution into the reactor, wherein the supplementing amount of the fresh hydrogen peroxide solution is the same as the original adding amount.
(4) And (3) after supplementing the fresh hydrogen peroxide solution, reacting for 2 hours, supplementing the fresh hydrogen peroxide solution for the second time, wherein the adding amount of the fresh hydrogen peroxide solution for the second time is the same as that of the first time, continuously reacting for 2 hours, taking out a sample, cleaning with ultrapure water, and drying for 6 hours at the vacuum degree of 0.09MPa and the temperature of 50 ℃ to obtain the nano flaky copper oxide.
And (4) drying to obtain a copper-based material sample with nano flaky copper oxide grown on the surface. The SEM image of this sample is shown in fig. 2, and it can be seen from fig. 2: the thickness of the copper oxide nano sheet structure in the sample is 25-35 nm, the root width is about 250-350 nm, and the height is about 2.5-3.5 μm. As can be seen from fig. 3: the nano-sheet copper oxide has excellent hydrophilic property, and the contact angle is about 0.
Example 2
The preparation method of the nano flaky copper oxide comprises the following specific steps:
(1) Bulk packing of xita ringTin phosphor bronze with 97% copper purity) is copper-based material, and is respectively ultrasonically cleaned in concentrated hydrochloric acid, absolute ethyl alcohol and ultrapure water for 30min, and then dried by nitrogen for standby.
(2) Immersing the tin-phosphor bronze bulk filling material treated in the step (1) in deionized water for 20min at 25 ℃ for full wetting, immersing the wetted tin-phosphor bronze bulk filling material in a kettle-type reactor 4 filled with a strong alkali solution, wherein the reactor 4 is a kettle-type reactor with the length of 400mm and the inner diameter of 50mm, both ends of a filling layer are covered by copper meshes, a hydrogen peroxide solution is conveyed into the reactor by a first metering pump 3 for mixing, the molar concentration ratio of sodium hydroxide and hydrogen peroxide in the mixed solution is 15, the concentration of sodium hydroxide is 1.5mol.L < -1 >, the concentration of hydrogen peroxide is 0.1mol.L < -1 >, the ratio of the molar amount of copper to the molar amount of hydrogen peroxide in the mixed solution is 150, and the flow rate of the mixed solution in the reactor is 0.005 m.s < -1 >. The reaction solution is conveyed to the kettle type reactor for circulation through a second metering pump.
(3) And (3) circularly reacting for 2 hours, wherein the reaction solution is changed from a colorless transparent solution into a grey transparent solution, and the first metering pump 2 is used for conveying fresh hydrogen peroxide solution into the reactor, wherein the supplementing amount of the fresh hydrogen peroxide solution is the same as the original adding amount.
(4) And (3) after supplementing the fresh hydrogen peroxide solution, reacting for 2 hours, supplementing the fresh hydrogen peroxide solution for the second time, wherein the adding amount of the fresh hydrogen peroxide solution for the second time is the same as that of the first time, continuously reacting for 2 hours, taking out a sample, cleaning with ultrapure water, and drying for 6 hours at the vacuum degree of 0.09MPa and the temperature of 50 ℃ to obtain the nano flaky copper oxide.
And (4) drying to obtain a copper-based material sample with nano flaky copper oxide grown on the surface. The SEM image of this sample is shown in fig. 4, and as can be seen from fig. 4: the thickness of the copper oxide nano sheet structure in the sample is 25-35 nm, the root width is about 350-450 nm, and the height is about 2.5-3.5 μm. As can be seen from fig. 5: the nano-sheet copper oxide has excellent hydrophilic property, and the contact angle is about 0.
Example 3
The preparation method of the nano flaky copper oxide comprises the following specific steps:
(1) Taking silk screen corrugated structured packing (CY 700, CY800, CY900, tin phosphor bronze with copper purity of 97%) as copper-based material, respectively ultrasonically cleaning in concentrated hydrochloric acid, absolute ethyl alcohol and ultrapure water for 30min, and drying with nitrogen for later use.
(2) Immersing the tin-phosphor bronze structured packing treated in the step (1) in deionized water for 20min at 25 ℃ for full wetting, immersing the wetted tin-phosphor bronze structured packing in a kettle reactor 4 filled with a strong alkali solution, wherein the reactor 7 is a kettle reactor with the length of 600mm and the inner diameter of 300mm, both ends of a packing layer are covered by copper mesh, and a hydrogen peroxide solution is conveyed into the reactor by a first metering pump 3 for mixing, wherein the molar concentration ratio of sodium hydroxide and hydrogen peroxide in the mixed solution is 15, the concentration of sodium hydroxide is 1.5mol.L < -1 >, the concentration of hydrogen peroxide is 0.1mol.L < -1 >, the ratio of the molar amount of copper to the molar amount of hydrogen peroxide in the mixed solution is 150, and the flow rate of the mixed solution in the reactor is 0.003 m.s < -1 >. The reaction solution is conveyed to the kettle type reactor for circulation through a second metering pump.
