CN105688868A - Precious metal-carbon nanometer tube three-dimensional porous compound and preparing method and application thereof - Google Patents
Precious metal-carbon nanometer tube three-dimensional porous compound and preparing method and application thereof Download PDFInfo
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Abstract
The invention provides a precious metal-carbon nanometer tube three-dimensional porous compound and a preparing method and application thereof. The compound comprises precious metal nanometer particles, a carbon nanometer tube sponge and a connecting layer used for connecting the precious metal nanometer particles with the carbon nanometer tube sponge. The connecting layer wraps the carbon nanometer tube sponge. The precious metal nanometer particles are loaded on the connecting layer. The porosity and the specific area of the precious metal-carbon nanometer tube three-dimensional porous compound are ultrahigh, and the elemental mercury adsorption efficiency is high; in addition, for an alloy formed by precious metal and elemental mercury, adsorption mercury can be removed by means of heating and deallolying, so that an adsorption agent is recovered. The compound is of a three-dimensional porous structure, has magnetism and is convenient to use and recycle.
Description
Technical field
The invention belongs to nano material preparation and applied technical field thereof, relate to a kind of three-dimensional porous complex of noble metal-CNT and its preparation method and application。
Background technology
In recent years, atmospheric pollution is day by day serious, is increasingly becoming the subject matter in environmental pollution。In atmospheric pollution, mercury pollution is one of them importance, and in coal combustion process, the mercury fume of release is the main source of Mercury In The Air pollutant。Ending 2010, the whole world is annual is about 2000 tons by coal-fired flue-gas to discharge mercury quantity in air, and wherein China discharges hydrargyrum every year is 500-600 ton, occupies first of the whole world。Hydrargyrum in air can pass through deposition and washing effect enters soil and water body, and is assembled in human body by food chain further, and human brain, kidney, pulmonary and other organs are produced serious harm。Therefore, high-efficient cleaning, except the hydrargyrum in coal-fired flue-gas, controls the discharge of mercury contaminants, is extremely important to solving day by day serious environmental problem。
Hydrargyrum in coal-fired flue-gas is with Elemental Mercury (Hg), oxidation state hydrargyrum (Hg2+) and graininess hydrargyrum (Hgp) three kinds of forms exist。Wherein the content of Elemental Mercury accounts for more than 90%, and, elemental mercury vapor pressure height, water insoluble, be a class be difficult to remove mercury contaminants。Therefore, the removing to elemental mercury from coal-fired flue gas, is the key point removing mercury pollution。Remove Elemental Mercury at present and mainly adopt activated carbon adsorption, but adsorption capacity is not high。Although activated carbon can be improved its adsorption capacity to a certain extent by surface chemical modification, but can not change that activated carbon adsorption speed is slow, chemical stability is not high, poor selectivity and the deficiency such as be not readily separated。In recent years, it has been found that metal-oxide can catalytic oxidation Elemental Mercury, and there is higher heat stability。But such adsorbent specific surface area is little, and adsorption capacity is not high。And, when applied at elevated temperature, a large amount of SO existed in coal-fired flue dust2、HCl、NOxDeng with adsorbing material generation chemical reaction, metal-oxide being made to become the oxysalt of correspondence, thus losing adsorption activity。Finally, Elemental Mercury is adsorbed on material surface to be existed with the HgO form being difficult to decompose, and makes regneration of adsorbent material difficulty。
Carried noble metal composite is the Elemental Mercury adsorbing material being presently considered to have using value most, and the absorption of Elemental Mercury is mainly based upon Elemental Mercury by it can form stable alloy with noble metal (Au, Ag, Cu, Pd)。Compared with other hydrargyrum adsorbing material, noble metal composite adsorbing material has the advantage that
1) having stronger interaction between noble metal and Elemental Mercury, the combination such as Hg and Pd, Au, Ag, Cu can be followed successively by-0.84eV ,-0.35eV ,-0.38eV and-0.55eV, and under room temperature, Elemental Mercury just can form stable alloy with noble metal。So, hydrargyrum is had the adsorption efficiency of adsorption rate and Geng Gao faster by precious metal adsorption material, and noble metal nano particles is used for adsorbing Elemental Mercury, it is easy to reunites, namely can lose activity in the shorter time。
