CN108295778B - Noble metal aerogel and preparation method thereof - Google Patents

Noble metal aerogel and preparation method thereof Download PDF

Info

Publication number
CN108295778B
CN108295778B CN201810372573.5A CN201810372573A CN108295778B CN 108295778 B CN108295778 B CN 108295778B CN 201810372573 A CN201810372573 A CN 201810372573A CN 108295778 B CN108295778 B CN 108295778B
Authority
CN
China
Prior art keywords
aerogel
noble metal
solution
parts
cellulose diacetate
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
CN201810372573.5A
Other languages
Chinese (zh)
Other versions
CN108295778A (en
Inventor
王朝阳
周小草
付志兵
杨曦
钟铭龙
米睿
袁磊
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.)
Laser Fusion Research Center China Academy of Engineering Physics
Original Assignee
Laser Fusion Research Center China Academy of Engineering Physics
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 Laser Fusion Research Center China Academy of Engineering Physics filed Critical Laser Fusion Research Center China Academy of Engineering Physics
Priority to CN201810372573.5A priority Critical patent/CN108295778B/en
Publication of CN108295778A publication Critical patent/CN108295778A/en
Application granted granted Critical
Publication of CN108295778B publication Critical patent/CN108295778B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals

Abstract

The invention discloses a noble metal aerogel and a preparation method thereof, wherein the preparation method comprises the following steps: adopting cellulose triacetate aerogel containing uniformly distributed Pd catalyst as a template to obtain non-noble metal/cellulose triacetate composite aerogel by a chemical plating method, and placing the non-noble metal/cellulose triacetate composite aerogel in a noble metal solution for chemical replacement reaction to obtain noble metal/cellulose triacetate composite aerogel; placing the noble metal/cellulose triacetate composite aerogel in LiOH/urea solution, and performing a cellulose triacetate template removing process to obtain nano porous noble metal gel; washing the nano porous noble metal gel with deionized water; carrying out solvent exchange on the obtained nano porous noble metal gel by using acetone; finally passing through supercritical CO2And drying to obtain the noble metal aerogel. The noble metal aerogel obtained by the method has a uniform structure and a high specific surface area, and has a good application prospect in the fields of hydrogen storage, fuel cells, laser inertial confinement fusion and the like.

