CN105688868B - A kind of three-dimensional porous compound of noble metal-carbon nanotube and its preparation method and application - Google Patents

A kind of three-dimensional porous compound of noble metal-carbon nanotube and its preparation method and application Download PDF

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CN105688868B
CN105688868B CN201610149755.7A CN201610149755A CN105688868B CN 105688868 B CN105688868 B CN 105688868B CN 201610149755 A CN201610149755 A CN 201610149755A CN 105688868 B CN105688868 B CN 105688868B
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carbon nanotube
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方英
李红变
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National Center for Nanosccience and Technology China
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Abstract

The present invention provides a kind of three-dimensional porous compounds of noble metal carbon nanotube and its preparation method and application, the compound includes noble metal nano particles, carbon nanotube sponge and the articulamentum for connecting noble metal nano particles and carbon nanotube sponge, the articulamentum is wrapped on the carbon nanotube sponge, and the noble metal nano particles are carried on articulamentum.The three-dimensional porous compound porosity of the noble metal carbon nanotube and specific surface area superelevation, it is high to the adsorption efficiency of Elemental Mercury, in addition, the alloy that noble metal is formed with Elemental Mercury, can remove institute's Adsorption of Mercury, to be recycled to adsorbent by heating removal alloying；The compound is three-dimensional porous structure, has magnetism, easy to use and recycling.

Description

A kind of three-dimensional porous compound of noble metal-carbon nanotube and its preparation method and application
Technical field
The invention belongs to nano material preparation and its applied technical fields, and it is three-dimensional more to be related to a kind of noble metal-carbon nanotube Hole compound and its preparation method and application.
Background technology
In recent years, atmosphere pollution getting worse, the main problem being increasingly becoming in environmental pollution.In atmosphere pollution, mercury is dirty Dye is one of importance, and the mercury fume discharged in coal combustion process is the main source of air mercury contaminants. Cut-off 2010, it is about 2000 tons that the whole world discharges mercury quantity into air by coal-fired flue-gas every year, and wherein mercury is discharged in China every year It is 500-600 tons, occupies first of the whole world.Mercury in air can enter soil and water body by deposition and washing effect, go forward side by side One step is assembled by food chain in human body, and serious harm is generated to human brain, kidney, lung and other organs.Therefore, high Effect removes the mercury in coal-fired flue-gas, controls the discharge of mercury contaminants, and the environmental problem to solving getting worse has of crucial importance Meaning.
Mercury in coal-fired flue-gas is with Elemental Mercury (Hg), oxidation state mercury (Hg2+) and graininess mercury (Hgp) three kinds of forms exist. The content of wherein Elemental Mercury accounts for 90% or more, moreover, elemental mercury vapor pressure is high, it is not soluble in water, it is a kind of it is difficult to the mercury removed Pollutant.Therefore, it is the key point for removing mercury pollution to the removing of elemental mercury from coal-fired flue gas.Removal Elemental Mercury master at present Activated carbon adsorption is used, but adsorption capacity is not high.Although can be to a certain extent by surface chemical modification by activated carbon Its adsorption capacity is improved, but can not change that activated carbon adsorption rate is slow, chemical stability is not high, poor selectivity and is not easy point From the deficiencies of.In recent years, it has been found that metal oxide can be with catalysis oxidation Elemental Mercury, and has higher thermal stability. But such adsorbent specific surface area is small, adsorption capacity is not high.Moreover, in applied at elevated temperature, it is a large amount of existing in coal-fired cigarette ash SO2、HCl、NOxEtc. can be chemically reacted with sorbing material, metal oxide is set to become corresponding oxysalt, to lose Adsorption activity.Finally, exist in the form of the HgO that Elemental Mercury is adsorbed on material surface to be difficult to decompose, keep regneration of adsorbent material difficult.
Carried noble metal composite material is the Elemental Mercury sorbing material for being presently considered to most have application value, it is to simple substance The absorption of mercury, which is mainly based upon Elemental Mercury, to form stable alloy with noble metal (Au, Ag, Cu, Pd).It is adsorbed with other mercury Material is compared, and noble metal composite adsorbing material has the following advantages that：
1) have stronger interaction between noble metal and Elemental Mercury, as the combination of Hg and Pd, Au, Ag, Cu can be followed successively by- 0.84eV, -0.35eV, -0.38eV and -0.55eV, at room temperature Elemental Mercury stable alloy can be formed with noble metal.Institute With precious metal adsorption material has faster adsorption rate and higher adsorption efficiency to mercury, and noble metal nano particles are for inhaling Attached Elemental Mercury is easy to reunite, can lose activity in the shorter time.
2) noble metal has certain chemical inertness, can SO in fire-resistant flue-gas to a certain extent2、HCl、NOxDeng altogether The interference for depositing gas has good selectivity Elemental Mercury absorption.
3) mercury-precious metal alloys easily decompose at high temperature, facilitate Elemental Mercury recycling and regneration of adsorbent material, make sorbing material It can recycled for multiple times.
Noble metal decorated carbon nanomaterial becomes apparent from raising when adsorbing Elemental Mercury compared with other materials, and by SO2、 NOx、CO2The influence very little of equal co-existing gases.Adsorbed Elemental Mercury can be discharged completely after material is heated, realize adsorption material The regeneration of material.
