CN105970193A - Metal aerogel with high specific surface area and preparation method thereof - Google Patents

Metal aerogel with high specific surface area and preparation method thereof Download PDF

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Publication number
CN105970193A
CN105970193A CN201610349518.5A CN201610349518A CN105970193A CN 105970193 A CN105970193 A CN 105970193A CN 201610349518 A CN201610349518 A CN 201610349518A CN 105970193 A CN105970193 A CN 105970193A
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metal
aeroge
surface area
solution
cellulose
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CN105970193B (en
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赵海波
王朝阳
付志兵
袁磊
杨曦
米睿
瞿静
周小草
钟铭龙
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Laser Fusion Research Center China Academy of Engineering Physics
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Laser Fusion Research Center China Academy of Engineering Physics
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    • 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
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1644—Composition of the substrate porous substrates
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/1648—Porous product
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1657—Electroless forming, i.e. substrate removed or destroyed at the end of the process
    • 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
    • C23C18/44—Coating with noble metals using reducing agents

Abstract

The invention discloses metal aerogel with a high specific surface area and a preparation method thereof. The method comprises the steps that (1) cellulose aerogel is placed in a sensitizing solution to be soaked and then is washed with water; (2) the treated cellulose aerogel is soaked in a metal chemical plating solution for chemical plating, and metal/cellulose composite aerogel is obtained; (3) the metal/cellulose composite aerogel is placed in a LiOH/urea solution, the process of removing a cellulose aerogel template is conducted at a low temperature, and a nanometer porous metal solution is obtained; and (4) the prepared nanometer porous metal solution is washed with water, then is subjected to solvent exchange with acetone and is dried, and the metal aerogel with the high specific surface area is obtained. The method adopting the cellulose aerogel as the template for preparing the metal aerogel with the high specific surface area is provided for the first time. The cellulose aerogel has a high specific surface area and is of a pore structure suitable for chemical plating. Meanwhile, the template is easy to remove after the chemical plating, and reference is provided for preparation of metal aerogel with other templates.

Description

A kind of metal in height ratio surface area aeroge and preparation method thereof
Technical field
The invention belongs to aerogel material preparing technical field, be specifically related to a kind of metal in height ratio surface area gas Gel and preparation method thereof.
Background technology
Aeroge is a kind of star's material of rising in recent years, its due to the higher porosity of material self, Specific surface area, the lowest apparent intensity, density and refractive index, study target material, heat insulation in light laser The fields such as material, energy storage material, catalysis material, adsorbing material, Cherenkov's threshold detector show Preferred application prospect.The many that metal aerogel has had metal material and porous aerogel material concurrently is superior Character, including low-density, high porosity, high electricity/thermal conductivity, good catalysis activity and high intensity/weight Than etc.；Which represent a kind of limiting form of metal, electrochemistry pole piece, catalysis, electrochemical sensor, Many fields such as magnetizing mediums, biological skeleton and hydrogen storage, separation film, inertial confinement fusion (ICF) are great should Use prospect.
At present about the research of metal aerogel with prepare still at an early stage, it is different from polymer airsetting Glue and carbon aerogels, metal aerogel is difficult to be obtained by corresponding hydrogel convection drying.Porous gold at present The preparation method belonging to aeroge mainly includes template, goes alloyage, combustion method and sol-gel process etc.. Though can obtaining, by these methods, the metal aerogel that density is relatively low, but the specific surface of aeroge being the least (＜ 50m2g-1).Specific surface area is an important parameter of aeroge, and high-ratio surface can effectively increase Metallic surface activity, is more conducive to play the functional characteristic of metal aerogel.Such as use as catalyst, The high-specific surface area of metal aerogel can effectively increase the catalytic site of metallic catalyst, and then improves The catalytic efficiency of material；Using as electrochemistry pole piece, the high-specific surface area of metal aerogel can increase electricity The avtive spot of chemical material, and improve the specific capacity of material.
