CN110787799A - Preparation method of foamed copper oxide/TNTs photoelectric composite material - Google Patents
Preparation method of foamed copper oxide/TNTs photoelectric composite material Download PDFInfo
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- CN110787799A CN110787799A CN201910759115.1A CN201910759115A CN110787799A CN 110787799 A CN110787799 A CN 110787799A CN 201910759115 A CN201910759115 A CN 201910759115A CN 110787799 A CN110787799 A CN 110787799A
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 56
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000006260 foam Substances 0.000 claims abstract description 65
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010936 titanium Substances 0.000 claims abstract description 36
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 36
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 238000000137 annealing Methods 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 52
- 238000005498 polishing Methods 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 9
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 238000002048 anodisation reaction Methods 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- -1 iron oxyhydroxide modified titanium Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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Abstract
The invention relates to the field of photoelectric materials, in particular to a preparation method of a foamy copper oxide/TNTs photoelectric composite material. The preparation method comprises the following steps: anodic oxidation: taking specially pretreated titanium foam as an anode, and carrying out constant potential anodic oxidation on the titanium foam to obtain a pre-matrix; annealing: annealing the pre-matrix to obtain a matrix; coating and growing: and (3) soaking the substrate in the copper-containing coating solution for a period of time, and then sequentially drying and calcining, wherein the cycle is one cycle, and the foamed copper oxide/TNTs photoelectric composite material can be obtained after a plurality of cycles. The invention greatly reduces the difficulty of preparation, has low requirement on manufacturing equipment, has the advantages of low cost, high efficiency, easy realization and the like, and can well realize mass production; the specific surface area of the whole photoelectric composite material is improved, and the performance is optimized; the copper oxide foam and the TNTs are reasonably compounded, and the catalyst has good stability and photocatalytic performance.
Description
Technical Field
The invention relates to the field of photoelectric materials, in particular to a preparation method of a foamy copper oxide/TNTs photoelectric composite material.
Background
Titanium dioxide as an n-type semiconductor has a series of advantages of good light responsiveness, low price, stable performance, no toxicity and the like, is an excellent photoelectric material, and is widely applied to the fields of photocatalysis and photoelectrocatalysis. However, the energy of the ultraviolet light only accounts for about 4% of the total energy of the sunlight, and the application of the ultraviolet light is greatly limited because the forbidden band width is 3.2ev, and the ultraviolet light can only absorb the ultraviolet light below 387nm in the middle wave band of the sunlight. Scholars at home and abroad usually adopt doped p-type semiconductors to form p-n junctions to enhance photoresponse and reduce electron hole recombination, the commonly used p-type semiconductors comprise copper oxide and cuprous oxide, and the p-type semiconductors are compounded with titanium dioxide nanotube arrays (TNTs) to some extent, however, the TNTs prepared on flat titanium have smaller specific surface area and limit the application thereof.
In order to overcome the defects, foamed titanium is used as a substrate, a grown TNTs structure is prepared in an anodic oxidation mode to form the foamed TNTs structure, and copper oxide is loaded on the foamed TNTs structure to effectively improve the photocatalytic performance of the foamed TNTs structure. At present, methods for loading copper oxide on foam TNTs include magnetron sputtering, electrodeposition, chemical plating, sol-gel method and the like. The electrodeposition method has the advantages that the surface of the foamed TNTs is uneven, so that the deposition current density is uneven, and the deposited layer is uneven; the chemical plating method is difficult to control the thickness of the plating layer, and the performance is easily affected by the excessive thickness of the plating layer; the magnetron sputtering method is more efficient, can uniformly cover copper oxide on the surface of the foam TNTs, but is expensive, and is difficult to sputter the copper oxide into the foam TNTs and make the titanium oxide nanotubes extend out; the sol-gel method can uniformly permeate, and copper oxide is uniformly dispersed on the foam TNTs through heat treatment, so that the method is simple, efficient, low in cost and easy to implement, but the surface layer of the foam TNTs is single and flat in structure, small in specific surface area and further optimized and improved in space.