(3) And (3) circularly reacting for 2 hours, wherein the reaction solution is changed from a colorless transparent solution into a grey transparent solution, and the first metering pump 2 is used for conveying fresh hydrogen peroxide solution into the reactor, wherein the supplementing amount of the fresh hydrogen peroxide solution is the same as the original adding amount.
(4) After the fresh hydrogen peroxide solution is replenished, the reaction is carried out for 2 hours, the replenishment of the fresh hydrogen peroxide solution is carried out for the second time, the adding amount of the hydrogen peroxide solution for the second time is the same as that of the first time, and the reaction is continued for 2 hours.
Then adding an anti-caking agent, wherein the addition amount is 0.5 percent of the copper-based compound material by mass, and the preparation method comprises the following steps: 27g of 2, 3-dimercaptosuccinic acid, 10g of allylboronic acid pinacol ester, 0.05g of copper acrylate, 2g of potassium tert-butoxide and 200g of tert-butanol are added into a closed reaction kettle, nitrogen is introduced into the kettle, stirring is carried out for 3 hours at 60 ℃, and then the tert-butanol is removed by reduced pressure distillation, so that the anti-caking agent is obtained.
And taking out the sample, cleaning with ultrapure water, and drying for 6 hours at the vacuum degree of 0.09MPa and the temperature of 50 ℃ to obtain the nano flaky copper oxide.
And (4) drying to obtain a copper-based material sample with nano flaky copper oxide grown on the surface. The SEM image of this sample is shown in fig. 6, and as can be seen from fig. 6: the thickness of the copper oxide nano sheet structure in the sample is 30-40 nm, the root width is about 400-500 nm, and the height is about 3-4 mu m. As can be seen from fig. 7: the nano-sheet copper oxide has excellent hydrophilic property, and the contact angle is about 0.
Example 4
The preparation method of the nano flaky copper oxide comprises the following specific steps:
(1) Taking silk screen corrugated structured packing (CY 700, CY800, CY900, tin phosphor bronze with copper purity of 97%) as copper-based material, respectively ultrasonically cleaning in concentrated hydrochloric acid, absolute ethyl alcohol and ultrapure water for 30min, and drying with nitrogen for later use.
(2) Immersing the tin-phosphor bronze structured packing treated in the step (1) in deionized water for 20min at 25 ℃ for full wetting, immersing the wetted tin-phosphor bronze structured packing in a kettle reactor 4 filled with a strong alkali solution, wherein the reactor 7 is a kettle reactor with the length of 600mm and the inner diameter of 300mm, both ends of a packing layer are covered by copper mesh, and a hydrogen peroxide solution is conveyed into the reactor by a first metering pump 3 for mixing, wherein the molar concentration ratio of sodium hydroxide and hydrogen peroxide in the mixed solution is 15, the concentration of sodium hydroxide is 1.5mol.L < -1 >, the concentration of hydrogen peroxide is 0.1mol.L < -1 >, the ratio of the molar amount of copper to the molar amount of hydrogen peroxide in the mixed solution is 150, and the flow rate of the mixed solution in the reactor is 0.003 m.s < -1 >. The reaction solution is conveyed to the kettle type reactor for circulation through a second metering pump.
(3) And (3) circularly reacting for 2 hours, wherein the reaction solution is changed from a colorless transparent solution into a grey transparent solution, and the first metering pump 2 is used for conveying fresh hydrogen peroxide solution into the reactor, wherein the supplementing amount of the fresh hydrogen peroxide solution is the same as the original adding amount.
(4) And (3) after supplementing the fresh hydrogen peroxide solution, carrying out reaction for 2 hours, supplementing the fresh hydrogen peroxide solution for the second time, wherein the adding amount of the hydrogen peroxide solution for the second time is the same as that of the first time, and continuing the reaction for 2 hours.
Then adding an anti-caking agent, wherein the addition amount is 2.5 percent of the copper-based compound material by mass percent, and the preparation method comprises the following steps: 35g of 2, 3-dimercaptosuccinic acid, 20g of allylboronic acid pinacol ester, 0.3g of copper acrylate, 5g of potassium tert-butoxide and 300g of tert-butanol are added into a closed reaction kettle, nitrogen is introduced into the reaction kettle, stirring is carried out for 1h at 70 ℃, and then the tert-butanol is removed by reduced pressure distillation, so that the anti-caking agent is obtained.
And taking out the sample, cleaning with ultrapure water, and drying for 6 hours at the vacuum degree of 0.09MPa and the temperature of 50 ℃ to obtain the nano flaky copper oxide.