Although specific surface area is most important to metal aerogel, but it's a pity, study report the most both at home and abroad In road, specific surface is more than 100m2g-1Metal aerogel there is not been reported.This is because one side metal The preparation research of aeroge is still in the starting stage, and the official documents and correspondence being available for reference is less；The most then It it is owing to the density of metal is bigger so that the more difficult acquisition of aeroge of high-specific surface area.
Summary of the invention
It is an object of the invention to solve at least the above and/or defect, and provide after at least and will say Bright advantage.
In order to realize according to object of the present invention and further advantage, it is provided that a kind of high-specific surface area gold Belong to the preparation method of aeroge, comprise the following steps:
Step one, cellulose aerogels is placed in sensitizing solution and soaks at least 1h, then rinse fiber with water Element aeroge；
Step 2, will step one process after cellulose aerogels be soaked in metallochemistry plating solution and carry out Chemical plating, it is thus achieved that metal/cellulose composite aerogel；
Step 3, metal/cellulose composite aerogel is placed in LiOH/ urea liquid, leads at low temperatures Cross LiOH/ urea liquid dissolving cellulose and carry out cellulose aerogels template procedure, it is thus achieved that nanoporous Metallic solution；
Step 4, prepared nano porous metal solution with water is cleaned, then carry out solvent friendship with acetone Change, be dried, it is thus achieved that metal in height ratio surface area aeroge.
Preferably, in described step one, cellulose aerogels is prepared by method of reproduction, and its method is: By weight, take 0.5～2 part of microcrystalline Cellulose and 45～55 parts of ionic liquids add in reaction vessel, will Reaction vessel is placed in the oil bath of 80 DEG C 3～6h makes microcrystalline Cellulose dissolve, the then crystallite after dissolving Cellulose solution is put into and is processed 1～3d in the vacuum drying oven of 80 DEG C, is subsequently adding EtOH/H2O solution is again Raw gel, prepares cellulose aerogels；Described EtOH/H2Volume shared by EtOH in O solution Mark is 80%.
Preferably, described ionic liquid is 1-pi-allyl-3-Methylimidazole. villaumite, 1-ethyl-3-methyl chloride Change imidazoles, 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazole acetate, 1-hexyl-3-methyl Tetrafluoroborate, 1,3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole lactic acid, 1- One in n-hexadecyl-3 methy limidazolium.
Preferably, in described step one, cellulose aerogels is prepared by method of reproduction, and its method is: By weight, 0.5～2 part of microcrystalline Cellulose is added in 40～60 parts of LiOH/ urea liquids, -24～-20 DEG C under conditions of dissolve microcrystalline Cellulose, add EtOH/H after dissolving completely2The regeneration of O solution is solidifying Glue, prepares cellulose aerogels；Described EtOH/H2Volume fraction shared by EtOH in O solution It is 80%；The compound method of described LiOH/ urea liquid is: by weight, takes LiOH4～5 parts and urine Element 15 parts, adds in 80～90 parts of deionized waters, and stirring and dissolving obtains LiOH/ urea liquid.
Preferably, described sensitizing solution is PdCl2Or SnCl2At least one in solution；Described PdCl2 Or SnCl2The preparation method of solution is: by weight, takes 0.03～0.08 part of PdCl2Or SnCl2In burning In Bei, add 45 parts of EtOH and 5 parts of 1mol L-1HCl is placed in ultrasonic dissolution in ultrasonic washing instrument, Obtain sensitizing solution.
Preferably, described metallochemistry plating solution is Ni chemical plating fluid, Cu chemical plating fluid, Ag chemical plating One in liquid；Described Ni chemical plating fluid formula is: by weight: 0.1～0.3 part of NiCl2·6H2O、 20 parts of deionized waters, 5 parts of ethanol, 2 parts of ammonia and 2 parts of hydrazine hydrates；Described ammonia mass percent For 28wt%；Described Cu chemical plating fluid formula is: sodium citrate 15g/L, boric acid 30g/L, anhydrous sulfur Acid copper 10g/L and sodium hypophosphite 30g/L；Described Ag chemical plating fluid formula is: AgNO310～20 G/L, NaOH5～10g/L, ammonia 50～80mL/L, glucose 3～8g/L, Polyethylene Glycol 3-8g/L, Ethanol 15mL/L；Described ammonia mass percent is 28wt%.