Description

Noble metal aerogel and preparation method thereof
Technical Field
The invention belongs to the field of material preparation, and relates to a noble metal aerogel and a preparation method thereof.
Background
The metal aerogel with the nano structure is a novel material integrating the structure and the function, and in recent years, the metal aerogel has excellent application prospects in the fields of energy storage, catalysis, heat insulation, adsorption, sensors and the like because the metal aerogel simultaneously has good electric/heat conduction, ductility and catalytic activity of metal and a continuous nano-scale structure with high specific surface area, low density and high porosity of the aerogel. Especially, the noble metal aerogel with high purity and low density has great application prospect in the field of Inertial Confinement Fusion (ICF).
Currently, research and preparation of metallic aerogels is still in the quest and trial phase. At present, the preparation method mainly comprises an alloy removing method, a self-assembly method and a template method. The dealloying method is also called selective corrosion, namely, an element with more active chemical properties in the alloy is selectively dissolved under the action of electrolyte to leave an element with more stable electrochemical properties, and finally the nano porous metal is obtained. Although the dealloying method is adopted to obtain the low-density nano-porous metal, the specific surface area is very low (<50m2In terms of/g). However, the metal aerogel obtained by the self-assembly method generally has poor mechanical properties and cannot be self-supported. The template method is the most important method for preparing the metal aerogel with high specific surface area at present because the pore structure can be synthesized and controlled by sacrificing organic or inorganic materials, but the template method is generally used for preparing the metal aerogel with non-noble metal such as Ni, Cu and the like. For noble metal aerogel, the reaction rate is fast in the direct chemical plating process, metal ions are not yet in the template channel, namely, the metal ions are reduced to nano particles on the surface of the template, and the like, so that the nano porous metal with particle and ligament structures is difficult to obtain. In the patent of invention, we propose that non-noble metal Ni and Cu aerogel with high specific surface area can be prepared by a template method.
Based on this, the invention provides a method for obtaining noble metal aerogel by replacing non-noble metal aerogel. Firstly, a non-noble metal aerogel with a nano porous structure and a high specific surface area is obtained by a template method, and then the non-noble metal is replaced by noble metal through chemical replacement reaction, so that the noble metal aerogel with a reproducible structure can be obtained.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a noble metal aerogel, comprising the steps of:
step one, taking cellulose triacetate aerogel containing uniformly distributed Pd catalyst as a template to obtain Ni/cellulose triacetate composite aerogel through a chemical plating method, and placing the Ni/cellulose triacetate composite aerogel in a noble metal solution for a chemical replacement reaction to obtain the noble metal/cellulose triacetate composite aerogel;
secondly, placing the noble metal/cellulose triacetate composite aerogel obtained in the first step into a LiOH/urea solution, and performing a cellulose triacetate template removing process to obtain a nano porous noble metal gel;
step three, washing the nano porous noble metal gel obtained in the step two with deionized water for 4-8 times, 2 hours per time; until no noble metal ion exists in the cleaning solution;
step four, carrying out solvent exchange on the nano porous noble metal gel obtained in the step three by using acetone, wherein fresh acetone is replaced every day for 5-8 days for 1 day; finally passing through supercritical CO2And drying to obtain the noble metal aerogel.
Preferably, in the first step, the cellulose triacetate aerogel containing uniformly distributed Pd catalyst therein is prepared by a sol-gel method, which comprises: according to the weight portion, 0.1-10 portions of cellulose triacetate particles and 5-500 portions of 1, 4-dioxane are added into a reaction container together, the reaction container is placed on a device with a circulating cooling water system, stirring is continuously carried out for 3-5 hours under the conditions that the temperature is 50-80 ℃ and the rotating speed is 300-500 r/min, then the same temperature and rotating speed are kept, anhydrous alcohol solvents which are the same with the amount of the 1, 4-dioxane are added into the reaction container at the speed of 1-5 mL/min, stirring is fully carried out for 20-40 min, and then 0.5-2 portions of PdCl are added into the solution2And continuously stirring the solution for 5-10 min, transferring the finally formed solution into a forming die, sealing and standing for 12-48 hours, naturally cooling to be near room temperature, and aging to obtain the cellulose triacetate aerogel with uniformly distributed Pd activation centers.
Preferably, the anhydrous alcohol solvent is one of methanol, ethanol and isopropanol.
Preferably, in the first step, the chemical nickel plating solution used in the chemical plating has a formula of: taking 0.1-0.3 parts of NiCl by weight2·H2O, 4-6 parts of ethanol and 18-22 parts of deionized water are fully stirred and dissolved to obtain a light green clear solution, and then 1-3 parts of ammonia water and 1-3 parts of hydrazine hydrate are sequentially added, wherein the ammonia water: continuously stirring hydrazine hydrate at the ratio of 1:1 to obtain chemical nickel plating solution; the number of times of chemical plating is 1-3, and the time of chemical plating is 12-24 hours.
Preferably, the noble metal solution is HAuCl4Solution, H2PtCl6Solution, PdCl2Solution, AgNO3Any one of the solutions.
Preferably, in the second step, the formulation of the LiOH/urea solution is: adding 4-5 parts of LiOH and 14-16 parts of urea into 80-90 parts of deionized water according to parts by weight, and fully stirring and dissolving to obtain a LiOH/urea solution; the process of removing the template by the cellulose triacetate is as follows: and (2) placing the noble metal/cellulose triacetate composite aerogel in LiOH/urea, freezing and freezing at-20 to-12 ℃, taking out the noble metal/cellulose triacetate composite aerogel, thawing while stirring, and repeating the template removing process for 3 to 5 times to obtain the nano porous noble metal gel.
Preferably, the specific surface area of the cellulose triacetate aerogel is 300-1500 m2A density of 0.01 to 0.05g/cm3The holes are distributed in a concentrated way at 30 nm-100 nm.