The Chinese patent office discloses a cerium-doped iron oxyhydroxide modified titanium foam material, a preparation method thereof and an invention patent application of the application in water treatment on 29/11/2018, wherein the application publication number is CN 109261140A. According to the technical scheme, foamed titanium is used as a working electrode, a platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode to form a three-electrode system, an aqueous solution containing ferric chloride, cerium chloride, sodium sulfate, polyvinylpyrrolidone and hydrogen peroxide is used as an electrolyte, and a circulating sweep ring is adopted by adopting a circulating voltammetry method to prepare the cerium-doped iron oxyhydroxide modified foamed titanium material. The preparation process is stable and has good controllability, but the process is complex, and the uniformity of electrodeposition on the titanium foam is difficult to ensure.
In addition, the Chinese patent office also discloses Cu in 2013, 7 and 31 months2O/TNTs heterostructure nano composite material and photo-reduction CO thereof2The invention patent application of the method has the application publication number CN 103225097A. According to the technical scheme, the TNTs structure is prepared through an anodic oxidation method, and cuprous oxide is further deposited on the TNTs structure in an electrodeposition mode, so that the composition of the cuprous oxide and the TNTs structure is realized, but the technical scheme also has the problem that the uniformity of a deposited layer is poor due to the influence of the TNTs structure in the electrodeposition process.
Disclosure of Invention
The invention provides a preparation method of a foamy copper oxide/TNTs photoelectric composite material, aiming at solving a series of problems that the existing p-type photoelectric composite material has great limitation in use, and the existing p-n-type photoelectric composite material has small specific surface area, difficult preparation, poor performance and the like. Its main purpose includes: the limitation of the existing photoelectric composite material in application is reduced, and better performance is exerted; secondly, the specific surface area of the photoelectric composite material is improved, and the performance is optimized; and thirdly, the preparation difficulty is reduced, so that the method is suitable for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of a foamy copper oxide/TNTs photoelectric composite material,
the preparation method comprises the following preparation steps:
1) anodic oxidation: taking specially pretreated titanium foam as an anode, and carrying out constant potential anodic oxidation on the titanium foam to obtain a pre-matrix;
2) annealing: annealing the pre-matrix to obtain a matrix;
3) coating and growing: and (3) soaking the substrate in the copper-containing coating solution for a period of time, and then sequentially drying and calcining, wherein the cycle is one cycle, and the foamed copper oxide/TNTs photoelectric composite material can be obtained after a plurality of cycles.
In the preparation method, the titanium foam is subjected to anodic oxidation treatment, so that the high specific surface area of the titanium foam is kept, and the TNTs structure is further prepared on the surface of the titanium foam, so that the specific surface area of the titanium foam is further improved. And then annealing to form a matrix suitable for loading copper oxide, coating copper-containing coating liquid on the surface of the TNTs structure in a dipping mode, and growing the copper-containing coating liquid to form copper oxide foam through drying and calcining processes.
After repeated dipping coating, drying and calcining cycles, the copper oxide foam coating can be thickened, the thickness is controllable, the uniformity is higher, the bonding strength of the copper oxide foam and a matrix can be improved through repeated drying and calcining, the service life and the stability of the photoelectric composite material are greatly improved, and an excellent technical effect is generated.
As a preference, the first and second liquid crystal compositions are,
step 1) in the anodic oxidation electrochemical system:
taking specially pretreated titanium foam as an anode, a graphite electrode or a platinum electrode as a cathode, and 1-5 wt% of hydrofluoric acid solution as electrolyte;
step 1) the constant potential anodic oxidation conditions are as follows:
the oxidation temperature is 25-40 ℃, the oxidation voltage is 15-35V, and the oxidation time is 5-25 min.
