CN115449876A - Gradient wetting copper-nickel multilayer composite material and preparation method and application thereof - Google Patents

Gradient wetting copper-nickel multilayer composite material and preparation method and application thereof Download PDF

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Publication number
CN115449876A
CN115449876A CN202211415794.9A CN202211415794A CN115449876A CN 115449876 A CN115449876 A CN 115449876A CN 202211415794 A CN202211415794 A CN 202211415794A CN 115449876 A CN115449876 A CN 115449876A
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copper
nickel
foam block
metal foam
composite material
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CN115449876B (en
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朱丽静
曾志翔
马付良
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • 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
    • 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
    • C02F1/048—Purification of waste water by evaporation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • 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
    • 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
    • Y02A20/138—Water desalination using renewable energy
    • Y02A20/142—Solar thermal; Photovoltaics
    • 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

Abstract

The invention discloses a gradient wetting copper-nickel multilayer composite material and a preparation method and application thereof. The gradient wetting copper-nickel multilayer composite material comprises a metal foam block wrapped by a super-hydrophilic copper-nickel coating which is sequentially stacked in the thickness direction, a hydrophobic polyolefin salt-resistant anticorrosive layer and a hydrophobic photo-thermal evaporation layer with a micro-nano structure. The preparation method comprises the following steps: and (2) electrodepositing a porous copper coating on the metal foam block to form a metal foam block wrapped by the super-hydrophilic copper-nickel coating, then depositing a hydrophobic polyolefin salt-resistant anticorrosive layer, and finally generating a hydrophobic photo-thermal evaporation layer with a micro-nano structure to prepare the gradient-wetting copper-nickel multilayer composite material. The functional layers of the gradient wetting copper-nickel multilayer composite material provided by the invention have complementary advantages and multifunctional coupling, so that the gradient wetting multilayer composite material from bottom to top is obtained, and the gradient wetting multilayer composite material can be used in the fields of photo-thermal seawater desalination, photo-thermal sewage purification and the like.

Description

Gradient wetting copper-nickel multilayer composite material and preparation method and application thereof
Technical Field
The invention relates to a composite material, in particular to a gradient wetting copper-nickel multilayer composite material and a preparation method and application thereof, belonging to the technical field of functional materials.
Background
The metal foam is a novel three-dimensional porous material, has the advantages of high porosity, large specific surface area, good mechanical strength and the like, and has strong application strength in the fields of sewage treatment, photo-thermal seawater desalination and the like when being used as an adsorption material, a filtering material, a heat dissipation material and the like. The photothermal seawater desalination utilizes the heat energy converted from solar energy to obtain purified water from seawater and sewage, and is a promising water purification technology for solving the shortage of clean water resources. In the field of photo-thermal seawater desalination, the metal foam material has high heat conductivity coefficient, can quickly convert solar energy into heat energy, promotes the quick evaporation of water molecules, and improves the seawater desalination capacity. However, when the hydrophilic metal foam is directly used for the photothermal seawater desalination, inorganic salts in seawater are transmitted to the photothermal evaporation layer along with water molecules, and after water is evaporated, the inorganic salts are deposited and hardened on the surface of the photothermal conversion material, so that the photothermal conversion rate is reduced. In addition, the metal foam is easy to corrode when used in a high-salt environment, so that the mechanical stability and the service life of the photothermal conversion material are reduced.
Disclosure of Invention
The invention mainly aims to provide a gradient wetting copper-nickel multilayer composite material to overcome the defects in the prior art.
The invention also aims to provide a preparation method of the corresponding gradient wetting copper-nickel multilayer composite material.
The invention also aims to provide application of the gradient wetting copper-nickel multilayer composite material.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a gradient wetting copper-nickel multilayer composite material which comprises a metal foam block wrapped by a super-hydrophilic copper-nickel coating, a hydrophobic polyolefin salt-resistant anticorrosive layer and a hydrophobic photo-thermal evaporation layer with a micro-nano structure, wherein the metal foam block, the hydrophobic polyolefin salt-resistant anticorrosive layer and the hydrophobic photo-thermal evaporation layer are sequentially stacked in the thickness direction.
The embodiment of the invention also provides a preparation method of the gradient wetting copper-nickel multilayer composite material, which comprises the following steps:
(1) Mixing nickel salt, sulfur-containing organic matter, complexing agent and surfactant to obtain sulfur-containing nickel electroplating solution;
a metal foam block is used as a first anode, and a first electrochemical working system is constructed by the first anode, a first cathode and a sulfur-containing nickel electroplating solution; electrifying the first electrochemical working system, carrying out a first electrodeposition reaction, and depositing a sulfur-containing nickel coating on the metal foam block to obtain a metal foam block wrapped by the sulfur-containing nickel coating;
(2) The metal foam block wrapped by the sulfur-containing nickel plating layer is used as a second anode, and a second electrochemical working system is constructed by the second anode, a second cathode and the copper electroplating solution; electrifying the second electrochemical working system, carrying out a second electrodeposition reaction to generate a porous copper plating layer, and sintering to obtain a metal foam block wrapped by the super-hydrophilic copper-nickel plating layer;
(3) Depositing a hydrophobic polyolefin salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel plating layer to obtain a gradient-wetting metal foam block;
(4) And (3) immersing the gradient wetting metal foam block into water, immersing into a mixed solution consisting of a nano material, bismuth oxyiodide micro-particles, PDMS (polydimethylsiloxane), a curing agent and an organic solvent, soaking, and finally performing thermocuring to generate a hydrophobic photo-thermal evaporation layer with a micro-nano structure, thereby obtaining the gradient wetting copper-nickel multilayer composite material.