And (4) drying to obtain a copper-based material sample with nano flaky copper oxide grown on the surface. The SEM image of this sample is shown in fig. 8, and as can be seen from fig. 8: the thickness of the copper oxide nano sheet structure in the sample is 15-25 nm, the root width is about 400-500 nm, and the height is about 1.5-3.0 μm. As can be seen from fig. 9: the nano-sheet copper oxide has excellent hydrophilic property, and the contact angle is about 0.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (4)
1. The preparation method of the structure-controllable super-hydrophilic copper-based compound material comprises the following steps:
(1) Soaking copper or copper alloy material in deionized water for 5-30min;
(2) Completely immersing the soaked copper or copper alloy material in strong alkali solution, and then dropwise adding peroxide solution;
(3) Fully mixing strong alkali and peroxide solution by using a metering pump, and simultaneously carrying out a cyclic reaction;
(4) The reaction solution recycled in the step (3) is changed from a colorless solution into a blue-black solution rapidly, and when the reaction solution is converted into a grey solution, fresh peroxide solution is added into the reaction solution to continue the recycling reaction;
(5) Repeating the step (4) for 1-3 times;
(6) When the operation in the step (5) is completed, adding an anti-caking agent, heating to 50-70 ℃, stirring for 10-40 minutes, filtering, and then washing and drying the obtained copper-based compound material to obtain the copper oxide super-hydrophilic material with a stable nano lamellar structure;
in the step (6): the addition amount of the anti-caking agent is 0.5-2.5% of the copper-based compound material by mass percent; the preparation method of the anti-caking agent comprises the following steps: adding 27-35 parts of 2, 3-dimercaptosuccinic acid, 10-20 parts of allylboronic acid pinacol ester, 0.05-0.3 part of copper acrylate, 2-5 parts of potassium tert-butoxide, 200-300 parts of tert-butanol into a closed reaction kettle, introducing nitrogen, stirring at 60-70 ℃ for 1-3 hours, and then distilling under reduced pressure to remove the tert-butanol to obtain an anti-caking agent;
in the step (2): the strong alkali is alkali metal oxide, and is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide, and the concentration is 0.1-4.0mol.L < -1 >; the peroxide is one or more of hydrogen peroxide, sodium peroxide and potassium peroxide, and the concentration of the peroxide is 0.1-0.95 mol.L < -1 >; the molar concentration ratio of the strong base to the peroxide is (1-35): 1, a step of;
in the step (3): the cyclic reaction is carried out at the temperature of 5-70 ℃ to obtain a nano flaky copper oxide structure;
in the step (4): the mass ratio of the addition amount of the fresh peroxide solution to the addition amount of the peroxide solution in the step (1) is 0.5-4, and the cycle reaction time is 0.5-3h.
2. The method of manufacturing according to claim 1, characterized in that: in step (1): the copper or copper alloy material is bulk or structured packing, wherein the bulk packing is at least one of a Sita ring, a Raschig ring, a rectangular saddle ring, a stepped ring and a pall ring; the regular packing is at least one of silk screen corrugated packing, perforated plate corrugated packing, pore plate corrugated packing and plate net corrugated packing.
3. The method for preparing the structure-controllable super-hydrophilic copper-based compound material according to any one of claims 1 to 2, which is characterized in that: the surface of the copper-based compound material is provided with a nano-sheet copper oxide structure, wherein the height of the nano-sheet is 0.5-5 mu m, and the edge thickness is 5-200nm.
4. The method for preparing the structure-controllable super-hydrophilic copper-based compound material according to claim 1, which is characterized in that: the preparation device used for the preparation method comprises: the reactor is a cylindrical reactor for carrying out the reaction of the mixed solution of strong alkali and peroxide and copper or copper alloy material, the diameter of the cylindrical reactor is 5-400mm, the length is 20-700mm, and a filter screen is arranged in the cylindrical reactor; the liquid storage tank is used for storing fresh alkali and peroxide mixed solution, and the outlet of the liquid storage tank is connected with the second inlet of the reactor through a pipeline; a first metering pump is arranged on a pipeline between the outlet of the liquid storage tank and the second inlet of the reactor and is used for supplementing fresh peroxide solution into the reactor; a second metering pump is arranged on a pipeline between the outlet and the first inlet of the reactor and is used for circulating the mixed solution of the alkali and the peroxide in the reactor; a first liquid flow controller is mounted on the line between the first metering pump and the second inlet of the reactor for displaying the flow rate when replenishing the fresh peroxide solution; a second liquid flow controller is installed on the line between the second metering pump and the first inlet of the reactor for displaying the flow rate of the reaction liquid at the time of the cyclic reaction, where the flow rate can be used to calculate the flow rate of the reaction liquid at the time of the cyclic reaction, i.e., flow rate=flow rate of the reaction liquid/cross-sectional area of the reactor.
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| CN104805428A (en) * | 2015-04-15 | 2015-07-29 | 西安交通大学 | Method for growing CuO (copper oxide) film on surface of copper sheet |
| CN112897567A (en) * | 2021-03-31 | 2021-06-04 | 江南大学 | Preparation method of copper oxide with nanometer flower-like structure |
| CN114014350A (en) * | 2021-11-24 | 2022-02-08 | 武汉工程大学 | Preparation method of copper oxide |
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| CN104805428A (en) * | 2015-04-15 | 2015-07-29 | 西安交通大学 | Method for growing CuO (copper oxide) film on surface of copper sheet |
| CN112897567A (en) * | 2021-03-31 | 2021-06-04 | 江南大学 | Preparation method of copper oxide with nanometer flower-like structure |
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