CN110777561B - Metal nanoparticle-polymer composite material and preparation method and application thereof - Google Patents

Metal nanoparticle-polymer composite material and preparation method and application thereof Download PDF

Info

Publication number
CN110777561B
CN110777561B CN201911000688.2A CN201911000688A CN110777561B CN 110777561 B CN110777561 B CN 110777561B CN 201911000688 A CN201911000688 A CN 201911000688A CN 110777561 B CN110777561 B CN 110777561B
Authority
CN
China
Prior art keywords
metal
solution
solid matrix
seeds
polymer composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911000688.2A
Other languages
Chinese (zh)
Other versions
CN110777561A (en
Inventor
顾佳俊
刘庆雷
董昌林
袁洋
张荻
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiaotong University
Original Assignee
Shanghai Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jiaotong University filed Critical Shanghai Jiaotong University
Priority to CN201911000688.2A priority Critical patent/CN110777561B/en
Publication of CN110777561A publication Critical patent/CN110777561A/en
Application granted granted Critical
Publication of CN110777561B publication Critical patent/CN110777561B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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 provides a metal nanoparticle-polymer composite material and a preparation method and application thereof, relating to the field of composite materials; the composite material comprises a solid matrix and a filler, wherein the filler comprises metal nano-particles with the particle size range of 5-99 nanometers, and the distance between adjacent metal nano-particles is 1-200 nanometers; the solid matrix is internally provided with pores with the pore diameter of 2-500 nanometers, the solid matrix comprises polymer fiber materials, the filling bodies are dispersed and filled in the pores in the solid matrix, and the pores are used for dispersing the filling bodies and preventing the filling bodies from agglomerating; preparing metal seeds in internal pores of a solid matrix, and then putting the metal seeds into a metal nanoparticle growth solution for growth to obtain a metal nanoparticle-polymer composite material; the material has strong light absorption and high photo-thermal conversion efficiency, has an average absorption rate of 97% to the solar spectrum of 300-2500nm, can be prepared in a large area, and can be applied to the fields of photo-thermal conversion, solar seawater desalination and the like.

Description

Metal nanoparticle-polymer composite material and preparation method and application thereof
Technical Field
The invention relates to the field of composite materials, in particular to a metal nanoparticle-polymer composite material and a preparation method and application thereof.
Background
Solar energy is inexhaustible clean energy and is expected to replace fossil energy which is exhausted. There are many methods of utilizing solar energy, such as solar cells, solar water heaters, focused solar power generation, solar seawater desalination, photocatalysis, and the like.
In any method using solar energy, sunlight is absorbed in the first step. For the full wave band of the solar spectrum, the utilization efficiency of solar energy can be effectively improved by efficient absorption. To this end, scientists have proposed and studied various methods of improving the light absorption rate, including designing a broadband superstructure, exciting plasmon resonance enhanced absorption, and anti-reflection fine nanostructure array. The full-wave band of sunlight means light in all wavelength ranges of the industry standard solar spectrum (Air Mass 1.5G), which ranges from 300 nm to 2500 nm.
Although these methods of increasing light absorption can increase bandwidth and reduce reflection, it is still difficult to achieve full-band absorption of the solar spectrum, and even with few materials available, these materials suffer from complicated preparation processes and difficult large-scale application. Although plasmon resonance can collect incident light and enhance light absorption, plasmon resonance absorption is resonance absorption in nature, and the bandwidth is very narrow, so that a fine and complex structure needs to be designed to improve the bandwidth to achieve the purpose of full-spectrum absorption.
Metals are generally considered to have a specular reflection effect on light, but when the size of the metal is close to the wavelength of light, i.e., becomes nanoparticles, the specular reflection will disappear but the scattering will still be large, and when the size of the metal nanoparticles is less than 40 nanometers, both the reflection and scattering losses will disappear. Therefore, controlling the size and distribution state of the metal nanoparticles can significantly affect their absorption characteristics for light. In fact, there is a certain requirement for the regulation of the size and distribution state of metal nanoparticles not only in optical absorption but also in the fields of catalysis, energy storage, and the like.
In the existing research, nanoparticles are attached to the surface of a material, the problem of nanoparticle agglomeration cannot be substantially solved, and the nanoparticles are mixed in a plasmon composite film reported by Ting Xu et al in 2019, and are subjected to suction filtration to form a light absorption composite material (Nanoscale,2019,11, 437-443). The nano particles are deposited on the surface of the nano material, the nano material plays a certain role in dispersion, but the distribution state of the nano particles is still difficult to control in the preparation process of the composite material, and the nano particles cannot be guaranteed not to agglomerate. In addition, during the use of the composite materials, the nano particles on the surfaces of the fibers are completely exposed outside, so that the nano particles are easy to fall off and agglomerate; when metal nanoparticles are loaded on a polymer material, common polymer materials comprise a polyethyleneimine/polyvinyl alcohol nanofiber membrane, a polyacrylic acid/polyvinyl alcohol electrostatic spinning nanofiber membrane and the like, and at present, no research on directly embedding nanoparticles in the polymer material exists.
Disclosure of Invention
In view of the shortcomings of the prior art, it is an object of the present invention to provide a metal nanoparticle-polymer composite; the second purpose of the invention is to provide a preparation method of the metal nanoparticle-polymer composite material; the third purpose of the invention is to provide an application of the metal nanoparticle-polymer composite material.
