CN112980399A - Super-hydrophilic copper-based MOF (metal organic framework) photo-thermal material as well as preparation method and application thereof - Google Patents
Super-hydrophilic copper-based MOF (metal organic framework) photo-thermal material as well as preparation method and application thereof Download PDFInfo
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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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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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- 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
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- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/138—Water desalination using renewable energy
- Y02A20/142—Solar thermal; Photovoltaics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- 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
Abstract
The invention discloses a super-hydrophilic copper-based MOF photo-thermal fabric and a preparation method and application thereof, belonging to the technical field of photo-thermal material preparation. The preparation method comprises the steps of carrying out plasma etching treatment and deposition treatment by taking a polymer fabric film as a substrate to prepare a copper-coated polymer fabric film; subjecting the resulting copper-coated polymer fabric film to Cu (OH)2And (3) growing the nanowires, and then carrying out hydrothermal treatment to obtain the super-hydrophilic copper-based MOF photo-thermal material. The super-hydrophilic copper-based MOF photo-thermal material has excellent super-hydrophilicity and ultrahigh evaporation efficiency due to the unique metal organic porous carbon skeleton structure, and provides a brand new light for the solar-driven interface seawater desalination technologyA heat transfer material. The preparation method is simple in preparation process, can realize large-scale production, and can be well applied to the field of preparation and application of the portable solar evaporator.
Description
Technical Field
The invention belongs to the technical field of preparation of photo-thermal materials, and relates to a super-hydrophilic copper-based MOF photo-thermal material, and a preparation method and application thereof.
Background
Fresh water resources are one of the most important resources for public health and social development. However, the shortage of fresh water resources has become one of the major social problems, and although 75% of the earth's surface is covered with seawater, the residents can use only 10% of it, and 12 hundred million people worldwide cannot obtain safe drinking water with the rapid growth of population and the rapid increase of pollution caused by industrial activities. Therefore, the development of an expandable and environment-friendly seawater desalination technology is crucial to meet the increasing demand for fresh water. To solve this problem, scientists have looked at the ocean and proposed two of the most common solutions-reverse osmosis and multi-stage distillation. But the application of industrial desalination is restricted due to long process flow, expensive equipment and high energy consumption. One possible solution therefore requires the use of abundant solar energy to generate heat to generate steam. Solar desalination is a promising strategy for large-scale seawater purification using sustainable energy as the sole energy, in which case water can be evaporated from the sun, thus achieving purification of wastewater or seawater, simple and inexpensive. The internal heat localization utilizes the floating structure to concentrate heat on the surface, so that the water body is prevented from being heated, the heat loss is reduced, and the efficient solar evaporation is realized. Meanwhile, the generation of steam driven by solar energy is widely concerned because of the huge solar energy utilization potential in various applications such as seawater desalination, wastewater treatment and sterilization.
Solar-driven interfacial desalination currently utilizes photo-thermal materials with high solar absorptivity, such as metal nanoparticles, black semiconductors, carbon-based materials, porous polymers, and other absorber materials, as carriers for the photo-thermal effect. The photo-thermal material floats or suspends on water, and the local heating on the surface of the evaporator avoids heating water, reduces heat loss and realizes effective solar interface evaporation. However, although the carbon-based material has a high broadband solar absorption rate, the carbon-based material is easily polluted by oil-based water pollutants commonly existing in seawater in the actual seawater desalination process. Most metals have a narrow solar absorption bandwidth, thus limiting their solar thermal conversion efficiency. The plasma metal nano-particles have good photo-thermal conversion performance, but the preparation cost is high, so that the large-scale application of the plasma metal nano-particles is limited. Similarly, the traditional carbon-based material and biomass material have the advantages of wide wavelength range, good light absorption and light stability, and the like, but the manufacturing process is complex and cannot be expanded. Therefore, there is a strong need to develop a new material and/or structure that can combine high solar absorption and evaporation properties.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a super-hydrophilic copper-based MOF photo-thermal fabric, a preparation method and application thereof, and provides a material with excellent solar energy absorption performance and evaporation performance through a simple and efficient preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a super-hydrophilic copper-based MOF photo-thermal material, which comprises the steps of carrying out plasma etching treatment and deposition treatment by taking a polymer fabric film as a substrate to prepare a copper-coated polymer fabric film; subjecting the resulting copper-coated polymer fabric film to Cu (OH)2And (3) growing the nanowires, and then carrying out hydrothermal treatment to obtain the super-hydrophilic copper-based MOF photo-thermal material.
