CN113354018B - Solar evaporation hierarchical structure and preparation method thereof - Google Patents
Solar evaporation hierarchical structure and preparation method thereof Download PDFInfo
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- CN113354018B CN113354018B CN202110781748.XA CN202110781748A CN113354018B CN 113354018 B CN113354018 B CN 113354018B CN 202110781748 A CN202110781748 A CN 202110781748A CN 113354018 B CN113354018 B CN 113354018B
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- 238000001704 evaporation Methods 0.000 title claims abstract description 82
- 230000008020 evaporation Effects 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000243 solution Substances 0.000 claims abstract description 50
- 229920006254 polymer film Polymers 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000003486 chemical etching Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000001788 irregular Effects 0.000 claims abstract description 11
- 230000000149 penetrating effect Effects 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 71
- 238000005530 etching Methods 0.000 claims description 68
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 22
- 238000004544 sputter deposition Methods 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical group [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- -1 polyethylene terephthalate Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000007733 ion plating Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001771 vacuum deposition Methods 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 10
- 239000011780 sodium chloride Substances 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 40
- 229920002799 BoPET Polymers 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000006096 absorbing agent Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000005477 sputtering target Methods 0.000 description 6
- 239000013077 target material Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010884 ion-beam technique Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012267 brine Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 210000002381 plasma Anatomy 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000112598 Pseudoblennius percoides Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a solar evaporation hierarchical structure and a preparation method thereof. The light-heat conversion layer comprises a polymer film layer and a light-heat conversion layer; the polymer film layer is provided with pore channels (namely water and/or water vapor conveying channels) penetrating through the polymer film, and the upper surface and the lower surface of the polymer film layer are provided with irregular cone structures; the light-heat conversion layer is positioned on one side of the polymer film layer. The invention uses the heavy ion irradiation and chemical etching method to obtain the straight hole vertical to the film surface, which not only can be used as the water vapor escape channel of the photo-thermal conversion layer, but also can be used as the continuous water transmission channel of the upper surface evaporation. The integral structure and the hierarchical structure of the invention reduce the dependence of the evaporation system on the incident light angle, and the salt particles are not accumulated in the high-concentration salt solution (30 wt% NaCl solution) by circular evaporation, when the incident light is inclined at a certain angle, the light absorption rate is increased, the evaporation efficiency is increased, and the conditions and requirements of most of the time of the sunlight in practical application are fully met.
Description
Technical Field
The invention belongs to the technical field of novel functional film materials and high-salt wastewater treatment, relates to a solar evaporation hierarchical structure and a preparation method thereof, and in particular relates to a photo-thermal conversion evaporation structure with a rough interface and two different hierarchical structures, a preparation method thereof and application of the photo-thermal conversion evaporation structure in solar drive high-salt wastewater treatment.
Background
The problem of energy and water shortage is one of the biggest challenges facing humans at present. Solar energy is one of the most abundant energy sources on the earth, and solar energy evaporation technology can solve the urgent problem of global water resources by utilizing solar energy, and is considered to be one of the most promising green and sustainable technologies in solar energy technology. The solar evaporator has the unique advantages of energy conservation, environmental protection, high efficiency and the like, so that the solar evaporator has important significance in a plurality of engineering applications, such as basic applications of generating steam and clean water from waste water or seawater, industrial solid waste treatment and the like.
The traditional solar evaporation method is that the absorber is arranged at the bottom of the water source, the light-heat conversion efficiency is low and is only 30% -45%, and the actual application of the absorber is limited due to the poor solar energy absorption effect and great heat loss caused by the arrangement of the absorber at the bottom of the water source. Later, a bulk heating system was developed that disperses the light absorber throughout the reservoir, resulting in a significant improvement in the light absorption effect of such designs, but heating the reservoir throughout the system during evaporation results in still significant heat loss. Recently developed interfacial solar energy evaporation systems place light absorbers at the air-water interface so that only the air-liquid interface is heated during evaporation, thereby improving the photo-thermal efficiency.