In order to realize the first purpose of the invention, the invention provides the following technical scheme that the metal nanoparticle-polymer composite material comprises a solid matrix and a filler, wherein the filler comprises metal nanoparticles, the particle size range of the metal nanoparticles is 5-99 nanometers, and the distance between every two adjacent metal nanoparticles is 1-200 nanometers; the solid matrix comprises a polymer fiber material, the polymer fiber material is composed of polymer fibers, and pores of 2-500 nanometers are formed in the polymer fibers; the filler is dispersed and filled in pores in the solid matrix, and the pores are used for dispersing the filler and preventing the filler from agglomerating.
The pores are long and narrow pores with the diameter of 2-50 nanometers and the length of 50-500 nanometers.
More preferably, the metal nanoparticles have a particle size in the range of 10-25 nm.
More preferably, the metal nanoparticles have a particle size in the range of 14 to 25 nanometers.
The metal nanoparticles may form a dispersed, non-agglomerated distribution on the polymer surface, or may be absent, but the metal nanoparticles may not form a continuous film on the polymer surface. The particle size of the metal nanoparticles is obtained by measuring the length and width of the minimum external rectangle of the metal nanoparticles in a transmission electron microscope and then opening a root number.
Preferably, the material of the metal nanoparticles comprises one or more of gold, silver, palladium, platinum, rhodium, ruthenium, osmium, iridium, copper, zinc, chromium, molybdenum, tungsten, titanium, zirconium, niobium, cobalt, iron and nickel.
Preferably, the shape of the metal nanoparticle includes one or more of a spherical shape, an ellipsoidal shape, a square shape, a rod shape, a star shape, and an irregular shape.
Preferably, the material of the metal nanoparticles comprises one of gold, silver, copper and nickel, and the average absorption rate of the metal nanoparticle-polymer composite material to the solar spectrum in the 300-2500nm band is greater than or equal to ninety percent.
Preferably, the metal nanoparticles are nickel nanoparticles, and the average absorption rate of the metal nanoparticle-polymer composite material to the solar spectrum in the wavelength band of 300-2500nm is greater than or equal to ninety-seven percent.
Preferably, the polymer fiber material comprises a natural fiber material and a synthetic porous fiber material; the natural fiber material comprises a cellulose material, a chitin material and a silk fiber material; the cellulose material comprises one of wet strength paper, printing paper, filter paper, dust-free paper, mirror wiping paper and cotton cloth.
More preferably, the polymer fiber material is one of wet strength paper and cotton cloth, which is common in life, easy to obtain and low in price.
In order to achieve the second object of the present invention, the present invention provides the following technical solutions: a preparation method of a metal nanoparticle-polymer composite material specifically comprises the following steps of growing metal nanoparticles: preparing metal seeds in the internal pores of the solid matrix; putting the solid matrix containing the metal seeds into a metal nanoparticle growth solution, and growing for 3-20 minutes to obtain a metal nanoparticle-polymer composite material; the metal nanoparticle growth solution comprises a metal main salt solution, a complexing agent, a reducing agent and a pH regulator; the metal seeds comprise metal ion seeds and metal simple substance seeds.
The metal seeds are directly reduced or catalytically reduced into corresponding metal nanoparticles in a metal nanoparticle growth solution, and are nucleation sites for the growth of the metal nanoparticles.
Preferably, the metal ion seed comprises Sn2+、Pd2+The metal elementary substance seeds comprise one or more of elementary substance Au, elementary substance Ag, elementary substance Pd, elementary substance Pt, elementary substance Cu and elementary substance Ni.
When the metal ions are used as seeds, the interaction of complexation or electrostatic attraction between the matrix and the metal ions is required, so that the seed ions can be adsorbed; when the metal simple substance is used as a seed, the gold simple substance can be used as a seed for growth of all metals, and other metal simple substance seeds can grow metal nanoparticles with the same material as the seed, so that the self-catalytic reduction effect is achieved (for example, nickel metal nanoparticles grow from nickel seeds, and silver metal nanoparticles grow from silver seeds); in the embodiment, the gold is taken as an example, and other metal ion seeds or metal elemental seeds are also within the protection scope of the present invention.
Preferably, the preparation of the metal ion seeds in the internal pores of the solid matrix comprises in particular: cleaning the solid matrix, and then putting the solid matrix into a metal ion seed solution to be soaked for 3-5 hours to obtain metal ion seeds in the internal pores of the solid matrix; the metal ion seed solution comprises one of a tin dichloride solution, a palladium dichloride solution and a diammine palladium dichloride solution; the preparation of the metal elementary seeds in the internal pores of the solid matrix specifically comprises: cleaning the solid matrix, putting the solid matrix into a metal simple substance seed salt solution, soaking for 3-5 hours, cleaning, and then putting the solid matrix into a seed reducing agent for 2-4 minutes to obtain metal simple substance seeds in the internal pores of the solid matrix; the metal elementary substance seed salt solution comprises one of a chloroauric acid solution, a silver nitrate solution, a palladium dichloride solution, a chloroplatinic acid solution, a copper sulfate solution and a nickel sulfate solution; the seed reducing agent comprises one or more of sodium borohydride solution, hydrazine hydrate solution and dimethylamino borane solution.
More preferably, the preparation of the metal ion seeds in the internal pores of the solid matrix comprises in particular: and cleaning the solid matrix, and then putting the solid matrix into a metal salt solution to soak for 4 hours to obtain metal ion seeds in the internal pores of the solid matrix.
More preferably, the preparation of elemental metal seeds in the internal pores of the solid matrix comprises in particular: cleaning the solid matrix, putting the solid matrix into a metal salt solution, soaking for 4 hours, cleaning, and then putting the solid matrix into a reducing agent for 3 minutes to obtain metal simple substance seeds in the internal pores of the solid matrix.