The TNTs array structure with controllable growth rule, length and density can be prepared by combining the anode oxidation conditions (namely various parameters) recorded in the anode oxidation system, and the stability of the subsequent coating growth process and the good uniformity of the grown copper oxide foam are ensured. In addition, under the action of hydrofluoric acid, the time required by the formed TNTs structure is shorter, and the length of the titanium oxide nanotube is shorter, so that the conductivity of the titanium oxide nanotube is more excellent.
As a preference, the first and second liquid crystal compositions are,
the special pretreatment operation of the step 1) comprises oil removal, chemical polishing, cleaning and drying;
wherein:
the polishing solution adopted by the chemical polishing contains 45-90 g/L of chromium oxide, 45-90 mL/L of 38-42 wt% of hydrogen fluoride solution and the balance of water, and the polishing time is controlled to be 10-20 min and the polishing temperature is controlled to be 50-60 ℃;
the titanium foam selected in the step 1) is titanium foam with the purity of more than or equal to 99.0 percent.
The special pretreatment is carried out on the titanium foam, which is mainly embodied in the aspect of chemical polishing. Because the titanium foam is different from the flat titanium, the flat titanium has a flat surface and is easy to polish, but when the titanium foam is polished, the conventional chemical polishing easily damages or unevenly polishes the three-dimensional structure of the titanium foam, so that the polishing effect and the integrity of the three-dimensional structure of the titanium foam can be finally influenced decisively by regulating and controlling the components of the polishing solution and adjusting the polishing parameters. When the concentrations of chromium oxide and hydrogen fluoride are higher than the above ranges, problems such as destruction of the three-dimensional structure and formation of large-area depressions on the surface may occur, and when the concentrations of these two components are too low, the polishing effect may be insufficient. Therefore, the chemical polishing of the special pretreatment in the present invention is one of the most critical steps in the pretreatment, and the composition of the polishing solution and the polishing parameters need to be strictly controlled.
As a preference, the first and second liquid crystal compositions are,
step 2) during the annealing treatment:
controlling the annealing temperature to be 450-550 ℃, heating at the speed of 5-10 ℃/min, preserving the heat for 2-4 h after the annealing temperature is reached, and finally cooling to finish annealing.
The matrix obtained by annealing under the condition can be well used for loading the copper oxide foam, and good technical effects are generated.
As a preference, the first and second liquid crystal compositions are,
step 3) the copper-containing coating solution is prepared by dissolving soluble copper salt and polyvinylpyrrolidone as solutes in an organic solvent; wherein the concentration of copper ions is 0.05-0.2 mol/L.
The copper-containing coating liquid mainly takes soluble copper salt as a main component, and the polyvinylpyrrolidone mainly plays a role in dispersing copper ions formed after the copper salt is dissolved, so that copper ions are prevented from being enriched, the copper ions in the copper-containing coating liquid are dispersed more uniformly, the polyvinylpyrrolidone can also improve the viscosity and reduce the fluidity of the copper-containing coating liquid, the coating liquid is difficult to flow around during drying, a more uniform coating layer can be formed on the surface of foam TNTs in a coating mode, and the uniformity of the formed foam copper oxide layer is improved.
As a preference, the first and second liquid crystal compositions are,
the soluble copper salt comprises copper nitrate, copper sulfate and copper chloride;
the concentration of the polyvinylpyrrolidone is 3-15 g/L;
the organic solvent is ethanol and glycol in a volume ratio (15-3): 1, and mixing the components in the ratio of 1.
Most preferably, the soluble copper salt is copper nitrate. By controlling the proportion of each component of the copper-containing coating solution, the stability of the copper-containing coating solution in the coating process can be ensured. Ethanol and glycol are selected as solvents and matched with polyvinylpyrrolidone, so that gas is generated when the coating is solidified to form copper oxide in the subsequent sintering process, the coating is propped open to form cells, and then porous copper oxide foam is formed.
As a preference, the first and second liquid crystal compositions are,
the dipping time is 30-900 s;
the cycle times are 4-12.