Preferably, described in perform step 4 after, also include step 5: the high-ratio surface that will obtain Long-pending metal aerogel is soaked into the H of 1～3mol/L2PtCl6Or HAuCl4In solution 8～12 hours, then Metal aerogel dilute hydrochloric acid is removed, is dried and i.e. obtains Pt aeroge or Au aeroge；Described dilute salt The concentration of acid is 0.5～1mol/L.
Preferably, in described step 2, the time of chemical plating is 1～12d；
In described step 3, the compound method of LiOH/ urea liquid is: by weight, takes LiOH4～5 Part and 15 parts of carbamide, add in 80～90 parts of deionized waters, and stirring and dissolving obtains LiOH/ urea liquid； Described go cellulose aerogels template process be: metal/cellulose composite aerogel is placed in LiOH/ urine In cellulose solution, be placed in-24～-20 DEG C make it be frozen into ice, then taking out thaws stirs, solve Repeat aforesaid operations 3～4 times after freezing, until cellulose is completely dissolved, obtain nano porous metal solution；
In described step 4, the number of times that deionized water cleans is 5～8 times, and acetone carries out solvent exchange every day Change fresh acetone, continue 5～8 days；The mode being dried is normal temperature drying, lyophilization, supercritical drying One in dry.
Preferably, the specific surface area of described cellulose aerogels is 100～1000m2/g；Described Gao Bibiao The specific surface area of area metal aeroge is 30～200m2/g。
Present invention also offers metal in height ratio surface area aeroge prepared by a kind of above-mentioned preparation method, institute The specific surface area stating metal in height ratio surface area aeroge is 30～200m2/g。
The present invention at least includes following beneficial effect:
(1) metal aerogel prepared by the present invention is by any one metal in Ni, Cu, Ag, Pt, Au Constitute, there is metallic character and the low-density of aeroge and the characteristic of high-specific surface area simultaneously, catalysis, Many fields such as electrochemical sensor, magnetizing mediums, biological skeleton and hydrogen storage, separation film, brake have Preferred application prospect.
(2) metal aerogel of the present invention has higher specific surface area, specific surface area between 30～200m2/g。
(3) present invention firstly provides with cellulose aerogels as template, prepare metal in height ratio surface area airsetting The method of glue.Cellulose aerogels has higher specific surface area and the pore structure of applicable chemical plating, simultaneously After chemical plating, easy stripper plate, prepares metal aerogel for other template and offers reference.
Part is embodied by the further advantage of the present invention, target and feature by description below, and part also will By the research of the present invention and practice are understood by the person skilled in the art.
Accompanying drawing illustrates:
Fig. 1 is the scanning electron microscope sem figure of the Ni aeroge of the embodiment of the present invention 1 preparation；
Fig. 2 is the N of the Ni aeroge of the embodiment of the present invention 1 preparation2Adsorption isothermal curve schematic diagram.
Detailed description of the invention:
The present invention is described in further detail below in conjunction with the accompanying drawings, to make those skilled in the art's reference Description word can be implemented according to this.
Should be appreciated that used herein such as " have ", " comprising " and " including " term do not allot one Individual or multiple other element or the existence of a combination thereof or interpolation.