Preferably, the metal main salt solution comprises one of a chloroauric acid solution, a silver nitrate solution, a copper sulfate solution and a nickel sulfate solution; the complexing agent comprises one or more of tartaric acid, sodium chloride, ammonia water, potassium sodium tartrate, sodium citrate and lactic acid; the reducing agent comprises one or more of ethanol, potassium sodium tartrate, formaldehyde and dimethylamino borane; the pH regulator comprises one or more of sodium hydroxide and ammonia water.
In order to achieve the third objective of the present invention, the present invention provides the following technical solutions: the application of the metal nanoparticle-polymer composite material has the advantages that the average absorption rate of the metal nanoparticle-polymer composite material to the solar spectrum of 300-2500nm is more than or equal to 90%, the metal nanoparticle-polymer composite material has a high-efficiency photothermal conversion effect and is used for photothermal conversion and solar seawater desalination; the efficiency of photothermal water evaporation of the metal nanoparticle-polymer composite material is greater than or equal to 75%; the efficiency of the metal nanoparticle-polymer composite material for solar seawater desalination is 46.9-65.8%
Preferably, the average absorption rate of the metal nanoparticle-polymer composite material to the solar spectrum in the wavelength region of 300-.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the metal nanoparticle-polymer composite material provided by the invention can control the size of metal nanoparticles through pores in the polymer, prevent agglomeration among the metal nanoparticles, and also can prevent agglomeration of the metal nanoparticles in the use process of the composite material and prevent falling-off of the metal nanoparticles, so that the optical reflection and optical scattering of the material are minimized;
(2) according to the metal nanoparticle-polymer composite material provided by the invention, metal nanoparticles can be densely distributed in a polymer matrix without agglomeration, so that optical reflection and optical scattering of the metal nanoparticles are reduced, the full-band optical absorption rate of solar spectrum (97.1%) is improved, the water steaming efficiency is high (75%), and the solar seawater desalination efficiency is high (46.9% -65.8%);
(3) the preparation process of the metal nanoparticle-polymer composite material provided by the invention is carried out in an aqueous solution, the preparation method is simple, and large-scale preparation can be realized; the material cost is low, and the method has a practical application prospect.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a scanning electron micrograph of the small-magnification nickel nanoparticle-wet strength paper composite material of example 4;
FIG. 2 is a scanning electron microscope image of the high-multiple nickel nanoparticle-wet strength paper composite material in example 4;
FIG. 3 is a scanning electron micrograph of a small-magnification nickel nanoparticle-cotton composite material in example 5;
FIG. 4 is a scanning electron micrograph of a high-magnification nickel nanoparticle-cotton composite material in example 5;
FIG. 5 is a transmission electron micrograph of the gold nanoparticle-wet strength paper composite of example 1;
FIG. 6 is a transmission electron micrograph of the silver nanoparticle-wet strength paper composite of example 2;
FIG. 7 is a transmission electron micrograph of the copper nanoparticle-wet strength paper composite of example 3;
FIG. 8 is a transmission electron micrograph of the nickel nanoparticle-wet strength paper composite of example 4;
FIG. 9 is a transmission electron micrograph of a nickel nanoparticle-cotton composite of example 5;
FIG. 10 is an optical absorption diagram of five metal nanoparticle-polymer composites of examples 1-5;
FIG. 11 is a graph showing the results of photothermal conversion effect tests on nickel nanoparticle-wet strength paper composites and gold nanoparticle-wet strength paper composites;
FIG. 12 is a schematic view of the experimental apparatus for photo-thermal water evaporation in example 4 and comparative example 1;
FIG. 13 is a graph of water mass versus time for a nickel nanoparticle-wet strength paper composite in a photothermal water evaporation test;
FIG. 14 is a graph of evaporation rate and enhancement factor for a nickel nanoparticle-wet strength paper composite in a photothermal water evaporation test;
FIG. 15 is a drawing of an experimental apparatus for desalinating outdoor seawater in example 6 and a schematic view thereof;
FIG. 16 is a water production efficiency chart of sea water desalination and sewage purification in example 6;
FIG. 17 is a transmission electron micrograph of a nickel nanoparticle-wet strength paper composite grown for 0.5 minutes in comparative example 2;
FIG. 18 is a transmission electron micrograph of a nickel nanoparticle-wet strength paper composite grown for 20.5 minutes in comparative example 3;
FIG. 19 is a graph comparing the optical absorption of the nickel nanoparticle-wet strength paper composites of example 4, comparative example 2, and comparative example 3;
FIG. 20 is a transmission electron microscope image of the nickel nanoparticle-polyester fiber composite material in comparative example 4;
FIG. 21 is a scanning electron microscope image of the nickel nanoparticle-bacterial cellulose composite material in comparative example 6;
fig. 22 is a schematic structural view of the metal nanoparticle-polymer composite in examples 1-5.
Detailed Description
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The present invention will be described in detail with reference to the following specific examples:
the particle size of the metal nanoparticles is obtained by measuring the length and width of the minimum external rectangle of the metal nanoparticles in a transmission electron microscope and then opening a root number. The following examples select four typical metal materials: gold, silver, copper and nickel and two common polymeric materials: wet strength paper and cotton cloth to illustrate the technical characteristics of the metal nanoparticle-polymer composite provided by the present invention. In addition, the metal nano-particle-polymer composite material provided by the invention is subjected to optical absorption and photothermal conversion effect test and analysis, and outdoor solar seawater desalination and sewage treatment test.