The embodiment of the invention also provides the gradient wetting copper-nickel multilayer composite material prepared by the method.
The embodiment of the invention also provides application of the gradient wetting copper-nickel multilayer composite material in the fields of photo-thermal seawater desalination, photo-thermal sewage purification and the like.
Compared with the prior art, the invention has the beneficial effects that:
1) The advantages of the functional layers of the gradient wetting copper-nickel multilayer composite material are complementary to each other, so that the gradient wetting multilayer composite material from bottom to top is formed, and the gradient wetting copper-nickel multilayer composite material can be used in the field of photo-thermal seawater desalination/photo-thermal sewage purification;
2) The metal foam block wrapped by the super-hydrophilic copper-nickel coating has high porosity and good hydrophilicity, and can quickly supply water molecules for the photo-thermal evaporation layer; the mechanical strength is good, the chemical stability is excellent, and the service life of the composite material is long;
3) The hydrophobic polyolefin salt-resistant anticorrosive layer can prevent excessive moisture from being transmitted to the photo-thermal evaporation layer, effectively prevent the formation of a water film on the photo-thermal evaporation layer and the loss of photo-thermal, inhibit the accumulation of salt on the photo-thermal evaporation layer and reduce the corrosion of the salt on a metal foam block wrapped by the super-hydrophilic copper-nickel coating;
4) The hydrophobic photo-thermal evaporation layer contains nano materials with micro-nano structures, has strong light absorption capacity and photo-thermal conversion capacity, and the advantages of all functional layers are complementary and multifunctional coupled to obtain the high-performance composite material with the gradient wetting characteristic.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural view of a gradient-wetting copper-nickel multilayer composite in an exemplary embodiment of the invention;
FIG. 2 is an SEM picture of the upper surface of a gradient wetting copper nickel multilayer composite material prepared by the example 3 of the invention;
FIG. 3 is a photograph of the contact angle of the upper surface of the gradient wetting copper nickel multilayer composite material prepared in example 3 of the present invention with water;
fig. 4 is a picture of the contact angle of the lower surface of the gradient wetting copper-nickel multilayer composite material prepared in example 3 of the present invention with water.
Detailed Description
In view of the problems in the prior art, the inventor of the present invention has proposed the technical solution through long-term research and numerous experiments, and further explains the technical solution, the implementation process and principles thereof, and the like as follows.
As one aspect of the technical solution of the present invention, please refer to fig. 1, which relates to a gradient wetting copper-nickel multilayer composite material, including a metal foam block 1 wrapped by a super-hydrophilic copper-nickel plating layer, a hydrophobic polyolefin salt-resistant anticorrosive layer 2, and a hydrophobic photothermal evaporation layer 3 having a micro-nano structure, which are sequentially stacked in a thickness direction.
Further, the gradient wetting copper-nickel multilayer composite material comprises 3 layers from bottom to top, namely a metal foam block body 1 wrapped by a super-hydrophilic copper-nickel coating, and a hydrophobic polyolefin salt-resistant anticorrosive layer 2 and a hydrophobic photothermal evaporation layer 3 with a micro-nano structure, which are sequentially covered on the metal foam block body 1 wrapped by the super-hydrophilic copper-nickel coating. According to the invention, the metal foam block wrapped by the super-hydrophilic copper-nickel coating has high porosity and good hydrophilicity, and can rapidly supply water molecules for the photo-thermal evaporation layer; the mechanical strength is good, the chemical stability is excellent, and the service life of the composite material is long; the hydrophobic polyolefin salt-resistant anticorrosive layer prevents excessive moisture from being transmitted to the photo-thermal evaporation layer, effectively prevents the formation of a water film on the photo-thermal evaporation layer and the loss of photo-thermal, and inhibits the accumulation of salt on the photo-thermal evaporation layer; the hydrophobic photo-thermal evaporation layer contains nano materials with micro-nano structures and has strong light absorption capacity and photo-thermal conversion capacity.
As another aspect of the technical scheme of the invention, the invention also relates to a preparation method of the gradient wetting copper-nickel multilayer composite material, which mainly utilizes an electrochemical technology to wrap a super-hydrophilic copper-nickel plating layer on a metal foam framework so as to improve the seawater corrosion resistance and the seawater transmission rate of the metal foam framework; an ultrathin hydrophobic polyolefin salt-resistant anticorrosive layer is constructed, and the problems of salting out and hardening are solved; and finally, a hydrophobic photo-thermal evaporation layer containing nano materials with a micro-nano structure is constructed, so that the light absorption capacity and the photo-thermal conversion capacity are improved.