2) noble metal has certain chemical inertness, it is possible to SO in fire-resistant flue-gas to a certain extent2、HCl、NOxDeng the interference of co-existing gases, Elemental Mercury absorption had good selectivity。
3) hydrargyrum-precious metal alloys easily at high temperature decompose, and facilitate Elemental Mercury to reclaim and regneration of adsorbent material, make the adsorbing material can recycled for multiple times。
Noble metal decorated carbon nanomaterial when adsorbing Elemental Mercury relatively other materials become apparent from improving, and by SO2、NOx、CO2Only small Deng the impact of co-existing gases。Adsorbed Elemental Mercury can be discharged completely after material is heated, it is achieved the regeneration of adsorbing material。
Bibliographical information is by directly mixing CNT with silver nitrate, and is prepared for Ag-carbon mano-tube composite in 240 DEG C of methods heated, and Elemental Mercury is had good absorption property (G.Q.Luo by this complex, EnergyFuels, 2010,24,419-426)。But, in this material, Ag load on the carbon nanotubes is very uneven, have impact on the absorption property of material；It addition, this material is mealy structure, after Adsorption of Mercury terminates, adsorbing material, due to its microscopic dimensions, not easily separates with coal-fired flue dust, easily causes secondary pollution。
Summary of the invention
For the deficiency that prior art exists, it is an object of the invention to provide a kind of three-dimensional porous complex of noble metal-CNT and its production and use, the described three-dimensional porous complex of noble metal-CNT has high-specific surface area, high porosity, the absorption property of hydrargyrum is splendid, conveniently use and reclaim。
For reaching this purpose, the present invention by the following technical solutions:
An object of the present invention is in that to provide a kind of three-dimensional porous complex of noble metal-CNT, described complex includes noble metal nano particles, CNT sponge and for connecting noble metal nano particles and the articulamentum of CNT sponge, described articulamentum is wrapped on described CNT sponge, and described noble metal nano particles is carried on described articulamentum equably。
The present invention adopt have high-specific surface area, high stability CNT sponge as carrier, CNT sponge is wrapped up articulamentum, and at articulamentum area load noble metal nano particles, obtains the three-dimensional porous complex of noble metal-CNT。The introducing of articulamentum makes CNT sponge surface have the functional groups such as substantial amounts of-OH and-COOH, add the interaction of CNT sponge and precious metal ion, make noble metal nano particles load equably on CNT sponge, the mutual synergism of three so that hydrargyrum is not only had higher absorption property and also has the feature being prone to coal-fired flue dust separation by the described three-dimensional porous complex of noble metal-CNT。
The particle diameter of described noble metal nano particles is 5-20nm, such as 6nm, 7nm, 8nm, 10nm, 12nm, 15nm, 17nm or 19nm etc.。
Preferably, the thickness of described articulamentum is 5-10nm, such as 6nm, 7nm, 8nm or 9nm etc., to realize the preparation of the three-dimensional porous complex of noble metal-CNT of different porosities。
Preferably, CNT in described CNT sponge, its diameter is 30-50nm, such as 32nm, 35nm, 38nm, 40nm, 42nm, 45nm or 48nm etc., length is tens to hundreds of micron, such as 10 microns, 20 microns, 30 microns, 50 microns, 80 microns, 100 microns, 200 microns, 300 microns, 500 microns, 700 microns or 900 microns etc.。Described CNT sponge can prepare according to the method disclosed in 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)。
Preferably, the component of described noble metal nano particles is the combination of any one or at least two in Ag, Au, Pt or Pd。Typical but non-limiting it is combined as: Ag and Au, Ag and Pt, Ag and Pd, Ag, Au and Pt, Au, Pt and Pd, Ag, Au, Pt and Pd。
Preferably, described articulamentum is titanium dioxide layer and/or carbon-coating。
The two of the purpose of the present invention are in that the preparation method providing a kind of three-dimensional porous complex of noble metal-CNT, and described method comprises the steps:
(1) the CNT sponge of articulamentum parcel is prepared；
(2) the CNT sponge that articulamentum wraps up is immersed in noble metal precursor liquid solution, afterwards, dry, pyrolysis, obtain the three-dimensional porous complex of noble metal-CNT。
The preparation of the CNT sponge of the described articulamentum parcel of step (1) can refer to the method for the titanium dioxide parcel three-dimensional porous sponge described in CN103736475B and carries out, particularly as follows: CNT sponge is dipped in successively in Organic Alcohol solution and the water of organotitanium precursor body, obtain CNT sponge impregnating body, afterwards, remove unreacted organotitanium precursor body in CNT sponge impregnating body, obtain the CNT sponge of titanium dioxide parcel。