Document report is prepared for Ag- carbon by directly mixing carbon nanotube with silver nitrate, and in the method for 240 DEG C of heating Nanotube complex, the compound to Elemental Mercury have good absorption property (G.Q.Luo, Energy Fuels, 2010,24, 419-426).But the loads of Ag on the carbon nanotubes are very uneven in the material, affect the absorption property of material；In addition, The material is mealy structure, and after Adsorption of Mercury, sorbing material is not easy to detach with fire coal cigarette ash, Yi Zao due to its microscopic dimensions At secondary pollution.
Invention content
It is three-dimensional more in view of the deficiencies of the prior art, the present invention intends to provide a kind of noble metal-carbon nanotube Hole compound and its preparation method and application, the three-dimensional porous compound of noble metal-carbon nanotube have high-specific surface area, height Porosity, easy to use and recycling splendid to the absorption property of mercury.
For this purpose, the present invention uses following technical scheme：
One of the objects of the present invention is to provide a kind of three-dimensional porous compound of noble metal-carbon nanotube, the compounds Including noble metal nano particles, carbon nanotube sponge and connection for connecting noble metal nano particles and carbon nanotube sponge Layer, the articulamentum are wrapped on the carbon nanotube sponge, and the noble metal nano particles are equably carried on the connection On layer.
The present invention uses the carbon nanotube sponge with high-specific surface area, high stability to be used as carrier, extra large in carbon nanotube Articulamentum is wrapped up on silk floss, and in articulamentum area load noble metal nano particles, it is three-dimensional porous multiple to obtain noble metal-carbon nanotube Close object.The introducing of articulamentum makes carbon nanotube sponge surface have a large amount of functional groups such as-OH and-COOH, increases carbon and receives The interaction of mitron sponge and precious metal ion so that noble metal nano particles are equably supported on carbon nanotube sponge, Three mutually acts synergistically so that the three-dimensional porous compound of noble metal-carbon nanotube not only has higher absorption to mercury Performance also has the characteristics that be easy to coal-fired cigarette ash separation.
The grain size of the noble metal nano particles is 5-20nm, such as 6nm, 7nm, 8nm, 10nm, 12nm, 15nm, 17nm or 19nm etc..
Preferably, the thickness of the articulamentum is 5-10nm, such as 6nm, 7nm, 8nm or 9nm, to realize different porosities The three-dimensional porous compound of noble metal-carbon nanotube preparation.
Preferably, the carbon nanotube in the carbon nanotube sponge, a diameter of 30-50nm, as 32nm, 35nm, 38nm, 40nm, 42nm, 45nm or 48nm etc., length be tens to hundreds of microns, such as 10 microns, 20 microns, 30 microns, 50 microns, 80 Micron, 100 microns, 200 microns, 300 microns, 500 microns, 700 microns or 900 microns etc..The carbon nanotube sponge can root According to document (X.C.Gui, J.Q.Wei, K.L.Wang, A.Y.Cao, H.W.Zhu, Y.Jia, Q.K.Shu, D.H.Wu.Adv.Mater.2010,22,617-621) method is prepared disclosed in.
Preferably, the groups of the noble metal nano particles is divided into any one in Ag, Au, Pt or Pd or at least two Combination.It is typical but non-limiting to be combined as：Ag and Au, Ag and Pt, Ag and Pd, Ag, Au and Pt, Au, Pt and Pd, Ag, Au, Pt With Pd.
Preferably, the articulamentum is titanium dioxide layer and/or carbon-coating.
The second object of the present invention is to provide a kind of preparation method of the three-dimensional porous compound of noble metal-carbon nanotube, Described method includes following steps：
(1) the carbon nanotube sponge of articulamentum package is prepared；
(2) the carbon nanotube sponge of articulamentum package is immersed in noble metal precursor liquid solution, later, dry, pyrolysis obtains To the three-dimensional porous compound of noble metal-carbon nanotube.
The preparation of the carbon nanotube sponge of step (1) the articulamentum package can refer to two described in CN 103736475B The method that titanium oxide wraps up three-dimensional porous sponge carries out, specially：Carbon nanotube sponge is dipped in organotitanium precursor body successively In organic alcoholic solution and water, carbon nanotube sponge impregnating body is obtained, later, is removed unreacted in carbon nanotube sponge impregnating body Organotitanium precursor body obtains the carbon nanotube sponge of titanium dioxide package.
The preparation method of the carbon nanotube sponge of step (1) the articulamentum package is as a preferred technical solution,：It will Carbon nanotube sponge is dipped in organic alcoholic solution of organotitanium precursor body, and 10min-2h is mixed on shaking table, obtains mixture, Wherein, the volume ratio of organotitanium precursor body and Organic Alcohol is 1:15-1:1, the quality of carbon nanotube sponge and organotitanium precursor body Than being 1:10-1:500；Later, mixture is immersed in water, ultrasonic 15-40min obtains hydrolysate, wherein carbon nanometer The volume ratio of pipe sponge and water is 1:10-1:1000；Unreacted organotitanium precursor body in hydrolysate is removed again, is connected The carbon nanotube sponge of layer package.