Embodiment 1:
The preparation method of a kind of metal in height ratio surface area aeroge, comprises the following steps:
Step one, weigh 1g microcrystalline Cellulose and 49g 1-pi-allyl-3-Methylimidazole. villaumite (purity 98%) In beaker, after under the conditions of being placed in 80 DEG C, oil bath 4h makes cellulose be completely dissolved, then beaker is placed on 80 DEG C of vacuum drying ovens process 2d；Above-mentioned beaker is taken out from drying baker, adds EtOH/H2O is molten Liquid rejuvenation gel, is prepared into cellulose aerogels；Described EtOH/H2Body shared by EtOH in O solution Fraction is 80%；
Step 2, weigh 0.05g PdCl2In beaker, add 45mL ethanol (EtOH) and 5mL 1mol·L-1HCl is placed in ultrasonic dissolution in ultrasonic washing instrument, obtains PdCl2Sensitizing solution；By cellulose Aeroge is placed in PdCl2Sensitizing solution carries out sensitized treatment, takes out after 1d, with deionized water rinsing to remove Remove the PdCl of cellulose aerogels surface enrichment2；
Step 3, will in step 2 process after cellulose aerogels be placed in Ni chemical plating fluid, in room temperature Under carry out chemical plating, within every two days, change 1 Ni chemical plating fluid, such repetitive cycling, until solution is by indigo plant Purple becomes colorless, and obtains Ni/ cellulose composite aerogel；Ni chemical plating fluid formula is: 0.2g NiCl2·6H2O, 20mL deionized water, 5mL ethanol, 2mL ammonia and 2mL hydrazine hydrate；Institute Stating ammonia mass percent is 28wt%；
Step 4, weighing LiOH4.6g, carbamide 15g, in beaker, is subsequently adding 80.4mL deionization Water stirring makes it be completely dissolved to obtain template LiOH/ urea liquid, put by Ni/ cellulose composite aerogel In LiOH/ urea liquid, it is transferred in-22 DEG C of refrigerators make it be frozen into ice, then takes out defrosting While stirring, repeat this operation 3～4 times, until cellulose is completely dissolved, obtain nanoporous nickel solution；
Step 5, prepared nanoporous nickel solution deionized water is cleaned several times, then enter with acetone Row solvent exchange, changes fresh acetone every day, continues 7d, then carries out supercritical drying, i.e. obtain Ni aeroge；Fig. 1 shows the scanning electron microscope sem figure of Ni aeroge, it can be seen that this airsetting Glue is fine and close cellular structures；Fig. 2 is the N of Ni aeroge2Adsorption isothermal curve is intended to, by scheming Middle curve result of calculation understands, and the specific surface area of this aeroge is up to 112m2/g；This Ni aeroge density For 1.1g/cm3。
Embodiment 2:
The preparation method of a kind of metal in height ratio surface area aeroge, comprises the following steps:
Method in step one, employing embodiment 1 prepares cellulose aerogels；
Step 2, respectively preparation 100mL 0.1mol L-1PdCl2Solution and SnCl2Solution, will system Standby cellulose aerogels is respectively at SnCl2And PdCl2Solution soaks 1 day, then rushes with deionized water Wash；
Step 3, will in step 2 process after cellulose aerogels be placed in Cu chemical plating fluid, in room temperature Under carry out chemical plating, within every two days, change 1 Cu chemical plating fluid, such repetitive cycling, until solution becomes Colourless, obtain Cu/ cellulose composite aerogel；Cu chemical plating fluid formula is: sodium citrate 15g/L, Boric acid 30g/L, anhydrous cupric sulfate 10g/L and sodium hypophosphite 30g/L；
Step 4, weighing LiOH4.6g, carbamide 15g, in beaker, is subsequently adding 80.4mL deionization Water stirring makes it be completely dissolved to obtain template LiOH/ urea liquid, put by Cu/ cellulose composite aerogel In LiOH/ urea liquid, it is transferred in-22 DEG C of refrigerators make it be frozen into ice, then takes out defrosting While stirring, repeat this operation 3～4 times, until cellulose is completely dissolved, obtain nanoporous copper solution；
Step 5, prepared nanoporous copper solution is spent ionized water clean several times, then enter with acetone Row solvent exchange, changes fresh acetone every day, continues 7d, then carries out supercritical drying, i.e. obtain Cu Aeroge；This Cu aeroge density is 0.9g/cm3, specific surface area is 148m2/g。