Too short impregnation time can cause insufficient impregnation in the pores of the TNTs, the performance improvement is not obvious, the bonding strength of the foamed copper oxide and the matrix is low, and too long impregnation time can cause excessive impregnation, so that a large amount of copper-containing coating solution is filled in the foamed TNTs, the three-dimensional nano structure of the matrix is seriously damaged in the subsequent drying and calcining processes, and the production efficiency is reduced. Within the duration of the impregnation, the impregnation effect can be ensured to be certain, and the problems of damage to the three-dimensional structure, reduction in production efficiency and the like can be avoided.
The thickness and the dipping depth of the foam copper oxide layer can be controlled through multiple cycles, so that the controllability of the whole preparation process is stronger.
As a preference, the first and second liquid crystal compositions are,
the drying temperature in the drying process in the step 3) is 60-80 ℃, and the single drying time is more than or equal to 10 min;
the calcining temperature in the calcining process in the step 3) is 450-550 ℃, and the single calcining time is more than or equal to 20 min.
The drying process removes a large amount of organic solvent to cure the coating, the organic solvent is volatilized and can be recycled in the process, the required time is short, the temperature needs to be controlled within a certain reasonable range, the problems that the organic matter is decomposed to generate gas before the coating is cured, the uniformity of the coating is reduced and the like are solved, the calcining process is a process for completely removing the organic matter, the required temperature is high but not high enough, the oxidation of the foam titanium of the core part and the damage of the foam structure can be caused by the high temperature, the required temperature does not need to be high due to the easy thermal decomposition of the selected organic matter, and the calcining time is relatively short.
The invention has the beneficial effects that:
1) the preparation difficulty is greatly reduced, the requirement on manufacturing equipment is low, the advantages of low cost, high efficiency, easy realization and the like are achieved, and the mass production can be well realized;
2) the specific surface area of the whole photoelectric composite material is improved, and the performance is optimized;
3) the copper oxide foam and the TNTs are reasonably compounded, and the catalyst has good stability and photocatalytic performance.
Drawings
FIG. 1 is an SEM image of a cross section of a foamed copper oxide/TNTs photoelectric composite material prepared according to an embodiment of the present invention;
FIG. 2 is an SEM image of the structure of TNTs on the surface of a substrate prepared in an embodiment of the present invention;
FIG. 3 is an SEM image of the surface of a copper oxide foam/TNTs photoelectric composite material prepared according to an embodiment of the present invention;
FIG. 4 is a graph showing photocurrent measurements of the photoelectric composite materials prepared in example 1 and comparative example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Example 1.
A preparation method of a foamed copper oxide/TNTs photoelectric composite material comprises the following preparation steps:
1) pretreatment: the preparation method comprises the following steps of pretreating flake titanium foam with the purity of 99.5%, wherein the pretreatment comprises oil removal, chemical polishing, cleaning and drying, and the flake titanium foam is firstly placed in acetone and absolute ethyl alcohol 1: 1, ultrasonic cleaning for 10min in mixed liquid, then chemical polishing, wherein the polishing liquid used for the chemical polishing contains 75g/L of zirconium oxide and 100mL/L of hydrogen fluoride solution with the concentration of 40 wt%, the solvent is water, the polishing temperature is 50 ℃, the polishing time is 20min, finally cleaning by using deionized water, placing the cleaning solution in a protective atmosphere for drying, and obtaining specially pretreated titanium foam after drying;
2) anodic oxidation: taking specially pretreated titanium foam as an anode, and carrying out constant-potential anodic oxidation on the specially pretreated titanium foam to obtain a pre-matrix, wherein the specially pretreated titanium foam is taken as the anode, a graphite electrode is taken as a cathode, a 2 wt% hydrofluoric acid solution is taken as an electrolyte, the oxidation temperature is 25 ℃, the oxidation voltage is 20V, and the oxidation time is 20 min;
3) annealing: annealing the pre-substrate for 2h at 450 ℃ at a heating rate of 5 ℃/min, and cooling with a furnace to obtain a substrate;
4) coating and growing: immersing the substrate in a copper-containing coating solution for 60s, wherein the coating solution contains 0.1mol/L of copper nitrate and 10g/L of polyvinylpyrrolidone, and the volume ratio of the copper nitrate to the polyvinylpyrrolidone is 10: 1, taking ethanol and ethylene glycol as organic solvents, drying at 80 ℃ for 10min and calcining at 450 ℃ for 20min after the impregnation is finished, wherein the process is a cycle, and the foamed copper oxide/TNTs photoelectric composite material can be obtained after 5 cycles.