In recent years, the rapid development of novel photo-thermal materials and various photo-thermal evaporation structures effectively improves the solar evaporation efficiency of an interface. Currently the main photothermal materials are plasmonic absorbers, which are locally heated by plasmas, semiconductors, which generate heat by electron hole generation and relaxation, and carbonaceous or polymeric materials based on molecular vibrations. The absorption spectrum of the photo-thermal materials comprises the complete solar spectrum, and the cost is low and the long-term stability meets the current application prospect. The most common typical interface solar evaporation system at present mainly comprises two types, namely a solar evaporation device formed by assembling a plurality of components such as a light absorber/photo-thermal material, a water delivery channel, a supporting layer/heat insulation layer and the like, but the design of the solar evaporator is lack of integrity due to the independent existence of the water absorbing material and the supporting or heat insulation material, so that the practical operation is complicated, the application range of equipment is limited, and the used supporting/heat insulation material occupies a large area and is inconvenient to carry. Another type of interfacial solar energy evaporator system is an integrally structured solar energy evaporator, and its simple integral design makes it have a wider application range, and the integrally structured solar energy evaporator has unique advantages in practical applications. Some common thin film integrated evaporation structures known at present are graphene thin film structures, carbon nanotube thin film structures, porous polymer thin film structures and the like, but the evaporation effect of the structures is not ideal, and particularly the evaporation efficiency of salt solution is very low. Various structures are designed for strong brine evaporation in many researches, and the ultimate evaporation concentration of the structures to the strong brine is 20wt%, but in practical application, industrial wastewater with concentration of more than 20wt% is present, and how to enable the solar evaporation structure to be suitable for a wider and more practical application range is a great challenge of the solar evaporation technology. In addition, in practical application, the sun falls on east and west to make the incident angle difference of sunlight in the morning and evening very big, so how to reduce the dependence of evaporation structure and device on incident light angle and compromise the requirement of evaporation efficiency simultaneously is a huge challenge to current technology.
In summary, the existing solar evaporation structure and device are difficult to apply to a wider range and scene on the basis of guaranteeing the evaporation efficiency. In addition, in a real application scene, the sun rises and falls, the incident angle of sunlight changes greatly, and the light absorption efficiency and the evaporation efficiency are reduced. Therefore, aiming at the problems, developing an integrated solar evaporation structure meeting the conditions and a preparation method thereof have important application value.
Disclosure of Invention
The invention aims to provide a solar evaporation hierarchical structure and a preparation method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a solar energy evaporation hierarchy comprising a polymer film layer and a photo-thermal conversion layer; the polymer film layer is provided with straight hole channels (namely water and water vapor conveying channels) penetrating through the polymer film, and the upper surface and the lower surface of the polymer film layer are both provided with irregular cone structures; the light-heat conversion layer is positioned on one side of the polymer film layer.
Further, the cone structure is an irregular cone structure having a large aspect ratio.
The polymer film forms straight holes, namely water and water vapor conveying channels, perpendicular to the surface of the film after the first heavy ion irradiation and chemical etching, and the water and water vapor conveying channels convey water to the upper surface for evaporation and convey water vapor generated by the photothermal conversion layer on the lower surface to the upper surface. The two surfaces of the polymer film with the straight holes form an irregular cone-shaped structure with large length-diameter ratio after the second heavy ion irradiation and chemical overetching, a layer of light dissipation material is deposited on one surface by a coating technology to form a photo-thermal conversion layer for water evaporation, and the other surface is subjected to surface water evaporation by heat conduction.
In the invention, the polymer film can be selected from but not limited to polyethylene terephthalate (PET) or Polycarbonate (PC) and the like, and the required thickness is required to ensure that the film material still has self-sustaining mechanical strength under the premise of obtaining a straight hole and irregular cone-shaped structure, and can float on the liquid surface only under the action of self buoyancy. For example, the first shot fluence is 1X 10 5 ions/cm 2 The second irradiation fluence was 1X 10 9 ions/cm 2 The PET film of (2) may have a film thickness of 30 μm or more.
The material of the photo-thermal conversion layer can be gold, silver, copper, aluminum, palladium, cobalt, chromium, iron, indium, molybdenum, niobium, nickel, lead, platinum, tin, tantalum, vanadium, tungsten, zinc, manganese, antimony, bismuth, germanium and other metals, can be nickel-chromium, nickel-iron, titanium-aluminum and other alloys, can be inorganic nonmetallic materials such as graphite and the like, and can be a combination of various materials. The thickness of the photothermal conversion layer is not less than 50nm, preferably 100nm.