Embodiment 3:
The preparation method of a kind of metal in height ratio surface area aeroge, comprises the following steps:
Step one, 1g microcrystalline Cellulose is added in 50mL LiOH/ urea liquid, the condition of-22 DEG C Lower dissolving microcrystalline Cellulose, adds EtOH/H after dissolving completely2O solution rejuvenation gel, prepares fibre Dimension element aeroge；Described EtOH/H2In O solution, the volume fraction shared by EtOH is 80%；Described LiOH/ The compound method of urea liquid is: weighs LiOH4.6g, carbamide 15g and, in beaker, is subsequently adding 80.4mL Deionized water stirring makes it be completely dissolved to obtain LiOH/ urea liquid；
Step 2, respectively preparation 100mL 0.1mol L-1PdCl2Solution and SnCl2Solution, will system Standby cellulose aerogels is respectively at SnCl2And PdCl2Solution soaks 1 day, then rushes with deionized water Wash；
Step 3, will in step 2 process after cellulose aerogels be placed in Ag chemical plating fluid, Yu Chang Carry out chemical plating under temperature, within every two days, change 1 Ag chemical plating fluid, such repetitive cycling, until solution Become colorless, obtain Ag/ cellulose composite aerogel；Ag chemical plating fluid formula is: AgNO320g/L、 NaOH 5g/L, ammonia 50mL/L, glucose 3g/L, Polyethylene Glycol 8g/L, ethanol 15mL/L；Institute Stating ammonia mass percent is 28wt%；
Step 4, weighing LiOH4.6g, carbamide 15g, in beaker, is subsequently adding 80.4mL deionization Water stirring makes it be completely dissolved to obtain template LiOH/ urea liquid, put by Ag/ cellulose composite aerogel In LiOH/ urea liquid, it is transferred in-22 DEG C of refrigerators make it be frozen into ice, then takes out defrosting While stirring, repeat this operation 3～4 times, until cellulose is completely dissolved, obtain nano-porous silver solution；
Step 5, prepared nano-porous silver solution deionized water is cleaned several times, then enter with acetone Row solvent exchange, changes fresh acetone every day, continues 7d, then carries out supercritical drying, i.e. obtain Ag aeroge；This Ag aeroge specific surface area is 178m2/g。
Embodiment 4:
Prepare Ni aeroge according to embodiment 1, Ni aeroge is soaked into the H of 2M2PtCl6In solution 10h, until solution gradually becomes colourless, then removes the hydrochloric acid of Ni aeroge template 0.8mol/L, Being dried and i.e. obtain Pt aeroge, the specific surface area of this Pt aeroge is 159m2/g。
Embodiment 5:
Prepare Ni aeroge according to embodiment 1, Ni aeroge is soaked into the HAuCl of 2M4In solution 10h, until solution gradually becomes colourless, then removes the hydrochloric acid of Ni aeroge template 0.8mol/L, Being dried and i.e. obtain Au aeroge, the specific surface area of this Au aeroge is 165m2/g。
Embodiment 6:
The preparation method of a kind of metal in height ratio surface area aeroge, comprises the following steps:
Step one, weigh 2g microcrystalline Cellulose and 55g 1-pi-allyl-3-Methylimidazole. villaumite (purity 98%) In beaker, after under the conditions of being placed in 80 DEG C, oil bath 5h makes cellulose be completely dissolved, then beaker is placed on 80 DEG C of vacuum drying ovens process 3d；Above-mentioned beaker is taken out from drying baker, adds EtOH/H2O is molten Liquid rejuvenation gel, is prepared into cellulose aerogels；Described EtOH/H2Body shared by EtOH in O solution Fraction is 80%；
Step 2, weigh 0.08g SnCl2In beaker, add 45mL ethanol (EtOH) and 5mL 1mol·L-1HCl is placed in ultrasonic dissolution in ultrasonic washing instrument, obtains SnCl2Sensitizing solution；By cellulose Aeroge is placed in SnCl2Sensitizing solution carries out sensitized treatment, takes out after 1d, with deionized water rinsing to remove Remove the SnCl of cellulose aerogels surface enrichment2；
Step 3, will in step 2 process after cellulose aerogels be placed in Cu chemical plating fluid, in room temperature Under carry out chemical plating, within every two days, change 1 Cu chemical plating fluid, such repetitive cycling, until solution becomes Colourless, obtain Cu/ cellulose composite aerogel；Cu chemical plating fluid formula is: sodium citrate 15g/L, Boric acid 30g/L, anhydrous cupric sulfate 10g/L and sodium hypophosphite 30g/L；