As preferred technical scheme, the preparation method of the CNT sponge of the described articulamentum parcel of step (1) is: be dipped in the Organic Alcohol solution of organotitanium precursor body by CNT sponge, and on shaking table, mix 10min-2h, obtain mixture, wherein, the volume ratio of organotitanium precursor body and Organic Alcohol is 1:15-1:1, and the mass ratio of CNT sponge and organotitanium precursor body is 1:10-1:500；Afterwards, mixture is immersed in water, ultrasonic 15-40min, obtain hydrolyzate, wherein, the volume ratio of CNT sponge and water is 1:10-1:1000；Remove unreacted organotitanium precursor body in hydrolyzate again, obtain the CNT sponge of articulamentum parcel。
The preparation method of the CNT sponge of the described articulamentum parcel of step (1) can be also: is placed in glucose solution by CNT sponge, carries out hydro-thermal reaction, obtains the CNT sponge of carbon-coating parcel。
Preferably, the concentration of described glucose solution is 0.2-3M, such 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 described CNT sponge and D/W 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 described 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 described hydro-thermal reaction is 1-4h, such as 1.5h, 2h, 2.5h, 3h or 3.5h etc.。
Preferably, the preparation method of the CNT sponge of the described articulamentum parcel of step (1) is: be placed in by CNT sponge in the D/W that concentration is 0.2-3M, the mass ratio of CNT sponge and D/W is 1:4000-1:400, in 180-200 DEG C of Water Under thermal response 1-4h, obtain the CNT sponge of carbon-coating parcel。
The described noble metal precursor liquid solution of step (2) is AgNO3Solution, HAuCl4Solution, H2PtCl6Solution or PdCl2The combination of any one or at least two in solution。Typical but non-limiting it is combined as: AgNO3Solution and HAuCl4Solution, H2PtCl6Solution and PdCl2Solution, AgNO3Solution, HAuCl4Solution and H2PtCl6Solution, HAuCl4Solution, H2PtCl6Solution and PdCl2Solution, AgNO3Solution, HAuCl4Solution, H2PtCl6Solution and PdCl2Solution。
Preferably, the concentration of described noble metal precursor liquid solution is 10mM-10M, such as 20mM, 30mM, 50mM, 80mM, 100mM, 200mM, 500mM, 800mM, 1M, 2M, 3M, 4M, 5M, 6M, 8M or 9M etc.。To realize the preparation of the three-dimensional porous complex of noble metal-CNT of variety classes, different loads amount。
Preferably, the CNT sponge of described articulamentum parcel soaks 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 described 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, described pyrolysis carries out in an inert atmosphere。Noble metal and CNT sponge that described inert atmosphere produces when decomposing for protecting precious metal salt are not oxidized。Described inert atmosphere can be nitrogen atmosphere and/or argon gas atmosphere。
As preferred technical scheme, comprise the steps: using titanium dioxide as the preparation method of the described three-dimensional porous complex of noble metal-CNT of articulamentum
1) TiO is prepared with reference to CN103736475B2-CNT sponge nucleocapsid structure, wherein, CNT sponge namely for mutually to be overlapped the three-dimensional porous sponge formed by CNT；
2)TiO2-CNT sponge nucleocapsid structure immerses 1-24h in the precious metal solution that concentration is 10mM-10M and adsorbs precious metal ion, dries afterwards；
3) by the dried TiO having adsorbed precious metal ion2-CNT sponge is under noble gas gas shielded, 500-600 DEG C of pyrolysis, obtains the three-dimensional porous complex of noble metal-CNT；
Wherein, step 1) particularly as follows: CNT sponge is dipped in the Organic Alcohol solution of organotitanium precursor body, and on shaking table, mix 10min-2h, obtain mixture, wherein, the volume ratio of organotitanium precursor body and Organic Alcohol is 1:15-1:1, and the mass ratio of CNT sponge and organotitanium precursor body is 1:10-1:500；Afterwards, mixture is immersed in water, ultrasonic 15-40min, obtain hydrolyzate, wherein, the volume ratio of CNT sponge and water is 1:10-1:1000；Remove unreacted organotitanium precursor body in hydrolyzate again, obtain TiO2-CNT sponge nucleocapsid structure。
As preferred technical scheme, comprise the steps: with the preparation method of the described three-dimensional porous complex of noble metal-CNT that carbon-coating is articulamentum
1) CNT sponge is placed in the D/W that concentration is 0.2-3M, the mass ratio of CNT sponge and D/W is 1:4000-1:400, afterwards, CNT sponge and D/W mixture are placed in reactor at 180-200 DEG C and carry out hydro-thermal reaction, response time is 1-4h, obtains the CNT sponge of carbon parcel；