Preferably, the method specifically comprises the following steps: 1) depositing the sputtered copper clusters on the polymer fabric film etched by the argon plasma by adopting a magnetron sputtering technology to prepare a copper-coated polymer fabric film; 2) washing the copper-coated polymer fabric film obtained in the step 1), and then placing the film in a mixed solution containing NaOH and ammonium persulfate to carry out Cu (OH)2Nanowire growth reaction, and rinsing after the reaction is finished to obtain the product with Cu (OH)2A polymer fabric film of nanowires; 3) growing Cu (OH) obtained in the step 2)2And immersing the polymer fabric film of the nanowires into a solution containing hexahydroxy benzophenanthrene for hydrothermal treatment, and cooling and cleaning after the treatment is finished to prepare the super-hydrophilic copper-based MOF photothermal material.
Preferably, in step 1), the plasma etching includes the following operations: performing argon plasma etching under the pressure of 5Pa for 10-20 minutes.
Preferably, in the step 2), the mixed solution is prepared by mixing a 2.5mol/L NaOH solution and a 0.13mol/L ammonium persulfate solution; wherein the mixing volume ratio of the NaOH solution to the ammonium persulfate solution is 80-100: 80-100 parts.
Preferably, in step 2), Cu (OH)2The temperature of the nanowire growth reaction is 20-35 ℃, and the time is 15-30 min.
Preferably, in the step 3), the solution containing hexahydroxy triphenylene comprises water, DMF and hexahydroxy triphenylene, and the mixing ratio of the water, the DMF and the hexahydroxy triphenylene is 80-120 mL: 8-12 mL: 170-200 mg.
Preferably, in step 3), the operating parameters of the hydrothermal treatment include: the temperature is 70-100 ℃, the preheating time is 30-40 minutes, and the air-cooled water is naturally cooled after preheating.
The invention discloses a super-hydrophilic copper-based MOF photo-thermal material prepared by the preparation method.
Preferably, the contact angle of the super-hydrophilic copper-based MOF photo-thermal material and water is 0-20 degrees, the broadband light absorption rate in the solar radiation range is 90-95.9 percent, and the water evaporation rate is 1.34-1.52 kg-m-2·h-1。
The invention discloses application of the super-hydrophilic copper-based MOF photo-thermal material in preparation of a portable solar evaporator.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a super-hydrophilic copper-based MOF photo-thermal material, which improves the adhesive force strength of copper and a polymer fabric film in deposition treatment through plasma etching treatment; by Cu (OH)2Carrying out nanowire growth treatment to form a copper-based MOF absorbent coating with super-hydrophilicity and firmness; wherein the copper-coated polymeric fabric film produced by depositing copper enhances the adhesion stability between the polymeric fabric film substrate and the copper-based MOF absorbent coating. In the meantime, Cu (OH) is used2The nanowires and the copper film in the obtained copper-coated polymer fabric film form a Cu-MOF light-capturing layer-shaped structure, so that the finally prepared super-hydrophilic copper-based MOF photo-thermal material has excellent light absorption rate, excellent air permeability and high evaporation rate. Therefore, the temperature of the molten metal is controlled,compared with the traditional metal plasma element material, semiconductor material, composite material and the like, the preparation method provided by the invention has the advantages that the preparation process is simple, and the large-scale production can be realized.
Further, by adopting a magnetron sputtering technology, a sputtered copper film is used as a bonding layer to firmly fix the super-hydrophilic and firm copper-based MOF absorbent coating on the surface of the commercial textile, so that firm adhesion between the polymer fabric film substrate and copper is strengthened and ensured; by growing Cu (OH) on a copper-coated polymer fabric film2Nano-wire, utilizing its capillary action and water-pumping capacity to make the obtained growth possess Cu (OH)2The polymer fabric film of the nanowires can rapidly transport water to the surface, so that the prepared super-hydrophilic copper-based MOF photo-thermal material has excellent solar energy absorption performance and evaporation performance; in addition, in the preparation method, raw materials in each step are easy to obtain, the operation process is simple, and the super-hydrophilic copper-based MOF photo-thermal material with a unique Cu-MOF light-harvesting layered structure is efficiently prepared.