Step 4, weighing LiOH5g, carbamide 15g, in beaker, is subsequently adding 85mL deionized water and stirs Mix and make it be completely dissolved to obtain template LiOH/ urea liquid, be placed in by Cu/ cellulose composite aerogel In LiOH/ urea liquid, it is transferred in-22 DEG C of refrigerators make it be frozen into ice, then takes out defrosting one Limit is stirred, and repeats this operation 3～4 times, until cellulose is completely dissolved, obtains nanoporous copper solution；
Step 5, prepared nanoporous copper solution is spent ionized water clean several times, then enter with acetone Row solvent exchange, changes fresh acetone every day, continues 8d, then carries out supercritical drying, i.e. obtain Cu Aeroge；This Cu aeroge density is 1g/cm3, specific surface area is 156m2/g。
Embodiment 7:
The preparation method of a kind of metal in height ratio surface area aeroge, comprises the following steps:
Step one, 1.5g microcrystalline Cellulose is added in 60mL LiOH/ urea liquid, at the bar of-22 DEG C Dissolve microcrystalline Cellulose under part, after dissolving completely, add EtOH/H2O solution rejuvenation gel, prepares Cellulose aerogels；Described EtOH/H2In O solution, the volume fraction shared by EtOH is 80%；Described The compound method of LiOH/ urea liquid is: weighs LiOH5g, carbamide 15g and, in beaker, is subsequently adding The stirring of 85mL deionized water makes it be completely dissolved to obtain LiOH/ urea liquid；
Step 2, respectively preparation 100mL 0.1mol L-1PdCl2Solution and SnCl2Solution, will system Standby cellulose aerogels is respectively at SnCl2And PdCl2Solution soaks 1 day, then rushes with deionized water Wash；
Step 3, will in step 2 process after cellulose aerogels be placed in Ag chemical plating fluid, Yu Chang Carry out chemical plating under temperature, within every two days, change 1 Ag chemical plating fluid, such repetitive cycling, until solution Become colorless, obtain Ag/ cellulose composite aerogel；Ag chemical plating fluid formula is: AgNO315g/L、 NaOH 10g/L, ammonia 60mL/L, glucose 8g/L, Polyethylene Glycol 7g/L, ethanol 15mL/L； Described ammonia mass percent is 28wt%；
Step 4, weighing LiOH5g, carbamide 15g, in beaker, is subsequently adding 85mL deionized water and stirs Mix and make it be completely dissolved to obtain template LiOH/ urea liquid, be placed in by Ag/ cellulose composite aerogel In LiOH/ urea liquid, it is transferred in-23 DEG C of refrigerators make it be frozen into ice, then takes out defrosting one Limit is stirred, and repeats this operation 3～4 times, until cellulose is completely dissolved, obtains nano-porous silver solution；
Step 5, prepared nano-porous silver solution deionized water is cleaned several times, then enter with acetone Row solvent exchange, changes fresh acetone every day, continues 6d, then carries out supercritical drying, i.e. obtain Ag aeroge, after tested, this Ag aeroge specific surface area is 200m2/g。
Embodiment 8:
Prepare Cu aeroge according to embodiment 2, Cu aeroge is soaked into the HAuCl of 2M4Solution Middle 10h, until solution gradually becomes colourless, then removes the hydrochloric acid of Cu aeroge template 1mol/L Go, be dried and i.e. obtain Au aeroge；The specific surface area of this Au aeroge is 145m2/g。
Embodiment 9:
Prepare Cu aeroge according to embodiment 2, Cu aeroge is soaked into the H of 2M2PtCl6Solution Middle 10h, until solution gradually becomes colourless, then removes the hydrochloric acid of Cu aeroge template 1mol/L Go, be dried and i.e. obtain Pt aeroge；The specific surface area of this Pt aeroge is 155m2/g。
Although embodiment of the present invention are disclosed as above, but it is not restricted to description and embodiment party Listed utilization in formula, it can be applied to various applicable the field of the invention completely, for being familiar with ability For the personnel in territory, be easily achieved other amendment, therefore without departing substantially from claim and etc. homotype Enclosing under limited general concept, the present invention is not limited to specific details and shown here as the figure with description Example.