When the metal ions are used as seeds, the matrix and the metal ions are required to have complexation or electrostatic attraction interaction, so that the matrix can adsorb the seed ions; when the metal simple substance is used as a seed, the gold simple substance can be used as a seed for growth of all metals, and other metal simple substance seeds can grow metal nanoparticles with the same material as the seed, so that the self-catalytic reduction effect is achieved (for example, nickel metal nanoparticles grow from nickel seeds, and silver metal nanoparticles grow from silver seeds); in the embodiment, the gold is taken as an example, and other metal ion seeds or metal elemental seeds are also within the protection scope of the present invention.
Wherein the average absorption rate alpha of the solar spectrum wave band 300-sThe calculating method of (2):
Figure BDA0002241215070000061
wherein EsolarIs AM 1.5G standard solar spectrum, and alpha (lambda) is the absorption spectrum measured by UV-Vis-NIR spectroscopy (i.e., the absorption spectra measured in FIGS. 10 and 19).
Example 1:
a metal nanoparticle-polymer composite material and a preparation method thereof specifically comprise the following steps:
the method comprises the following steps: washing a piece of wet strength paper with the thickness of 3cm multiplied by 3cm with distilled water for three times, and then soaking the wet strength paper in 20mL of chloroauric acid solution with the concentration of 0.1 wt.% for 4 hours; the wet strength paper is commercial industrial grade wet strength paper.
Step two: and after 4 hours, taking out the wet strength paper, washing the wet strength paper with distilled water for three times, and then putting the wet strength paper into 50mL of 0.1M sodium borohydride solution for reduction to obtain the gold seeds.
Step three: taking out the wet strength paper containing the gold seeds, washing the wet strength paper with distilled water for three times, and putting the wet strength paper into 50mL of gold growth solution for growing the gold nanoparticles, wherein the 50mL of gold growth solution comprises the following components: 0.5g of chloroauric acid, 0.3g of sodium chloride, 0.2g of tartaric acid, 2.57g of sodium hydroxide and 1mL of ethanol.
Step four: after growing for 6 minutes, the composite material is taken out, washed with distilled water for three times and then naturally dried.
Finally, the metal nanoparticle-polymer composite material shown in fig. 22 is obtained as a gold nanoparticle-wet strength paper composite material; as shown in the transmission electron micrograph of fig. 5, the average size of the gold nanoparticles is 12.0 nm, the distance between the gold nanoparticles and the particles is 1 nm to 100 nm, the diameter of the pores in the polymer fiber material is 10 nm, the length is 100 nm, and the gold nanoparticles are dispersed inside the cellulose fiber without agglomeration.
The optical absorption test of the metal nanoparticle-polymer composite material obtained in example 1 above showed that the average absorption rate in the solar spectrum of wavelength band 300-2500nm was 90.0%, as shown in FIG. 10.
Carrying out a photothermal conversion effect test: the above composite material having a diameter of 2.6 cm was placed on a quartz glass plate at 1kW m-2The average temperature of the composite surface was recorded with a thermal infrared camera under light. After 5.5 minutes of illumination, the temperature of the surface of the composite material reached 55 ℃.
Example 2:
a metal nanoparticle-polymer composite and a method for preparing the same, which are different from example 1 in that:
step three: taking out the wet strength paper containing the gold seeds, washing the wet strength paper with distilled water for three times, and putting 50mL of silver growth solution for growing the silver nanoparticles, wherein the 50mL of silver growth solution comprises the following components: 0.5g of silver nitrate, 1mL of ammonia water and 2.5g of potassium sodium tartrate.
Step four: after the growth of 20 minutes, the composite material is taken out, washed with distilled water for three times and then naturally dried.
The final metal nanoparticle-polymer composite shown in fig. 22 was a silver nanoparticle-wet strength paper composite, as shown in the transmission electron micrograph of fig. 6, the average size of the silver nanoparticles was 10.8 nm, the distance between the silver nanoparticles and the particles was between 1 nm and 50 nm, the diameter of the pores within the polymer fiber material was 10 nm, the length was 100 nm, and the silver nanoparticles were dispersed inside the cellulose fibers without agglomeration.
The optical absorption test was performed on the metal nanoparticle-polymer composite obtained in example 2 above, and the results are shown in fig. 10. The average absorptivity of the composite material in the solar spectrum wave band of 300-2500nm is 93.7 percent
Example 3:
a metal nanoparticle-polymer composite and a method for preparing the same, which are different from example 1 in that:
step three: taking out wet strength paper containing gold seeds, washing the wet strength paper with distilled water for three times, putting the wet strength paper into 50mL of copper growth solution for growing copper nanoparticles, wherein the 50mL of copper growth solution comprises the following components: 1.5g copper sulfate, 2g sodium hydroxide, 7g potassium sodium tartrate, 5mL formaldehyde.
Step four: after growing for 10 minutes, the composite material is taken out, washed with distilled water for three times and then naturally dried.
The final metal nanoparticle-polymer composite shown in fig. 22 was a copper nanoparticle-wet strength paper composite, as shown in the transmission electron micrograph of fig. 7, the average size of the copper nanoparticles was 20.5 nm, the distance between the copper nanoparticles and the particles was between 1 nm and 200 nm, the diameter of the pores within the polymer fiber material was 10 nm, the length was 100 nm, and the copper nanoparticles were dispersed inside the cellulose fibers without agglomeration.
The optical absorption test was performed on the metal nanoparticle-polymer composite material obtained in example 3 above, and the results are shown in fig. 10. The average absorptivity of the composite material in the solar spectrum wave band of 300-2500nm is 93.0 percent
Example 4:
a metal nanoparticle-polymer composite and a method for preparing the same, which are different from example 1 in that:
step three: taking out wet strength paper containing gold seeds, washing the wet strength paper with distilled water for three times, putting the wet strength paper into 50mL of nickel growth solution for growing nickel nanoparticles, wherein the 50mL of nickel growth solution comprises the following components: 2g of nickel sulfate, 1g of sodium citrate, 0.5g of lactic acid, 1.5mL of ammonia water and 0.1g of dimethylaminoborane.