The invention discloses a super-hydrophilic copper-based MOF photo-thermal material prepared by the preparation method, wherein a copper film is used as a bonding layer to firmly fix a super-hydrophilic and firm copper-based MOF absorbent coating on the surface of a polymer fabric film, so that firm adhesion between a polymer fabric film substrate and copper is ensured. Meanwhile, due to the excellent capillary action and the strong water pumping capacity, the pumping of water can be rapidly completed in a large amount, and even in the evaporation process, the salt content is 9.5 wt% through related experiments, and no salt content accumulation is observed on the upper surface of the Cu-based MOF photothermal textile fabric within more than 12 h. Therefore, the super-hydrophilic copper-based MOF photo-thermal material disclosed by the invention has excellent solar energy absorption performance and evaporation performance.
Furthermore, related performance tests show that the contact angle of the super-hydrophilic copper-based MOF photo-thermal material and water is 0-20 degrees, the excellent light absorption rate induced by the unique Cu-MOF light-capturing layer-shaped structure is 90-95.9 percent, the super-hydrophilic copper-based MOF photo-thermal material has excellent air permeability, and the super-hydrophilic copper-based MOF photo-thermal material realizes the purpose of one-time sunlight irradiation1.34～1.52kg·m-2·h-1High evaporation rate. In addition, due to the excellent structural design, the super-hydrophilic copper-based MOF photo-thermal material shows high flexibility and excellent mechanical stability under various severe environments.
The invention also discloses application of the super-hydrophilic copper-based MOF photo-thermal material in preparation of a portable solar evaporator. The seawater desalination can be stably and efficiently completed for a long time through strong photo-thermal conversion capability.
Drawings
FIG. 1 is a graph of the results of the surface wettability test of the present invention; wherein, (a) is polyester textile, (b) is the super-hydrophilic copper MOF photothermal material;
FIG. 2 is a SEM test chart of the present invention; wherein, (a) is polyester textile, (b) is the super-hydrophilic copper MOF photothermal material;
FIG. 3 is a spectrum of reflected and transmitted light spectra of a superhydrophilic copper-based MOF photothermal material of the present invention;
FIG. 4 is a graph showing the results of the evaporation rates of the superhydrophilic copper-based MOF photothermal material and bulk water and water in the dark field under one solar irradiation in accordance with the present invention;
FIG. 5 is a graph showing the results of the mechanical stability test of the present invention; wherein (a) is 500g push-pull, (b) is 600g push-pull, (c) is 1100g push-pull, and (d) is 30 times of abrasion.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is further illustrated by the following specific examples:
the first embodiment is as follows:
(1) the commercial polyester fabric is first cut to the desired size (e.g., 21 cm)-2) And then washed with deionized water and acetone solution to clean the polyester fabric.
(2) The cleaned polyester fabric was placed in a magnetron sputtering vacuum chamber. Selecting DC power supply as sputtering source, and pumping the vacuum degree of the sputtering chamber to 9.0 × 10 by mechanical pump and molecular pump-4Pa, and then Ar plasma etching was performed at a pressure of 5Pa for 10 minutes to improve the adhesion of the thin film. A high-purity copper target (purity 99.9%) and argon gas were used in the deposition process, and the pressure in the vacuum chamber was adjusted to 0.5 Pa. Sputtering was carried out for 20 minutes under the conditions of Ar flow rate of 40sccm and current of 0.25A so that sputtered copper clusters were deposited on the textile surface to produce a copper-coated polymer fabric film.
(3) Respectively using dilute H2SO4The resulting copper coated polymer fabric film was washed with deionized water and acetone (5 vol%). Next, in order to grow Cu (OH) on the copper-coated polymer fabric film2Nanowires, a copper-coated polymer fabric film was immersed in 160mL of a mixed solution (mixed volume ratio of NaOH solution and ammonium persulfate solution: 80) containing NaOH (2.5M) and ammonium persulfate (0.13M) at room temperature (25 ℃) for 30min, and Cu (OH) was performed2And (4) nanowire growth reaction. After the reaction is finished, Cu (OH) is grown on the surface of the silicon substrate2Polymerisation of nanowiresA woven fabric film was thoroughly rinsed with deionized water to grow Cu (OH)2Cu (OH) grown on polymer fabric film of nanowires2A nanowire.
(4) Will grow Cu (OH)2The polymer fabric film of nanowires was immersed in a mixed solution petri dish of deionized water and DMF (v/v ═ 80mL:8mL), 180mg of HHTP (hexahydroxytriphenylene) was further added to the petri dish, and then placed in an oven at 70 ℃ to be preheated for 30 minutes. And after naturally cooling to room temperature, thoroughly washing the obtained sample with acetone to obtain the super-hydrophilic copper-based MOF photo-thermal material.