Preferably, the cellulose triacetate aerogel containing uniformly distributed Pd catalyst inside is replaced by an aerogel prepared by the following method: placing cellulose diacetate in a bipolar square wave high-voltage pulse electric field for processing at the temperature of 75 ℃ to obtain pretreated cellulose diacetate; adding 35-50 parts by weight of pretreated cellulose diacetate, 5-10 parts by weight of itaconic anhydride, 60-80 parts by weight of toluene and 1-2 parts by weight of pyridine into a supercritical reaction device, sealing the system, introducing carbon dioxide to 25-30 MPa, stirring and reacting at 75-85 ℃ for 5-10 hours, releasing pressure, adding 3-5 parts by weight of 4-aminophthalic anhydride, 10-30 parts by weight of toluene and 0.5-1.5 part by weight of pyridine, sealing the system, and introducing carbon dioxide to 35-45 MPa. Stirring and reacting for 3-5 hours at the temperature of 75-85 ℃, and decompressing to obtain a reacted mixture; cooling the reacted mixture to room temperature, filtering, drying, and distilling to remove the solvent to obtain modified cellulose diacetate; according to the weight portion, 2-10 portions of modified cellulose diacetate, 10-500 portions of 1, 4-dioxane and 0.3-0.5 portion of 1-hexyl-3-methylimidazolium tetrafluoroborate are added into a reaction vessel, the reaction vessel is placed on a device with a circulating cooling water system, the mixture is continuously stirred for 3-5 hours at the temperature of 50-80 ℃ and the rotating speed of 300-500 r/min, then the same temperature and rotating speed are kept, isopropanol with the same quantity as that of 1, 4-dioxane is added into the reaction vessel at the speed of 1-5 mL/min, the mixture is fully stirred for 20-40 minutes, and then 0.5-2 portions of PdCl are added into the solution2And continuously stirring the solution, carrying out ultrasonic treatment for 15-30 min, transferring the finally formed solution into a forming die, sealing and standing for 12-48 h, naturally cooling to the temperature near room temperature, and aging to obtain the modified cellulose diacetate aerogel with uniformly distributed Pd activation centers.
Preferably, the bipolar square wave high-voltage pulse electric field has the pulse electric field intensity of 40-50 kV/cm, the frequency of 1000-1200 Hz and the processing time of 30-45 minutes; the frequency of the ultrasonic wave is 30-45 KHz, the ultrasonic wave adopts intermittent irradiation, and the time of the intermittent irradiation is 10-15 s/5-10 s.
The invention also provides the noble metal aerogel prepared by the preparation method, and the specific surface area of the noble metal aerogel is 80-320m2The grain size is 20-100nm, the pore size is 3-50nm, and the nano-skeleton has a three-dimensional network structure formed by the mutual connection of nano-skeletons.
The invention at least comprises the following beneficial effects:
(1) the preparation method has the characteristics of mild conditions, simplicity and easiness in operation, good controllability, strong repeatability, low cost and the like.
(2) The non-noble metal sacrificed in the invention is one of Ni and Cu, and the prepared noble metal aerogel is formed by any one of Ag, Au, Pt and Pd, has the characteristics of metal and high specific surface area of aerogel, and has excellent application prospect in the fields of catalysis, energy storage and laser research target materials.
(3) The invention provides a method for preparing noble metal aerogel by a sacrifice method, wherein the pore structure and the specific surface area of the noble metal aerogel are determined by the cellulose aerogel template and the non-noble metal structure, so that the cellulose aerogel has higher specific surface area and proper chemical plating pore structure and can be effectively removed by a chemical method.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a scanning electron microscope image of Au/cellulose triacetate composite aerogel prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of an Au aerogel prepared according to example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern of Au aerogel prepared in example 1 of the present invention;
FIG. 4 shows Au aerogel N prepared in example 1 of the present invention2Adsorption and desorption isotherm graphs.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
the preparation method of the Au aerogel comprises the following steps:
step one, preparing chemical nickel plating solution, and taking 0.2g NiCl2·H2O, 5mL of ethanol and 20mL of deionized water are fully stirred and dissolved to obtain a light green clear solution, and then 2mL of ammonia water and 2mL of hydrazine hydrate are sequentially added; continuously stirring to obtain chemical nickel plating solution; wet preparation of cellulose triacetate with uniformly distributed Pd catalytic activation centers in structure by sol-gel methodGel, soaking the wet gel in prepared chemical nickel plating solution, and performing chemical plating for 1 time at room temperature, wherein the time for the chemical plating for 1 time is 24 hours; until the solution turns colorless from blue to obtain Ni/cellulose triacetate composite aerogel, and placing the aerogel in 0.01g/mL HAuCl4Carrying out replacement reaction in the solution, and reacting for 2 days at room temperature until the aerogel has no magnetism, so as to obtain Au/cellulose triacetate composite aerogel;
weighing 4.6g of LiOH and 15g of urea in a beaker, adding 80.4mL of deionized water, fully stirring to completely dissolve the LiOH and urea to obtain a LiOH/urea template removing solution, placing the Au/cellulose triacetate composite aerogel in the LiOH/urea solution, placing the Au/cellulose triacetate composite aerogel in a refrigerator at the temperature of-20 ℃ to freeze and freeze the Au/cellulose triacetate composite aerogel, then thawing and stirring simultaneously, repeating the template removing process for 3-5 times until the cellulose triacetate is completely dissolved, and finally obtaining the nano-porous Au gel;
step three, washing the nano-porous Au gel obtained in the step two with deionized water for 4-8 times, 2 hours/time, until no Au ions exist in the washing liquid;
step four, performing solvent exchange on the nano-porous Au gel obtained in the step three by using acetone for 1 day/time, and replacing fresh acetone every day for 7 days; finally passing through supercritical CO2Drying to obtain Au aerogel;