In some embodiments, the method of making the gradient wetting copper nickel multilayer composite comprises the steps of:
(1) Mixing nickel salt, sulfur-containing organic matter, complexing agent and surfactant to obtain sulfur-containing nickel electroplating solution;
a metal foam block is used as a first anode, and a first electrochemical working system is constructed by the first anode, a first cathode and the sulfur-containing nickel electroplating solution; electrifying the first electrochemical working system, carrying out a first electrodeposition reaction, and depositing on the metal foam block to form a sulfur-containing nickel coating to prepare a metal foam block wrapped by the sulfur-containing nickel coating;
(2) A metal foam block wrapped by the sulfur-containing nickel plating layer is used as a second anode, and a second electrochemical working system is constructed by the second anode, a second cathode and the copper electroplating solution; electrifying the second electrochemical working system, carrying out a second electrodeposition reaction to generate a porous copper plating layer, and sintering to obtain a metal foam block wrapped by the super-hydrophilic copper-nickel plating layer;
(3) Depositing a hydrophobic polyolefin salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel plating layer to obtain a gradient-wetting metal foam block;
(4) And (3) immersing the gradient wetting metal foam block into water, immersing into a mixed solution composed of a nano material, bismuth oxyiodide micron particles, PDMS, a curing agent and an organic solvent, and finally performing thermocuring to generate a hydrophobic photo-thermal evaporation layer with a micro-nano structure, thereby obtaining the gradient wetting copper-nickel multilayer composite material.
In some embodiments, in step (1), the sulfur-containing nickel electroplating solution comprises 5 to 25wt% of nickel salt, 1 to 5wt% of sulfur-containing organic matter, 0.05 to 11wt% of complexing agent and 0.01 to 3wt% of surfactant.
In some embodiments, in step (1), the nickel salt includes any one of nickel sulfate, nickel chloride, and the like, or a combination of both, but is not limited thereto.
Further, the sulfur-containing organic substance includes any one or a combination of two or more of benzenesulfonic acid, ethylenethiourea, benzoylsulfonimide, and the like, but is not limited thereto.
Further, the complexing agent includes any one or a combination of two of boric acid and citric acid, etc., but is not limited thereto.
Further, the surfactant includes any one or a combination of two or more of sodium dodecyl sulfate, behenyl trimethyl ammonium chloride, and ethyl hexyl sodium sulfate, etc., but is not limited thereto.
Further, the material of the metal foam block comprises at least one of nickel, copper and the like.
In some embodiments, in step (1), the process conditions of the first electrodeposition reaction include: the current density is 1 to 10A/dm 2 The temperature of the first electrodeposition reaction is 30 to 60 ℃, and the time is 1 to 100h.
Further, the first cathode may be a nickel plate, but is not limited thereto.
In some embodiments, in step (2), the copper electroplating solution comprises 10 to 30wt% copper salt, 1 to 10wt% acid and 0.5 to 10wt% inorganic salt.
Further, the copper salt includes any one or a combination of two of copper sulfate, copper chloride, and the like, but is not limited thereto.
Further, the acid includes any one or a combination of two of sulfuric acid, hydrochloric acid, and the like, but is not limited thereto.
Further, the inorganic salt includes any one or a combination of two of sodium chloride, potassium chloride, and the like, but is not limited thereto.
In some embodiments, in step (2), the process conditions of the second electrodeposition reaction include: the current density is 0.5 to 10A/dm 2 The temperature of the second electrodeposition reaction is 30 to 60 ℃, and the time is 0.1 to 2h.
In some embodiments, in the step (2), the sintering temperature is 200 to 600 ℃ and the sintering time is 0.5 to 24h.
Further, the second cathode may be a copper sheet, but is not limited thereto.
In some embodiments, the pore diameter of pores contained in the porous copper plating layer is 0.01 to 100 μm, and the porosity is 10 to 90%.
In some embodiments, step (3) specifically comprises:
depositing a hydrophobic polyolefin salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel coating by adopting a low-temperature plasma technology to obtain a gradient-wetted metal foam block; wherein the helium gas flow rate is 100 to 200sccm, the olefin gas flow rate is 10 to 100sccm, the pressure is 10 to 1000mToor, the duty ratio is 10 to 100 percent, the power is 40 to 80W, and the reaction time is 10 to 180min.
Further, the olefin gas may include any one or a combination of two or more of ethylene, propylene, vinyl chloride, and the like, but is not limited thereto.
In some embodiments, step (4) specifically comprises:
soaking the gradient wetting metal foam block in water for 10 to 30min, and taking out; and then soaking the mixture into a mixed solution consisting of 0.1 to 10wt% of a nano material, 0.1 to 10wt% of bismuth oxyiodide micron particles, 0.1 to 10wt% of PDMS, 0.01 to 2wt% of a curing agent and an organic solvent for 1 to 30min, taking out the mixture, and finally performing thermal curing at 50 to 120 ℃ for 10 to 300min to generate the hydrophobic photothermal evaporation layer with the micro-nano structure.
In some embodiments, in step (4), the bismuth oxyiodide microparticles have a particle size of 0.1 to 5 μm.
Furthermore, the nano material comprises at least one of zero-dimensional nano particles, two-dimensional reduced graphene oxide and one-dimensional carbon nanotubes, and a micro-nano structure, namely a multi-stage structure, is formed. Specifically, the nano material comprises any one or a combination of more than two of ferroferric oxide nano particles with the particle size of 10 to 100nm, reduced graphene oxide with the diameter of 100nm to 5 mu m and the number of layers of 1~8, carbon nano tubes with the diameter of 2 to 50nm and the like, but the nano material is not limited to the above.