The contact angle test of the super-hydrophilic copper-based MOF photo-thermal material is carried out by adopting a video optical contact angle instrument, the contact angle of the super-hydrophilic copper-based MOF photo-thermal material with water is 10 degrees, the light absorption performance test is carried out by adopting an ultraviolet-near infrared spectrophotometer (Carry 5000) instrument, the broadband light absorption rate of the super-hydrophilic copper-based MOF photo-thermal material in the solar radiation range is 90 percent, the mass loss test is carried out by adopting a microbalance (AR224CN) instrument, and the water evaporation rate of the super-hydrophilic copper-based MOF photo-thermal material is-2·h-1。
Salt resistance performance test of the Cu-based MOF photothermal textile prepared by the specific embodiment is carried out for 3-12 hours, and under the condition that the salinity is 9.5 wt%, salt accumulation is not observed on the upper surface of the Cu-based MOF photothermal textile within a time of more than 12 hours.
The second embodiment is as follows:
(1) the commercial polyester fabric is first cut to the desired size (e.g., 21 cm)-2) And then washed with deionized water and acetone solution to clean the polyester fabric.
(2) The cleaned polyester fabric was placed in a magnetron sputtering vacuum chamber. Selecting DC power supply as sputtering source, and pumping the vacuum degree of the sputtering chamber to 9.0 × 10 by mechanical pump and molecular pump-4Pa, and then Ar plasma etching was performed for 15 minutes under a pressure of 5Pa to improve the adhesion of the thin film. A high-purity copper target (purity 99.9%) and argon gas were used in the deposition process, and the pressure in the vacuum chamber was adjusted to 0.5 Pa. Sputtering for 20 minutes under Ar flow of 40sccm and current of 0.25A to deposit sputtered copper clusters on the textile surface to produce a copper coated polymerA woven fabric film.
(3) Respectively using dilute H2SO4The resulting copper coated polymer fabric film was washed with deionized water and acetone (5 vol%). Next, in order to grow Cu (OH) on the copper-coated polymer fabric film2Nanowires, a copper-coated polymer fabric thin film was immersed in 180mL of a mixed solution (mixed volume ratio of NaOH solution and ammonium persulfate solution is 90: 90) containing NaOH (2.5M) and ammonium persulfate (0.13M) at room temperature (35 ℃) for 15min, and Cu (OH) was performed2And (4) nanowire growth reaction. After the reaction is finished, Cu (OH) is grown on the surface of the silicon substrate2Thin film of polymer fabric of nanowires, and thoroughly rinsed with deionized water grown with Cu (OH)2Cu (OH) grown on polymer fabric film of nanowires2A nanowire.
(4) Will grow Cu (OH)2The polymer fabric film of nanowires was immersed in deionized water and DMF (v/v ═ 100mL:10mL), 190mg HHTP was added to the petri dish, and then placed in an oven at 100 ℃ to preheat for 30 minutes. And after naturally cooling to room temperature, thoroughly washing the obtained sample with acetone to obtain the super-hydrophilic copper-based MOF photo-thermal material.
The contact angle test of the super-hydrophilic copper-based MOF photo-thermal material is carried out by adopting a video optical contact angle instrument, the contact angle of the super-hydrophilic copper-based MOF photo-thermal material with water is 1 degree, the light absorption performance test is carried out by adopting an ultraviolet-near infrared spectrophotometer (Carry 5000) instrument, the broadband light absorption rate of the super-hydrophilic copper-based MOF photo-thermal material in the solar radiation range is 93 percent, the mass loss test is carried out by adopting a microbalance (AR224CN) instrument, and the water evaporation rate of the super-hydrophilic copper-based MOF photo-thermal material is-2·h-1。
Salt resistance performance test of the Cu-based MOF photothermal textile prepared by the specific embodiment is carried out for 3-12 hours, and under the condition that the salinity is 9.5 wt%, salt accumulation is not observed on the upper surface of the Cu-based MOF photothermal textile within a time of more than 12 hours.
The third concrete implementation mode:
(1) the commercial polyester fabric is first cut to the desired size (e.g., 21 cm)-2) And then washed with deionized water and acetone solution to clean the polyester fabric.
(2) The cleaned polyester fabric was placed in a magnetron sputtering vacuum chamber. Selecting DC power supply as sputtering source, and pumping the vacuum degree of the sputtering chamber to 9.0 × 10 by mechanical pump and molecular pump-4Pa, and then Ar plasma etching was performed at a pressure of 5Pa for 20 minutes to improve the adhesion of the thin film. A high-purity copper target (purity 99.9%) and argon gas were used in the deposition process, and the pressure in the vacuum chamber was adjusted to 0.5 Pa. Sputtering was carried out for 20 minutes under the conditions of Ar flow rate of 40sccm and current of 0.25A so that sputtered copper clusters were deposited on the textile surface to produce a copper-coated polymer fabric film.