The preparation method of the carbon nanotube sponge of step (1) articulamentum package can also be：Carbon nanotube sponge is set In glucose solution, hydro-thermal reaction is carried out, obtains the carbon nanotube sponge of carbon-coating package.
Preferably, a concentration of 0.2-3M of the glucose solution, as 0.3M, 0.4M, 0.5M, 0.8M, 1.0M, 1.2M, 1.5M, 2.0M, 2.5M or 2.8M etc..
Preferably, the mass ratio of the carbon nanotube sponge and glucose solution is 1:4000-1:400, such as 1:3500、 1:3000、1:2500、1:2000、1:1000 or 1:500 etc..
Preferably, the temperature of the hydro-thermal reaction is 180-200 DEG C, such as 182 DEG C, 185 DEG C, 190 DEG C, 192 DEG C, 195 DEG C Or 198 DEG C etc..
Preferably, the time of the hydro-thermal reaction is 1-4h, such as 1.5h, 2h, 2.5h, 3h or 3.5h.
Preferably, the preparation method of the carbon nanotube sponge of step (1) the articulamentum package is：By carbon nanotube sponge It is placed in the glucose solution of a concentration of 0.2-3M, the mass ratio of carbon nanotube sponge and glucose solution is 1:4000- 1:400, the hydro-thermal reaction 1-4h under the conditions of 180-200 DEG C obtain the carbon nanotube sponge of carbon-coating package.
Step (2) the noble metal precursor liquid solution is AgNO3Solution, HAuCl4Solution, H2PtCl6Solution or PdCl2It is molten In liquid any one or at least two combination.It is typical but non-limiting to be combined as：AgNO3Solution and HAuCl4Solution, H2PtCl6Solution and PdCl2Solution, AgNO3Solution, HAuCl4Solution and H2PtCl6Solution, HAuCl4Solution, H2PtCl6Solution With PdCl2Solution, AgNO3Solution, HAuCl4Solution, H2PtCl6Solution and PdCl2Solution.
Preferably, a concentration of 10mM-10M of the noble metal precursor liquid solution, as 20mM, 30mM, 50mM, 80mM, 100mM, 200mM, 500mM, 800mM, 1M, 2M, 3M, 4M, 5M, 6M, 8M or 9M etc..To realize variety classes, different loads amount The three-dimensional porous compound of noble metal-carbon nanotube preparation.
Preferably, the carbon nanotube sponge of the articulamentum package impregnates 1-24h in noble metal precursor liquid solution, such as 2h, 3h, 5h, 8h, 10h, 12h, 15h, 18h, 20h, 22h or 23h etc.
Preferably, the temperature of the pyrolysis is 500-600 DEG C, such as 510 DEG C, 520 DEG C, 530 DEG C, 550 DEG C, 570 DEG C or 590 DEG C etc..
Preferably, the pyrolysis carries out in an inert atmosphere.The inert atmosphere is for protecting precious metal salt when decomposing The noble metal of generation and carbon nanotube sponge are not oxidized.The inert atmosphere can be nitrogen atmosphere and/or argon gas atmosphere.
Noble metal-the carbon nanotube as a preferred technical solution, using titanium dioxide as articulamentum is three-dimensional porous The preparation method of compound includes the following steps：
1) TiO is prepared with reference to CN 103736475B2Carbon nanotube sponge nucleocapsid, wherein carbon nanotube sponge is Mutually to overlap the three-dimensional porous sponge formed by carbon nanotube；
2)TiO2Carbon nanotube sponge nucleocapsid immerses 1-24h in the precious metal solution of a concentration of 10mM-10M and adsorbs Precious metal ion is dried later；
3) by the TiO for having adsorbed precious metal ion after drying2Carbon nanotube sponge under inert gas gas shielded, 500-600 DEG C of pyrolysis, obtains the three-dimensional porous compound of noble metal-carbon nanotube；
Wherein, step 1) is specially：Carbon nanotube sponge is dipped in organic alcoholic solution of organotitanium precursor body, and is being shaken 10min-2h is mixed on bed, obtains mixture, wherein the volume ratio of organotitanium precursor body and Organic Alcohol is 1:15-1:1, carbon is received The mass ratio of mitron sponge and organotitanium precursor body is 1:10-1:500；Later, mixture is immersed in water, ultrasonic 15- 40min obtains hydrolysate, wherein the volume ratio of carbon nanotube sponge and water is 1:10-1:1000；Hydrolysate is removed again In unreacted organotitanium precursor body, obtain TiO2Carbon nanotube sponge nucleocapsid.
As a preferred technical solution, using carbon-coating as the three-dimensional porous compound of noble metal-carbon nanotube of articulamentum Preparation method include the following steps：
1) carbon nanotube sponge is placed in the glucose solution of a concentration of 0.2-3M, carbon nanotube sponge and glucose The mass ratio of aqueous solution is 1:4000-1:400, later, carbon nanotube sponge and glucose solution mixture are placed in reaction Hydro-thermal reaction is carried out in kettle at 180-200 DEG C, reaction time 1-4h obtains the carbon nanotube sponge of carbon package；
2) the carbon nanotube sponge that carbon wraps up is immersed in the noble metal precursor liquid solution of a concentration of 10mM-10M, impregnates 1- Precious metal ion is adsorbed for 24 hours, it is later, dry；
3) will adsorb precious metal ion carbon package carbon nanotube sponge under inert gas protection, in 500-600 DEG C pyrolysis, obtain the three-dimensional porous compound of noble metal-carbon nanotube.