Further, the organic solvent may include any one or a combination of two or more of chloroform, n-hexane, ethyl acetate, and the like, but is not limited thereto.
As a more specific embodiment, the preparation method of the gradient wetting copper-nickel multilayer composite material can comprise the following steps:
(1) Immersing the pretreated metal foam block and the nickel sheet into the sulfur-containing nickel electroplating solution A to form an electrochemical working system with the metal foam block as an anode and the nickel sheet as a cathode; the power supply is switched on, and the current density is applied between the anode and the cathode within 1 to 10A/dm 2 Carrying out electrodeposition reaction at 30 to 60 ℃ for 1 to 100 hours to obtain the metal wrapped by the sulfur-containing nickel plating layerA foam block; the sulfur-containing nickel electroplating solution A comprises 5 to 25wt% of nickel salt, 1 to 5wt% of sulfur-containing organic matter, 0.05 to 11wt% of complexing agent and 0.01 to 3wt% of surfactant;
(2) Immersing the metal foam block wrapped by the sulfur-containing nickel plating layer prepared in the step (1) and a copper sheet into a copper electroplating solution B to form an electrochemical working system taking the metal foam block wrapped by the sulfur-containing nickel plating layer as an anode and the copper sheet as a cathode; the power supply is switched on, and the current density is applied between the anode and the cathode within 0.5-10A/dm 2 Carrying out reduction current, and carrying out electrodeposition reaction at 30-60 ℃ for 0.1-2 hours to generate a porous copper plating layer; sintering at 200 to 600 ℃ to obtain a metal foam block wrapped by the super-hydrophilic copper-nickel plating layer; the copper electroplating solution B comprises 10 to 30wt% of copper salt, 1 to 10wt% of acid and 0.5 to 10wt% of inorganic salt;
(3) Depositing a hydrophobic polyolefin salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel plating layer by using a low-temperature plasma technology to obtain a gradient-wetting metal foam block; wherein the helium gas flow rate is 100 to 200sccm, the olefin gas flow rate is 10 to 100sccm, the pressure is 10 to 1000mToor, the duty ratio is 10 to 100 percent, the power is 40 to 80W, and the reaction time is 10 to 180 minutes;
(4) Soaking the gradient wetting metal foam block prepared in the step (3) in water for 10 to 30 minutes, taking out, and wiping off excessive water; then soaking the mixture into a mixed solution consisting of 0.1 to 10wt% of nano material, 0.1 to 10wt% of bismuth oxyiodide micron particles, 0.1 to 10wt% of PDMS, 0.01 to 2wt% of curing agent and an organic solvent for 1 to 30 minutes, taking out the mixture, and carrying out thermal curing at 50 to 120 ℃ for 10 to 300 minutes to generate a hydrophobic photothermal evaporation layer with a micro-nano structure; the particle size of the bismuth oxyiodide micron particles is 0.1 to 5 mu m; the nano material comprises ferroferric oxide nano particles with the particle size of 10-100nm, reduced graphene oxide with the diameter of 100nm-5 mu m and a 1~8 layer, and any one or combination of more than two of carbon nano tubes with the diameter of 2-50nm.
In conclusion, the invention takes the metal foam block as a carrier, a super-hydrophilic copper-nickel coating is electroplated on the carrier layer through an electrodeposition technology, a low-temperature plasma technology is utilized to deposit a hydrophobic polyolefin salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel coating, and finally a hydrophobic photothermal evaporation layer with a micro-nano structure is prepared through a solution dip coating method.
As another aspect of the technical solution of the present invention, it also relates to a gradient wetting copper nickel multilayer composite material prepared by the foregoing method.
In some embodiments, the gradient wetting copper-nickel multilayer composite material comprises a metal foam block wrapped by a super-hydrophilic copper-nickel plating layer, a hydrophobic polyolefin salt-resistant anticorrosive layer and a hydrophobic photothermal evaporation layer with a micro-nano structure, which are sequentially stacked in the thickness direction.
Further, the thickness of the super-hydrophilic copper-nickel plating layer is 0.1 to 300 mu m, and the porosity is 50 to 85%.
Further, the thickness of the hydrophobic polyolefin salt-resistant anticorrosive layer is 0.05 to 50 mu m.
Further, the thickness of the hydrophobic photothermal evaporation layer with the micro-nano structure is 0.1 to 800 mu m.
Further, the contact angle between the upper surface of the gradient wetting copper-nickel multilayer composite material and water is 151-157 degrees, the contact angle between the lower surface of the gradient wetting copper-nickel multilayer composite material and water is 0 degree, and the water evaporation rate is 2.5-2.9 kg m under the condition of simulated sunlight illumination -2 h -1 The photothermal conversion efficiency is 91 to 95%.
The embodiment of the invention also provides application of the gradient wetting copper-nickel multilayer composite material in the fields of photo-thermal seawater desalination or photo-thermal sewage purification and the like.
By the technical scheme, the advantages of the functional layers of the gradient wetting copper-nickel multilayer composite material are complementary, the gradient wetting multilayer composite material from bottom to top is formed, and the gradient wetting copper-nickel multilayer composite material can be used in the field of photo-thermal seawater desalination/photo-thermal sewage purification.
The technical solution of the present invention is explained in more detail below with reference to several preferred embodiments and the accompanying drawings. The specific examples set forth below are presented only to further illustrate and explain the present invention and are not intended to be limiting; all variations that may be suggested or derived from the present disclosure are to be considered within the scope of the present invention.
Example 1
(1) Immersing the nickel foam block and the nickel sheet which are subjected to pretreatment into the sulfur-containing nickel electroplating solution A to form an electrochemical working system with the metal foam block as an anode and the nickel sheet as a cathode; switching on the power supply, and applying a current density of 1A/dm between the anode and the cathode 2 Carrying out electrodeposition reaction at 30 ℃ for 100 hours to obtain a metal foam block wrapped by a sulfur-containing nickel plating layer; the sulfur-containing nickel electroplating solution A comprises 5wt% of nickel sulfate, 1wt% of benzenesulfonic acid, 0.05wt% of boric acid and 0.01wt% of sodium dodecyl sulfate;
(2) Immersing the metal foam block wrapped by the sulfur-containing nickel plating layer prepared in the step (1) and a copper sheet into a copper electroplating solution B to form an electrochemical working system taking the metal foam block wrapped by the sulfur-containing nickel plating layer as an anode and the copper sheet as a cathode; switching on the power supply, and applying a current density of 10A/dm between the anode and the cathode 2 Reducing current, and carrying out electrodeposition reaction at 60 ℃ for 0.1 hour to generate a porous copper coating; sintering at 200 ℃ for 24 hours to obtain a metal foam block wrapped by the super-hydrophilic copper-nickel plating layer; the copper electroplating solution B comprises 10wt% of copper sulfate, 1wt% of sulfuric acid and 0.5wt% of sodium chloride;
(3) Depositing a hydrophobic polyethylene salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel plating layer by using a low-temperature plasma technology to obtain a gradient-wetting metal foam block; wherein the helium gas flow rate is 100sccm, the ethylene gas flow rate is 10sccm, the pressure is 10mToor, the duty ratio is 10%, the power is 40W, and the reaction time is 180 minutes;
(4) Immersing the gradient wetting nickel foam block prepared in the step (3) into water, taking out after soaking for 10 minutes, and removing excessive water; then immersing the mixture into a mixed solution consisting of 0.1wt% of ferroferric oxide nano particles (the particle diameter is 10 nm), 10wt% of bismuth oxyiodide micro particles (the particle diameter is 0.1 mu m), 0.1wt% of PDMS, 0.01wt% of curing agent and chloroform, taking out after soaking for 30 minutes, and carrying out heat curing at 50 ℃ for 10 minutes to generate a hydrophobic photo-thermal evaporation layer with a micro-nano structure.
Upon testing, the composites prepared in this exampleThe water contact angle of the upper surface of the material is 152 degrees, and the water contact angle of the lower surface of the material is 0 degree; under the condition of simulating sunlight illumination, the water evaporation rate is 2.5 kg m -2 h -1 And the photothermal conversion efficiency was 91%.
Example 2
(1) Immersing the pretreated copper foam block and the nickel sheet into the sulfur-containing nickel electroplating solution A to form an electrochemical working system with the metal foam block as an anode and the nickel sheet as a cathode; switching on the power supply, and applying a current density of 10A/dm between the anode and the cathode 2 Carrying out electrodeposition reaction at 60 ℃ for 1 hour to obtain a metal foam block wrapped by the sulfur-containing nickel plating layer; the sulfur-containing nickel electroplating solution A comprises 25wt% of nickel chloride, 5wt% of ethylene thiourea, 11wt% of citric acid and 3wt% of behenyl trimethyl ammonium chloride;
(2) Immersing the metal foam block wrapped by the sulfur-containing nickel plating layer prepared in the step (1) and a copper sheet into a copper electroplating solution B to form an electrochemical working system taking the metal foam block wrapped by the sulfur-containing nickel plating layer as an anode and the copper sheet as a cathode; powering on, and applying a current density of 0.5A/dm between the anode and the cathode 2 Carrying out reduction current and carrying out electrodeposition reaction at 30 ℃ for 2 hours to generate a porous copper coating; sintering at 600 ℃ for 0.5h to obtain a metal foam block wrapped by the super-hydrophilic copper-nickel plating layer; the copper electroplating solution B comprises 30wt% of copper chloride, 10wt% of hydrochloric acid and 10wt% of potassium chloride;
(3) Depositing a hydrophobic polyvinyl chloride salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel plating layer by using a low-temperature plasma technology to obtain a gradient-wetting metal foam block; wherein the helium gas flow rate is 200sccm, the chloroethylene gas flow rate is 100sccm, the pressure is 1000mToor, the duty ratio is 100%, the power is 80W, and the reaction time is 10 minutes;
(4) Soaking the gradient wetting copper foam block prepared in the step (3) in water for 30 minutes, taking out, and removing excessive water; then immersing the membrane into a mixed solution consisting of 10wt% of reduced graphene oxide (the diameter is 100nm, the number of layers is 1), 0.1wt% of bismuth oxyiodide microparticles (the particle size is 5 mu m), 10wt% PDMS, 2wt% of curing agent and ethyl acetate, taking out after soaking for 1 minute, and thermally curing at 120 ℃ for 300 minutes to generate a hydrophobic photo-thermal evaporation layer with a micro-nano structure.
Through testing, the water contact angle of the upper surface of the composite material prepared by the embodiment is 157 degrees, and the water contact angle of the lower surface of the composite material is 0 degree; under the condition of simulated sunlight illumination, the water evaporation rate is 2.8 kg m -2 h -1 And the photothermal conversion efficiency was 94%.
Example 3
(1) Immersing the pretreated copper foam block and the nickel sheet into the sulfur-containing nickel electroplating solution A to form an electrochemical working system with the metal foam block as an anode and the nickel sheet as a cathode; switching on the power supply, and applying a current density of 2A/dm between the anode and the cathode 2 Carrying out electrodeposition reaction at 50 ℃ for 48 hours to obtain a metal foam block wrapped by the sulfur-containing nickel plating layer; the sulfur-containing nickel electroplating solution A comprises 15wt% of nickel sulfate, 2wt% of benzoylsulfimide, 1wt% of boric acid and 1wt% of sodium ethylhexyl sulfate;
(2) Immersing the metal foam block wrapped by the sulfur-containing nickel plating layer prepared in the step (1) and a copper sheet into a copper electroplating solution B to form an electrochemical working system taking the metal foam block wrapped by the sulfur-containing nickel plating layer as an anode and the copper sheet as a cathode; switching on the power supply, and applying a current density of 3A/dm between the anode and the cathode 2 Reducing current, and carrying out electrodeposition reaction at 40 ℃ for 0.5 hour to generate a porous copper coating; sintering for 2h at 450 ℃ to obtain a metal foam block wrapped by the super-hydrophilic copper-nickel plating layer; the copper electroplating solution B comprises 15wt% of copper sulfate, 5wt% of sulfuric acid and 4wt% of sodium chloride;
(3) Depositing a hydrophobic polypropylene salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel plating layer by using a low-temperature plasma technology to obtain a gradient-wetting metal foam block; wherein the helium gas flow rate is 150sccm, the propylene gas flow rate is 40sccm, the pressure is 600mToor, the duty ratio is 60%, the power is 60W, and the reaction time is 90 minutes;
(4) Soaking the gradient wetting copper foam block prepared in the step (3) in water for 20 minutes, taking out, and removing excessive water; immersing into a mixed solution consisting of 2wt% of carbon nanotubes (the diameter is 2 nm), 2wt% of bismuth oxyiodide particles (the particle size is 2 mu m), 2wt% of PDMS, 0.03wt% of curing agent and chloroform, taking out after soaking for 15 minutes, and carrying out thermal curing at 80 ℃ for 120 minutes to generate a hydrophobic photothermal evaporation layer with a micro-nano structure.
Through testing, the water contact angle of the upper surface of the composite material prepared by the embodiment is 151 degrees, and the water contact angle of the lower surface of the composite material is 0 degree; under the condition of simulated sunlight illumination, the water evaporation rate is 2.9 kg m -2 h -1 And the photothermal conversion efficiency was 95%.
Example 4
(1) Immersing the pretreated copper foam block and the nickel sheet into the sulfur-containing nickel electroplating solution A to form an electrochemical working system with the metal foam block as an anode and the nickel sheet as a cathode; switching on the power supply, and applying a current density of 2A/dm between the anode and the cathode 2 Carrying out electrodeposition reaction at 50 ℃ for 48 hours to obtain a metal foam block wrapped by the sulfur-containing nickel plating layer; the sulfur-containing nickel electroplating solution A comprises 10wt% of nickel sulfate, 3wt% of benzoylsulfimide, 5wt% of boric acid and 2wt% of sodium ethylhexyl sulfate;
(2) Immersing the metal foam block wrapped by the sulfur-containing nickel plating layer prepared in the step (1) and a copper sheet into a copper electroplating solution B to form an electrochemical working system taking the metal foam block wrapped by the sulfur-containing nickel plating layer as an anode and the copper sheet as a cathode; switching on the power supply, and applying a current density of 3A/dm between the anode and the cathode 2 Reducing current, and carrying out electrodeposition reaction at 40 ℃ for 0.5 hour to generate a porous copper coating; sintering at 350 ℃ for 12h to obtain a metal foam block wrapped by the super-hydrophilic copper-nickel plating layer; the copper electroplating solution B comprises 15wt% of copper sulfate, 5wt% of sulfuric acid and 4wt% of sodium chloride;
(3) Depositing a hydrophobic polypropylene salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel plating layer by using a low-temperature plasma technology to obtain a gradient-wetting metal foam block; wherein the helium gas flow rate is 180sccm, the propylene gas flow rate is 60sccm, the pressure is 500mToor, the duty ratio is 80%, the power is 50W, and the reaction time is 120 minutes;
(4) Soaking the gradient wetting copper foam block prepared in the step (3) in water for 20 minutes, taking out, and removing excessive water; then immersing the mixture into a mixed solution consisting of 0.1wt% of ferroferric oxide nano particles (the particle size is 100 nm), 10wt% of reduced graphene oxide (the diameter is 5 mu m, the number of layers is 8), 2wt% of carbon nano tubes (the diameter is 50 nm), 2wt% of bismuth oxyiodide particles (the particle size is 2 mu m), 2wt% of PDMS, 0.03wt% of curing agent and n-hexane, taking out after soaking for 15 minutes, and thermally curing at 80 ℃ for 120 minutes to generate a hydrophobic photo-thermal evaporation layer with a micro-nano structure.
Through testing, the water contact angle of the upper surface of the composite material prepared by the embodiment is 156 degrees, and the water contact angle of the lower surface of the composite material is 0 degree; under the condition of simulating sunlight illumination, the water evaporation rate is 2.7 kg m -2 h -1 And the photothermal conversion efficiency was 93%.
The inventors also take the gradient wetting copper-nickel multilayer composite material obtained in example 3 as an example, and characterize and test the gradient wetting copper-nickel multilayer composite material:
as shown in fig. 2, is an SEM picture of the upper surface of the gradient wetting copper nickel multilayer composite. The water contact angle of the gradient wetting copper-nickel multilayer composite material on the upper surface can be seen in fig. 3, and the water contact angle of the lower surface thereof on the lower surface can be seen in fig. 4.
Comparative example 1: this comparative example is essentially the same as example 3, except that: a sulfur-containing nickel plating layer is not formed.
The coating prepared by the comparative example lacks the sulfur-containing nickel coating, the adhesion force of the porous copper coating and the matrix is poor, and the complete composite material cannot be obtained.
Comparative example 2: this comparative example is essentially the same as example 3, except that: the super-hydrophilic porous copper plating layer is not constructed.
Through testing, the water contact angle of the upper surface of the composite material prepared in the comparative example is 155 degrees, and the water contact angle of the lower surface of the composite material is 105 degrees; under the condition of simulating sunlight illumination, the water evaporation rate is 0.3 kg m -2 h -1 The photothermal conversion efficiency was 12%.
Comparative example 3: this comparative example is essentially the same as example 3, except that: and a hydrophobic polyolefin salt-resistant anticorrosive layer is not constructed.
Through testing, the composite material prepared in the comparative example has a water contact angle of 113 degrees on the upper surface and water on the lower surfaceThe contact angle is 0 degree; under the condition of simulating sunlight illumination, the water evaporation rate is 0.4 kg m -2 h -1 The photothermal conversion efficiency was 17%.
Comparative example 4: this comparative example is essentially the same as example 3, except that: a hydrophobic photo-thermal evaporation layer with a micro-nano structure is not constructed.
Through testing, the water contact angle of the upper surface of the composite material prepared in the comparative example is 121 degrees, and the water contact angle of the lower surface of the composite material is 0 degree; under the condition of simulating sunlight illumination, the water evaporation rate is 0.2 kg m -2 h -1 And the photothermal conversion efficiency is 8%.
In addition, the inventor also refers to the mode of the embodiment 1 to the embodiment 4, and performs experiments by using other raw materials and conditions listed in the specification, and also prepares a metal foam block wrapped by the super-hydrophilic nickel-copper plating layer, a hydrophobic polyolefin salt-resistant anticorrosive layer and a hydrophobic photothermal evaporation layer with a micro-nano structure, and finally obtains the gradient wetting copper-nickel multilayer composite material.
It should be understood that the above is only a specific application example of the present invention, and the protection scope of the present invention is not limited in any way. The technical solutions formed by using equivalent transformation or equivalent substitution are all within the protection scope of the present invention.

Claims (10)

1. A preparation method of a gradient wetting copper-nickel multilayer composite material is characterized by comprising the following steps:
(1) Mixing nickel salt, sulfur-containing organic matter, complexing agent and surfactant to obtain sulfur-containing nickel electroplating solution;
a metal foam block is used as a first anode, and a first electrochemical working system is constructed by the first anode, a first cathode and the sulfur-containing nickel electroplating solution; electrifying the first electrochemical working system, carrying out a first electrodeposition reaction, and depositing on the metal foam block to form a sulfur-containing nickel coating to prepare a metal foam block wrapped by the sulfur-containing nickel coating;
(2) The metal foam block wrapped by the sulfur-containing nickel plating layer is used as a second anode, and a second electrochemical working system is constructed by the second anode, a second cathode and the copper electroplating solution; electrifying the second electrochemical working system, carrying out a second electrodeposition reaction to generate a porous copper plating layer, and sintering to obtain a metal foam block wrapped by the super-hydrophilic copper-nickel plating layer;
(3) Depositing a hydrophobic polyolefin salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel plating layer to obtain a gradient-wetting metal foam block;
(4) And (3) immersing the gradient wetting metal foam block into water, immersing into a mixed solution consisting of a nano material, bismuth oxyiodide micro-particles, PDMS (polydimethylsiloxane), a curing agent and an organic solvent, soaking, and finally performing thermocuring to generate a hydrophobic photo-thermal evaporation layer with a micro-nano structure, thereby obtaining the gradient wetting copper-nickel multilayer composite material.
2. The method of claim 1, wherein: in the step (1), the sulfur-containing nickel electroplating solution comprises 5-25wt% of nickel salt, 1-5wt% of sulfur-containing organic matter, 0.05-11wt% of complexing agent and 0.01-3wt% of surfactant;
and/or the nickel salt comprises any one of nickel sulfate and nickel chloride or the combination of the two; and/or the sulfur-containing organic matter comprises any one or the combination of more than two of benzene sulfonic acid, ethylene thiourea and benzoyl sulfimide; and/or the complexing agent comprises any one or combination of two of boric acid and citric acid; and/or the surfactant comprises any one or the combination of more than two of sodium dodecyl sulfate, behenyl trimethyl ammonium chloride and sodium ethylhexyl sulfate;
and/or the material of the metal foam block comprises at least one of nickel and copper.
3. The production method according to claim 1, wherein in the step (1), the process conditions of the first electrodeposition reaction include: the current density is 1 to 10A/dm 2 The temperature of the first electrodeposition reaction is 30 to 60 ℃, and the time is 1 to 100h;
and/or, the first cathode comprises a nickel sheet.
4. The preparation method according to claim 1, wherein in the step (2), the copper electroplating solution comprises 10 to 30wt% of copper salt, 1 to 10wt% of acid and 0.5 to 10wt% of inorganic salt;
and/or the copper salt comprises any one or the combination of copper sulfate and copper chloride; and/or, the acid comprises any one or a combination of two of sulfuric acid and hydrochloric acid; and/or, the inorganic salt comprises any one or a combination of two of sodium chloride and potassium chloride.
5. The production method according to claim 1, wherein in the step (2), the process conditions of the second electrodeposition reaction include: the current density is 0.5 to 10A/dm 2 The temperature of the second electrodeposition reaction is 30 to 60 ℃, and the time is 0.1 to 2h;
and/or the sintering temperature is 200 to 600 ℃, and the sintering time is 0.5 to 24h;
and/or the second cathode comprises a copper sheet;
and/or the aperture of a hole contained in the porous copper plating layer is 0.01 to 100 mu m, and the porosity is 10 to 90 percent.
6. The method according to claim 1, wherein the step (3) comprises: depositing a hydrophobic polyolefin salt-resistant anticorrosive layer on the metal foam block wrapped by the super-hydrophilic copper-nickel plating layer by adopting a low-temperature plasma technology to obtain a gradient-wetting metal foam block; wherein the helium gas flow rate is 100 to 200sccm, the olefin gas flow rate is 10 to 100sccm, the pressure is 10 to 1000mToor, the duty ratio is 10 to 100 percent, the power is 40 to 80W, and the reaction time is 10 to 180min;
wherein, the olefin gas comprises any one or the combination of more than two of ethylene, propylene and chloroethylene.
7. The method according to claim 1, wherein the step (4) comprises: soaking the gradient wetting metal foam block in water for 10 to 30min, and taking out; then soaking the mixture into a mixed solution consisting of 0.1 to 10wt% of nano material, 0.1 to 10wt% of bismuth oxyiodide micron particles, 0.1 to 10wt% of PDMS, 0.01 to 2wt% of curing agent and an organic solvent for 1 to 30min, taking out the mixture, and finally performing thermal curing at 50 to 120 ℃ for 10 to 300min to generate a hydrophobic photothermal evaporation layer with a micro-nano structure;
and/or the particle size of the bismuth oxyiodide micron particles is 0.1 to 5 mu m;
and/or the nano material comprises ferroferric oxide nano particles with the particle size of 10 to 100nm, reduced graphene oxide with the diameter of 100nm to 5 mu m and the number of layers of 1~8 and carbon nano tubes with the diameter of 2 to 50nm, or a combination of more than two of the reduced graphene oxide and the carbon nano tubes;
and/or the organic solvent comprises any one or the combination of more than two of chloroform, normal hexane and ethyl acetate.
8. The gradient wetting copper-nickel multilayer composite material prepared by the preparation method of any one of claims 1 to 8 is characterized by comprising a metal foam block, a hydrophobic polyolefin salt-resistant anticorrosive layer and a hydrophobic photothermal evaporation layer with a micro-nano structure, which are wrapped by a super-hydrophilic copper-nickel plating layer and are sequentially stacked in the thickness direction.
9. The gradient wetting cupronickel multilayer composite of claim 8, characterized in that: the thickness of the super-hydrophilic copper-nickel plating layer is 0.1 to 300 mu m, and the porosity is 50 to 85 percent; and/or the thickness of the hydrophobic polyolefin salt-resistant anticorrosive layer is 0.05 to 50 mu m; and/or the thickness of the hydrophobic photothermal evaporation layer with the micro-nano structure is 0.1 to 800 mu m;
and/or the contact angle between the upper surface of the gradient wetting copper-nickel multilayer composite material and water is 151 to 157 degrees, the contact angle between the lower surface of the gradient wetting copper-nickel multilayer composite material and water is 0 degree, and the water evaporation rate is 2.5 to 2.9 kg m under the condition of simulated sunlight illumination -2 h -1 The photothermal conversion efficiency is 91 to 95%.
10. Use of the gradient wetting copper nickel multilayer composite material according to claim 8 or 9 in the field of photothermal seawater desalination or photothermal sewage purification.
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