in the first step, the cellulose triacetate aerogel containing uniformly distributed Pd catalyst inside is prepared by a sol-gel method, and the method comprises the following steps: adding 5g cellulose triacetate particles and 200g1, 4-dioxane into a reaction vessel, placing the reaction vessel on a device with a circulating cooling water system, continuously stirring for 5h at 60 ℃ and 500r/min, keeping the same temperature and rotation speed, adding isopropanol solvent with the same amount as that of 1, 4-dioxane into the reaction vessel at the speed of 3mL/min, stirring for 40min, and adding 1g PdCl into the solution2Continuously stirring the solution for 10min, transferring the finally formed solution into a forming die, sealing and standing for 48 hours, naturally cooling the solution to be near room temperature, and aging to obtain cellulose triacetate aerogel with uniformly distributed Pd activation centers;
FIG. 1 shows a scanning electron microscope image of Au/cellulose triacetate composite aerogel, from which it can be seen that the composite aerogel is formed into a three-dimensional network structure by the interconnection of a skeleton of triacetic acid and Au nanoparticles; fig. 2 is a scanning electron microscope image of Au aerogel obtained after removing the cellulose triacetate template in the composite aerogel, and it can be seen from the image that the aerogel is formed by stacking and connecting Au particles to each other to form a compact cellular porous structure, which is similar to the morphology structure of Ni aerogel obtained by the template method, and illustrates that the noble metal aerogel can be obtained by the sacrificial method, and the structure of the Ni aerogel can be reproduced. Fig. 3 is an X-ray diffraction pattern of the Au aerogel, and it can be seen from the pattern that the Au aerogel obtained by the preparation method provided by the present invention has a typical triple strong peak of the simple substance Au. Other impurity peaks are almost absent. FIG. 4 shows N of Au aerogel2Adsorption isotherm graph, and it can be seen from the graph that the Au aerogel prepared by the method is opposite to N2Has high adsorption capacity, and the BET specific surface area can be obtained by the adsorption isotherm curve of the adsorbent of (1)2(iv)/g, average pore diameter 9.53 nm.
Example 2:
preparation of Au aerogel, according to the implementation of example 1 of the preparation process of Au aerogel, except that the technical parameters of the electroless Ni plating times is 2, each time 24 hours, each time Ni plating amount is 0.2gNiCl2·H2Changing the content of Ni in the chemical plating solution of O into fresh plating solution when the chemical plating solution is changed from blue to colorless; the specific surface area of the prepared Au aerogel is 218.5m2In terms of/g, the mean pore diameter is 9.45 nm.
Example 3:
preparation of Au aerogel, according to the implementation of example 1 of the preparation process of Au aerogel, except that the technical parameters of the chemical Ni plating times is 3 times, each time 24 hours, each time Ni plating amount is 0.2gNiCl2·H2And when the content of Ni in the chemical plating solution of O is changed from blue to colorless, replacing the fresh plating solution. The specific surface area of the prepared Au aerogel is 225.2m2(iv)/g, average pore diameter 9.35 nm.
Example 4:
preparation of Au aerogel, the preparation of Au aerogel described in example 1 was carried out, except that the number of electroless Ni plating was 6 times, and the amount of Ni plating was 0.2g NiCl2·H2And when the content of Ni in the chemical plating solution of O is changed from blue to colorless, replacing the fresh plating solution. The specific surface area of the prepared Au aerogel is 233.8m2In terms of/g, the mean pore diameter was 9.26 nm.
Example 5:
the preparation method of the Pt aerogel comprises the following steps:
step one, preparing chemical nickel plating solution, and taking 0.2g NiCl2·H2O, 5mL of ethanol and 20mL of deionized water are fully stirred and dissolved to obtain a light green clear solution, and then 2mL of ammonia water and 2mL of hydrazine hydrate are sequentially added; continuously stirring to obtain chemical nickel plating solution; preparing cellulose triacetate wet gel with uniformly distributed Pd catalytic activation centers in the structure by using a sol-gel method, soaking the wet gel in prepared chemical nickel plating solution, performing chemical plating for 1 time at room temperature for 24 hours each time until the solution is colorless from blue to obtain Ni/cellulose triacetate composite aerogel, and placing the aerogel in a container with the volume of 0.01g/mLH2PtCl6And (3) carrying out a displacement reaction in the solution, and reacting for 2 days at room temperature until the aerogel has no magnetism, so as to obtain the Pt/cellulose triacetate composite aerogel.
Weighing 4.6g of LiOH and 15g of urea in a beaker, adding 80.4mL of deionized water, fully stirring to completely dissolve the LiOH and urea to obtain a LiOH/urea template removing solution, placing the Pt/cellulose triacetate composite aerogel in the LiOH/urea solution, placing the LiOH/urea solution in a refrigerator at the temperature of-20 ℃ to freeze and freeze the Pt/cellulose triacetate composite aerogel, then unfreezing and stirring, repeating the template removing process for 3-5 times until the cellulose triacetate is completely dissolved, and finally obtaining the nano porous Pt gel.
Step three, washing the nano-porous Pt gel obtained in the step two with deionized water for 4-8 times, 2 hours per time, until no Pt ions exist in the washing liquid;
step four, the nano porous Pt gel obtained in the step three is subjected to solvent exchange by using acetone, wherein fresh acetone is replaced every day for 7 days for 1 day; finally passing through supercritical CO2And drying to obtain the Pt aerogel.
In the first step, the cellulose triacetate aerogel containing uniformly distributed Pd catalyst inside is prepared by a sol-gel method, and the method comprises the following steps: adding 5g cellulose triacetate particles and 200g1, 4-dioxane into a reaction vessel, placing the reaction vessel on a device with a circulating cooling water system, continuously stirring for 5h at 80 ℃ and 500r/min, keeping the same temperature and rotation speed, adding isopropanol solvent with the same amount as that of 1, 4-dioxane into the reaction vessel at the speed of 3mL/min, stirring for 40min, and adding 2g PdCl into the solution2Continuously stirring the solution for 10min, transferring the finally formed solution into a forming die, sealing and standing for 48 hours, naturally cooling the solution to be near room temperature, and aging to obtain cellulose triacetate aerogel with uniformly distributed Pd activation centers;
the specific surface area of the Pt aerogel is 207.2m2(iv)/g, average pore diameter 9.87 nm.
Example 6:
preparation of Pt aerogel, according to the preparation process of Pt aerogel described in example 5, except that the number of times of electroless Ni plating is 2 times, 24 hours each time, and the amount of Ni plating is 0.2g NiCl2·H2And when the content of Ni in the chemical plating solution of O is changed from blue to colorless, replacing the fresh plating solution. The specific surface area of the prepared Pt aerogel is 214.5m2In terms of/g, the mean pore diameter was 9.58 nm.
Example 7:
preparation of Pt aerogel, according to the preparation process of Pt aerogel described in example 5, except that the number of times of electroless Ni plating is 3 times, 24 hours each time, and the amount of Ni plating is 0.2g NiCl2·H2And when the content of Ni in the chemical plating solution of O is changed from blue to colorless, replacing the fresh plating solution. The prepared Pt aerogel has the specific surface area of 223.8m2(iv)/g, average pore diameter 9.35 nm.
Example 8:
preparation of Pt aerogel, preparation of Pt aerogel according to example 5The preparation process is different from the prior art that the Ni plating times in the technical parameters are 6 times, each time is 24 hours, the Ni content in the chemical plating solution of which the Ni plating amount is 0.2g NiCl 2. H2O is changed into fresh plating solution when the color of the chemical plating solution is changed from blue to colorless. The prepared Pt aerogel has the specific surface area of 236.8m2(iv)/g, average pore diameter 9.21 nm.
Example 9:
the preparation of the Ag aerogel comprises the following steps:
step one, adopting the same method as Ni chemical plating in example 1 to perform chemical plating on Cu, namely, taking non-noble metal Cu as a sacrifice to prepare Ag aerogel. Firstly, preparing chemical Cu plating solution, wherein the chemical Cu plating solution comprises the following components: 15g/L of sodium citrate, 30g/L of boric acid, 10g/L of anhydrous copper sulfate and 30g/L of sodium hypophosphite. Preparing cellulose triacetate wet gel with uniformly distributed Pd catalytic activation centers in the structure by using a sol-gel method, soaking the wet gel in prepared chemical plating Cu solution, chemically plating for 1 time at room temperature for 24 hours each time until the solution is colorless from blue to obtain Cu/cellulose triacetate composite aerogel, and placing the aerogel in 0.01g/mLAgNO3Carrying out replacement reaction in the solution, and reacting for 2 days at room temperature until copper is completely replaced by Ag to obtain Ag/cellulose triacetate composite aerogel;
weighing 4.6g of LiOH and 15g of urea in a beaker, adding 80.4mL of deionized water, fully stirring to completely dissolve the LiOH and urea to obtain a LiOH/urea template removing solution, placing the Ag/cellulose triacetate composite aerogel in the LiOH/urea solution, placing the solution in a refrigerator at the temperature of-20 ℃ to freeze and freeze the solution, then thawing and stirring simultaneously, repeating the template removing process for 3-5 times until the cellulose triacetate is completely dissolved, and finally obtaining the nano-porous Ag gel;
step three, washing the nano-porous Ag gel obtained in the step two with deionized water for 4-8 times, 2 hours per time, until no Ag ions exist in the washing liquid;
step four, the nano-porous Ag gel obtained in the step three is subjected to solvent exchange by using acetone for 1 day/time, and fresh acetone is replaced every day for 7 days; finally passing through supercritical CO2Drying to obtain the Ag aerogel. The specific surface area of the Ag aerogel is 78.0m2(ii)/g, average pore diameter 11.23 nm.
In the first step, the cellulose triacetate aerogel containing uniformly distributed Pd catalyst inside is prepared by a sol-gel method, and the method comprises the following steps: adding 10g cellulose triacetate particles and 500g 1, 4-dioxane into a reaction vessel, placing the reaction vessel on a device with a circulating cooling water system, continuously stirring for 5h at 80 ℃ and 500r/min, keeping the same temperature and rotation speed, adding isopropanol solvent with the same amount as that of 1, 4-dioxane into the reaction vessel at the speed of 3mL/min, stirring for 40min, and adding 2g PdCl into the solution2Continuously stirring the solution for 10min, transferring the finally formed solution into a forming die, sealing and standing for 48 hours, naturally cooling the solution to be near room temperature, and aging to obtain cellulose triacetate aerogel with uniformly distributed Pd activation centers;
the specific surface area of the Ag aerogel is 218.5m2(ii)/g, average pore diameter 11.23 nm.
Example 10:
preparation of Ag aerogel, according to the preparation process of Ag aerogel described in example 9, except that the number of times of electroless Cu plating was 2 times, each time for 24 hours, the Cu content in electroless plating solution plated with 10g/L of anhydrous copper sulfate per time, and when the electroless plating solution changed from blue to colorless, the plating solution was replaced with fresh one. The specific surface area of the prepared Ag aerogel is 226.5m2In terms of/g, the mean pore diameter was 11.05 nm.
Example 11:
preparation of Ag aerogel, according to the preparation process of Ag aerogel described in example 8, except that the number of times of electroless Cu plating in the technical parameters was 3 times, each time for 24 hours, the Cu content in electroless plating solution plated with 10g/L of anhydrous copper sulfate per time, and when the electroless plating solution changed from blue to colorless, the plating solution was replaced with fresh one. The specific surface area of the prepared Ag aerogel is 237.2m2In terms of/g, the mean pore diameter is 10.58 nm.
Example 12:
preparation of Ag aerogel, following the preparation of Ag aerogel as described in example 8,the difference is that the number of chemical plating of Cu in the technical parameters is 6, each time is 24 hours, the content of Cu in the chemical plating solution of which the Cu plating amount is 10g/L anhydrous copper sulfate is changed into colorless when the chemical plating solution is changed from blue, and the fresh plating solution is replaced. The specific surface area of the prepared Ag aerogel is 242.6m2In terms of/g, the mean pore diameter is 10.12 nm.
Example 13:
the cellulose triacetate aerogel containing uniformly distributed Pd catalyst inside is replaced by the aerogel prepared by the following method: placing cellulose diacetate in a bipolar square wave high-voltage pulse electric field for processing at the temperature of 75 ℃ to obtain pretreated cellulose diacetate; adding 50g of pretreated cellulose diacetate, 10g of itaconic anhydride, 80g of toluene and 2g of pyridine into a supercritical reaction device, sealing the system, introducing carbon dioxide to 30MPa, stirring and reacting at the temperature of 80 ℃ for 8 hours, releasing the pressure, adding 5g of 4-aminobenzoic anhydride, 30g of toluene and 1.5g of pyridine, sealing the system, introducing carbon dioxide to 45MPa, stirring and reacting at the temperature of 85 ℃ for 5 hours, and releasing the pressure to obtain a reacted mixture; cooling the reacted mixture to room temperature, filtering, drying, and distilling to remove the solvent to obtain modified cellulose diacetate; adding 5g of modified cellulose diacetate, 200g of 1, 4-dioxane and 0.5g of 1-hexyl-3-methylimidazolium tetrafluoroborate into a reaction vessel, placing the reaction vessel on a device with a circulating cooling water system, continuously stirring for 5 hours at the temperature of 60 ℃ and the rotating speed of 500r/min, keeping the same temperature and rotating speed, adding isopropanol which is the same as the 1, 4-dioxane into the reaction vessel at the speed of 3mL/min, fully stirring for 40 minutes, and then adding 1g of PdCl into the solution2Continuously stirring the solution and carrying out ultrasound for 15min, transferring the finally formed solution into a forming die, sealing and standing for 48 hours, naturally cooling the solution to be near room temperature and aging the solution to obtain the modified cellulose diacetate aerogel with uniformly distributed Pd activation centers; the bipolar square wave high-voltage pulse electric field has the pulse electric field intensity of 50kV/cm, the frequency of 1200Hz and the processing time of 45 minutes; the frequency of the ultrasonic wave is 45KHz, the ultrasonic wave adopts intermittent irradiation, and the time of the intermittent irradiation is 10s/5s (evenContinuous irradiation time/intermittent time).
The rest of the process parameters and procedures are exactly the same as in example 1;
the specific surface area of the prepared Au aerogel is 285.2m2In terms of/g, the mean pore diameter is 5.58 nm.
Example 14:
the cellulose triacetate aerogel containing uniformly distributed Pd catalyst inside is replaced by the aerogel prepared by the following method: placing cellulose diacetate in a bipolar square wave high-voltage pulse electric field for processing at the temperature of 75 ℃ to obtain pretreated cellulose diacetate; adding 40g of pretreated cellulose diacetate, 8g of itaconic anhydride, 80g of toluene and 2g of pyridine into a supercritical reaction device, sealing the system, introducing carbon dioxide to 30MPa, stirring and reacting at the temperature of 80 ℃ for 8 hours, releasing the pressure, adding 5g of 4-aminobenzoic anhydride, 30g of toluene and 1g of pyridine, sealing the system, introducing carbon dioxide to 45MPa, stirring and reacting at the temperature of 85 ℃ for 5 hours, and releasing the pressure to obtain a mixture after the reaction; cooling the reacted mixture to room temperature, filtering, drying, and distilling to remove the solvent to obtain modified cellulose diacetate; adding 5g of modified cellulose diacetate, 200g of 1, 4-dioxane and 0.5g of 1-hexyl-3-methylimidazolium tetrafluoroborate into a reaction vessel, placing the reaction vessel on a device with a circulating cooling water system, continuously stirring for 5 hours at 80 ℃ and 500r/min, keeping the same temperature and rotating speed, adding isopropanol which is the same as the 1, 4-dioxane into the reaction vessel at the speed of 3mL/min, fully stirring for 40 minutes, and then adding 2g of PdCl into the solution2Continuously stirring the solution and carrying out ultrasound for 15min, transferring the finally formed solution into a forming die, sealing and standing for 48 hours, naturally cooling the solution to be near room temperature and aging the solution to obtain the modified cellulose diacetate aerogel with uniformly distributed Pd activation centers; the bipolar square wave high-voltage pulse electric field has the pulse electric field intensity of 50kV/cm, the frequency of 1200Hz and the processing time of 45 minutes; the frequency of the ultrasonic wave is 45KHz, the ultrasonic wave adopts intermittent irradiation, and the time of the intermittent irradiation is 10s/5s (continuous irradiation time/intermittent time).
The rest of the process parameters and procedures are exactly the same as in example 5;
the specific surface area of the Pt aerogel is 277.3m2In terms of/g, the mean pore diameter is 5.23 nm.
Example 15:
the cellulose triacetate aerogel containing uniformly distributed Pd catalyst inside is replaced by the aerogel prepared by the following method: placing cellulose diacetate in a bipolar square wave high-voltage pulse electric field for processing at the temperature of 75 ℃ to obtain pretreated cellulose diacetate; adding 40g of pretreated cellulose diacetate, 8g of itaconic anhydride, 80g of toluene and 2g of pyridine into a supercritical reaction device, sealing the system, introducing carbon dioxide to 30MPa, stirring and reacting at the temperature of 80 ℃ for 8 hours, releasing the pressure, adding 5g of 4-aminobenzoic anhydride, 30g of toluene and 1g of pyridine, sealing the system, introducing carbon dioxide to 45MPa, stirring and reacting at the temperature of 85 ℃ for 5 hours, and releasing the pressure to obtain a mixture after the reaction; cooling the reacted mixture to room temperature, filtering, drying, and distilling to remove the solvent to obtain modified cellulose diacetate; adding 10g of modified cellulose diacetate, 500g of 1, 4-dioxane and 0.5g of 1-hexyl-3-methylimidazolium tetrafluoroborate into a reaction vessel, placing the reaction vessel on a device with a circulating cooling water system, continuously stirring for 5 hours at 80 ℃ and 500r/min, keeping the same temperature and rotation speed, adding isopropanol with the same amount as that of the 1, 4-dioxane into the reaction vessel at the speed of 3mL/min, fully stirring for 40 minutes, and then adding 2g of PdCl into the solution2Continuously stirring the solution and carrying out ultrasound for 15min, transferring the finally formed solution into a forming die, sealing and standing for 48 hours, naturally cooling the solution to be near room temperature and aging the solution to obtain the modified cellulose diacetate aerogel with uniformly distributed Pd activation centers; the bipolar square wave high-voltage pulse electric field has the pulse electric field intensity of 50kV/cm, the frequency of 1200Hz and the processing time of 45 minutes; the frequency of the ultrasonic wave is 45KHz, the ultrasonic wave adopts intermittent irradiation, and the time of the intermittent irradiation is 10s/5s (continuous irradiation time/intermittent time).
The rest of the process parameters and procedures are exactly the same as in example 9;
the specific surface area of the Pt aerogel is 267.3m2In terms of a/g, the mean pore diameter is 6.15 nm.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (4)