(3) Respectively using dilute H2SO4The resulting copper coated polymer fabric film was washed with deionized water and acetone (5 vol%). Next, in order to grow Cu (OH) on the copper-coated polymer fabric film2Nanowires, a copper-coated polymer fabric film was immersed in 200mL of a mixed solution (mixed volume ratio of NaOH solution and ammonium persulfate solution 100: 100) containing NaOH (2.5M) and ammonium persulfate (0.13M) at room temperature (30 ℃) for 20min, and Cu (OH) was performed2And (4) nanowire growth reaction. After the reaction is finished, Cu (OH) is grown on the surface of the silicon substrate2Thin film of polymer fabric of nanowires, and thoroughly rinsed with deionized water grown with Cu (OH)2Cu (OH) grown on polymer fabric film of nanowires2A nanowire.
(4) Will grow Cu (OH)2The polymer fabric film of nanowires was immersed in deionized water and DMF (v/v 120mL:12mL), and 170mg HHTP was added to the petri dish, which was then placed in an oven at 80 ℃ and preheated for 35 minutes. And after naturally cooling to room temperature, thoroughly washing the obtained sample with acetone to obtain the super-hydrophilic copper-based MOF photo-thermal material.
The contact angle test of the super-hydrophilic copper-based MOF photo-thermal material is carried out by adopting a video optical contact angle instrument, the contact angle of the super-hydrophilic copper-based MOF photo-thermal material with water is 0 degrees, the light absorption performance test is carried out by adopting an ultraviolet-near infrared spectrophotometer (Carry 5000) instrument, the broadband light absorption rate of the super-hydrophilic copper-based MOF photo-thermal material in the solar radiation range is 95.9 percent, the mass loss test is carried out by adopting a microbalance (AR224CN) instrument, and the water evaporation rate of the super-hydrophilic copper-based MOF photo-thermal material is-2·h-1。
Salt resistance performance test of the Cu-based MOF photothermal textile prepared by the specific embodiment is carried out for 3-12 hours, and under the condition that the salinity is 9.5 wt%, salt accumulation is not observed on the upper surface of the Cu-based MOF photothermal textile within a time of more than 12 hours.
The fourth concrete implementation mode:
(1) the commercial polyester fabric is first cut to the desired size (e.g., 21 cm)-2) And then washed with deionized water and acetone solution to clean the polyester fabric.
(2) The cleaned polyester fabric was placed in a magnetron sputtering vacuum chamber. Selecting DC power supply as sputtering source, and pumping the vacuum degree of the sputtering chamber to 9.0 × 10 by mechanical pump and molecular pump-4Pa, and then Ar plasma etching was performed at a pressure of 5Pa for 10 minutes to improve the adhesion of the thin film. A high-purity copper target (purity 99.9%) and argon gas were used in the deposition process, and the pressure in the vacuum chamber was adjusted to 0.5 Pa. Sputtering was carried out for 20 minutes under the conditions of Ar flow rate of 40sccm and current of 0.25A so that sputtered copper clusters were deposited on the textile surface to produce a copper-coated polymer fabric film.
(3) Respectively using dilute H2SO4The resulting copper coated polymer fabric film was washed with deionized water and acetone (5 vol%). Next, in order to grow Cu (OH) on the copper-coated polymer fabric film2Nanowires, a copper-coated polymer fabric thin film was immersed in 200mL of a mixed solution (mixed volume ratio of NaOH solution and ammonium persulfate solution 100: 100) containing NaOH (2.5M) and ammonium persulfate (0.13M) at room temperature (20 ℃) for 15min, and Cu (OH) was performed2And (4) nanowire growth reaction. After the reaction is finished, Cu (OH) is grown on the surface of the silicon substrate2Thin film of polymer fabric of nanowires, and thoroughly rinsed with deionized water grown with Cu (OH)2Cu (OH) grown on polymer fabric film of nanowires2A nanowire.
(4) Will grow Cu (OH)2The polymer fabric film of nanowires was immersed in deionized water and DMF (v/v ═ 110mL:11mL), 200mg of HHTP was added to the petri dish, which was then placed in an oven at 70 ℃ and preheated for 40 minutesA clock. And after naturally cooling to room temperature, thoroughly washing the obtained sample with acetone to obtain the super-hydrophilic copper-based MOF photo-thermal material.