Taking part of the substrate prepared in the step 3), shooting a Scanning Electron Microscope (SEM) of the surface of the substrate, and obtaining an SEM picture shown in figure 1, wherein a compact and ordered titanium oxide nanotube array (TNTs) structure is formed on the surface of the substrate, the length of the substrate is uniform, the formed surface is flat, and the subsequent step 4) is facilitated for further preparing the foamed copper oxide;
and taking the flaky foamed copper oxide/TNTs photoelectric composite material obtained in the step 4), shearing the flaky foamed copper oxide/TNTs photoelectric composite material, and respectively shooting the scanning electron microscope of the section and the surface of the flaky foamed copper oxide/TNTs photoelectric composite material. A cross section SEM image obtained by shooting is shown in FIG. 2, and the cross section SEM image still maintains a good three-dimensional network structure, namely a foam structure of the titanium foam; the SEM image of the obtained surface is taken as shown in fig. 3, and it is obvious from the image that after coating growth, compact and uniform copper oxide foam is prepared on the surface of the titanium oxide nanotube array structure, the formation of the copper oxide foam further increases the specific surface area of the copper oxide foam/TNTs photoelectric composite material, a large number of pores exist on the surface of the TNTs, the blockage of the TNTs is avoided, and the bonding strength of the copper oxide foam and the TNTs is obviously higher than that of a plane copper oxide layer and the TNTs, so that the copper oxide foam/TNTs photoelectric composite material is more stable as a whole.
Example 2
The specific procedure was the same as in example 1, except that the chemical polishing process in the special pretreatment was changed. The polishing solution used in this example contains 45g/L of chromium oxide, and 45mL of a 40 wt% hydrogen fluoride solution is added to each liter of polishing solution, that is, 45mL/L of a 40 wt% hydrogen fluoride solution is contained; in the present embodiment, the chemical polishing time is 20min, and the polishing temperature is 60 ℃.
Example 3
The specific procedure was the same as in example 1, except that the chemical polishing process in the special pretreatment was changed. The polishing solution used in this example contains chromium oxide with a concentration of 90g/L and a hydrogen fluoride solution with a concentration of 90mL/L and a concentration of 40 wt%; in the present embodiment, the chemical polishing time is 10min, and the polishing temperature is 60 ℃.
Example 4
The procedure was the same as in example 1, except that the conditions for potentiostatic anodization were changed. In this example, the anodization voltage was 15V.
Example 5
The procedure was the same as in example 1, except that the conditions for potentiostatic anodization were changed. In this example, the anodization temperature was 40 ℃, the anodization voltage was 35V, and the anodization time was 5 min.
Example 6
The procedure was the same as in example 4, except that the potentiostatic anodization conditions were varied. In this example, the anodizing time was 25 min.
Example 7
The specific procedure was the same as in example 1 except that the annealing conditions were changed. In this example, the annealing temperature is 550 ℃, the heating rate is 10 ℃/min, and the holding time is 2 h.
Example 8
The specific procedure was the same as in example 1 except that the annealing conditions were changed. In this example, the annealing temperature is 450 ℃, the heating rate is 10 ℃/min, and the holding time is 4 h.