The invention also provides a preparation method of the solar evaporation hierarchical structure.
The preparation method of the solar evaporation hierarchical structure provided by the invention comprises the following steps:
1) Sequentially carrying out first heavy ion irradiation and first chemical etching on the polymer film;
2) Then sequentially carrying out second heavy ion irradiation and second chemical etching on the polymer treated in the step 1);
3) And depositing a photo-thermal conversion material on any side of the etched polymer film to obtain the solar evaporation hierarchical structure.
In the present invention, the heavy ion irradiation can be, but is not limited to, kr, xe, ta, bi plasma, the ion energy depends on the type and thickness of the film, and the irradiation fluence depends on the type and design structure size of the film. The first time required under the conditions involved in the examples of the present inventionThe fluence of irradiation is generally 1X 10 4 ions/cm 2 -1×10 8 ions/cm 2 The fluence of the second irradiation is generally 1×10 8 ions/cm 2 -1×10 10 ions/cm 2 Ions are directed perpendicularly into the polymer film. A wider fluence range is also possible, but a lower fluence for the first irradiation reduces the final evaporation efficiency, a lower fluence for the second irradiation reduces the final absorption properties, and a higher fluence reduces the final mechanical strength.
In the invention, the chemical etching is carried out twice, and the etching solution is etched by adopting 5-9M NaOH aqueous solution at the temperature of 45-65 ℃ under the water bath heating during the first etching, wherein the etching time is 30min-15h (preferably 3.5h-6 h), and the specific etching time is related to the film thickness, the irradiation fluence and the required structural dimension. In the second etching, 2.5-9M NaOH solution is adopted as the etching solution, the solvent is a mixed solution of methanol and water, wherein the volume content of the methanol is 50-95%, the etching time is 15-60min at room temperature, and the two sides of the film are etched simultaneously. For PET film, the preferred second etching conditions are 2.5M NaOH solution, 50% methanol by volume, and an etching time of 40min.
The photo-thermal conversion layer coating film can be deposited on any side of the polymer film by using methods such as but not limited to ion sputtering deposition, vacuum evaporation, vacuum ion coating, chemical reaction deposition, electroplating and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is a structure of integrating the light absorber/photo-thermal material, the water absorber, the supporting layer/the heat insulating layer, the thickness of the evaporating system is in the micron order, the evaporating system is convenient to float on the liquid surface, and the evaporating system can bear the oscillation under different conditions of the liquid surface.
(2) The invention uses the heavy ion irradiation and chemical etching method to obtain the straight hole vertical to the film surface, which not only can be used as the water vapor escape channel of the photo-thermal conversion layer, but also can be used as the continuous water transmission channel of the upper surface evaporation.
(3) The hierarchical structure has high-efficiency absorption in ultraviolet-visible-near infrared bands, and the average light absorptivity can reach 96% at most in the band range of 250nm-2300 nm.
(4) The integral structure and the hierarchical structure of the invention reduce the dependence of the evaporation system on the incident light angle, increase the light absorptivity and increase the evaporation efficiency when the incident light angle is inclined in a certain range, and fully satisfy the condition of most of the time inclination of the sunlight in practical application.
(5) The irregular cone-shaped structure on the upper surface of the polymer film can lead the liquid to be rapidly diffused and infiltrated, increase the surface evaporation area, improve the evaporation efficiency, and carry out ion exchange with the liquid level through the water delivery channel, and do not accumulate salt particles after being circularly evaporated in 30wt percent NaCl solution for 10 days (10 hours after light irradiation every day).
(6) The photothermal conversion material provided by the invention can be made of metal, non-metal such as graphite and the like, and can meet the requirements of different application scenes.
(7) The preparation method is simple and can realize large-scale preparation. The polymer film irradiation, etching and photo-thermal conversion layer deposition contained in the method all realize large-scale preparation.
(8) The preparation method has higher tolerance to key parameters such as the type of radiation ions, the injection amount, the ratio of etching solution, the etching time, the thickness of the photo-thermal conversion layer and the like, thereby reducing the precision requirement of preparation and ensuring the yield.
Drawings
Fig. 1 is a schematic view of a solar evaporation hierarchical structure according to the present invention.