Step four: after 3.5 minutes of growth, the composite material was taken out, washed with distilled water three times, and then naturally dried.
The final metal nanoparticle-polymer composite shown in fig. 22 is a composite of nickel nanoparticle-wet strength paper, as shown in the transmission electron micrograph of fig. 8, the average size of the nickel nanoparticles is 14.8 nm, the distance between the nickel nanoparticles and the particles is 1 nm to 100 nm, the diameter of the pores in the polymer fiber material is 10 nm, the length is 100 nm, as shown in the scanning electron micrographs of fig. 1 and 2, the surface of the wet strength paper fiber has no agglomerated nickel nanoparticles, and as shown in the transmission electron micrograph of fig. 8, the nickel nanoparticles are dispersed inside the wet strength paper fiber and have no agglomeration.
The optical absorption test of the metal nanoparticle-polymer composite material obtained in example 4 above resulted in the average absorption rate of 97.1% in the solar spectrum band of 300-2500nm, as shown in FIG. 10.
Carrying out a photothermal conversion effect test: the above composite material having a diameter of 2.6 cm was placed on a quartz glass plate at 1kW m-2The average temperature of the composite surface was recorded with a thermal infrared camera under light. After 5.5 minutes of illumination, the temperature of the surface of the composite material reached 59 ℃.
The experiment of photo-thermal water evaporation was performed on the nickel nanoparticle-wet strength paper composite obtained in example 4, and the experimental apparatus consisted of the nickel nanoparticle-wet strength paper composite, absorbent paper, heat insulating foam and plastic container as shown in fig. 12; in intensity of sunlightIs 1kW m respectively-2,2kW m-2,3kW m-2,4kW m-2,5kW m-2,6kW m-2,7kW m-2The change in the mass of water over time is measured.
Example 5
A metal nanoparticle-polymer composite material and a preparation method thereof specifically comprise the following steps:
the method comprises the following steps: washing a piece of cotton cloth with the thickness of 3cm multiplied by 3cm with distilled water for three times, and then soaking the cotton cloth in 20mL of chloroauric acid solution with the concentration of 0.1 wt% for 4 hours; the cotton cloth is common pure cotton cloth in the market.
Step two: after 4 hours, the cotton cloth is taken out and washed with distilled water for three times, and then the cotton cloth is put into 50mL of 0.1M sodium borohydride solution to be reduced to obtain the gold seeds.
Step three: the cotton cloth containing the gold seeds was taken out and washed three times with distilled water and put into 50mL of nickel growth solution for the growth of nickel nanoparticles, and the composition of 50mL of nickel growth solution was the same as that of the growth solution in example 4.
Step four: after growing for 4 minutes, the composite material is taken out, washed with distilled water for three times and then naturally dried.
Finally, the metal nanoparticle-polymer composite material shown in fig. 22 is a nickel nanoparticle-cotton composite material, as shown in the transmission electron microscope image of fig. 9, the average size of the nickel nanoparticles is 23.6 nm, the distance between the nickel nanoparticles and the particles is 1 nm to 200 nm, the diameter of the pores in the polymer fiber material is 10 nm, the length of the pores is 100 nm, as shown in the scanning electron microscope images of fig. 3 and 4, the surface of the cellulose fiber has no agglomerated nickel nanoparticles, and as shown in the transmission electron microscope image of fig. 9, the nickel nanoparticles are dispersed in the interior of the cellulose fiber and have no agglomeration.
The optical absorption test of the metal nanoparticle-polymer composite material obtained in example 5 above showed that the average absorption rate in the solar spectrum of wavelength band 300-2500nm was 98.0%, as shown in FIG. 10.
Example 6
An experimental apparatus for the application of the metal nanoparticle-polymer composite material is shown in fig. 15 and mainly comprises a solar still, a nickel nanoparticle-wet strength paper composite material, absorbent paper and heat insulation foam. And carrying out outdoor solar seawater desalination and sewage treatment on the nickel nanoparticle-wet strength paper composite material to evaluate the water production efficiency.
Figure 16 shows the water production efficiency for 15 days and the corresponding solar radiation energy, from which it is seen that the water production efficiency is between 46.9% and 65.8%, indicating that the nickel nanoparticle-wet strength paper composite has potential value for large-scale practical applications.
Example 7
A metal nanoparticle-polymer composite and a method for preparing the same, which are different from example 4 only in that: the material used in step 1 is chitin material of 3cm × 3cm, and the rest of the operation is the same as that of example 4; the finally obtained metal nano-particle-polymer composite material is a nickel nano-particle-chitin composite material. Wherein the nickel nanoparticles are uniformly dispersed in the pores inside the chitin without agglomeration.
Comparative example 1
Experimental setup for hydrothermal evaporation as shown in fig. 12, the difference from the hydrothermal evaporation test in example 4 is that no nickel nanoparticle-wet strength paper composite was used; the sunlight intensity is 1kW m-2,2kW m-2,3kW m-2,4kW m-2,5kW m-2,6kW m-2,7kW m-2The change in the mass of water over time is measured.
Comparative example 2
A metal nanoparticle-polymer composite and a method for preparing the same, which are different from example 4 in that: step four: after 0.5 minute of growth, the composite material was taken out, washed with distilled water three times, and then naturally dried.