Example 9
The procedure was the same as in example 1, except that the composition of the coating liquid was changed. In this example, the coating liquid contained 0.1mol/L of copper nitrate and 10g/L of polyvinylpyrrolidone in a volume ratio of 5: 1 ethanol and ethylene glycol as organic solvents.
Example 10
The procedure was the same as in example 1, except that the composition of the coating liquid was changed. In this example, the coating liquid contained 0.05mol/L of copper nitrate and 3g/L of polyvinylpyrrolidone, and the ratio by volume was 3: 1 ethanol and ethylene glycol as organic solvents.
Example 11
The procedure was the same as in example 1, except that the composition of the coating liquid was changed. In this example, the coating liquid contained 0.2mol/L of copper nitrate and 15g/L of polyvinylpyrrolidone in a volume ratio of 15: 1 ethanol and ethylene glycol as organic solvents.
Example 12
The procedure was as in example 1, except that the length of time for which the substrate was immersed in the coating solution in a single time was changed. In this example, the length of time for a single immersion of the substrate in the coating solution was 900 s.
Example 13
The procedure was the same as in example 1 except that the number of cycles and drying conditions for coating and growing the substrate to form copper oxide foam were changed. In this example, the coating, drying and calcining were performed for a total of 4 cycles, each drying being performed at 60 ℃ for 15 min.
Example 14
The procedure was the same as in example 1 except that the number of cycles of coating and growing the substrate to form copper oxide foam was changed. In this example, the coating, drying and calcining were performed for a total of 10 cycles.
Example 15
The procedure was the same as in example 1 except that the number of cycles of coating and growing the substrate to form copper oxide foam was changed. In this example, the coating, drying and calcining were performed for a total of 12 cycles.
Example 16
The procedure was the same as in example 1, except that the conditions of the single calcination during the growth of the coated substrate were changed. In this example, each calcination was carried out at 500 ℃ for 20min in 5 cycles.
Example 17
The procedure was the same as in example 1, except that the conditions of the single calcination during the growth of the coated substrate were changed. In this example, each calcination was carried out at 550 ℃ for 20min in 5 cycles.
Comparative example 1
The specific procedure was the same as in example 1, except that the coating growth process was changed to electrodeposition. In the electrodeposition, the electrolyte is 0.1mol/L of copper nitrate solution, the pH value of the solution is 10.8-11.0, the deposition voltage is-0.8V, the total deposited charge amount is 1.2C, and the ambient temperature is 23 +/-1 ℃, so that a comparative sample 1 which is also a photoelectric composite material is obtained.
Comparative example 2
The procedure was the same as in example 1, except that the polishing solution used for chemical polishing in the special pretreatment process was changed. The polishing solution contained 110g/L of chromium oxide and 120mL/L of a 40 wt% hydrogen fluoride solution, and comparative sample 2, which was also a photoelectric composite material, was obtained.
Comparative example 3
The procedure was the same as in example 1, except that the polishing solution used for chemical polishing in the special pretreatment process was changed. The polishing solution contained 40g/L of chromium oxide and 30mL/L of a 40 wt% hydrogen fluoride solution, and comparative sample 3, which was also a photoelectric composite material, was obtained.
And (3) detection:
and (3) characterization of micro morphology: the same characterization as in example 1 was performed for examples 2 to 17 and comparative examples 1 to 3, and the characterization results are shown in table 1 below in combination with macroscopic observation (since the characterization results of some examples are too close, the characterization results of examples 1 to 8 and comparative examples 1 to 3 are taken only):
table 1 morphology characterization results
As is apparent from the table above, the foamed copper oxide/TNTs photoelectric composite material prepared by the method of the invention has good morphological characteristics.
In addition, photocurrent tests were performed on the copper oxide foam/TNTs photoelectric composite material prepared in example 1 of the present invention and comparative example 1 prepared in comparative example 1.