2) the CNT sponge that carbon wraps up is immersed in the noble metal precursor liquid solution that concentration is 10mM-10M, soak 1-24h and adsorb precious metal ion, afterwards, dry；
3) the CNT sponge wrapped up by the carbon having adsorbed precious metal ion is under inert gas shielding, 500-600 DEG C of pyrolysis, obtains the three-dimensional porous complex of noble metal-CNT。
The three of the purpose of the present invention are in that to provide the purposes of a kind of three-dimensional porous complex of noble metal-CNT, and it is used for adsorbing Elemental Mercury。
The temperature of the three-dimensional porous complex absorption Elemental Mercury of described noble metal-CNT 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, the invention have the benefit that
1) noble metal nano particles in the three-dimensional porous complex of noble metal-CNT provided by the invention, between articulamentum and CNT sponge, there is synergism, interaction between articulamentum and noble metal nano particles, noble metal nano particles is made to be evenly distributed on articulamentum, improve the specific surface area of noble metal nano particles, thus improve its adsorbance to Elemental Mercury, additionally, CNT sponge has the enrichment to Elemental Mercury, therefore, the described three-dimensional porous complex of noble metal-CNT is high to the adsorption efficiency of Elemental Mercury, adsorbance is up to 11.1mg/g；
2) the three-dimensional porous complex of noble metal-CNT provided by the invention has superelevation porosity (> 99% due to CNT sponge porous material), Elemental Mercury is had certain enrichment, it is possible to increase the noble metal nano particles adsorption efficiency to Elemental Mercury；
3) in the three-dimensional porous complex of noble metal-CNT provided by the invention, CNT sponge porous material has significantly high heat stability, when 600 DEG C without decomposition, ensure that composite adsorbing material is when applied at elevated temperature and regeneration, structure will not change；
4) in the three-dimensional porous complex of noble metal-CNT provided by the invention, CNT sponge porous material has a macro-size (>=15cm × 4cm × 1cm), and Stability Analysis of Structures, can conveniently separate with coal-fired flue dust；
5) the internal Fe formed containing partially catalyzed agent of CNT sponge in the three-dimensional porous complex of noble metal-CNT provided by the invention3C nano line, so CNT sponge porous material has certain magnetic, makes noble metal/CNT sponge porous composite adsorbing material be more easy to and separates with coal-fired flue dust。
Accompanying drawing explanation
Fig. 1 is the TiO that embodiment 1 provides2Electron scanning micrograph as the three-dimensional porous complex of silver-CNT prepared by articulamentum；
Fig. 2 is the TiO that embodiment 1 provides2Transmission electron microscope photo as the three-dimensional porous complex of silver-CNT prepared by articulamentum；
Fig. 3 is the TiO that embodiment 1 provides2X-ray diffraction image as the three-dimensional porous complex of silver-CNT prepared by articulamentum；
Fig. 4 is the TiO that embodiment 2 provides2Transmission electron microscope photo as the three-dimensional porous complex of gold-CNT prepared by articulamentum；
Fig. 5 is the transmission electron micrograph of the three-dimensional porous complex of silver-CNT that the carbon that embodiment 3 provides is prepared as articulamentum；
Fig. 6 is the TiO that embodiment 9 provides2The three-dimensional porous complex of silver-CNT prepared as the articulamentum adsorption curve to Elemental Mercury。
Fig. 7 is the CNT sponge of the comparative example 1 offer adsorption curve to Elemental Mercury。
Fig. 8 is titanium dioxide-CNT sponge complex adsorption curve to Elemental Mercury that comparative example 2 provides。
Fig. 9 is the carbon-to-carbon nanotube sponge complex of the comparative example 3 offer adsorption curve to Elemental Mercury。
Detailed description of the invention
Technical scheme is further illustrated below in conjunction with accompanying drawing and by detailed description of the invention。
Embodiment 1
TiO2As the method that articulamentum prepares the three-dimensional porous complex of silver-CNT, comprise the steps:
1) CNT sponge is placed in the alcoholic solution of butyl titanate, the volume ratio of butyl titanate and ethanol is 1:7, the mass ratio of CNT sponge and butyl titanate is 1:100, and jolting 1h on shaking table makes butyl titanate uniform adsorption in CNT sponge surface；
2) being transferred in water by the CNT sponge having adsorbed butyl titanate ultrasonic, the volume ratio of CNT sponge and water is 1:100, and ultrasonic time is 40min, and making tetrabutyl titanate hydrolysis is TiO2It is wrapped in CNT sponge surface and forms TiO2-CNT sponge nucleocapsid structure；