The third object of the present invention is to provide a kind of purposes of the three-dimensional porous compound of noble metal-carbon nanotube, use In absorption Elemental Mercury.
The temperature of the three-dimensional porous compound absorption Elemental Mercury of the noble metal-carbon nanotube is 20-150 DEG C, such as 30 DEG C, 50 DEG C, 70 DEG C, 90 DEG C, 100 DEG C, 120 DEG C, 130 DEG C, 140 DEG C or 145 DEG C etc..
Compared with prior art, beneficial effects of the present invention are：
1) noble metal nano particles in the three-dimensional porous compound of noble metal-carbon nanotube provided by the invention, articulamentum And there is synergistic effect, the interaction between articulamentum and noble metal nano particles so that noble metal between carbon nanotube sponge Nano-particle is evenly distributed on articulamentum, improves the specific surface area of noble metal nano particles, to improve it to list The adsorbance of matter mercury, in addition, carbon nanotube sponge has the enrichment to Elemental Mercury, therefore, the noble metal-carbon nanotube Three-dimensional porous compound is high to the adsorption efficiency of Elemental Mercury, and adsorbance is up to 11.1mg/g；
2) the three-dimensional porous compound of noble metal-carbon nanotube provided by the invention is due to carbon nanotube sponge porous material tool Have superelevation porosity (>99%), there is certain enrichment to Elemental Mercury, noble metal nano particles can be improved to Elemental Mercury Adsorption efficiency；
3) carbon nanotube sponge porous material has in the three-dimensional porous compound of noble metal-carbon nanotube provided by the invention Very high thermal stability will not be decomposed at 600 DEG C, ensure that composite adsorbing material in applied at elevated temperature and regeneration, structure It will not change；
4) carbon nanotube sponge porous material has in the three-dimensional porous compound of noble metal-carbon nanotube provided by the invention Macro-size (>=15cm × 4cm × 1cm), and stable structure, can facilitate and be detached with coal-fired cigarette ash；
5) contain part inside carbon nanotube sponge in the three-dimensional porous compound of noble metal-carbon nanotube provided by the invention The Fe that catalyst is formed3C nano line makes noble metal/carbon nanometer so carbon nanotube sponge porous material has certain magnetism The porous composite adsorbing material of pipe sponge is more easy to detach with coal-fired cigarette ash.
Description of the drawings
Fig. 1 is the TiO that embodiment 1 provides2Scanning as the three-dimensional porous compound of silver-carbon nanotube prepared by articulamentum Electron micrograph；
Fig. 2 is the TiO that embodiment 1 provides2Transmission as the three-dimensional porous compound of silver-carbon nanotube prepared by articulamentum Electron micrograph；
Fig. 3 is the TiO that embodiment 1 provides2The X of the three-dimensional porous compound of silver-carbon nanotube as articulamentum preparation is penetrated Ray diffraction diagram picture；
Fig. 4 is the TiO that embodiment 2 provides2Transmission as the three-dimensional porous compound of gold-carbon nanotube prepared by articulamentum Electron micrograph；
Fig. 5 is the transmission electricity for the three-dimensional porous compound of silver-carbon nanotube that the carbon that embodiment 3 provides is prepared as articulamentum Sub- microscope photograph；
Fig. 6 is the TiO that embodiment 9 provides2The three-dimensional porous compound of silver-carbon nanotube as articulamentum preparation is to simple substance The adsorption curve of mercury.
Fig. 7 is adsorption curve of the carbon nanotube sponge to Elemental Mercury of the offer of comparative example 1.
Fig. 8 is adsorption curve of the titanium dioxide-carbon nanotube sponge compound to Elemental Mercury of the offer of comparative example 2.
Fig. 9 is adsorption curve of the carbon-to-carbon nanotube sponge compound to Elemental Mercury of the offer of comparative example 3.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
TiO2As the method that articulamentum prepares the three-dimensional porous compound of silver-carbon nanotube, include the following steps：
1) carbon nanotube sponge is placed in the ethanol solution of butyl titanate, the volume ratio of butyl titanate and ethyl alcohol is 1:7, the mass ratio of carbon nanotube sponge and butyl titanate is 1:100, in shaking 1h on shaking table, butyl titanate is made uniformly to inhale Invest carbon nanotube sponge surface；
2) the carbon nanotube sponge for having adsorbed butyl titanate is transferred in water to ultrasonic, the body of carbon nanotube sponge and water Product is than being 1:100, ultrasonic time 40min, it is TiO to make tetrabutyl titanate hydrolysis2Carbon nanotube sponge surface is wrapped in be formed TiO2Carbon nanotube sponge nucleocapsid；
3) ethyl alcohol is added dropwise into three-dimensional composite, then compression is cleaned, and 3 times repeatedly, removes unreacted completely Butyl titanate；
4) there will be TiO2The carbon nanotube sponge of articulamentum modification immerses the AgNO of 1M38h adsorbs Ag in solution+, later, do It is dry；
5) Ag will have been adsorbed+Carbon nanotube sponge make AgNO in 550 DEG C of heating under inert gas protection3It decomposes, obtains The three-dimensional porous compound of Ag- carbon nanotubes.