Claims (10)

1. the preparation method of a metal in height ratio surface area aeroge, it is characterised in that comprise the following steps:
Step one, cellulose aerogels is placed in sensitizing solution and soaks at least 1h, then rinse fiber with water Element aeroge；
Step 2, will step one process after cellulose aerogels be soaked in metallochemistry plating solution and carry out Chemical plating, it is thus achieved that metal/cellulose composite aerogel；
Step 3, metal/cellulose composite aerogel is placed in LiOH/ urea liquid, leads at low temperatures Cross LiOH/ urea liquid dissolving cellulose and carry out cellulose aerogels template procedure, it is thus achieved that nanoporous Metallic solution；
Step 4, prepared nano porous metal solution with water is cleaned, then carry out solvent friendship with acetone Change, be dried, it is thus achieved that metal in height ratio surface area aeroge.
2. the preparation method of metal in height ratio surface area aeroge as claimed in claim 1, it is characterised in that In described step one, cellulose aerogels is prepared by method of reproduction, and its method is: by weight, takes 0.5～2 Part microcrystalline Cellulose and 45～55 parts of ionic liquids add in reaction vessels, and reaction vessel is placed in 80 DEG C In oil bath, 3～6h make microcrystalline Cellulose dissolve, and then the microcrystalline cellulose cellulose solution after dissolving puts into 80 DEG C Vacuum drying oven in process 1～3d, be subsequently adding EtOH/H2O solution rejuvenation gel, prepares fibre Dimension element aeroge；Described EtOH/H2In O solution, the volume fraction shared by EtOH is 80%.
3. the preparation method of metal in height ratio surface area aeroge as claimed in claim 2, it is characterised in that Described ionic liquid is 1-pi-allyl-3-Methylimidazole. villaumite, 1-ethyl-3-methylimidazolium chloride, 1-butyl -3-methylimidazolium chloride, 1-ethyl-3-methylimidazole acetate, 1-hexyl-3-methyl imidazolium tetrafluoroborate, 1,3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole lactic acid, 1-n-hexadecyl-3 methyl bromide Change the one in imidazoles.
4. the preparation method of metal in height ratio surface area aeroge as claimed in claim 1, it is characterised in that In described step one, cellulose aerogels is prepared by method of reproduction, and its method is: by weight, by 0.5～2 Part microcrystalline Cellulose adds in 40～60 parts of LiOH/ urea liquids, dissolves micro-under conditions of-24～-20 DEG C Crystalline cellulose, adds EtOH/H after dissolving completely2O solution rejuvenation gel, prepares cellulose airsetting Glue；Described EtOH/H2In O solution, the volume fraction shared by EtOH is 80%；Described LiOH/ carbamide is molten The compound method of liquid is: by weight, takes LiOH4～5 parts and 15 parts of carbamide, adds 80～90 parts and go In ionized water, stirring and dissolving obtains LiOH/ urea liquid.