The photocurrent curve test conditions were as follows:
the test solution system is 0.1mol/L sodium bicarbonate (NaHCO)3) An aqueous solution;
applying a bias voltage of-0.5V vs SCE;
carbon dioxide gas is introduced for half an hour before testing until the carbon dioxide is saturated in the testing environment.
The photocurrent test curve is shown in a photocurrent test curve chart of fig. 4, wherein a curve is the foamy copper oxide/TNTs photoelectric composite material prepared in example 1, and a curve B is a comparative example 1 prepared in comparative example 1, and it is obvious from the graph that the current density generated by the foamy copper oxide/TNTs photoelectric composite material prepared in example 1 of the present invention under the illumination condition is obviously higher than that of the comparative example 1, so that the excellent effect is generated.
Claims (8)
1. A preparation method of a foamy copper oxide/TNTs photoelectric composite material is characterized in that,
the preparation method comprises the following preparation steps:
1) anodic oxidation: taking specially pretreated titanium foam as an anode, and carrying out constant potential anodic oxidation on the titanium foam to obtain a pre-matrix;
2) annealing: annealing the pre-matrix to obtain a matrix;
3) coating and growing: and (3) soaking the substrate in the copper-containing coating solution for a period of time, and then sequentially drying and calcining, wherein the cycle is one cycle, and the foamed copper oxide/TNTs photoelectric composite material can be obtained after a plurality of cycles.
2. The method for preparing the copper foam/TNTs photoelectric composite material according to claim 1,
step 1) in the anodic oxidation electrochemical system:
taking specially pretreated titanium foam as an anode, a graphite electrode or a platinum electrode as a cathode, and 1-5 wt% of hydrofluoric acid solution as electrolyte;
step 1) the constant potential anodic oxidation conditions are as follows:
the oxidation temperature is 25-40 ℃, the oxidation voltage is 15-35V, and the oxidation time is 5-25 min.
3. The method for preparing the copper oxide foam/TNTs photoelectric composite material as claimed in claim 1 or 2, wherein the special pretreatment operation of step 1) comprises degreasing, chemical polishing, cleaning and drying;
wherein:
the polishing solution adopted by the chemical polishing contains 45-90 g/L of chromium oxide, 45-90 mL/L of 38-42 wt% of hydrogen fluoride solution and the balance of water, and the polishing time is controlled to be 10-20 min and the polishing temperature is controlled to be 50-60 ℃;
the titanium foam selected in the step 1) is titanium foam with the purity of more than or equal to 99.0 percent.
4. The method for preparing the copper oxide foam/TNTs photoelectric composite material according to claim 1,
step 2) during the annealing treatment:
controlling the annealing temperature to be 450-550 ℃, heating at the speed of 5-10 ℃/min, preserving the heat for 2-4 h after the annealing temperature is reached, and finally cooling to finish annealing.
5. The method for preparing the copper oxide foam/TNTs photoelectric composite material according to claim 1,
step 3) the copper-containing coating solution is prepared by dissolving soluble copper salt and polyvinylpyrrolidone as solutes in an organic solvent;
wherein the concentration of copper ions is 0.05-0.2 mol/L.
6. The method for preparing the copper oxide foam/TNTs photoelectric composite material according to claim 5,
the soluble copper salt comprises copper nitrate, copper sulfate and copper chloride;
the concentration of the polyvinylpyrrolidone is 3-15 g/L;
the organic solvent is ethanol and glycol in a volume ratio (15-3): 1, and mixing the components in the ratio of 1.
7. The method for preparing the copper oxide foam/TNTs photoelectric composite material according to claim 1, 5 or 6,
the dipping time is 30-900 s;
the cycle times are 4-12.
8. The method for preparing the copper oxide foam/TNTs photoelectric composite material according to claim 1,
the drying temperature in the drying process in the step 3) is 60-80 ℃, and the single drying time is more than or equal to 10 min;
the calcining temperature in the calcining process in the step 3) is 450-550 ℃, and the single calcining time is more than or equal to 20 min.
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