Scanning electron microscope (the model Hitachi for the three-dimensional porous compound of silver-carbon nanotube being prepared S4800 FESEM) picture is as shown in Figure 1.It can be seen from the figure that in the three-dimensional porous compound of silver-carbon nanotube obtained Length of carbon nanotube is tens to hundreds of microns, and Nano silver grain uniform load is in TiO2On articulamentum.
Transmission electron microscope (the model for the three-dimensional porous compound of silver-carbon nanotube that the present embodiment is prepared Tecnai F20) picture is as shown in Figure 2.The figure is measured it is found that carbon nanotube diameter is 30-50nm, TiO2Connecting layer thickness is 5nm, a diameter of 5-10nm of Nano silver grain.
X-ray diffraction (the model D/MAX- for the three-dimensional porous compound of silver-carbon nanotube that the present embodiment is prepared TTRIII) image is as shown in Figure 3.X-ray diffraction shows that prepared Ag nano-particles are face-centred cubic structure.
Embodiment 2
TiO2As the method that articulamentum prepares the three-dimensional porous compound of gold-carbon nanotube, include the following steps：
1) carbon nanotube sponge is placed in the ethanol solution of butyl titanate, the volume ratio of butyl titanate and ethyl alcohol is 1:7, the mass ratio of carbon nanotube sponge and butyl titanate is 1:100, in shaking 10min on shaking table, keep butyl titanate equal It is even to be adsorbed in carbon nanotube sponge surface；
2) the carbon nanotube sponge for having adsorbed butyl titanate is transferred in water to ultrasonic, the body of carbon nanotube sponge and water Product is than being 1:1000, ultrasonic time 40min, it is TiO to make tetrabutyl titanate hydrolysis2Carbon nanotube sponge surface is wrapped in be formed TiO2Carbon nanotube sponge nucleocapsid；
3) ethyl alcohol is added dropwise into three-dimensional composite, then compression is cleaned, and 3 times repeatedly, removes unreacted completely Butyl titanate；
4) TiO that will be cleaned2Carbon nanotube sponge nucleocapsid immerses the HAuCl of a concentration of 100mM4In solution for 24 hours Adsorb AuCl4 -, and it is dry；
5) AuCl will have been adsorbed after drying4 -TiO2Carbon nanotube sponge nucleocapsid under inert gas protection in 500 DEG C of heating make HAuCl4It decomposes and prepares the three-dimensional porous compound of Au- carbon nanotubes.
The three-dimensional porous compound of Au- carbon nanotubes being prepared by scanning electron microscope (model Hitachi S4800 FESEM) observation pattern, observing result is：Carbon nanotube in the three-dimensional porous compound of Au- carbon nanotubes obtained is long Degree is tens to hundreds of microns, and gold nanoparticle uniform load is in TiO2On articulamentum.
Transmission electron microscope (the model for the three-dimensional porous compound of Au- carbon nanotubes that the present embodiment is prepared Tecnai F20) picture is as shown in Figure 4.The carbon nanotube diameter measured from Fig. 4 is 30-50nm, TiO2Connecting layer thickness is 5nm, a diameter of 10-20nm of gold nanoparticle.
X-ray diffraction (model D/MAX-TTRIII) is shown, in the prepared three-dimensional porous compound of Au- carbon nanotubes Au nano-particles be face-centred cubic structure.
Embodiment 3
The method that carbon prepares the three-dimensional porous compound of silver-carbon nanotube as articulamentum, includes the following steps：
1) carbon nanotube sponge is placed in 1M glucose solutions, carbon nanotube sponge and glucose solution is placed in 190 DEG C of reaction 4h in reaction kettle make carbon nanotube sponge surface uniformly wrap up one layer of carbon as articulamentum；
2) surface there is into the AgNO that the carbon nanotube sponge of carbon articulamentum immerses 1M3Ag is adsorbed in solution for 24 hours+, and it is dry；
3) Ag will have been adsorbed+Carbon nanotube sponge make AgNO in 550 DEG C of heating under inert gas protection3It decomposes, obtains The three-dimensional porous compound of Ag- carbon nanotubes.
It is observed by scanning electron microscope (model Hitachi S4800 FESEM), carbon nanotube sponge length is Tens to hundreds of microns, Nano silver grain uniform load is on carbon articulamentum.
The transmission electron micrograph for the three-dimensional porous compound of silver-carbon nanotube being prepared is as shown in Figure 5.Pass through The carbon nanotube diameter that transmission electron microscope measures is 30-50nm, and it is 5nm that carbon, which connects layer thickness, and Nano silver grain is a diameter of 2-5nm。
X-ray diffraction (model D/MAX-TTRIII) shows that prepared Ag nano-particles are face-centred cubic structure.
Embodiment 4
TiO2As the method that articulamentum prepares the three-dimensional porous compound of silver-carbon nanotube, include the following steps：
1) carbon nanotube sponge is placed in the ethanol solution of butyl titanate, the volume ratio of butyl titanate and ethyl alcohol is 1:7, the mass ratio of carbon nanotube sponge and butyl titanate is 1:500, in being shaken 1 hour on shaking table, keep butyl titanate equal It is even to be adsorbed in carbon nanotube sponge surface；
2) the carbon nanotube sponge for having adsorbed butyl titanate is transferred in water to ultrasonic, the body of carbon nanotube sponge and water Product is than being 1:100, ultrasonic time 40min, it is TiO to make tetrabutyl titanate hydrolysis2Carbon nanotube sponge surface is wrapped in be formed TiO2Carbon nanotube sponge nucleocapsid.
3) ethyl alcohol is added dropwise into three-dimensional composite, then compression is cleaned, and 3 times repeatedly, removes unreacted completely Butyl titanate；
4) there will be TiO after cleaning2The carbon nanotube sponge of articulamentum modification immerses the AgNO of 10M38h adsorbs Ag in solution+, and it is dry；
5) Ag will have been adsorbed+Carbon nanotube sponge make AgNO in 550 DEG C of heating under inert gas protection3It decomposes, obtains The three-dimensional porous compound of Ag- carbon nanotubes.
It is observed by scanning electron microscope (model Hitachi S4800 FESEM), carbon nanotube sponge is length It it is tens to hundreds of microns, Nano silver grain uniform load is in TiO2On articulamentum.
It is 30-50nm, TiO by the carbon nanotube diameter that transmission electron microscope (model Tecnai F20) measures2 Connection layer thickness is 5nm, a diameter of 10-20nm of Nano silver grain.
Embodiment 5
With TiO2The preparation method of the three-dimensional porous compound of noble metal-carbon nanotube as articulamentum includes as follows Step：
1) carbon nanotube sponge is placed in the ethanol solution of butyl titanate, the volume ratio of butyl titanate and ethyl alcohol is 1:15, the mass ratio of carbon nanotube sponge and butyl titanate is 1:10, in shaking 2h on shaking table, make have butyl titanate uniform It is adsorbed in carbon nanotube sponge surface；
2) the carbon nanotube sponge for having adsorbed butyl titanate is immersed in water, ultrasound, carbon nanotube sponge and water Volume ratio is 1:10, ultrasonic time 15min, tetrabutyl titanate hydrolysis TiO2It is wrapped in carbon nanotube sponge surface, is formed TiO2Carbon nanotube sponge nucleocapsid；
3) to TiO2Ethyl alcohol is added dropwise in carbon nanotube sponge nucleocapsid, compression is cleaned, 3 times repeatedly, completely Remove unreacted butyl titanate；
4) TiO after cleaning2Carbon nanotube sponge nucleocapsid immerses the H of a concentration of 10mM2PtCl6It is inhaled for 24 hours in solution Attached PtCl6 4-, dry later；
5) by the TiO for having adsorbed precious metal ion after drying2Carbon nanotube sponge under inert gas gas shielded, 500 DEG C of pyrolysis, obtain the three-dimensional porous compound of Pt- carbon nanotubes.
It is observed by scanning electron microscope (model Hitachi S4800 FESEM), carbon nanotube sponge is length It it is tens to hundreds of microns, Nano silver grain uniform load is in TiO2On articulamentum.
It is 30-50nm, TiO by the carbon nanotube diameter that transmission electron microscope (model Tecnai F20) measures2 It is about 8nm to connect layer thickness, and Pt diameter of nano particles is about 5nm.
Embodiment 6
With TiO2The preparation method of the three-dimensional porous compound of noble metal-carbon nanotube as articulamentum includes as follows Step：
1) carbon nanotube sponge is placed in the butanol solution of butyl titanate, the volume ratio of butyl titanate and butanol is 1:1, the mass ratio of carbon nanotube sponge and butyl titanate is 1:500, in shaking 10min on shaking table, keep butyl titanate equal It is even to be adsorbed in carbon nanotube sponge surface；
2) the carbon nanotube sponge for having adsorbed butyl titanate is immersed in water, ultrasound, carbon nanotube sponge and water Volume ratio is 1:1000, ultrasonic time 25min, tetrabutyl titanate hydrolysis TiO2It is wrapped in carbon nanotube sponge surface, shape At TiO2Carbon nanotube sponge nucleocapsid；
3) to TiO2Ethyl alcohol is added dropwise in carbon nanotube sponge nucleocapsid, compression is cleaned, 3 times repeatedly, completely Remove unreacted butyl titanate；
4) TiO after cleaning2Carbon nanotube sponge nucleocapsid immerses the PdCl of a concentration of 10M21h adsorbs Pd in solution2 +, dry later；
5) Pd will have been adsorbed after drying2+TiO2Carbon nanotube sponge is under inert gas gas shielded, in 600 DEG C of heat Solution, obtains the three-dimensional porous compound of Pd- carbon nanotubes.
It is observed by scanning electron microscope (model Hitachi S4800 FESEM), carbon nanotube sponge is length It it is tens to hundreds of microns, Nano silver grain uniform load is in TiO2On articulamentum.
It is 30-50nm, TiO by the carbon nanotube diameter that transmission electron microscope (model Tecnai F20) measures2 It is about 7nm to connect layer thickness, and Pd diameter of nano particles is about 5nm.
Embodiment 7
Using carbon-coating as the preparation following steps of the three-dimensional porous compound of noble metal-carbon nanotube of articulamentum：
1) carbon nanotube sponge is placed in the glucose solution of a concentration of 3M, carbon nanotube sponge and glucose are water-soluble The mass ratio of liquid is 1:4000, later, carbon nanotube sponge and glucose solution mixture are placed in reaction kettle at 180 DEG C Lower carry out hydro-thermal reaction, reaction time 4h obtain the carbon nanotube sponge of carbon package；
2) the carbon nanotube sponge that carbon wraps up is immersed to the HAuCl of a concentration of 10mM4In solution, immersion is adsorbed for 24 hours AuCl4 -, later, dry；
3) AuCl will have been adsorbed4 -Carbon package carbon nanotube sponge under inert gas protection, at 500 DEG C be pyrolyzed, obtain To the three-dimensional porous compound of gold-carbon nanotube.
It is observed by scanning electron microscope (model Hitachi S4800 FESEM), carbon nanotube sponge is length It it is tens to hundreds of microns, gold nanoparticle uniform load is on carbon articulamentum.
It is 30-50nm, carbon-coating by the carbon nanotube diameter that transmission electron microscope (model Tecnai F20) measures Thickness is about 10nm, a diameter of 10-20nm of gold nanoparticle.
Embodiment 8
Using carbon-coating as the preparation following steps of the three-dimensional porous compound of noble metal-carbon nanotube of articulamentum：
1) carbon nanotube sponge is placed in the glucose solution of a concentration of 0.2M, carbon nanotube sponge and glucose water The mass ratio of solution is 1:400, later, carbon nanotube sponge and glucose solution mixture are placed in reaction kettle 200 Hydro-thermal reaction is carried out at DEG C, reaction time 1h obtains the carbon nanotube sponge of carbon package；
2) the carbon nanotube sponge that carbon wraps up is immersed to the AgNO of a concentration of 10M3In solution, impregnates 1h and adsorb Ag+, later, It is dry；
3) Ag will have been adsorbed+Carbon package carbon nanotube sponge under inert gas protection, at 550 DEG C be pyrolyzed, obtain The three-dimensional porous compound of silver-carbon nanotube.
It is observed by scanning electron microscope (model Hitachi S4800 FESEM), carbon nanotube is that length is several Ten to hundreds of microns, Nano silver grain uniform load is on carbon articulamentum.
It is 30-50nm, carbon-coating by the carbon nanotube diameter that transmission electron microscope (model Tecnai F20) measures Thickness is 5nm, a diameter of 10-20nm of Nano silver grain.
Embodiment 9
The three-dimensional porous compound of silver-carbon nanotube prepared by the embodiment 1 of 41.5mg is put into simple substance quartz ampoule, is passed through The mercury vapour of a concentration of 45 μ g/L, temperature are 150 DEG C, and carrier gas speed is 300mL/min.It is measured and is adsorbed using Elemental Mercury measuring instrument The concentration of Elemental Mercury later, the adsorption curve of Elemental Mercury is as shown in fig. 6, silver-carbon nanotube prepared by display is three-dimensional porous multiple Elemental Mercury, adsorbance 11.1mg/g can effectively be adsorbed by closing object.
Due to noble metal nano particles, TiO2And noble metal-TiO2Compound is not three-dimensional porous structure, is not had easy The characteristics of being detached with coal-fired cigarette ash, therefore, the present invention are only compound with pure nano-carbon tube sponge, titanium dioxide-carbon nanotube sponge Object and carbon-to-carbon nanotube sponge compound are made to ratio.
Comparative example 1：Carbon nanotube sponge is for adsorbing Elemental Mercury
20mg carbon nanotube sponges are put into quartz ampoule, the mercury vapour of a concentration of 45 μ g/L is passed through, temperature is 150 DEG C, Carrier gas speed is 300mL/min, and the concentration of Elemental Mercury after absorption, the adsorption curve of Elemental Mercury are measured using Elemental Mercury measuring instrument As shown in Figure 7.Elemental mercury illustrates that carbon nanotube sponge has one to Elemental Mercury by quickly being reduced after carbon nanotube sponge Determine enrichment, but elemental mercury concentration increases quickly, and be more than initial concentration, it is computed, simple carbon nanotube sponge To Elemental Mercury substantially without absorption.
Comparative example 2：Titanium dioxide-absorption of the carbon nanotube sponge compound to Elemental Mercury
The preparation method such as the step 1) -3 in embodiment 1 of titanium dioxide-carbon nanotube sponge).
20mg titanium dioxide-carbon nanotube sponge is put into quartz ampoule, the mercury vapour of a concentration of 45 μ g/L, temperature are passed through It it is 150 DEG C, carrier gas speed is 300mL/min, and the concentration of Elemental Mercury after absorption is measured using Elemental Mercury measuring instrument, Elemental Mercury Adsorption curve is as shown in Figure 8.Elemental mercury by quickly reducing after carbon nanotube sponge, but quickly concentration gradually rise to Original concentration is computed, and titanium dioxide-carbon nanotube sponge is 3.06mg/g. to the adsorbance of Elemental Mercury
Comparative example 3：Absorption of the carbon-to-carbon nanotube sponge compound to Elemental Mercury
The preparation method such as the step 1) in embodiment 3 of carbon-to-carbon nanotube sponge.
20mg carbon-to-carbon nanotube sponges are put into quartz ampoule, the mercury vapour of a concentration of 45 μ g/L, temperature 150 are passed through DEG C, carrier gas speed is 300mL/min, and the concentration of Elemental Mercury after absorption, the absorption of Elemental Mercury are measured using Elemental Mercury measuring instrument Curve is as shown in Figure 9.Elemental mercury is seldom by decline after carbon-to-carbon nanotube sponge and is increased to original concentration quickly, Illustrate carbon-to-carbon nanotube composite sponge to Elemental Mercury substantially without absorption.
Applicant states, the foregoing is merely the specific implementation mode of the present invention, but protection scope of the present invention not office It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention In the technical scope of dew, the change or replacement that can be readily occurred in are all fallen within protection scope of the present invention and the open scope.

Claims (15)

1. a kind of three-dimensional porous compound of noble metal-carbon nanotube, which is characterized in that the compound includes noble metal nano grain Son, carbon nanotube sponge and the articulamentum for connecting noble metal nano particles and carbon nanotube sponge, the articulamentum package In on the carbon nanotube sponge, the noble metal nano particles are equably carried on articulamentum；The noble metal nano grain The grain size of son is 5-20nm, and the thickness of the articulamentum is 5-10nm, and carbon nanotube is a diameter of in the carbon nanotube sponge 30-50nm, length are tens to hundreds of microns；The articulamentum is titanium dioxide layer and/or carbon-coating.
2. compound according to claim 1, which is characterized in that the group of the noble metal nano particles is divided into Ag, Au, Pt In Pd any one or at least two combination.
3. the preparation method of compound according to claim 1 or 2, which is characterized in that described method includes following steps：
(1) the carbon nanotube sponge of articulamentum package is prepared, the method is：Before carbon nanotube sponge is dipped in organic titanium successively In the organic alcoholic solution and water that drive body, carbon nanotube sponge impregnating body is obtained, later, is removed in carbon nanotube sponge impregnating body not The organotitanium precursor body of reaction obtains the carbon nanotube sponge of titanium dioxide package；Or, carbon nanotube sponge is placed in glucose In solution, hydro-thermal reaction is carried out, obtains the carbon nanotube sponge of carbon-coating package；
(2) the carbon nanotube sponge of articulamentum package is immersed in noble metal precursor liquid solution, later, dry, pyrolysis, pyrolysis Temperature is 500-600 DEG C, obtains the three-dimensional porous compound of noble metal-carbon nanotube.
4. according to the method described in claim 3, it is characterized in that, a concentration of 0.2-3M of the glucose solution.
5. according to the method described in claim 3, it is characterized in that, the quality of the carbon nanotube sponge and glucose solution Than being 1:4000-1:400.
6. according to the method described in claim 3, it is characterized in that, the temperature of the hydro-thermal reaction is 180-200 DEG C.
7. according to the method described in claim 3, it is characterized in that, the time of the hydro-thermal reaction is 1-4h.
8. according to the method described in claim 3, it is characterized in that, the carbon nanotube sponge of step (1) the articulamentum package Preparation method be：Carbon nanotube sponge is dipped in organic alcoholic solution of organotitanium precursor body, and is mixed on shaking table 10min-2h obtains mixture, wherein the volume ratio of organotitanium precursor body and Organic Alcohol is 1:15-1:1, carbon nanotube sponge Mass ratio with organotitanium precursor body is 1:10-1:500；Later, mixture is immersed in water, ultrasonic 15-40min is obtained Hydrolysate, wherein the volume ratio of carbon nanotube sponge and water is 1:10-1:1000；It removes again unreacted in hydrolysate Organotitanium precursor body obtains the carbon nanotube sponge of articulamentum package.
9. according to the method described in claim 3, it is characterized in that, the carbon nanotube sponge of step (1) the articulamentum package Preparation method be：Carbon nanotube sponge is placed in the glucose solution of a concentration of 0.2-3M, carbon nanotube sponge and Portugal The mass ratio of grape sugar aqueous solution is 1:4000-1:400, later, hydro-thermal reaction 1-4h, is connected under the conditions of 180-200 DEG C The carbon nanotube sponge of layer package.
10. according to the method described in claim 3, it is characterized in that, step (2) the noble metal precursor liquid solution is AgNO3It is molten Liquid, HAuCl4Solution, H2PtCl6Solution or PdCl2In solution any one or at least two combination.
11. according to the method described in claim 3, it is characterized in that, a concentration of 10mM- of the noble metal precursor liquid solution 10M。
12. according to the method described in claim 3, it is characterized in that, the carbon nanotube sponge of articulamentum package is in your gold Belong in precursor solution and impregnates 1-24h.
13. according to the method described in claim 3, it is characterized in that, the pyrolysis carries out in an inert atmosphere.
14. the purposes of the three-dimensional porous compound of noble metal-carbon nanotube according to claim 1 or 2, is used to adsorb list Matter mercury.
15. purposes according to claim 14, which is characterized in that the three-dimensional porous compound of noble metal-carbon nanotube The temperature for adsorbing Elemental Mercury is 20-150 DEG C.
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