1. The preparation method of the noble metal aerogel is characterized by comprising the following steps:
step one, adopting modified cellulose diacetate aerogel containing uniformly distributed Pd catalyst as a template to obtain non-noble metal/modified cellulose diacetate composite aerogel by a chemical plating method, and placing the non-noble metal/modified cellulose diacetate composite aerogel in a noble metal solution to perform chemical replacement reaction to obtain the noble metal/modified cellulose diacetate composite aerogel;
step two, placing the precious metal/modified cellulose diacetate composite aerogel gel obtained in the step one in LiOH/urea solution, and performing a template removing process of modified cellulose diacetate to obtain nano porous precious metal gel;
step three, washing the nano porous noble metal gel obtained in the step two with deionized water for 4-8 times, 2 hours per time; until no noble metal ion exists in the cleaning solution;
step four, carrying out solvent exchange on the nano porous noble metal gel obtained in the step three by using acetone, wherein fresh acetone is replaced every day for 5-8 days for 1 day; finally passing through supercritical CO2Drying to obtain noble metal aerogel;
the preparation method of the modified cellulose diacetate aerogel containing the uniformly distributed Pd catalyst comprises the following steps: putting cellulose diacetate into a bipolar square wave high-voltage pulse electric field for treatment at the temperature of 75 ℃ to obtain pretreated diacetate fibersA vitamin; adding 35-50 parts by weight of pretreated cellulose diacetate, 5-10 parts by weight of itaconic anhydride, 60-80 parts by weight of toluene and 1-2 parts by weight of pyridine into a supercritical reaction device, then sealing the system, introducing carbon dioxide to 25-30 MPa, stirring and reacting at 75-85 ℃ for 5-10 hours, releasing pressure, adding 3-5 parts by weight of 4-aminophthalic anhydride, 10-30 parts by weight of toluene and 0.5-1.5 parts by weight of pyridine, sealing the system, introducing carbon dioxide to 35-45 MPa, stirring and reacting at 75-85 ℃ for 3-5 hours, and releasing pressure to obtain a reacted mixture; cooling the reacted mixture to room temperature, filtering, drying, and distilling to remove the solvent to obtain modified cellulose diacetate; according to the weight portion, 2-10 portions of modified cellulose diacetate, 10-500 portions of 1, 4-dioxane and 0.3-0.5 portion of 1-hexyl-3-methylimidazolium tetrafluoroborate are added into a reaction vessel, the reaction vessel is placed on a device with a circulating cooling water system, the mixture is continuously stirred for 3-5 hours at the temperature of 50-80 ℃ and the rotating speed of 300-500 r/min, then the same temperature and rotating speed are kept, isopropanol with the same quantity as that of 1, 4-dioxane is added into the reaction vessel at the speed of 1-5 mL/min, the mixture is fully stirred for 20-40 minutes, and then 0.5-2 portions of PdCl are added into the solution2Continuously stirring the solution and carrying out ultrasonic treatment for 15-30 min, transferring the finally formed solution into a forming die, sealing and standing for 12-48 h, naturally cooling to the temperature near room temperature, and aging to obtain the modified cellulose diacetate aerogel with uniformly distributed Pd activation centers;
in the first step, the chemical nickel plating solution adopted by the chemical plating has the formula: taking 0.1-0.3 parts of NiCl by weight2·H2O, 4-6 parts of ethanol and 18-22 parts of deionized water are fully stirred and dissolved to obtain a light green clear solution, and then 1-3 parts of ammonia water and 1-3 parts of hydrazine hydrate are sequentially added, wherein the ammonia water: continuously stirring hydrazine hydrate at the ratio of 1:1 to obtain chemical nickel plating solution; the chemical copper plating solution adopted by the chemical plating has the formula as follows: 15g/L of sodium citrate, 30g/L of boric acid, 10g/L of anhydrous copper sulfate and 30g/L of sodium hypophosphite; the number of times of chemical plating is 1-6, and the time of one chemical plating is 12-24 hours;
the noble metal solution is HAuCl4Solutions of、H2PtCl6Solution, PdCl2Solution, AgNO3Any one of the solutions.
2. The method for preparing noble metal aerogel according to claim 1, wherein in the second step, the formulation of LiOH/urea solution is: adding 4-5 parts by weight of LiOH and 14-16 parts by weight of urea into 80-90 parts by weight of deionized water, and fully stirring and dissolving to obtain a LiOH/urea solution; the process for removing the template by the modified cellulose diacetate comprises the following steps: and (2) placing the noble metal/modified cellulose diacetate composite aerogel in LiOH/urea, freezing and freezing at the temperature of-20 to-12 ℃, taking out the noble metal/modified cellulose diacetate composite aerogel, thawing while stirring, and repeating the template removing process for 3-5 times to obtain the nano porous noble metal gel.
3. The preparation method of the noble metal aerogel as claimed in claim 1, wherein the bipolar square wave high-voltage pulse electric field has a pulse electric field intensity of 40-50 kV/cm, a frequency of 1000-1200 Hz, and a treatment time of 30-45 minutes; the frequency of the ultrasonic wave is 30-45 KHz, the ultrasonic wave adopts intermittent irradiation, and the time of the intermittent irradiation is 10-15 s/5-10 s.
4. The noble metal aerogel prepared by the preparation method according to any one of claims 1 to 3, wherein the specific surface area of the noble metal aerogel is 80-320m2The grain size is 20-100nm, the pore size is 3-50nm, and the nano-skeleton has a three-dimensional network structure formed by the mutual connection of nano-skeletons.
CN201810372573.5A 2018-04-24 2018-04-24 Noble metal aerogel and preparation method thereof Active CN108295778B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810372573.5A CN108295778B (en) 2018-04-24 2018-04-24 Noble metal aerogel and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810372573.5A CN108295778B (en) 2018-04-24 2018-04-24 Noble metal aerogel and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108295778A CN108295778A (en) 2018-07-20
CN108295778B true CN108295778B (en) 2020-02-18