Fig. 2 is a surface and cross-section sem image of the solar evaporation hierarchy in embodiment 1 of the present invention.
Fig. 3 is a graph showing the water evaporation rate during solar water evaporation in the solar evaporation hierarchical structure according to example 2 of the present invention.
Fig. 4 shows solar water evaporation rates of the solar evaporation hierarchy in embodiment 3 according to the present invention at different angles of incidence of the incident light.
FIG. 5 shows the cyclic evaporation rate of the solar water evaporation hierarchy in example 4 of the present invention in 30wt% NaCl solution for 10 days (10 hours of daily light irradiation, total 100 hours).
Detailed Description
The invention will be described in further detail below with reference to specific embodiments and corresponding drawings. The structural schematic diagram of the invention is only used for clearly showing the structure of the device, the arrangement of the conical structure is idealized, and the cone angle is properly enlarged. In a real structure, the aspect ratio of the cone structure is much larger than that shown in the schematic diagram, so the schematic diagram should not be considered as strictly reflecting the proportional relationship of the device geometry according to the present invention. In addition, the embodiments described in this specification are only some of the embodiments of the present invention, and are intended to further illustrate the present invention, and should not be construed as limiting the specific scope of the present invention. Based on the embodiments described in this specification, other embodiments that may be obtained by one skilled in the art without making any inventive effort are intended to be within the scope of the present invention.
Fig. 1 is a schematic view of a solar evaporation hierarchical structure according to the present invention, wherein the structure comprises a polymer film layer, a photo-thermal conversion layer and a conveying channel, and the specific preparation process comprises three steps:
1) Preparation of straight holes, i.e. delivery channels for water and water vapour
The purpose of this step is to form cylindrical straight holes in the polymer film through the polymer film. First, irradiation of the polymer film is aimed at forming etchable latent tracks throughout the entire film within the polymer film, so that ions whose electron energy loss in the irradiated polymer film is greater than the threshold required for track etching can be used for polymer film irradiation. The ion energy required is related to the polymer film thickness and the geometry of the straight holes required, so that the ions can completely penetrate the polymer film. The required fluence is related to the type of irradiated material and the required structural dimensions. Then chemical etching is carried out, after the polymer film is subjected to the irradiation process, etchable latent tracks are generated in the film, and under the action of etching liquid, cylindrical straight holes penetrating through the polymer film are formed by etching along the track direction, so that a conveying channel of water and water vapor is formed. The size of the straight hole involved in the present invention can be appropriately adjusted according to the irradiation fluence and etching time.
2) Preparation of double-sided irregular cone structure
The purpose of this step is to etch irregular cone-like structures of large aspect ratio on the polymer film surface. The first irradiation is the second irradiation of the polymer film with straight holes, and is the same as the first irradiation. Then a second chemical etching of the polymer film with straight holes, after a second irradiation process, again creating etchable latent tracks in the film. Under the action of etching liquid, the track etching rate along the track direction is far greater than the bulk etching rate parallel to the surface direction of the film, so that a biconical structure with large length-diameter ratio and opposite taper points is formed in the film, as the etching is further carried out, the diameter of the taper bottoms at the surface of the film is larger and larger, the adjacent taper bottoms are overlapped finally, and the unetched polymer between the taper holes forms an irregular cone-shaped protruding structure. The types and proportions of etching solutions are various, and the components and proportions of the etching solutions are different for different polymer films, so that the description cannot list the polymer films and etching solutions which are not mentioned in the examples of the description, but the irradiation and etching methods described in the description are adopted to obtain a hierarchical structure similar to the present invention, and the method is considered to be a simple equivalent substitution and is included in the protection scope of the present invention. Regarding etching time, it is sufficient to ensure that the taper bottoms overlap each other.
3) Deposition of photothermal conversion layers
The purpose of this step is to provide a photo-thermal conversion layer of sufficient thickness. When the photothermal conversion material is deposited on one side of the polymer film etched in step 2, the inner wall of the whole taper hole is covered and the remaining convex portion is etched. When light is incident from the other side, the whole light-heat conversion layer is equivalent to a hollow cone array. The number of the photo-thermal conversion materials in the photo-thermal conversion layer is not strictly required, and may be one or more, so long as the stability of the hierarchical structure can be ensured. The thickness is in principle not strictly required, and only the floating on the liquid surface by utilizing the self buoyancy is ensured. The used deposition coating equipment has no special requirement, and the deposited photo-thermal conversion material can cover the inner wall of the taper hole and etch the residual convex part.