The contact angle test of the super-hydrophilic copper-based MOF photo-thermal material is carried out by adopting a video optical contact angle instrument, the contact angle of the super-hydrophilic copper-based MOF photo-thermal material with water is 10 degrees, the light absorption performance test is carried out by adopting an ultraviolet-near infrared spectrophotometer (Carry 5000) instrument, the broadband light absorption rate of the super-hydrophilic copper-based MOF photo-thermal material in the solar radiation range is 95 percent, the mass loss test is carried out by adopting a microbalance (AR224CN) instrument, and the water evaporation rate of the super-hydrophilic copper-based MOF photo-thermal material is-2·h-1。
Salt resistance performance test of the Cu-based MOF photothermal textile prepared by the specific embodiment is carried out for 3-12 hours, and under the condition that the salinity is 9.5 wt%, salt accumulation is not observed on the upper surface of the Cu-based MOF photothermal textile within a time of more than 12 hours.
The fifth concrete implementation mode:
(1) the commercial polyester fabric is first cut to the desired size (e.g., 21 cm)-2) And then washed with deionized water and acetone solution to clean the polyester fabric.
(2) The cleaned polyester fabric was placed in a magnetron sputtering vacuum chamber. Selecting DC power supply as sputtering source, and pumping the vacuum degree of the sputtering chamber to 9.0 × 10 by mechanical pump and molecular pump-4Pa, and then Ar plasma etching was performed at a pressure of 5Pa for 10 minutes to improve the adhesion of the thin film. A high-purity copper target (purity 99.9%) and argon gas were used in the deposition process, and the pressure in the vacuum chamber was adjusted to 0.5 Pa. Sputtering was carried out for 20 minutes under the conditions of Ar flow rate of 40sccm and current of 0.25A so that sputtered copper clusters were deposited on the textile surface to produce a copper-coated polymer fabric film.
(3) Respectively using dilute H2SO4The resulting copper coated polymer fabric film was washed with deionized water and acetone (5 vol%). Next, in order to grow Cu (OH) on the copper-coated polymer fabric film2Nanowires, a copper-coated polymer fabric film was placed in 200mL of a mixed solution (NaOH solution and persulfuric acid) containing NaOH (2.5M) and ammonium persulfate (0.13M) at room temperature (25 ℃ C.)The mixing volume ratio of the ammonium solution is 100: 100) soaking for 25min, and performing Cu (OH)2And (4) nanowire growth reaction. After the reaction is finished, Cu (OH) is grown on the surface of the silicon substrate2Thin film of polymer fabric of nanowires, and thoroughly rinsed with deionized water grown with Cu (OH)2Cu (OH) grown on polymer fabric film of nanowires2A nanowire.
(4) Will grow Cu (OH)2The polymer fabric film of nanowires was immersed in deionized water and DMF (v/v ═ 90mL:9mL), 170mg HHTP was added to the petri dish, and then placed in an oven at 90 ℃ to preheat for 30 minutes. And after naturally cooling to room temperature, thoroughly washing the obtained sample with acetone to obtain the super-hydrophilic copper-based MOF photo-thermal material.
The contact angle test of the super-hydrophilic copper-based MOF photo-thermal material is carried out by adopting a video optical contact angle instrument, the contact angle of the super-hydrophilic copper-based MOF photo-thermal material with water is known to be 20 degrees, the light absorption performance test is carried out by adopting an ultraviolet-near infrared spectrophotometer (Carry 5000) instrument, the broadband light absorption rate of the super-hydrophilic copper-based MOF photo-thermal material in the solar radiation range is known to be 93 percent, the mass loss test is carried out by adopting a microbalance (AR224CN) instrument, and the water evaporation rate of the super-hydrophilic copper-based MO-2·h-1。
Salt resistance performance test of the Cu-based MOF photothermal textile prepared by the specific embodiment is carried out for 3-12 hours, and under the condition that the salinity is 9.5 wt%, salt accumulation is not observed on the upper surface of the Cu-based MOF photothermal textile within a time of more than 12 hours.
The specific implementation method six:
(1) the commercial polyester fabric is first cut to the desired size (e.g., 21 cm)-2) And then washed with deionized water and acetone solution to clean the polyester fabric.