Family

ID=62846299

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810372573.5A Active CN108295778B (en) 2018-04-24 2018-04-24 Noble metal aerogel and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108295778B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109225078B (en) * 2018-09-11 2021-05-25 陕西师范大学 Method for preparing noble metal aerogel based on ligand self-assembly
CN111250007B (en) * 2020-01-17 2022-04-22 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) Preparation method of pure metal aerogel and flexible composite material
CN112264628B (en) * 2020-10-28 2022-03-25 中国工程物理研究院激光聚变研究中心 Preparation method of gold aerogel
CN112387222B (en) * 2020-10-28 2022-04-19 中国工程物理研究院激光聚变研究中心 Preparation method of Co-Ni bimetallic aerogel
CN115415519B (en) * 2022-10-11 2023-07-28 雅安百图高新材料股份有限公司 Chemical nickel plating solution of graphite micropowder and method for judging nickel plating reaction end point

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3911557B2 (en) * 2001-12-07 2007-05-09 独立行政法人産業技術総合研究所 Method for producing porous material carrying ultrafine metal particles
JP5162752B2 (en) * 2007-03-20 2013-03-13 国立大学法人 東京大学 Cellulose airgel and method for producing the same
CN103993299B (en) * 2014-04-22 2016-10-05 中国工程物理研究院激光聚变研究中心 A kind of preparation method of nano porous metal material
CN104130444B (en) * 2014-07-24 2017-06-20 中国工程物理研究院激光聚变研究中心 A kind of preparation method of Triafol T aeroge
CN105970193B (en) * 2016-05-24 2018-04-10 中国工程物理研究院激光聚变研究中心 A kind of metal in height ratio surface area aeroge and preparation method thereof

Also Published As

Publication number Publication date
CN108295778A (en) 2018-07-20

Similar Documents

Publication Publication Date Title
CN108295778B (en) Noble metal aerogel and preparation method thereof
CN109638295B (en) Preparation method of oxygen reduction catalyst based on metal organic framework compound
Li et al. Rational microstructure design on metal–organic framework composites for better electrochemical performances: design principle, synthetic strategy, and promotion mechanism
CN110518257B (en) Preparation method of carbon-supported transition metal @ Pt core-shell structure catalyst
CN108336308A (en) A kind of lithium-sulphur cell positive electrode protection materials and its application
Feng et al. Tailoring the structure and function of metal organic framework by chemical etching for diverse applications
CN107224981B (en) PdNi alloy nano catalyst for ammonia borane hydrolysis hydrogen release and preparation method thereof
CN110639565B (en) Carbon-bimetal phosphide composite material and preparation method thereof
CN112087939B (en) FeCoNi @ C/carbon nanotube magnetic composite wave-absorbing material and application
CN100441342C (en) Preparation method of carbon-cladded magnetic metal nanometer material
CN111530486A (en) Novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material and preparation method thereof
Le et al. Metal-organic powder thermochemical solid-vapor architectonics toward gradient hybrid monolith with combined structure-function features
CN112387222B (en) Preparation method of Co-Ni bimetallic aerogel
CN111715248A (en) Cathode catalyst for hollow nano electrolyzed water and preparation method thereof
Xie et al. Recent Progress in 2D Metal‐Organic Framework‐Related Materials
Yu et al. Fullerene-Derived Carbon Nanotubes and Their Electrocatalytic Properties in Oxygen Reduction and Zn–Air Batteries
CN113903910A (en) Carbon cloth/cobaltosic oxide nanowire composite material and preparation method and application thereof
KR101628362B1 (en) Porous metal/cnt composite and method for manufacturing the same
Ge et al. Controllable synthesis of hierarchical Au/PdAg heterostructures consisting of nanosheets on nanorods with plasmon-enhanced electrocatalytic properties
CN110652992A (en) Synthesis method and application of hollow oxide/phosphide carbon-coated composite material for electrocatalytic hydrogen production
CN114273663B (en) Cu-M series nano porous amorphous alloy and preparation method thereof
CN106045552B (en) Preparation method of three-dimensional graphene macrostructure
Su et al. Recent progress in strategies for preparation of metal-organic frameworks and their hybrids with different dimensions
CN110317005B (en) Preparation method of graphene electrode material with three-dimensional hierarchical pore structure
Yang et al. Recent progress in the synthesis of metal-organic-framework-derived carbon materials

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