3) dripping ethanol in three-dimensional composite, then compression is carried out, and 3 times so repeatedly, completely removes unreacted butyl titanate；
4) will there is TiO2The CNT sponge that articulamentum is modified immerses the AgNO of 1M3In solution, 8h adsorbs Ag+, afterwards, dry；
5) Ag will have been adsorbed+CNT sponge under inert gas shielding, make AgNO in 550 DEG C of heating3Decompose, obtain the three-dimensional porous complex of Ag-CNT。
Picture is as shown in Figure 1 for the scanning electron microscope (model is HitachiS4800FESEM) of the silver-CNT three-dimensional porous complex prepared。It can be seen that the length of carbon nanotube in the three-dimensional porous complex of silver-CNT prepared is tens to hundreds of micron, Nano silver grain uniform load is at TiO2On articulamentum。
Picture is as shown in Figure 2 for the transmission electron microscope (model is TecnaiF20) of silver-CNT three-dimensional porous complex that the present embodiment prepares。Measure this figure it can be seen that carbon nanotube diameter is 30-50nm, TiO2Articulamentum thickness is 5nm, and Nano silver grain diameter is 5-10nm。
Image is as shown in Figure 3 for the X-ray diffraction (model is D/MAX-TTRIII) of silver-CNT three-dimensional porous complex that the present embodiment prepares。X-ray diffraction shows, prepared Ag nanoparticle is face-centred cubic structure。
Embodiment 2
TiO2As the method that articulamentum prepares the three-dimensional porous complex of gold-CNT, comprise the steps:
1) CNT sponge is placed in the alcoholic solution of butyl titanate, the volume ratio of butyl titanate and ethanol is 1:7, the mass ratio of CNT sponge and butyl titanate is 1:100, and jolting 10min on shaking table makes butyl titanate uniform adsorption in CNT sponge surface；
2) being transferred in water by the CNT sponge having adsorbed butyl titanate ultrasonic, the volume ratio of CNT sponge and water is 1:1000, and ultrasonic time is 40min, and making tetrabutyl titanate hydrolysis is TiO2It is wrapped in CNT sponge surface and forms TiO2-CNT sponge nucleocapsid structure；
3) dripping ethanol in three-dimensional composite, then compression is carried out, and 3 times so repeatedly, completely removes unreacted butyl titanate；
4) by cleaned TiO2It is the HAuCl of 100mM that-CNT sponge nucleocapsid structure immerses concentration4In solution, 24h adsorbs AuCl4 -, and dry；
5) AuCl has been adsorbed by dried4 -TiO2-CNT sponge nucleocapsid structure makes HAuCl in 500 DEG C of heating under inert gas shielding4Decompose the preparation three-dimensional porous complex of Au-CNT。
The three-dimensional porous complex of Au-CNT prepared observe pattern by scanning electron microscope (model is HitachiS4800FESEM), observed result is: the length of carbon nanotube in the three-dimensional porous complex of Au-CNT prepared is tens to hundreds of micron, and golden nanometer particle uniform load is at TiO2On articulamentum。
Picture is as shown in Figure 4 for the transmission electron microscope (model is TecnaiF20) of the Au-CNT three-dimensional porous complex that the present embodiment prepares。It is 30-50nm, TiO from Fig. 4 carbon nanotube diameter recorded2Articulamentum thickness is 5nm, and golden nanometer particle diameter is 10-20nm。
X-ray diffraction (model is D/MAX-TTRIII) shows, the prepared Au nanoparticle in the three-dimensional porous complex of Au-CNT is face-centred cubic structure。
Embodiment 3
The method that carbon prepares the three-dimensional porous complex of silver-CNT as articulamentum, comprises the steps:
1) CNT sponge is placed in 1M D/W, CNT sponge and D/W are placed in reactor 190 DEG C reaction 4h, make CNT sponge surface uniformly wrap up one layer of carbon as articulamentum；
2) the CNT sponge that surface has carbon articulamentum immerses the AgNO of 1M3In solution, 24h adsorbs Ag+, and dry；
3) Ag will have been adsorbed+CNT sponge under inert gas shielding, make AgNO in 550 DEG C of heating3Decompose, obtain the three-dimensional porous complex of Ag-CNT。
Being observed by scanning electron microscope (model is HitachiS4800FESEM), CNT sponge length is tens to hundreds of micron, and Nano silver grain uniform load is on carbon articulamentum。
The transmission electron micrograph of the three-dimensional porous complex of silver-CNT prepared is as shown in Figure 5。The carbon nanotube diameter recorded by transmission electron microscope is 30-50nm, and carbon articulamentum thickness is 5nm, and Nano silver grain diameter is 2-5nm。
X-ray diffraction (model is D/MAX-TTRIII) shows, prepared Ag nanoparticle is face-centred cubic structure。
Embodiment 4
TiO2As the method that articulamentum prepares the three-dimensional porous complex of silver-CNT, comprise the steps:
1) CNT sponge is placed in the alcoholic solution of butyl titanate, the volume ratio of butyl titanate and ethanol is 1:7, the mass ratio of CNT sponge and butyl titanate is 1:500, and jolting 1 hour on shaking table makes butyl titanate uniform adsorption in CNT sponge surface；
2) being transferred in water by the CNT sponge having adsorbed butyl titanate ultrasonic, the volume ratio of CNT sponge and water is 1:100, and ultrasonic time is 40min, and making tetrabutyl titanate hydrolysis is TiO2It is wrapped in CNT sponge surface and forms TiO2-CNT sponge nucleocapsid structure。
3) dripping ethanol in three-dimensional composite, then compression is carried out, and 3 times so repeatedly, completely removes unreacted butyl titanate；
4) by clean after have TiO2The CNT sponge that articulamentum is modified immerses the AgNO of 10M3In solution, 8h adsorbs Ag+, and dry；
5) Ag will have been adsorbed+CNT sponge under inert gas shielding, make AgNO in 550 DEG C of heating3Decompose, obtain the three-dimensional porous complex of Ag-CNT。
Being observed by scanning electron microscope (model is HitachiS4800FESEM), CNT sponge is length is tens to hundreds of micron, and Nano silver grain uniform load is at TiO2On articulamentum。
The carbon nanotube diameter recorded by transmission electron microscope (model is TecnaiF20) is 30-50nm, TiO2Articulamentum thickness is 5nm, and Nano silver grain diameter is 10-20nm。
Embodiment 5
With TiO2Preparation method as the described three-dimensional porous complex of noble metal-CNT of articulamentum comprises the steps:
1) CNT sponge is placed in the alcoholic solution of butyl titanate, the volume ratio of butyl titanate and ethanol is 1:15, the mass ratio of CNT sponge and butyl titanate is 1:10, and jolting 2h on shaking table has made butyl titanate uniform adsorption in CNT sponge surface；
2) being immersed in water by the CNT sponge having adsorbed butyl titanate, ultrasonic, the volume ratio of CNT sponge and water is 1:10, and ultrasonic time is 15min, and tetrabutyl titanate hydrolysis is TiO2It is wrapped in CNT sponge surface, forms TiO2-CNT sponge nucleocapsid structure；
3) to TiO2Dripping ethanol in-CNT sponge nucleocapsid structure, compression is carried out, and 3 times so repeatedly, completely removes unreacted butyl titanate；
4) TiO after cleaning2It is the H of 10mM that-CNT sponge nucleocapsid structure immerses concentration2PtCl6In solution, 24h adsorbs PtCl6 4-, dry afterwards；
5) by the dried TiO having adsorbed precious metal ion2-CNT sponge is under noble gas gas shielded, 500 DEG C of pyrolysis, obtains the three-dimensional porous complex of Pt-CNT。
Being observed by scanning electron microscope (model is HitachiS4800FESEM), CNT sponge is length is tens to hundreds of micron, and Nano silver grain uniform load is at TiO2On articulamentum。
The carbon nanotube diameter recorded by transmission electron microscope (model is TecnaiF20) is 30-50nm, TiO2Articulamentum thickness is about 8nm, Pt diameter of nano particles and is about 5nm。
Embodiment 6
With TiO2Preparation method as the described three-dimensional porous complex of noble metal-CNT of articulamentum comprises the steps:
1) CNT 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 CNT sponge and butyl titanate is 1:500, and jolting 10min on shaking table makes butyl titanate uniform adsorption in CNT sponge surface；
2) being immersed in water by the CNT sponge having adsorbed butyl titanate, ultrasonic, the volume ratio of CNT sponge and water is 1:1000, and ultrasonic time is 25min, and tetrabutyl titanate hydrolysis is TiO2It is wrapped in CNT sponge surface, forms TiO2-CNT sponge nucleocapsid structure；
3) to TiO2Dripping ethanol in-CNT sponge nucleocapsid structure, compression is carried out, and 3 times so repeatedly, completely removes unreacted butyl titanate；
4) TiO after cleaning2It is the PdCl of 10M that-CNT sponge nucleocapsid structure immerses concentration2In solution, 1h adsorbs Pd2+, dry afterwards；
5) Pd has been adsorbed by dried2+TiO2-CNT sponge is under noble gas gas shielded, 600 DEG C of pyrolysis, obtains the three-dimensional porous complex of Pd-CNT。
Being observed by scanning electron microscope (model is HitachiS4800FESEM), CNT sponge is length is tens to hundreds of micron, and Nano silver grain uniform load is at TiO2On articulamentum。
The carbon nanotube diameter recorded by transmission electron microscope (model is TecnaiF20) is 30-50nm, TiO2Articulamentum thickness is about 7nm, Pd diameter of nano particles and is about 5nm。
Embodiment 7
Preparation following steps with the described three-dimensional porous complex of noble metal-CNT that carbon-coating is articulamentum:
1) CNT sponge is placed in the D/W that concentration is 3M, the mass ratio of CNT sponge and D/W is 1:4000, afterwards, CNT sponge and D/W mixture are placed in reactor at 180 DEG C and carry out hydro-thermal reaction, response time is 4h, obtains the CNT sponge of carbon parcel；
2) the CNT sponge that carbon wraps up being immersed concentration is the HAuCl of 10mM4In solution, soak 24h and adsorb AuCl4 -, afterwards, dry；
3) AuCl will have been adsorbed4 -Carbon parcel CNT sponge under inert gas shielding, 500 DEG C of pyrolysis, obtain the three-dimensional porous complex of gold-CNT。
Being observed by scanning electron microscope (model is HitachiS4800FESEM), CNT sponge is length is tens to hundreds of micron, and golden nanometer particle uniform load is on carbon articulamentum。
The carbon nanotube diameter recorded by transmission electron microscope (model is TecnaiF20) is 30-50nm, and carbon layers having thicknesses is about 10nm, and golden nanometer particle diameter is 10-20nm。
Embodiment 8
Preparation following steps with the described three-dimensional porous complex of noble metal-CNT that carbon-coating is articulamentum:
1) CNT sponge is placed in the D/W that concentration is 0.2M, the mass ratio of CNT sponge and D/W is 1:400, afterwards, CNT sponge and D/W mixture are placed in reactor at 200 DEG C and carry out hydro-thermal reaction, response time is 1h, obtains the CNT sponge of carbon parcel；
2) the CNT sponge that carbon wraps up being immersed concentration is the AgNO of 10M3In solution, soak 1h and adsorb Ag+, afterwards, dry；
3) Ag will have been adsorbed+Carbon parcel CNT sponge under inert gas shielding, 550 DEG C of pyrolysis, obtain the three-dimensional porous complex of silver-CNT。
Being observed by scanning electron microscope (model is HitachiS4800FESEM), CNT is length is tens to hundreds of micron, and Nano silver grain uniform load is on carbon articulamentum。
The carbon nanotube diameter recorded by transmission electron microscope (model is TecnaiF20) is 30-50nm, and carbon layers having thicknesses is 5nm, and Nano silver grain diameter is 10-20nm。
Embodiment 9
The three-dimensional porous complex of the silver-CNT embodiment 1 of 41.5mg prepared is put in simple substance quartz ampoule, passes into the mercury vapour that concentration is 45 μ g/L, and temperature is 150 DEG C, and carrier gas speed is 300mL/min。Utilize Elemental Mercury measuring instrument to measure the concentration of Elemental Mercury after absorption, the adsorption curve of Elemental Mercury as shown in Figure 6, the prepared three-dimensional porous complex of silver-CNT of display can active adsorption Elemental Mercury, adsorbance is 11.1mg/g。
Due to noble metal nano particles, TiO2And noble metal-TiO2Complex is not all three-dimensional porous structure, does not have the feature that easy and coal-fired flue dust separates, and therefore, the present invention only makees ratio with pure nano-carbon tube sponge, titanium dioxide-CNT sponge complex and carbon-to-carbon nanotube sponge complex。
Comparative example 1: CNT sponge is used for adsorbing Elemental Mercury
Putting in quartz ampoule by 20mg CNT sponge, pass into the mercury vapour that concentration is 45 μ g/L, temperature is 150 DEG C, and carrier gas speed is 300mL/min, and the concentration of Elemental Mercury after utilizing the measurement of Elemental Mercury measuring instrument to adsorb, the adsorption curve of Elemental Mercury is as shown in Figure 7。Elemental mercury quickly reduces by after CNT sponge, illustrate that Elemental Mercury is had certain enrichment by CNT sponge, but elemental mercury concentration quickly raises, and exceed initial concentration, be computed, simple CNT sponge to Elemental Mercury substantially without absorption。
Comparative example 2: titanium dioxide-CNT sponge complex absorption to Elemental Mercury
Step 1 in the preparation method of titanium dioxide-CNT sponge such as embodiment 1)-3)。
20mg titanium dioxide-CNT sponge is put in quartz ampoule, passing into the mercury vapour that concentration is 45 μ g/L, temperature is 150 DEG C, and carrier gas speed is 300mL/min, the concentration of Elemental Mercury after utilizing the measurement of Elemental Mercury measuring instrument to adsorb, the adsorption curve of Elemental Mercury is as shown in Figure 8。Elemental mercury quickly reduces by after CNT sponge, but quickly concentration gradually rises to original concentration, is computed, and the adsorbance of Elemental Mercury is 3.06mg/g. by titanium dioxide-CNT sponge
Comparative example 3: the carbon-to-carbon nanotube sponge complex absorption to Elemental Mercury
Step 1 in the preparation method of carbon-to-carbon nanotube sponge such as embodiment 3)。
Putting in quartz ampoule by 20mg carbon-to-carbon nanotube sponge, pass into the mercury vapour that concentration is 45 μ g/L, temperature is 150 DEG C, and carrier gas speed is 300mL/min, and the concentration of Elemental Mercury after utilizing the measurement of Elemental Mercury measuring instrument to adsorb, the adsorption curve of Elemental Mercury is as shown in Figure 9。Elemental mercury by declining seldom after carbon-to-carbon nanotube sponge and being quickly increased to original concentration, illustrate carbon-to-carbon nanotube composite sponge to Elemental Mercury substantially without adsorbing。