(2) The cleaned polyester fabric was placed in a magnetron sputtering vacuum chamber. Selecting DC power supply as sputtering source, and pumping the vacuum degree of the sputtering chamber to 9.0 × 10 by mechanical pump and molecular pump-4Pa, and then Ar plasma etching was performed at a pressure of 5Pa for 10 minutes to improve the adhesion of the thin film. A high-purity copper target (purity 99.9%) and argon gas were used in the deposition process, and the pressure in the vacuum chamber was adjusted to 0.5 Pa. At an Ar flow rate of 40sccm and a current of 0.25A for 20 minutes so that sputtered copper clusters are deposited on the textile surface to produce a copper coated polymeric fabric film.
(3) Respectively using dilute H2SO4The resulting copper coated polymer fabric film was washed with deionized water and acetone (5 vol%). Next, in order to grow Cu (OH) on the copper-coated polymer fabric film2Nanowires, a copper-coated polymer fabric film was immersed in 200mL of a mixed solution (mixed volume ratio of NaOH solution and ammonium persulfate solution 100: 100) containing NaOH (2.5M) and ammonium persulfate (0.13M) at room temperature (35 ℃ C.) for 15min, and Cu (OH) was performed2And (4) nanowire growth reaction. After the reaction is finished, Cu (OH) is grown on the surface of the silicon substrate2Thin film of polymer fabric of nanowires, and thoroughly rinsed with deionized water grown with Cu (OH)2Cu (OH) grown on polymer fabric film of nanowires2A nanowire.
(4) Will grow Cu (OH)2The polymer fabric film of nanowires was immersed in deionized water and DMF (v/v ═ 100mL:10mL), and 170mg HHTP was added to the petri dish, which was then placed in an oven at 70 ℃ and preheated for 35 minutes. And after naturally cooling to room temperature, thoroughly washing the obtained sample with acetone to obtain the super-hydrophilic copper-based MOF photo-thermal material.
The contact angle test of the super-hydrophilic copper-based MOF photo-thermal material is carried out by adopting a video optical contact angle instrument, the contact angle of the super-hydrophilic copper-based MOF photo-thermal material with water is 10 degrees, the light absorption performance test is carried out by adopting an ultraviolet-near infrared spectrophotometer (Carry 5000) instrument, the broadband light absorption rate of the super-hydrophilic copper-based MOF photo-thermal material in the solar radiation range is 91.5 percent, the mass loss test is carried out by adopting a microbalance (AR224CN) instrument, and the water evaporation rate of the super-hydrophilic copper-based MOF photo-thermal material is-2·h-1。
Salt resistance performance test of the Cu-based MOF photothermal textile prepared by the specific embodiment is carried out for 3-12 hours, and under the condition that the salinity is 9.5 wt%, salt accumulation is not observed on the upper surface of the Cu-based MOF photothermal textile within a time of more than 12 hours.
The invention is described in further detail below with reference to the accompanying drawings:
as in FIG. 1 (a)) As shown, the water droplets can be absorbed to the surface of the polyester fabric within 8s, with a contact angle of about 15 °. After surface treatment, the hydrophilicity of the super-hydrophilic copper-based MOF photothermal material is greatly improved, and water drops can rapidly spread on the surface and completely wet within 48ms (figure 1 (b)). Apparently, Cu (OH)2The nanometer wire framework enables the super-hydrophilic copper-based MOF photo-thermal material with the hierarchical structure to have excellent super-hydrophilicity.
Figure 2 is an SEM image of polyester textile before and after growing Cu-based MOF. As can be clearly seen from FIGS. 2(a) and 2(b), the superhydrophilic copper-based MOF photothermal material is uniformly and strongly coated on the fabric after the treatment.
As shown in FIG. 3, the light diffuse reflectance (Cu-MOF texture reflectance) and light transmittance (Cu-MOF texture transmittance) of the superhydrophilic copper-based MOF photothermal material decreased to nearly 2.95% and 1.15% respectively as Cu-MOF grows on the polyester textile. This is because the incident light in such a nanostructure undergoes multiple internal reflections, resulting in an increase in the optical path length of the incident light. As a result, the superhydrophilic copper-based MOF photothermal material has excellent broadband light absorption of up to 95.9% over the range of solar radiation (AM 1.5G weighting).
As shown in fig. 4, in order to quantitatively investigate the water evaporation rate of the superhydrophilic copper-based MOF photothermal material, the change in mass of water over time was recorded by an electronic balance. Thus, the photothermal conversion efficiency of our device was calculated indirectly. The super-hydrophilic copper-based MOF photo-thermal material has the evaporation rates of 1.52 kg.m for water (1 sun) and water (dark field) in one hour-2·h-1，0.33kg·m-2·h-1And 0.11kg · m-2·h-1。
As shown in FIG. 5, in order to quantify the mechanical stability of the superhydrophilic copper-based MOF photothermal material, weights of 500g, 600g, 1000g and 1100g were used to push and pull horizontally on the surface of the superhydrophilic copper-based MOF photothermal material, and it was found that the weights of 500g, 600g and 1000g did not significantly damage the surface of the material. Very little abrasive dust (abrasive dust) and scratches (scratch) were present at 1100g weight. Wherein, fig. 5(a) is 500g weight of horizontal push-pull on the surface of the superhydrophilic copper-based MOF photothermal material, fig. 5(b) is 600g weight of horizontal push-pull on the surface of the superhydrophilic copper-based MOF photothermal material, fig. 5(c) is 1100g weight of horizontal push-pull on the surface of the superhydrophilic copper-based MOF photothermal material, and fig. 5(d) is the surface of the material after 30 abrasion experiments, it can be seen that no significant abrasion is observed on the surface of the material.
In conclusion, the super-hydrophilic copper-based MOF photothermal material has excellent super-hydrophilicity and ultrahigh evaporation efficiency due to the unique metal organic porous carbon skeleton structure, and provides a brand-new photothermal conversion material for the solar-driven interface seawater desalination technology.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a super-hydrophilic copper-based MOF photo-thermal material is characterized in that a polymer fabric film is used as a substrate to carry out plasma etching treatment and deposition treatment to prepare a copper-coated polymer fabric film; subjecting the resulting copper-coated polymer fabric film to Cu (OH)2And (3) growing the nanowires, and then carrying out hydrothermal treatment to obtain the super-hydrophilic copper-based MOF photo-thermal material.
2. The preparation method of the superhydrophilic copper-based MOF photothermal material according to claim 1, specifically comprising the following steps:
1) depositing the sputtered copper clusters on the polymer fabric film etched by the argon plasma by adopting a magnetron sputtering technology to prepare a copper-coated polymer fabric film;
2) washing the copper-coated polymer fabric film obtained in the step 1), and then placing the film in a mixed solution containing NaOH and ammonium persulfate to carry out Cu (OH)2Nanowire growth reaction, and rinsing after the reaction is finished to obtain the product with Cu (OH)2A polymer fabric film of nanowires;
3) subjecting the product of step 2)To grow Cu (OH)2And immersing the polymer fabric film of the nanowires into a solution containing hexahydroxy benzophenanthrene for hydrothermal treatment, and cooling and cleaning after the treatment is finished to prepare the super-hydrophilic copper-based MOF photothermal material.
3. The method for preparing the superhydrophilic copper-based MOF photothermal material according to claim 2, wherein in the step 1), the plasma etching comprises the following operations: performing argon plasma etching under the pressure of 5Pa for 10-20 minutes.
4. The preparation method of the superhydrophilic copper-based MOF photothermal material according to claim 2, wherein in the step 2), the mixed solution is prepared by mixing a 2.5mol/L NaOH solution and a 0.13mol/L ammonium persulfate solution; wherein the mixing volume ratio of the NaOH solution to the ammonium persulfate solution is 80-100: 80-100 parts.
5. The method for preparing the superhydrophilic copper-based MOF photothermal material according to claim 2, wherein in the step 2), Cu (OH)2The temperature of the nanowire growth reaction is 20-35 ℃, and the time is 15-30 min.
6. The preparation method of the superhydrophilic copper-based MOF photothermal material according to claim 2, wherein in step 3), the solution containing hexahydroxytriphenylene comprises water, DMF and hexahydroxytriphenylene, and the mixing ratio of water, DMF and hexahydroxytriphenylene is 80-120 mL: 8-12 mL: 170-200 mg.
7. The method for preparing the superhydrophilic copper-based MOF photothermal material according to claim 2, wherein in step 3), the operational parameters of the hydrothermal treatment comprise: the temperature is 70-100 ℃, the preheating time is 30-40 minutes, and the air-cooled water is naturally cooled after preheating.
8. The super-hydrophilic copper-based MOF photothermal material prepared by the preparation method of any one of claims 1-7.
9. The superhydrophilic copper-based MOF photothermal material according to claim 8, wherein the contact angle of the superhydrophilic copper-based MOF photothermal material with water is 0-20 degrees, the broadband light absorption rate in the solar radiation range is 90-95.9%, and the water evaporation rate is 1.34-1.52 kg-m-2·h-1。
10. Use of a superhydrophilic copper-based MOF photothermal material of claim 8 for making a portable solar evaporator.
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