The finally obtained metal nanoparticle-polymer composite material is a nickel nanoparticle-wet strength paper composite material (growth time is 0.5 min), and a transmission electron microscope thereof is shown in fig. 17, wherein the average size of the nickel nanoparticles is 4.8 nm, and the distance between the particles is 1 nm to 50 nm; the optical absorption was measured and, as shown in fig. 19, the average absorption of the solar spectrum was 80.2%.
Comparative example 3
A metal nanoparticle-polymer composite and a method for preparing the same, which are different from example 4 in that: step four: after the growth for 20.5 minutes, the composite material is taken out, washed with distilled water for three times and then naturally dried.
The finally obtained metal nanoparticle-polymer composite material is a nickel nanoparticle-wet strength paper composite material (the growth time is 20.5 minutes), the transmission electron microscope is shown in fig. 18, the average size of nickel nanoparticles is 100 nanometers, severe agglomeration exists among particles, and a continuous nickel metal thin film is formed on the surface of cellulose fibers; the optical absorption was measured and, as shown in fig. 19, the average absorption of the solar spectrum was 87.1%.
Comparative example 4
A metal nanoparticle-polymer composite and a method for preparing the same, which are different from example 4 only in that: the material used in step 1 was a synthetic polyester fiber of 3cm × 3cm, and the rest of the operation was the same as in example 4; the finally obtained metal nanoparticle-polymer composite material is a nickel nanoparticle-polyester fiber composite material. As shown in the transmission electron microscope image of fig. 20, nickel forms a continuous metal thin film on the surface of the fiber.
Comparative example 5
A metal nanoparticle-polymer composite and a method for preparing the same, which are different from example 4 in that: the steps of preparing the metal seeds in the steps 1 and 2 are omitted; the finally obtained metal nanoparticle-polymer composite material is a nickel nanoparticle-wet strength paper composite material, so that the fact that the subsequent nanoparticles of the material with metal seeds can grow in the material can be obviously seen, the seeds do not exist, the metal particles grow randomly, part of the metal particles are separated out from the solution, part of the metal particles are deposited on the surfaces of fibers, and the metal particles are also obviously agglomerated.
Comparative example 6
A metal nanoparticle-polymer composite and a method for preparing the same, which are different from example 4 in that: step 1, a piece of bacterial cellulose hydrogel with the thickness of 3cm multiplied by 3cm is taken out and washed with distilled water for three times, and then the bacterial cellulose hydrogel is placed into 20mL of chloroauric acid solution with the concentration of 0.1 wt.% to be soaked for 4 hours. The rest of the operation is the same as in example 4; the finally obtained metal nanoparticle-polymer composite material is a nickel nanoparticle-bacterial cellulose composite material. As shown in the scanning electron microscope image of FIG. 21, it can be seen that the nickel particles are agglomerated and connected together, and the digital photograph can also see the metallic luster, which indicates that the metal particles are still more obviously agglomerated in the bacterial fiber.
(1) Characterization of the optical absorption tests performed on the metal nanoparticle-polymer composites obtained according to examples 1-5, as shown in fig. 10, all metal nanoparticle-polymer composites have higher absorption in the solar spectral range, and the optical absorption is ordered as nickel nanoparticle-cotton composite > nickel nanoparticle-wet strength paper composite > silver nanoparticle-wet strength paper composite > copper nanoparticle-wet strength paper composite > gold nanoparticle-wet strength paper composite.
(2) Comparing the photothermal conversion effect test of the gold nanoparticle-wet strength paper composite obtained in example 1 and the nickel nanoparticle-wet strength paper composite obtained in example 4, as shown in fig. 11, the temperature rise rate and the maximum temperature of the nickel nanoparticle-wet strength paper composite were higher than those of the gold nanoparticle-wet strength paper composite.
(3) According to the experimental comparison of photo-thermal water evaporation of example 4 and comparative example 1, FIG. 13 shows that the solar intensity of the composite material is 1kW m-2,2kW m-2,3kW m-2,4kW m-2,5kW m-2,6kW m-2,7kW m-2The change in the quality of the water over time. Fig. 14 shows the evaporation rate with and without the nickel nanoparticle-wet strength paper composite under the above conditions, and the ratio of the two, i.e. the evaporation rate enhancement factor. It can be seen that the evaporation rate of the nickel nanoparticle-wet strength paper composite material to water can be increased by 3 to 34 times. The energy conversion efficiency is about 80%.
(4) In accordance with the optical absorption comparison of example 4 with comparative examples 2, 3, fig. 19 shows the optical absorption comparison of nickel nanoparticle-wet strength paper composites with growth times of 3.5 min, 0.5 min, 20.5 min, respectively, whereby the highest optical absorption can be obtained for a nickel nanoparticle growth time of 3.5 min.
(5) As can be seen from the scanning electron microscope image of example 4 and the transmission electron microscope image of comparative example 4, as shown in fig. 2, the surface of the cellulose fiber is almost free of nickel nanoparticles; as shown in fig. 20, since there is no nano-pore inside the synthetic polyester fiber, the nickel nanoparticles can only grow on the surface of the polyester fiber, thereby forming a continuous metal film, generating a large metal reflection, and reducing the optical absorption.
