CN114804272A - Wood-like black body material and preparation method and application thereof - Google Patents

Wood-like black body material and preparation method and application thereof Download PDF

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CN114804272A
CN114804272A CN202210459468.1A CN202210459468A CN114804272A CN 114804272 A CN114804272 A CN 114804272A CN 202210459468 A CN202210459468 A CN 202210459468A CN 114804272 A CN114804272 A CN 114804272A
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wood
black body
body material
sodium alginate
water
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CN114804272B (en
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俞书宏
赵浩雨
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • 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
    • Y02A20/124—Water desalination

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  • 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)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

The invention provides a preparation method of a wood-like black body material, and develops an artificial asymmetric structure wood-like material with an oriented nano structure by an ice template method. The invention provides a wood-like black body material, which comprises: the polypyrrole-carboxymethylcellulose-alginate composite material (CCAP) and the calcium-cured carboxymethylcellulose/sodium alginate composite material (CCA) have a double-layer structure, and the CCAP layer contains black polypyrrole, so that the solar energy absorption rate can be effectively improved, and the evaporation enthalpy of interfacial water is reduced; the CCA layer is a hydrophilic polyhydroxy macroporous structure, and not only has considerable water transmission capacity and salt resistance, but also is an excellent heavy metal capture agent. In addition, all precursors of the artificial asymmetric structure wood material provided by the invention are biomass, so that the influence on the water ecological environment is minimum in the regeneration process of the metal ion-removed drinking water. The invention also provides application of the wood-like black body material.

Description

Wood-like black body material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photo-thermal conversion water evaporation, and particularly relates to a wood-like black body material, and a preparation method and application thereof, in particular to preparation of a black body material with efficient photo-thermal conversion and hydrophilic-hydrophobic interface treatment of the material.
Background
With population growth, urbanization and socioeconomic development, water shortage occurs to different degrees in more than 100 countries. The reason of water shortage mainly has three aspects, one is that more than 97% of water on the earth surface is high-salinity seawater which cannot be directly utilized; secondly, with the rapid development of the industry, 2.5% of surface fresh water faces various pollution problems, such as mine pollution, domestic sewage and the like; thirdly, the problem of water resource shortage is aggravated by unbalanced water resource distribution. With the rise of interface photothermal conversion (ISSG) technology, seawater and sewage can be purified with little energy consumption and carbon footprint, showing broad industrialization prospects.
Various methods for desalinating seawater, such as continuous microfiltration, reverse osmosis, etc., are available, which inherently alleviate the problem of water shortage, but they are not versatile because not all water-deficient areas are coastal. The ideal goal of sewage treatment in the future tends to be low energy consumption, and although the reported hydrogel technology can reduce the concentration of heavy metal ions in water by 7 orders of magnitude to meet the demand of drinkable fresh water, no expansion in the aspects of environmental protection and high-efficiency heavy metal enrichment while producing healthy drinking water has been made.
At present, the mainstream black body materials mainly comprise black polymers, plasmons and carbon-based absorbents, and although the black polymers, the plasmons and the carbon-based absorbents can achieve 95% of photothermal conversion efficiency, the swelling behavior of the polymers enables the polymers to have poor drought resistance; the plasma absorber form is easily destroyed and still presents challenges for practical photothermal water evaporation. Although carbon-based absorbers have the remarkable properties of natural broadband solar absorption, resistance to heat acid/base and ultraviolet light, and excellent heat conversion performance, they are considered to be one of the best candidates for efficient photothermal conversion water evaporation; moreover, its economic, sustainable and good processing characteristics contribute to its wide spread use. However, the inherent hydrophobicity and poor thermal insulation properties of carbon-based materials are not suitable for water transport and efficient thermal management, and although hydrophilicity can be achieved by surface modification or doping to induce heteroatoms, the incorporation of other materials inevitably affects the tolerance of the carbon-based system.
Disclosure of Invention
In view of this, the invention aims to provide a wood-like black body material, and a preparation method and an application thereof.
The invention provides a wood-like black body material, which comprises:
a calcified polypyrrole-carboxymethylcellulose-alginate composite layer;
a calcified carboxymethyl cellulose-sodium alginate composite layer.
Preferably, the wood-like blackbody material has the solar energy absorption capacity of 96-99%, the saturation capacity ratio of 18-22 and the heat transmission coefficient of 30-35 mW.m -1 ·K -1 The evaporation enthalpy of interfacial water is 1450-1500 J.g -1 。
The invention provides a preparation method of an artificial wood black body material, which comprises the following steps:
freezing and casting a mixed solution of carboxymethyl cellulose and sodium alginate to obtain a composite material;
reacting a mixed solution of sodium alginate and carboxymethyl cellulose, polypyrrole and ammonium persulfate to obtain a reaction product;
compounding the reaction product with the composite material and drying to obtain an intermediate product;
and calcifying the intermediate product to obtain the wood-like black body material.
Preferably, the method of freeze casting comprises:
arranging a mould on the copper sheet, and pouring the mixed solution of the carboxymethyl cellulose and the sodium alginate into the mould;
and (3) putting the copper block into liquid nitrogen, and placing the die on the copper block to obtain the composite material.
Preferably, the compounding method comprises:
and pouring the reaction product into a mold filled with the composite material for solidification.
Preferably, the method of calcification comprises:
soaking the intermediate product in CaCl 2 And drying the solution to obtain the wood-like black body material.
The invention provides a metal recovery and enrichment device, which comprises: the wood-like blackbody material according to the technical scheme or the wood-like blackbody material prepared by the method according to the technical scheme.
The invention provides a sewage regeneration device, comprising: the wood-like blackbody material according to the technical scheme or the wood-like blackbody material prepared by the method according to the technical scheme.
The invention provides a heavy metal wastewater treatment device, which comprises: the wood-like blackbody material according to the technical scheme or the wood-like blackbody material prepared by the method according to the technical scheme.
The invention provides a solar seawater desalination evaporator, which comprises: the wood-like blackbody material according to the technical scheme or the wood-like blackbody material prepared by the method according to the technical scheme.
In order to improve the photothermal conversion efficiency and the vapor accumulation rate, the existing research is usually dedicated to changing the composition of the used material, and there is little research on the nano-structure engineering. The invention reasonably designs the nano structure by combining with the ISSG technology, and has very important significance for improving the photo-thermal conversion efficiency, removing heavy metal impurity ions and producing healthy drinking water. The natural plants have a directional parallel structure and can enrich nutrient ions in soil in the process of photosynthesis and transpiration. The invention is inspired by the above and provides an artificial biocompatible asymmetric structure wood evaporator which can realize the enrichment of a large amount of metal ions during ISSG. The invention provides a preparation method of an enriched and recovered metal ion wood-like black body material inspired by plant photosynthesis and transpiration mechanisms, and provides application advantages of the enriched and recovered metal ion wood-like black body material in the aspects of sewage purification and the like. The invention is inspired by the arrangement of nano structures of nutrient ions in the enriched soil under the physiological action of plants in the nature, and provides an artificial double-sided structure wood-like black body material with a directional nano structure for the first time by using an ice template method so as to convey water in sewage and enrich heavy metal ions in the sewage.
The invention is inspired by the arrangement of nano structures for enriching nutrient ions in soil in plant transpiration, provides an artificial asymmetric structure wood-like material with a directional nano structure by an ice template method, and has a double-layer structure of a polypyrrole-carboxymethylcellulose-alginate composite material (CCAP) and a calcium-cured carboxymethylcellulose/sodium alginate composite material (CCA); the CCAP layer contains black polypyrrole, so that the solar energy absorption rate can be effectively improved, and the evaporation enthalpy of interfacial water is reduced; the CCA layer is of a hydrophilic polyhydroxy macroporous structure, not only has water transmission capacity and salt tolerance, but also is an excellent heavy metal capture agent, salt water or sewage is transmitted to an evaporation interface through solar energy and undergoes a phase change process, as the leaves do, fresh water regeneration is realized through condensed steam, and when water evaporates, ions in the water can be enriched in the CCA layer of the artificial wood, just like roots absorb nutrient elements from soil. In addition, all precursors of the artificial asymmetric structure wood material provided by the invention are biomass, so that the influence on the water ecological environment is minimum in the regeneration process of the metal ion-removed drinking water.
The blackbody material provided by the invention has excellent solar energy absorption capacity (98%), hydrophilicity and thermal management performance (lambda is 32.8mW (m)) -1 ·K -1 ) And low enthalpy of water evaporation (1475J "g) -1 ) And can reach 2.3kg "m under 1 unit of solar radiation -2 〃h -1 Can exhibit excellent long-term evaporation stability and less performance decay in metal solutions due to their macroporous super-hydrophilic framework sufficient for water transport and spontaneous salt diffusion. The wood-like black body material prepared by the invention provides a new idea for heavy metal enrichment in the construction process of the high-performance solar seawater desalination evaporator, and has important significance for various applications including sewage regeneration and heavy metal wastewater treatment.
Drawings
FIG. 1 is a schematic diagram of the application principle of the wood-like blackbody material provided by the present invention;
FIG. 2 is a schematic structural diagram of a wood-like blackbody material that can be used for metal recovery and enrichment according to an embodiment of the present invention;
FIG. 3 is a physical diagram of the wood-like blackbody material prepared in example 1 of the present invention;
FIG. 4 is an SEM photograph of a wood-like blackbody material prepared in example 1 of the present invention;
FIG. 5 is an XPS energy spectrum of a wood-like blackbody material prepared in example 1 of the present invention;
FIG. 6 is a graph of time dependent water contact angle performance of a wood-like blackbody material prepared in example 1 of the present invention;
FIG. 7 is an FT-IR absorption spectrum of a wood-like blackbody material prepared in example 1 of the present invention;
FIG. 8 is a performance testing environment chart of the wood-like blackbody material prepared in example 1 of the present invention;
FIG. 9 shows the light absorption rate of the artificial wood black body material prepared in example 1 of the present invention within the wavelength range of 250-2500 nm;
FIG. 10 is a surface temperature curve of the wood-like blackbody material prepared in example 1 of the present invention when immersed in water under 1 unit of solar radiation;
FIG. 11 is a comparison graph of the adsorbed metal ions during evaporation of the wood-like blackbody material prepared in example 1 of the present invention;
FIG. 12 is a graph comparing the stability in water of the wood-like blackbody materials (CAPs) prepared in examples 1, 2 and 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a wood-like black body material, which comprises:
a calcified polypyrrole-carboxymethylcellulose-alginate composite layer;
a calcified carboxymethyl cellulose-sodium alginate composite layer.
In the invention, the calcified polypyrrole-carboxymethylcellulose-alginate composite material layer is arranged on the surface of the calcified carboxymethylcellulose-sodium alginate composite material layer, the calcified polypyrrole-carboxymethylcellulose-alginate composite material layer is an upper layer, the calcified carboxymethylcellulose-sodium alginate composite material layer is a lower layer, and the calcified carboxymethylcellulose-sodium alginate composite material layer contains a cage-shaped complex formed after calcification. The wood-like black body material provided by the embodiment of the invention has a structure schematic diagram shown in fig. 2, wherein 1 is a wood-like black body material inspired by plant physiological action and capable of being used for metal recovery and enrichment, 2 is a sodium alginate-carboxymethyl cellulose-polypyrrole composite material layer on the upper layer of the wood-like material, 3 is a sodium alginate-carboxymethyl cellulose composite material layer on the lower layer of the wood-like material, and 4 is a caged complex formed after calcification.
The invention provides a preparation method of an artificial wood black body material, which comprises the following steps:
freezing and casting a mixed solution of carboxymethyl cellulose and sodium alginate to obtain a composite material;
reacting a mixed solution of sodium alginate and carboxymethyl cellulose, polypyrrole and ammonium persulfate to obtain a reaction product;
compounding the reaction product with the composite material and drying to obtain an intermediate product;
and calcifying the intermediate product to obtain the wood-like black body material.
The invention provides a preparation method of a wood-like black body material for metal recovery and enrichment, which comprises the steps of firstly, freezing and casting a mixed solution of carboxymethyl cellulose and sodium alginate on flat copper to prefabricate a parallel channel structure similar to wood; then adding polypyrrole into the mixed solution of sodium alginate and carboxymethyl cellulose, oxidizing by ammonium persulfate, and then covering on the carboxymethyl cellulose/sodium alginate composite material; then freeze-drying the obtained sample in a cold trap at-50 ℃; finally, a cage-shaped complex is formed by calcium ions in the alcohol phase and sodium alginate, so that a molecular network is crosslinked, the stability of the material in water is improved, and the material is prevented from being dissolved in water. The invention utilizes an ice template method to freeze and cast a mixed solution of carboxymethyl cellulose and sodium alginate on a copper flat plate to form a wood-like parallel channel structure; oxidizing the white polypyrrole into black by utilizing the oxidability of ammonium persulfate; and exchanging calcium ions in the alcohol solution with sodium ions in the sodium alginate by using an ion exchange technology to form a cage-shaped compound. The directional parallel structure not only can effectively convey water, but also has the function of enriching metal ions.
In the present invention, the preparation method of the mixed solution of carboxymethyl cellulose and sodium alginate preferably includes:
dissolving carboxymethyl cellulose powder and sodium alginate powder in water, stirring, and removing bubbles to obtain mixed solution (CA solution) of carboxymethyl cellulose and sodium alginate.
In the present invention, the water is preferably deionized water.
In the invention, the mass ratio of the carboxymethyl cellulose to the sodium alginate is preferably (0.5-2.0): 1, more preferably (1 to 1.5): 1, most preferably 1: 1; the preferable dosage ratio of the carboxymethyl cellulose to the water is (0.5-2.0) g: 100mL, more preferably (1-1.5) g: 100mL, most preferably 1 g: 100 mL.
In the present invention, the stirring time is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, and most preferably 3 hours.
In the present invention, the method for removing bubbles is preferably a vacuum treatment.
In the present invention, the method of freeze casting preferably comprises:
arranging a mould on the copper sheet, and pouring the mixed solution of the carboxymethyl cellulose and the sodium alginate into the mould;
and (3) putting the copper block into liquid nitrogen, and placing the mould on the copper block to obtain a parallel channel structure (composite material) similar to wood.
In the present invention, the mold is preferably a polydimethylsiloxane mold.
In the present invention, it is preferable to pour a mixed solution of carboxymethyl cellulose and sodium alginate into 1/2 of the mold volume.
In the present invention, the copper block is preferably immersed in liquid nitrogen at the lower part and exposed to air at the upper part; the liquid nitrogen is preferably placed in an insulated open container.
In the present invention, the method of freeze casting more preferably comprises:
pouring liquid nitrogen into an insulated open container, putting a copper block into the container, so that the lower part of the copper block is immersed in the liquid nitrogen, and the upper part of the copper block is exposed in the air;
taking a copper sheet, placing a polydimethylsiloxane mold on the upper part of the copper sheet, pouring a CA solution with half volume of the mold, and placing the copper sheet on a copper block in liquid nitrogen; after the solution is solidified, a parallel channel structure similar to wood is obtained.
In the present invention, the method of the reaction preferably includes:
mixing a mixed solution of sodium alginate and carboxymethyl cellulose with polypyrrole for the first time to obtain a mixed solution;
and carrying out second mixing on the mixed solution and the ammonium persulfate solution to obtain a reaction product (CAP black solution).
In the present invention, the preparation method of the mixed solution of sodium alginate and carboxymethyl cellulose is the same as the preparation method of the mixed solution of carboxymethyl cellulose and sodium alginate in the above technical scheme, and is not described herein again.
In the invention, the volume ratio of the mixed solution of sodium alginate and carboxymethyl cellulose to polypyrrole is preferably (40-60): (1-2), more preferably (45-55): (1.3 to 1.7), most preferably 50: 1.5.
in the present invention, the first mixing is preferably performed under stirring, and the stirring time is preferably 0.3 to 0.7 hours, more preferably 0.4 to 0.6 hours, and most preferably 0.5 hours.
In the present invention, the method for preparing the ammonium persulfate solution preferably comprises:
and mixing ammonium persulfate and water to obtain an ammonium persulfate solution.
In the present invention, the water is preferably deionized water.
In the invention, the using amount ratio of the ammonium persulfate to the water is preferably (0.2-0.6) g: (8-12) mL, more preferably (0.3-0.5) g: (9-11) mL, most preferably 0.4 g: 10 mL.
In the invention, the preferable dosage ratio of the mixed solution of sodium alginate and carboxymethyl cellulose and ammonium persulfate is (40-60) mL: (0.2-0.6) g, more preferably (45-55) mL: (0.3-0.5) g, most preferably 50 mL: 0.4 g.
In the present invention, the second mixing is preferably performed under stirring; the stirring time is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, and most preferably 3 hours, until no lump gel exists in the solution.
In the present invention, it is preferable that the second mixture further comprises:
the obtained product was subjected to vacuum treatment to remove air bubbles, and a CAP black solution was obtained.
In the present invention, the compounding method preferably includes:
and pouring the reaction product into a mold filled with the composite material for solidification.
In the present invention, the compounding method more preferably includes:
and pouring a CAP solution onto the solidified CA in the polydimethylsiloxane mold, and drying after the solution is completely solidified to obtain an intermediate product (the wood-like material with the two-sided structure).
In the present invention, the reaction product is preferably 1/2 of the above-described mold volume.
In the present invention, the drying is preferably freeze-drying, and the drying time is preferably more than 4 days; the temperature of the drying is preferably-40 to-60 ℃, more preferably-45 to-55 ℃, and most preferably-50 ℃.
In the present invention, the method of calcification preferably comprises:
soaking the intermediate product in CaCl 2 After being dissolved in the solution, the solution is dried to obtain the wood-like black body material (cage complex of the two-sided structure material).
In the present invention, the CaCl is 2 The solution is preferably CaCl 2 Ethanol solution; said CaCl 2 The method of preparing the solution preferably comprises:
adding CaCl 2 The powder was dissolved in ethanol.
In the present invention, the ethanol is preferably anhydrous ethanol.
In the present invention, the CaCl is 2 And the preferable dosage proportion of the ethanol is (4-5) g: (180-220) mL, more preferably (4.2-4.8) g: (190-210) mL, most preferably 4.44 g: 200 mL.
In the present invention, the soaking time is preferably more than 2 days.
In the invention, the drying temperature is preferably 70-90 ℃, more preferably 75-85 ℃, and most preferably 80 ℃; the drying is preferably carried out overnight to obtain the cage complex of the double-faced structural material.
The interface photothermal conversion water evaporation black body material is prepared by the following method: firstly, freezing and casting a mixed solution of carboxymethyl cellulose and sodium alginate on flat copper to prefabricate a parallel channel structure similar to wood; then adding polypyrrole into the mixed solution of sodium alginate and carboxymethyl cellulose, oxidizing with ammonium persulfate to obtain a black solution, and then covering the black solution on the carboxymethyl cellulose/sodium alginate composite material to obtain a material with a two-sided structure; all samples were then freeze dried in a cold trap at-50 ℃; finally, a cage-shaped complex is formed by calcium ions in the alcohol phase and sodium alginate, so that the molecular network is crosslinked, the stability of the material in water is improved, and the material is prevented from being dissolved in water.
The invention provides a metal recovery and enrichment device, which comprises: the wood-like blackbody material according to the technical scheme or the wood-like blackbody material prepared by the method according to the technical scheme.
The invention provides a sewage regeneration device, comprising: the wood-like blackbody material according to the technical scheme or the wood-like blackbody material prepared by the method according to the technical scheme.
The invention provides a heavy metal wastewater treatment device, which comprises: the wood-like blackbody material according to the technical scheme or the wood-like blackbody material prepared by the method according to the technical scheme.
The invention provides a solar seawater desalination evaporator, which comprises: the wood-like blackbody material according to the technical scheme or the wood-like blackbody material prepared by the method according to the technical scheme.
The application schematic diagram of the wood-like blackbody material provided by the invention is shown in figure 1.
The invention provides a useful method based on plant physiological effect elicitationThe wood-like black body material enriched in metal recovery has excellent solar energy absorption capacity (98%), hydrophilicity (saturation capacity ratio of 19.2) and heat management performance (lambda is 32.8mW "m) -1 〃K -1 ) (ii) a Has high steam regeneration rate; the metal liquid still shows good evaporation stability and less performance attenuation in a metal solution for a long time; has lower interfacial water evaporation enthalpy (1475J "g) -1 ) A more efficient water evaporation process can be achieved.
Example 1
Dissolving 1.0g of sodium alginate powder and 1.0g of carboxymethyl cellulose powder in 100mL of deionized water, stirring for 3h, and then carrying out vacuum treatment on the solution to remove bubbles to obtain a CA solution. Pouring liquid nitrogen into an insulated open container, putting a copper block into the container, so that the lower part of the copper block is immersed in the liquid nitrogen, and the upper part of the copper block is exposed in the air; taking a copper sheet, placing a polydimethylsiloxane mold on the upper part of the copper sheet, pouring a CA solution with half volume of the mold, and placing the copper sheet on a copper block in liquid nitrogen; after the solution is solidified, a parallel channel structure similar to wood is obtained.
Taking 50mL of CA solution (the preparation method is the same as the above), adding 1.5mL of polypyrrole, and stirring for 0.5 h; adding 0.4g of ammonium persulfate into 10mL of deionized water, adding the obtained ammonium persulfate solution into the CA solution, and stirring for 3 hours until no blocky gel exists in the solution; and (4) carrying out vacuum treatment on the solution to remove bubbles to obtain a CAP black solution.
And pouring CAP solution (the residual volume of 1/2) onto the solidified CA in the polydimethylsiloxane mold, and freeze-drying for more than 4 days at (-50 ℃) after the solution is completely solidified to obtain the wood-like material with the two-sided structure.
Taking 4.44g of CaCl 2 Dissolving the powder in 200mL of absolute ethyl alcohol; soaking the wood-like material with the two-sided structure in CaCl 2 Ethanol solution for more than 2 days, followed by drying at 80 ℃ overnight, gave a cage complex of bifacial structure material (wood-like black body material).
Fig. 3 is a real object diagram of the wood-like black body material prepared in example 1, in the left diagram, the upper part is a sodium alginate/carboxymethyl cellulose solution, a sodium alginate/carboxymethyl cellulose/polypyrrole solution before oxidation, and a sodium alginate/carboxymethyl cellulose/polypyrrole solution after oxidation, the lower part is a double-layer wood-like material, the upper layer is a sodium alginate-carboxymethyl cellulose-polypyrrole composite layer, and the lower part is a sodium alginate-carboxymethyl cellulose layer; in the right drawing, the upper part is a sodium alginate-carboxymethyl cellulose composite layer before calcification and a sodium alginate-carboxymethyl cellulose-polypyrrole composite layer before calcification from left to right, and the lower part is a sodium alginate-carboxymethyl cellulose composite layer after calcification and a sodium alginate-carboxymethyl cellulose-polypyrrole composite layer after calcification from left to right.
Fig. 4 is an SEM image of the wood-like material prepared in example 1, the left image is a calcified sodium alginate-carboxymethyl cellulose composite layer, the right image is a calcified sodium alginate-carboxymethyl cellulose-polypyrrole composite layer, and the middle image is an interface between the two.
Fig. 5 is an XPS spectrum of the wood-like black body material prepared in example 1, which shows that polypyrrole exists in the sodium alginate-carboxymethylcellulose-polypyrrole composite layer, and calcification of both the sodium alginate-carboxymethylcellulose composite layer and the sodium alginate-carboxymethylcellulose-polypyrrole composite layer acts on the position of calcium alginate.
Fig. 7 is an FT-IR absorption spectrum of the wood-like black body material prepared in example 1, where the four absorption spectra are, from top to bottom, a sodium alginate-carboxymethylcellulose-polypyrrole composite layer before calcification, a sodium alginate-carboxymethylcellulose-polypyrrole composite layer after calcification, and a sodium alginate-carboxymethylcellulose-polypyrrole composite layer after calcification.
Example 2
Dissolving 2.0g of sodium alginate powder and 1.0g of carboxymethyl cellulose powder in 100mL of deionized water, stirring for 3h, and then carrying out vacuum treatment on the solution to remove bubbles to obtain a CA solution. Pouring liquid nitrogen into an insulated open container, putting a copper block into the container, so that the lower part of the copper block is immersed in the liquid nitrogen, and the upper part of the copper block is exposed in the air; taking a copper sheet, placing a polydimethylsiloxane mold on the upper part of the copper sheet, pouring a CA solution with half volume of the mold, and placing the copper sheet on a copper block in liquid nitrogen; after the solution is solidified, a parallel channel structure similar to wood is obtained.
Taking 50mL of CA solution (the preparation method is the same as the above), adding 1.5mL of polypyrrole, and stirring for 0.5 h; adding 0.4g of ammonium persulfate into 10mL of deionized water, adding the obtained ammonium persulfate solution into the CA solution, and stirring for 3 hours until no blocky gel exists in the solution; and (4) carrying out vacuum treatment on the solution to remove bubbles to obtain a CAP black solution.
And pouring CAP solution (the residual volume of 1/2) onto the solidified CA in the polydimethylsiloxane mold, and freeze-drying for more than 4 days at (-50 ℃) after the solution is completely solidified to obtain the wood-like material with the two-sided structure.
Taking 4.44g of CaCl 2 Dissolving the powder in 200mL of absolute ethyl alcohol; soaking the wood-like material with the two-sided structure in CaCl 2 Ethanol solution for more than 2 days, followed by drying at 80 ℃ overnight, gave a cage complex of bifacial structure material (wood-like black body material).
Example 3
Dissolving 1.0g of sodium alginate powder and 2.0g of carboxymethyl cellulose powder in 100mL of deionized water, stirring for 3h, and then carrying out vacuum treatment on the solution to remove bubbles to obtain a CA solution. Pouring liquid nitrogen into an insulated open container, putting a copper block into the container, so that the lower part of the copper block is immersed in the liquid nitrogen, and the upper part of the copper block is exposed in the air; taking a copper sheet, placing a polydimethylsiloxane mold on the upper part of the copper sheet, pouring a CA solution with half volume of the mold, and placing the copper sheet on a copper block in liquid nitrogen; after the solution is solidified, a parallel channel structure similar to wood is obtained.
Taking 50mL of CA solution (the preparation method is the same as the above), adding 1.5mL of polypyrrole, and stirring for 0.5 h; adding 0.4g of ammonium persulfate into 10mL of deionized water, adding the obtained ammonium persulfate solution into the CA solution, and stirring for 3 hours until no blocky gel exists in the solution; and (4) carrying out vacuum treatment on the solution to remove bubbles to obtain a CAP black solution.
And pouring CAP solution (the residual volume of 1/2) onto the solidified CA in the polydimethylsiloxane mold, and freeze-drying for more than 4 days at (-50 ℃) after the solution is completely solidified to obtain the wood-like material with the two-sided structure.
Taking 4.44g of CaCl 2 Powder, solutionDissolving in 200mL of absolute ethyl alcohol; soaking the wood-like material with the two-sided structure in CaCl 2 Ethanol solution for more than 2 days, followed by drying at 80 ℃ overnight, gave a cage complex of bifacial structure material (wood-like black body material).
Performance detection
The water contact angle of the wood-like blackbody material prepared by the embodiment of the invention is detected, the contact angle of the dropped liquid drop is recorded in real time by utilizing a Dataphysics OCA 25 device, and the detection result is as follows: the water contact angle detection result of the wood-like blackbody material prepared in example 1 is shown in fig. 6, and it can be seen that all the materials are super-hydrophilic materials, and the hydrophilicity of the calcified materials is slightly improved. The water contact angles of the wood-like blackbody materials prepared in example 2 and example 3 are both 0 °, i.e., super-hydrophilic.
The interface photothermal conversion performance of the wood-like blackbody material prepared in the embodiment of the invention is detected, the performance test environment is shown in fig. 8, and the test method of the solar energy absorption capacity comprises the following steps: obtaining the ultraviolet-visible-near infrared reflectivity and transmission spectrum by an ultraviolet-visible-near infrared spectrometer (SOLID 3700); the hydrophilicity was tested as follows: recording the infiltration process in real time by using a Dataphysics OCA 25 device; the test method of the thermal management performance comprises the following steps: thermal conductivity was measured by Hot Disk Techmax TPS1500 thermometer; the method for testing the water evaporation enthalpy comprises the following steps: differential Scanning Calorimetry (DSC) analysis on DSC Q2000; the method for testing the steam regeneration rate under 1 unit of solar irradiation comprises the following steps: a xenon lamp simulates a sunlight tester; as a result, the wood-like blackbody material prepared in example 1 had a solar absorption capacity of 98%, and as shown in fig. 9, the hydrophilicity, i.e., the saturation capacity ratio, was 19.2, and the thermal management performance λ was 32.8mW · m -1 ·K -1 The water evaporation enthalpy is 1475J g -1 And can reach 2.3 kg.m under 1 unit solar radiation -2 ·h -1 High steam regeneration rate; FIG. 10 is a graph of the surface temperature of the wood-like material prepared in example 1 immersed in water at 1 unit of solar radiation, measured by: by means of a thermal imaging camera (
Figure BDA0003619570800000111
head HiRes 640) to redAn external thermography; compared with pure deionized water (DIW), the temperature rise of CAP and CCAP is respectively increased by 3 ℃ and 10 ℃, and the high temperature is more beneficial to water regeneration; FIG. 11 is a comparison graph of metal ions adsorbed during evaporation of the wood-like blackbody material prepared in example 1, and the detection method is as follows: inductively coupled plasma atomic absorption spectroscopy (ICP-AAS); it can be seen that after the photo-thermal treatment, the heavy metal ions in the water body are enriched in the CAP composite material.
The wood-like blackbody materials prepared in the examples 2 and 3 can realize the same photothermal conversion function similar to the material prepared in the example 1; however, the wood-like black body materials prepared in examples 2 and 3 were relatively poor in water stability, as shown in fig. 12, the wood-like black body materials prepared in examples 2 and 3 both collapsed after being soaked in water for 2 days, and the CAP prepared in example 1 had a longer service life.
The macroporous super-hydrophilic skeleton of the wood-like black body material prepared in the embodiment is enough for water transmission and spontaneous salt diffusion, and can show excellent long-term evaporation stability and smaller performance attenuation in a metal solution, so that a new way is opened for further developing a high-speed evaporation system and purifying waste water containing metal ions.
The invention is inspired by the arrangement of nano structures of nutrient ions in the enriched soil under the physiological action of plants in the nature, and provides a method for preparing an artificial double-sided wood-like black body material with an oriented nano structure by using an ice template method for conveying water in sewage and enriching heavy metal ions in the sewage for the first time. The blackbody material provided by the invention has excellent solar energy absorption capacity (98%), hydrophilicity (saturation capacity ratio of 19.2) and heat management performance (lambda is 32.8mW m) -1 〃K -1 ) And less than the enthalpy of vaporization (1475J "g) of bulk water -1 ) Up to 2.3kg "m under 1 unit of solar radiation -2 〃h -1 High steam generation rate. Meanwhile, the invention provides the wood-like black body material which can still show excellent long-term evaporation stability and smaller performance attenuation even in a high-concentration metal solution. The wood-like black body material provided by the invention provides a new direction for heavy metal enrichment in the construction process of the high-performance solar seawater desalination evaporator, and is suitable for the heavy metal enrichment in the construction process of the high-performance solar seawater desalination evaporatorVarious applications including sewage regeneration and heavy metal wastewater treatment are of great significance.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (10)

1. An artificial wood black body material comprising:
a calcified polypyrrole-carboxymethylcellulose-alginate composite layer;
a calcified carboxymethyl cellulose-sodium alginate composite layer.
2. The wood-like black body material of claim 1, wherein the wood-like black body material has a solar absorption capacity of 96-99%, a saturation capacity ratio of 18-22, and a heat transfer coefficient of 30-35 mW "m -1 〃K -1 The evaporation enthalpy of interfacial water is 1450-1500J "g -1 。
3. A preparation method of an artificial wood black body material comprises the following steps:
freezing and casting a mixed solution of carboxymethyl cellulose and sodium alginate to obtain a composite material;
reacting a mixed solution of sodium alginate and carboxymethyl cellulose, polypyrrole and ammonium persulfate to obtain a reaction product;
compounding the reaction product with the composite material and drying to obtain an intermediate product;
and calcifying the intermediate product to obtain the wood-like black body material.
4. The method of claim 3, wherein the method of freeze casting comprises:
arranging a mould on the copper sheet, and pouring the mixed solution of the carboxymethyl cellulose and the sodium alginate into the mould;
and (3) putting the copper block into liquid nitrogen, and placing the die on the copper block to obtain the composite material.
5. The method of claim 3, wherein the compounding comprises:
and pouring the reaction product into a mold filled with the composite material for solidification.
6. A method according to claim 3, wherein the method of calcification comprises:
soaking the intermediate product in CaCl 2 And drying the solution to obtain the wood-like black body material.
7. A metal recovery enrichment device, comprising: the wood-like black body material of claim 1, or the wood-like black body material produced by the method of claim 3.
8. An apparatus for regenerating wastewater, comprising: the wood-like black body material of claim 1, or the wood-like black body material produced by the method of claim 3.
9. A heavy metal wastewater treatment device comprises: the wood-like black body material of claim 1, or the wood-like black body material produced by the method of claim 3.
10. A solar desalination evaporator comprising: the wood-like black body material of claim 1, or the wood-like black body material produced by the method of claim 3.
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