5. the preparation method of metal in height ratio surface area aeroge as claimed in claim 1, it is characterised in that Described sensitizing solution is PdCl2Or SnCl2At least one in solution；Described PdCl2Or SnCl2Solution Preparation method is: by weight, takes 0.03～0.08 part of PdCl2Or SnCl2In beaker, add 45 parts EtOH and 5 parts of 1mol L-1HCl is placed in ultrasonic dissolution in ultrasonic washing instrument, obtains sensitizing solution.
6. the preparation method of metal in height ratio surface area aeroge as claimed in claim 1, it is characterised in that Described metallochemistry plating solution is the one in Ni chemical plating fluid, Cu chemical plating fluid, Ag chemical plating fluid；Institute Stating Ni chemical plating fluid formula is: by weight: 0.1～0.3 part of NiCl2·6H2O, 20 parts of deionized waters, 5 parts of ethanol, 2 parts of ammonia and 2 parts of hydrazine hydrates；Described ammonia mass percent is 28wt%；Described Cu chemical plating fluid formula is: sodium citrate 15g/L, boric acid 30g/L, anhydrous cupric sulfate 10g/L and Sodium hypophosphite 30g/L；Described Ag chemical plating fluid formula is: AgNO310～20g/L, NaOH5～10 G/L, ammonia 50～80mL/L, glucose 3～8g/L, Polyethylene Glycol 3-8g/L, ethanol 15mL/L；Institute Stating ammonia mass percent is 28wt%.
7. the preparation method of metal in height ratio surface area aeroge as claimed in claim 6, it is characterised in that Described perform step 4 after, also include step 5: the metal in height ratio surface area aeroge leaching that will obtain Steep the H into 1～3mol/L2PtCl6Or HAuCl4In solution 8～12 hours, then metal aerogel is used Dilute hydrochloric acid removes, and is dried and i.e. obtains Pt aeroge or Au aeroge；The concentration of described dilute hydrochloric acid is 0.5～1mol/L.
8. the preparation method of metal in height ratio surface area aeroge as claimed in claim 1, it is characterised in that
In described step 2, the time of chemical plating is 1～12d；
In described step 3, the compound method of LiOH/ urea liquid is: by weight, takes LiOH4～5 Part and 15 parts of carbamide, add in 80～90 parts of deionized waters, and stirring and dissolving obtains LiOH/ urea liquid； Described go cellulose aerogels template process be: metal/cellulose composite aerogel is placed in LiOH/ urine In cellulose solution, be placed in-24～-20 DEG C make it be frozen into ice, then taking out thaws stirs, solve Repeat aforesaid operations 3～4 times after freezing, until cellulose is completely dissolved, obtain nano porous metal solution；
In described step 4, the number of times that deionized water cleans is 5～8 times, then carries out solvent friendship with acetone Changing, every day changes fresh acetone, continues 5～8 days；Be dried mode be normal temperature drying, lyophilization, One in supercritical drying.
9. the preparation method of metal in height ratio surface area aeroge as claimed in claim 1, it is characterised in that The specific surface area of described cellulose aerogels is 100～1000m2/g；Described metal in height ratio surface area aeroge Specific surface area be 30～200m2/g。
10. the metal in height ratio surface area that prepared by the preparation method as described in any one of claim 1～9 Aeroge, it is characterised in that the specific surface area of described metal in height ratio surface area aeroge is 30～200m2/g。
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CN106340726A (en) * 2016-10-31 2017-01-18 中国工程物理研究院激光聚变研究中心 Magnetic conductive nano-metal/carbon airgel absorbing material and the preparation method thereof
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CN111250007A (en) * 2020-01-17 2020-06-09 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
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CN117398974A (en) * 2023-11-09 2024-01-16 长沙大山新材料有限公司 Magnetic aerogel and preparation method and application thereof

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