(6) As can be seen from the transmission electron microscope image of example 4 and the scanning electron microscope image of comparative example 6, the nickel nanoparticles are uniformly distributed inside the cellulose fiber without agglomeration as shown in fig. 8; as shown in fig. 21, the nickel nanoparticles are agglomerated into larger particles inside the bacterial cellulose and are connected to each other in one piece.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (8)

1. A metal nanoparticle-polymer composite comprising a solid matrix and a filler, wherein the filler comprises metal nanoparticles, the metal nanoparticles have a particle size in the range of 5 to 99 nm, and the distance between adjacent metal nanoparticles is in the range of 1 to 200 nm; the solid matrix comprises a polymer fiber material, the polymer fiber material is composed of polymer fibers, and pores of 2-500 nanometers are formed in the polymer fibers; the filler is dispersed and filled in pores in the solid matrix, and the pores are used for dispersing the filler and preventing the filler from agglomerating;
in the preparation process of the metal nanoparticle-polymer composite material, metal seeds are prepared in the internal pores of the solid matrix; putting the solid matrix containing the metal seeds into a metal nanoparticle growth solution, and growing for 3-20 minutes to obtain a metal nanoparticle-polymer composite material; the metal seeds comprise metal ion seeds and metal simple substance seeds;
the preparation of the metal ion seeds in the internal pores of the solid matrix specifically comprises: cleaning the solid matrix, and then putting the solid matrix into a metal ion seed solution to be soaked for 3-5 hours to obtain metal ion seeds in the internal pores of the solid matrix; the metal ion seed solution comprises one of a tin dichloride solution, a palladium dichloride solution and a diammine palladium dichloride solution;
the preparation of the metal elementary seeds in the internal pores of the solid matrix specifically comprises: cleaning the solid matrix, putting the solid matrix into a metal simple substance seed salt solution, soaking for 3-5 hours, cleaning, and then putting the solid matrix into a seed reducing agent for 2-4 minutes to obtain metal simple substance seeds in the internal pores of the solid matrix; the metal elementary substance seed salt solution comprises one of a chloroauric acid solution, a silver nitrate solution, a palladium dichloride solution, a chloroplatinic acid solution, a copper sulfate solution and a nickel sulfate solution; the seed reducing agent comprises one or more of sodium borohydride solution, hydrazine hydrate solution and dimethylamino borane solution.
2. The metal nanoparticle-polymer composite material according to claim 1, wherein the material of the metal nanoparticle comprises one or more of gold, silver, palladium, platinum, rhodium, ruthenium, osmium, iridium, copper, zinc, chromium, molybdenum, tungsten, titanium, zirconium, niobium, cobalt, iron, and nickel.
3. The metal nanoparticle-polymer composite material of claim 1, wherein the material of the metal nanoparticle comprises one of gold, silver, copper and nickel, and the average absorption rate of the metal nanoparticle-polymer composite material to the solar spectrum in the wavelength region of 300-2500nm is greater than or equal to ninety percent.
4. The metal nanoparticle-polymer composite of claim 1, wherein the metal nanoparticles are nickel nanoparticles, and the average absorption rate of the metal nanoparticle-polymer composite is greater than or equal to ninety-seven percent in the solar spectrum in the wavelength region of 300-2500 nm.
5. The metal nanoparticle-polymer composite of claim 1, wherein the polymer fiber material comprises a natural fiber material and a synthetic porous fiber material; the natural fiber material comprises a cellulose material, a chitin material and a silk fiber material; the cellulose material comprises one of wet strength paper, printing paper, filter paper, dust-free paper, mirror wiping paper and cotton cloth.
6. A method for preparing a metal nanoparticle-polymer composite according to any one of claims 1 to 5, comprising the following steps of growing metal nanoparticles:
preparing metal seeds in the internal pores of the solid matrix; putting the solid matrix containing the metal seeds into a metal nanoparticle growth solution, and growing for 3-20 minutes to obtain a metal nanoparticle-polymer composite material;
the metal nanoparticle growth solution comprises a metal main salt solution, a complexing agent, a reducing agent and a pH regulator; the metal seeds comprise metal ion seeds and metal simple substance seeds;
wherein, preparing the metal ion seeds in the internal pores of the solid matrix specifically comprises: cleaning the solid matrix, and then putting the solid matrix into a metal ion seed solution to be soaked for 3-5 hours to obtain metal ion seeds in the internal pores of the solid matrix; the metal ion seed solution comprises one of a tin dichloride solution, a palladium dichloride solution and a diammine palladium dichloride solution;
the preparation of the metal elementary seeds in the internal pores of the solid matrix specifically comprises: cleaning the solid matrix, putting the solid matrix into a metal simple substance seed salt solution, soaking for 3-5 hours, cleaning, and then putting the solid matrix into a seed reducing agent for 2-4 minutes to obtain metal simple substance seeds in the internal pores of the solid matrix; the metal elementary substance seed salt solution comprises one of a chloroauric acid solution, a silver nitrate solution, a palladium dichloride solution, a chloroplatinic acid solution, a copper sulfate solution and a nickel sulfate solution; the seed reducing agent comprises one or more of sodium borohydride solution, hydrazine hydrate solution and dimethylamino borane solution.
7. The method for preparing a metal nanoparticle-polymer composite according to claim 6,
the metal main salt solution comprises one of chloroauric acid solution, silver nitrate solution, copper sulfate solution and nickel sulfate solution;
the complexing agent comprises one or more of tartaric acid, sodium chloride, ammonia water, potassium sodium tartrate, sodium citrate and lactic acid;
the reducing agent comprises one or more of ethanol, potassium sodium tartrate, formaldehyde and dimethylamino borane;
the pH regulator comprises one or more of sodium hydroxide and ammonia water.
8. The use of the metal nanoparticle-polymer composite material according to any one of claims 1 to 5, wherein the average absorption rate of the metal nanoparticle-polymer composite material to the solar spectrum of 300-2500nm is greater than or equal to 90%, and the metal nanoparticle-polymer composite material has high-efficiency photothermal conversion effect and is used for solar seawater desalination including photothermal conversion; the efficiency of photothermal water evaporation of the metal nanoparticle-polymer composite material is greater than or equal to 75%; the efficiency of the metal nanoparticle-polymer composite material for solar seawater desalination is 46.9-65.8%.