Applicant states; the foregoing is only the specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; person of ordinary skill in the field it should be understood that; any those skilled in the art of belonging to are in the technical scope that the invention discloses; the change that can readily occur in or replacement, all fall within protection scope of the present invention and open scope。
Claims (10)
1. the three-dimensional porous complex of noble metal-CNT, it is characterized in that, described complex includes noble metal nano particles, CNT sponge and for connecting the articulamentum of noble metal nano particles and CNT sponge, described articulamentum is wrapped on described CNT sponge, and described noble metal nano particles is carried on articulamentum equably。
2. complex according to claim 1, it is characterised in that the particle diameter of described noble metal nano particles is 5-20nm；
Preferably, the thickness of described articulamentum is 5-10nm；
Preferably, in described CNT sponge, the diameter of CNT is 30-50nm, and length is tens to hundreds of micron。
3. complex according to claim 1 and 2, it is characterised in that the component of described noble metal nano particles is the combination of any one or at least two in Ag, Au, Pt or Pd；
Preferably, described articulamentum is titanium dioxide layer and/or carbon-coating。
4. the preparation method according to the complex one of claim 1-3 Suo Shu, it is characterised in that described method comprises the steps:
(1) the CNT sponge of articulamentum parcel is prepared；
(2) the CNT sponge that articulamentum wraps up is immersed in noble metal precursor liquid solution, afterwards, dry, pyrolysis, obtain the three-dimensional porous complex of noble metal-CNT。
5. preparation method according to claim 4, it is characterized in that, the preparation method of the CNT sponge of the described articulamentum parcel of step (1) is: be dipped in by CNT sponge in Organic Alcohol solution and the water of organotitanium precursor body successively, obtain CNT sponge impregnating body, afterwards, remove unreacted organotitanium precursor body in CNT sponge impregnating body, obtain the CNT sponge of titanium dioxide parcel。
6. method according to claim 4, it is characterized in that, the preparation method of the CNT sponge of the described articulamentum parcel of step (1) is: is placed in glucose solution by CNT sponge, carries out hydro-thermal reaction, obtains the CNT sponge of carbon-coating parcel；
Preferably, the concentration of described glucose solution is 0.2-3M；
Preferably, described CNT sponge is 1:4000-1:400 with the mass ratio of D/W；
Preferably, the temperature of described hydro-thermal reaction is 180-200 DEG C；
Preferably, the time of described hydro-thermal reaction is 1-4h。
7. according to the method one of claim 4-6 Suo Shu, it is characterized in that, the preparation method of the CNT sponge of the described articulamentum parcel of step (1) is: be dipped in the Organic Alcohol solution of organotitanium precursor body by CNT sponge, and on shaking table, mix 10min-2h, obtain mixture, wherein, the volume ratio of organotitanium precursor body and Organic Alcohol is 1:15-1:1, and the mass ratio of CNT sponge and organotitanium precursor body is 1:10-1:500；Afterwards, mixture is immersed in water, ultrasonic 15-40min, obtain hydrolyzate, wherein, the volume ratio of CNT sponge and water is 1:10-1:1000；Remove unreacted organotitanium precursor body in hydrolyzate again, obtain the CNT sponge of articulamentum parcel；
Preferably, the preparation method of the CNT sponge of the described articulamentum parcel of step (1) is: be placed in by CNT sponge in the D/W that concentration is 0.2-3M, the mass ratio of CNT sponge and D/W is 1:4000-1:400, afterwards, at 180-200 DEG C of Water Under thermal response 1-4h, obtain the CNT sponge of articulamentum parcel。
8. method according to claim 4, it is characterised in that the described noble metal precursor liquid solution of step (2) is AgNO3Solution, HAuCl4Solution, H2PtCl6Solution or PdCl2The combination of any one or at least two in solution；
Preferably, the concentration of described noble metal precursor liquid solution is 10mM-10M；
Preferably, the CNT sponge of described articulamentum parcel soaks 1-24h in noble metal precursor liquid solution；
Preferably, the temperature of described pyrolysis is 500-600 DEG C；
Preferably, described pyrolysis carries out in an inert atmosphere。
9. the purposes according to the three-dimensional porous complex of noble metal-CNT one of claim 1-4 Suo Shu, it is used for adsorbing Elemental Mercury。
10. purposes according to claim 9, it is characterised in that the temperature of the three-dimensional porous complex absorption Elemental Mercury of described noble metal-CNT is 20-150 DEG C。
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