The following are some examples, which are intended to illustrate the technical solution of the present invention in detail.
Example 1
The embodiment discloses a preparation method of a solar evaporation hierarchical structure, which comprises the following steps:
1) The Ta ion provided by the high-energy heavy ion accelerator is adopted to irradiate the PET film, the ion energy is 16MeV/u, and the irradiation fluence is 6 multiplied by 10 4 ions/cm 2 The film thickness was 38. Mu.m, and the ions completely penetrated the film. And then placing the irradiated PET film into 400ml of etching solution, ensuring that the two sides of the film are fully contacted with the etching solution, wherein the etching solution is 5M NaOH aqueous solution, and heating and etching the PET film in a water bath at 50 ℃ for 6 hours.
2) Repeatedly cleaning the PET film etched in the step 1) with deionized water for multiple times, naturally airing, and performing the second irradiation with the same ion beam as in the step 1) for the second time, wherein the irradiation fluence is 1 multiplied by 10 9 ions/cm 2 The ions penetrate the film completely. And then placing the PET film after the second irradiation into 400ml of etching solution, ensuring that the two sides of the film are fully contacted with the etching solution, wherein the etching solution is 2.5M NaOH, the solvent is a mixed solution of methanol and water, the volume ratio of the methanol to the water is 1:1, and etching for 40min at room temperature.
3) And repeatedly cleaning the etched PET film with deionized water for a plurality of times, naturally airing, putting into an ion sputtering coating instrument, selecting a sputtering target material as a gold target, setting the sputtering current as 10mA, and obtaining a required hierarchical structure after the sputtering is finished, wherein the coating time is 3000 s.
FIG. 2 is a scanning electron microscope image of the surface and cross section of the structure photo-thermal conversion in this embodiment. As can be seen from fig. 2, the straight holes are regular in shape, uniform in distribution, perpendicular to the surface of the film and penetrate through the film; the sizes of the cone structures at the two sides of the membrane tend to be consistent, and the cone structures are uniformly distributed.
Example 2
The embodiment discloses a preparation method of a solar evaporation hierarchical structure, which comprises the following steps:
1) The Ta ion provided by the high-energy heavy ion accelerator is adopted to irradiate the PET film, the ion energy is 16MeV/u, and the irradiation fluence is 6 multiplied by 10 4 ions/cm 2 The film thickness was 38. Mu.m, and the ions completely penetrated the film. Then the irradiated PET film is put into 400ml etching solution to ensure both sides of the film and etchingThe etching solution is 5M NaOH solution, and the etching solution is heated in a water bath at 50 ℃ for 3.5h.
2) Repeatedly cleaning the PET film etched in the step 1) with deionized water for multiple times, naturally airing, and performing the second irradiation with the same ion beam as in the step 1) for the second time, wherein the irradiation fluence is 1 multiplied by 10 9 ions/cm 2 The ions penetrate the film completely. And then placing the PET film after the second irradiation into 400ml of etching solution, ensuring that the two sides of the film are fully contacted with the etching solution, wherein the etching solution is 2.5M NaOH, the solvent is a mixed solution of methanol and water, the volume ratio of the methanol to the water is 1:1, and etching for 40min at room temperature.
3) And repeatedly cleaning the etched PET film with deionized water for a plurality of times, naturally airing, putting into an ion sputtering coating instrument, selecting a sputtering target material as a gold target, setting the sputtering current as 10mA, and obtaining a required hierarchical structure after the sputtering is finished, wherein the coating time is 3000 s.
And placing the prepared hierarchical structure on the surface of deionized water, and placing the hierarchical structure under a sunlight simulator to test the water evaporation efficiency under the condition of solar light intensity.
Fig. 3 is a graph showing the water evaporation efficiency of the layered structure during solar water evaporation in this embodiment. As can be seen from FIG. 3, the hierarchical structure under this condition can reach 1.4kg m under a solar light intensity (incident light is perpendicular to the film surface) -2 h -1 The above evaporation rate, and a stable evaporation rate is maintained.
Example 3
The embodiment discloses a preparation method of a solar evaporation hierarchical structure, which comprises the following steps:
1) The Ta ion provided by the high-energy heavy ion accelerator is adopted to irradiate the PET film, the ion energy is 16MeV/u, and the irradiation fluence is 6 multiplied by 10 4 ions/cm 2 The film thickness was 38. Mu.m, and the ions completely penetrated the film. And then placing the irradiated PET film into 400ml of etching solution, ensuring that the two sides of the film are fully contacted with the etching solution, wherein the etching solution is 5M NaOH solution, and heating and etching the PET film in a water bath at 50 ℃ for 3.5 hours.
2) Repeatedly cleaning the etched PET film with deionized water for multiple times, naturally airing, and carrying out the first time with the ion beam same as that in the step 1) for the second timeSecondary irradiation, irradiation fluence is 1 x 10 9 ions/cm 2 The ions penetrate the film completely. And then placing the PET film after the second irradiation into 400ml of etching solution, ensuring that the two sides of the film are fully contacted with the etching solution, wherein the etching solution is 2.5M NaOH, the solvent is a mixed solution of methanol and water, the volume ratio of the methanol to the water is 1:1, and etching for 40min at room temperature.
3) Repeatedly cleaning the etched PET film with deionized water for multiple times, naturally airing, putting into an ion sputtering coating instrument, selecting a sputtering target material as a titanium target, setting the sputtering current as 150mA, and coating for 1000s; selecting a sputtering target material as a gold target for the second time, setting the sputtering current as 10mA, and coating the film for 2000s; and thirdly, selecting a sputtering target material as a copper target, setting the sputtering current to be 40mA, and the coating time to be 2000s, so as to obtain the required hierarchical structure after sputtering.
And placing the prepared hierarchical structure on the surface of deionized water, and placing under a sunlight simulator of the intensity of the sun to test the water evaporation rate in the solar water evaporation process when the incident light is at different incident angles.
Fig. 4 shows the water evaporation rate of the solar water evaporation process of the layered structure at different incident angles of the incident light in this embodiment. As can be seen from FIG. 4, the evaporation rate increases when the incident light angle is inclined by 0-60 DEG, and reaches the optimal evaporation rate (1.68 kg m at a certain angle (30 DEG here) -2 h -1 )。
Example 4
The embodiment discloses a preparation method of a solar evaporation hierarchical structure, which comprises the following steps:
1) The Ta ion provided by the high-energy heavy ion accelerator is adopted to irradiate the PET film, the ion energy is 16MeV/u, and the irradiation fluence is 6 multiplied by 10 4 ions/cm 2 The film thickness was 38. Mu.m, and the ions completely penetrated the film. And then placing the irradiated PET film into 400ml of etching solution, ensuring that the two sides of the film are fully contacted with the etching solution, wherein the etching solution is 5M NaOH solution, and heating and etching the PET film in a water bath at 50 ℃ for 3.5 hours.
2) Repeatedly cleaning the etched PET film with deionized water for multiple times, naturally airing, and providing with a high-energy heavy ion accelerator for the second timeThe PET film was irradiated with Xe ions having an ion energy of 19.5MeV/u and an irradiation fluence of 1X 10 9 ions/cm 2 1X 10 irradiation fluence 9 ions/cm 2 The ions penetrate the film completely. And then placing the PET film after the second irradiation into 400ml of etching solution, ensuring that the two sides of the film are fully contacted with the etching solution, wherein the etching solution is 2.5M NaOH, the solvent is a mixed solution of methanol and water, the volume ratio of the methanol to the water is 1:1, and etching for 30min at room temperature.
3) And repeatedly cleaning the etched PET film with deionized water for multiple times, naturally airing, putting into an ion sputtering coating instrument, selecting a sputtering target material as a carbon target, setting the sputtering current as 40mA, and obtaining a required hierarchical structure after the sputtering is finished, wherein the coating time is 1000 s.
The prepared hierarchical structure was placed in 30wt% nacl solution and placed under a solar simulator of solar light intensity to test 10 days of cyclic evaporation efficiency.
FIG. 5 is the cyclic evaporation efficiency of the layered structure in this example in 30wt% NaCl solution for 10 days (10 h of light per day, 100h total). As can be seen from fig. 5, the hierarchical structure can maintain a stable cyclic evaporation efficiency in 30wt% nacl solution for 10 days.
It should be emphasized that the above-described embodiments are merely illustrative of the technical solutions of the present invention, and the specific implementation of the present invention should not be considered limited to these descriptions. The technical scheme of the invention is simply modified or equivalently replaced without departing from the conception of the technical scheme of the invention, and the technical scheme is covered in the protection scope of the invention.
Claims (5)
1. A solar energy evaporation hierarchy comprising a polymer film layer and a photo-thermal conversion layer; the polymer film layer is provided with a straight hole channel penetrating through the polymer film, and the upper surface and the lower surface of the polymer film layer are both provided with irregular cone structures; the light-heat conversion layer is positioned on one side of the polymer film layer;
the cone-shaped structure is an irregular cone-shaped structure with a large length-diameter ratio;
the material constituting the polymer film is polyethylene terephthalate or polycarbonate;
the material forming the light-heat conversion layer is at least one selected from metal, alloy and graphite;
the metal is specifically selected from at least one of gold, silver, copper, aluminum, palladium, cobalt, chromium, iron, indium, molybdenum, niobium, nickel, lead, platinum, tin, tantalum, vanadium, tungsten, zinc, manganese, antimony, bismuth and germanium;
the alloy is nickel-chromium, nickel-iron or titanium-aluminum;
the effective thickness of the light-heat conversion layer is not less than 50nm;
the preparation method of the solar evaporation hierarchical structure comprises the following steps:
1) Sequentially carrying out first heavy ion irradiation and first chemical etching on the polymer film;
2) Then sequentially carrying out second heavy ion irradiation and second chemical etching on the polymer treated in the step 1);
3) Carrying out deposition of a photo-thermal conversion material on any side of the polymer film treated in the step 2) to obtain the solar evaporation hierarchical structure;
in the step 1), the electron energy loss of the irradiation ions in the irradiated polymer film is larger than the threshold value required by track etching, in particular Kr, xe, ta or Bi;
the ion energy is determined according to the type and thickness of the film, and the irradiation fluence is determined according to the type and design structure size of the film;
the first chemical etching is carried out, etching solution is adopted to carry out etching under the water bath heating of 45-65 ℃ by adopting 5-9M NaOH aqueous solution, and the etching time is 30min-15h;
and the second chemical etching is carried out, wherein 2.5-9M NaOH solution is adopted as etching solution, and the solvent is mixed solution of methanol and water, wherein the volume content of the methanol is 50-95%, and the etching time is 15-60min at room temperature.
2. The method for preparing the solar evaporation hierarchical structure according to claim 1, comprising the following steps:
1) Sequentially carrying out first heavy ion irradiation and first chemical etching on the polymer film;
2) Then sequentially carrying out second heavy ion irradiation and second chemical etching on the polymer treated in the step 1);
3) Carrying out deposition of a photo-thermal conversion material on any side of the polymer film treated in the step 2) to obtain the solar evaporation hierarchical structure;
in the step 1), the electron energy loss of the irradiation ions in the irradiated polymer film is larger than the threshold value required by track etching, in particular Kr, xe, ta or Bi;
the ion energy is determined according to the type and thickness of the film, and the irradiation fluence is determined according to the type and design structure size of the film;
the first chemical etching is carried out, etching solution is adopted to carry out etching under the water bath heating of 45-65 ℃ by adopting 5-9M NaOH aqueous solution, and the etching time is 30min-15h;
and the second chemical etching is carried out, wherein 2.5-9M NaOH solution is adopted as etching solution, and the solvent is mixed solution of methanol and water, wherein the volume content of the methanol is 50-95%, and the etching time is 15-60min at room temperature.
3. The preparation method according to claim 2, characterized in that:
the first heavy ion irradiation fluence is 1×10 4 ions/cm 2 -1×10 8 ions/cm 2 ；
The second heavy ion irradiation fluence is 1×10 8 ions/cm 2 -1×10 10 ions/cm 2 。
4. The production method according to any one of claim 2, wherein: the deposition method in the step 3) is an ion sputtering method, a vacuum evaporation method, a vacuum ion plating method, a chemical reaction deposition method or an electroplating method.
5. Use of the solar evaporation hierarchy of claim 1 in photo-thermal water treatment.
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