CN201911000688.2A 2019-10-21 2019-10-21 Metal nanoparticle-polymer composite material and preparation method and application thereof Active CN110777561B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911000688.2A CN110777561B (en) 2019-10-21 2019-10-21 Metal nanoparticle-polymer composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911000688.2A CN110777561B (en) 2019-10-21 2019-10-21 Metal nanoparticle-polymer composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110777561A CN110777561A (en) 2020-02-11
CN110777561B true CN110777561B (en) 2022-02-18

Family

ID=69386108

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911000688.2A Active CN110777561B (en) 2019-10-21 2019-10-21 Metal nanoparticle-polymer composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110777561B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113276510B (en) * 2021-05-20 2022-03-29 上海交通大学 Janus flexible composite film for intelligent radiant heat control and preparation method thereof
CN113308026B (en) * 2021-06-21 2022-06-28 深圳大学 Evaporator and preparation method and application thereof
CN114870412A (en) * 2022-04-02 2022-08-09 深圳大学 Solar evaporator and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101624798A (en) * 2008-07-07 2010-01-13 中国科学院理化技术研究所 Method for in-situ preparation of silver nanoparticles loaded on natural cellulose sheet
CN103570084A (en) * 2012-07-30 2014-02-12 无锡市顺业科技有限公司 Nanosilver-based method for protecting and treating blue-green algae pollution
CN107347913A (en) * 2017-06-14 2017-11-17 南阳师范学院 The preparation method of paper substrate two dimension Au@Ag core-shell nano compound disinfectants
CN107406611A (en) * 2015-02-25 2017-11-28 拜罗伊特大学 Metallized openings foam and fiber base material
CN108779002A (en) * 2016-01-14 2018-11-09 弗利亚水公司 Substrate, correlated product with metal nanoparticle and its continuously manufacturing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101624798A (en) * 2008-07-07 2010-01-13 中国科学院理化技术研究所 Method for in-situ preparation of silver nanoparticles loaded on natural cellulose sheet
CN103570084A (en) * 2012-07-30 2014-02-12 无锡市顺业科技有限公司 Nanosilver-based method for protecting and treating blue-green algae pollution
CN107406611A (en) * 2015-02-25 2017-11-28 拜罗伊特大学 Metallized openings foam and fiber base material
CN108779002A (en) * 2016-01-14 2018-11-09 弗利亚水公司 Substrate, correlated product with metal nanoparticle and its continuously manufacturing
CN107347913A (en) * 2017-06-14 2017-11-17 南阳师范学院 The preparation method of paper substrate two dimension Au@Ag core-shell nano compound disinfectants

Also Published As

Publication number Publication date
CN110777561A (en) 2020-02-11

Similar Documents

Publication Publication Date Title
CN110777561B (en) Metal nanoparticle-polymer composite material and preparation method and application thereof
Liu et al. Black titania/graphene oxide nanocomposite films with excellent photothermal property for solar steam generation
JP4378513B2 (en) Metal nanoparticles with support, metal nanoparticle continuum and methods for producing them
Li et al. Cellulose controlled zinc oxide nanoparticles with adjustable morphology and their photocatalytic performances
Kadi et al. Decoration of mesoporous graphite-like C 3 N 4 nanosheets by NiS nanoparticle-driven visible light for hydrogen evolution
CN108654607B (en) Preparation method of silver nanoparticle/carbon/titanium dioxide nano composite with core-shell structure
Deng et al. One-step solvothermal method to prepare Ag/Cu 2 O composite with enhanced photocatalytic properties
CN110918095A (en) Carbon/titanium dioxide/noble metal composite material, photocatalyst and preparation method thereof
Chen et al. Effects of Ag particle geometry on photocatalytic performance of Ag/TiO2/reduced graphene oxide ternary systems
Zhang et al. Porous cellulose gel-regulated flower-like ZnO-Cu nanoparticles for enhancing interfacial catalysis activity and recyclability in environmental catalysis
Moafi Photocatalytic self-cleaning properties of lanthanum and silver co-doped TiO2 nanocomposite on polymeric fibers
Miyama et al. Photoinduced formation and aggregation of silver nanoparticles at the surface of carboxymethylcellulose films
US11896960B1 (en) High-efficiency visible-light catalytic material and preparation method and application thereof
Narakaew et al. Silver-nanowire/bamboo-charcoal composite percolation network on nylon sheet for improved PM2. 5 capture efficiency
CN110280313B (en) Three-dimensional structure loaded TiO2-xMethod for producing a material
KR20160002912A (en) Method for coating of carbon nanomaterials
Zhang et al. Boron nitride-Au (Ag) loaded eggshell membrane with enhanced photothermal property
KR20100128178A (en) Porous metal/cnt composite and method for manufacturing the same
CN108580883A (en) A kind of sandwich nanogold particle nanometer sheet of graphene and preparation method thereof
Xu Design and preparation of Ag/AgCl/NH2-MIL-101 (Fe) ternary composite photocatalysts with visible light application prospects
CN111085185B (en) CeO 2 :CDs/TiO 2 Nano material and application thereof in photocatalysis
Khairy et al. Enhanced the Catalytic activity of reduction of 4-nitrophenol on Ag/RGO nanocomposites
Li et al. Preparation of nano-Ag-Bi2WO6–TiO2/starch bionanocomposite membranes and mechanism of enhancing visible light degradation of ethylene
Chai et al. Effect of thermal treating temperature on characteristics of silver-doped titania
CN108067254B (en) Preparation method of copper oxide nanocrystal and silver/copper oxide heterostructure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant