CN104226374A - Supported core-shell catalyst with oxide coated shell and metal nanoparticle core and preparation method thereof - Google Patents
Supported core-shell catalyst with oxide coated shell and metal nanoparticle core and preparation method thereof Download PDFInfo
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- CN104226374A CN104226374A CN201410452301.8A CN201410452301A CN104226374A CN 104226374 A CN104226374 A CN 104226374A CN 201410452301 A CN201410452301 A CN 201410452301A CN 104226374 A CN104226374 A CN 104226374A
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Abstract
The invention discloses a supported core-shell catalyst with an oxide coated shell and a metal nanoparticle core and a preparation method of the catalyst. The preparation method comprises the following steps: by taking SiO2, graphite, carbon nano tubes (CNTs), Al2O3 and TiO2 as carriers, triggering heat on an interface between metal nanoparticles and a liquid-phase medium by illuminating by virtue of surface plasma resonance effects of the metal nanoparticles so as to trigger a shell forming thermal reaction of a metal oxide precursor to be localized on the interface, sequentially centrifuging, dipping, drying and calcining to obtain a supported metal @ oxide core-shell catalyst. The invention provides the novel preparation method of a core-shell structure; the method has the advantages that the preparation process is simple, the cost is low, the pollution is avoided and the shell forming reaction is only localized on the interface; and the supported core-shell catalyst has the characteristics that the dispersion performance is high, the particle diameter and shell thickness of the metal nanoparticles are uniform and controllable.
Description
Technical field
The metal core oxide on surface that the present invention relates to a kind of carried oxide clad metal (metal oxide) nucleocapsid catalyst and the initiation of local surface plasma resonance photo-thermal thereof becomes shell side method, especially can be used for thermal booster reaction and prepares metal oxide core-shell nano.
Background technology
In recent years, core-shell structured nanomaterials has been a great concern for catalytic reaction.This is because easily produce synergy between nucleocapsid component, metal oxide coated metal nanoparticles, not only be beneficial to the interaction between metal and oxide, and the confinement effect of oxide shell layer can avoid metal nanoparticle to sinter, this point is very valuable to metallic catalyst.By to core and shell component and proportion adjustment, and the modulation of particle size and shell thickness, its performance of controllable is used for different catalytic reactions.
At present, core shell nanoparticles mainly adopts chemical liquid phase reaction to prepare, and comprises two steps, first prepares the nano particle of kernel, and then carries out coated shell nanometer layer.The wherein technology of preparing comparative maturity of metal nanoparticle, key is to wrap up shell.Form the crucial interface of shell reaction only between nano metal core and liquid phase that be into of shell to occur, the shell of generation can interact with core, and shell " is glued " on core.
The preparation ratio of the bimetallic nucleocapsid structure of metallic cover metal is easier to, and this is because intermetallic character is identical, is easy to interact, is easy to in-situ reducing in addition obtains metal-back by seed mediated growth method and electrochemical deposition method.It is larger that corresponding metal oxide core-shell nano prepares difficulty.Due to metal and oxide lattice matching poor, two-way interaction is little, and common solution route makes the two that stronger interaction occur by adding organic additive, realizes oxide and become shell.This not only makes preparation process complicated and wayward, and organic pollution and removal problem can be brought, shell oxide precursor can be related in whole solution middle formation problem mutually simultaneously, namely the reaction generating oxide precursor not only comes across in metal core surface/interface, and solution mutually in occur and produce reunion, cause separation difficulty.
The present invention will solve in the preparation of existing core-shell structured nanomaterials to be controlled to the reaction local of shell or its presoma in this key issue of nano-metal particle surface/interface, and provides a kind of load metal oxide nano-core-shell structure Catalysts and its preparation method.
Summary of the invention
The object of the present invention is to provide a kind of load metal oxide nano-core-shell structure catalyst.
The present invention also aims to provide that a kind of preparation process is simple, cost is low, pollution-free and become shell reaction to be only confined to the nucleocapsid structure novel preparation method at interface.
The present invention relates to a kind of metal oxide core-shell nano, be that shell is evenly oxide coated, kernel is the catalyst with core-casing structure of the metal nanoparticle of different-grain diameter, and the thickness of shell can by the time modulation of illumination.
A kind of metal oxide catalyst with core-casing structure preparation method provided by the invention utilizes surfaces of metal nanoparticles plasma resonance effect, local is caused hot in the interface of metal nanoparticle and liquid phase medium by illumination, and then cause metal oxide precursor and become shell thermal response local to occur in this interface, obtain load metal oxide nucleocapsid catalyst through follow-up centrifugal, dipping, dry and calcination processing.
Concrete technical scheme of the present invention is as follows:
A kind of carried oxide clad metal nucleocapsid catalyst; Shell is evenly oxide coated, and kernel is the catalyst with core-casing structure of metal nanoparticle.
The preparation method of carried oxide clad metal nucleocapsid catalyst of the present invention, step is:
(1) configure metal-sol, the mol ratio of reducing agent and soluble metal salt is (1 ~ 1 × 10
6): 1;
(2) configuring concentration of metal ions is 1 × 10
-3~ 100 × 10
-3the metal oxide shell precursor solution of mol/l;
(3) the metal oxide shell precursor solution of metal-sol step (1) obtained and step (2) is (0.02 ~ 2) according to volume ratio: 1 mix after, join in built-in light irradiation apparatus, be under the condition of 25 ~ 50 DEG C in reaction temperature, photo-irradiation treatment 15min ~ 5h;
(4) by the product obtained in step (3) at rotating speed be 8000 ~ 10000r/min centrifuge on be separated, the whole ultrasonic disperse of gel of gained is in water, incipient impregnation is on solid carrier several times, and the product after dipping obtains load metal oxide nucleocapsid catalyst through super-dry, calcining.
In described step (1), be 10 × 10 by molar concentration
-3~ 100 × 10
-3the soluble metal salt solution of mol/l, through stirring and heat be back to solution boiling after, add the reductant solution that mass fraction is 1 ~ 100%, described mass fraction is the mass fraction of reducing agent in the reducing agent aqueous solution; Or be first the reductant solution of 1 ~ 100% by mass fraction, after agitating heating is back to boiling, then to add molar concentration be 10 × 10
-3~ 100 × 10
-3the soluble metal salt solution of mol/l.Continue back flow reaction 5 ~ 60min after solution mixing, be cooled to room temperature, obtain metal-sol.
Described step (2) metal oxide shell precursor solution: be 1:(0.5 ~ 3 according to the mol ratio of soluble metal salt, citric acid and chelating agent): (2 ~ 12) preparing metal ion concentration is 1 × 10
-3~ 100 × 10
-3the mixed solution of mol/l, then adjusting pH value of solution with the alkali lye that mass fraction is 1 ~ 10% is 6 ~ 7, obtains metal oxide shell precursor solution.
Described step (2) metal oxide shell precursor solution: be 1:(1 ~ 10 according to the mol ratio of soluble salt and urea), configuration concentration of metal ions is 1 × 10
-3~ 100 × 10
-3the metal oxide shell precursor solution of mol/l.
Described step (4) baking temperature is 60 ~ 120 DEG C; Drying time is 6 ~ 24; Then load metal oxide nucleocapsid catalyst is obtained after calcining 3 ~ 5h with the heating rate of 1 ~ 10 DEG C/min from room temperature to 300 ~ 750 DEG C.
Described step (1) soluble metal salt cation is the one in Au, Pt, Ag, Cu, Pd, Mg or Al; Anion is a kind of in gold chloride root, chloroplatinic acid root, nitrate anion, chlorion or sulphion; Described reducing agent is the one in natrium citricum, tannic acid, ascorbic acid, white phosphorus, sodium borohydride, glycerine, polyvinylpyrrolidone, ethanol, ethylene glycol, citric acid, glucose or hydrazine hydrate.
The described soluble metal salt cation of described step (2) is the one in Ce, La, Al, Ti, Mn, Fe, Co, Ni or Zn; Anion is a kind of in nitrate anion, chlorion; Described chelating agent is ethylene glycol or ethylenediamine tetra-acetic acid (EDTA); Described alkali lye is the one in ammoniacal liquor, NaOH or potassium hydroxide.
Described step (3) optical source wavelength is 200 ~ 800nm, and intensity of illumination is 10 ~ 500mW/cm
2.
Described step step (4) carrier is SiO
2, graphite, CNT (CNTs), A1
2o
3or TiO
2in one or more.
Described metal-to-metal adhesive particle size is 4 ~ 100nm.
In described loaded catalyst, the mass fraction of core-shell nano is 1 ~ 99%.
The present invention has following effect:
One: the load metal oxide nano-core-shell structure catalyst prepared by the present invention has the features such as good dispersion, metal nanoparticle particle diameter and outer casing thickness uniform, controllable.
Two: the load metal oxide nano-core-shell structure catalyst prepared by the present invention can be used as CO oxidation reaction, the reaction of CO preferential oxidation, water-gas shift reaction catalyst.
Three: the method for operating of load metal oxide nano-core-shell structure catalyst of the present invention is simple and easy to not use any organic additive in regulation and control, preparation process, reaction is easy to control.
Four: the shell oxide in the present invention, generate as long as can be caused by heat, then all available this method preparation.The reaction caused by heat can be sol gel reaction, decomposition reaction, hydrolysis and reduction reaction etc.
Accompanying drawing explanation
Fig. 1 is the TEM figure of 17nm Au nano particle prepared by embodiment 1;
Fig. 2 is the 17nm AuCe that in embodiment 1, illumination 15min obtains
3+the TEM figure of gel;
Fig. 3 is the 17nm AuCe that in embodiment 1, illumination 45min obtains
3+the TEM figure of gel;
Fig. 4 is the 17nm AuCe that in embodiment 1, illumination 2h obtains
3+the TEM figure of gel;
Fig. 5 is SiO in embodiment 1
2the 17nm AuCeO of load
2the TEM figure of catalyst with core-casing structure;
Fig. 6 is SiO in embodiment 1
2the 17nm AuCeO of load
2the XRD figure of catalyst with core-casing structure;
Fig. 7 is 17nm AuCeO in embodiment 1
2/ SiO
2for the catalytic performance figure of CO oxidation reaction, wherein the nucleocapsid structure of metal oxide accounts for the mass fraction of whole catalyst is 30%;
Fig. 8 is the 17nm AuCeO in embodiment 6
2/ SiO
2for the catalytic performance figure of CO oxidation reaction, wherein the nucleocapsid structure of metal oxide accounts for the mass fraction of whole catalyst is 15%.
Fig. 9 is the 17nm AuCe (OH) in embodiment 8
4tEM figure.
Detailed description of the invention
Below embodiments of the invention are elaborated: the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and process, but protection scope of the present invention is not limited only to following embodiment.
Embodiment 1
One: 1): in the round-bottomed flask that backflow cold flow pipe is housed, add 0.5ml24.28 × 10
-3the gold chloride of mol/l.Vigorous stirring after adding hot reflux, when adding 2.4ml natrium citricum (mass percent 1%) fast after solution boiling, stirring 30min in boiling situation, after removing thermal source, naturally cooling to room temperature, obtain 17nm Au nano particle for subsequent use, its TEM photo as shown in Figure 1.2): take 0.1736g cerous nitrate and be dissolved in 50ml water, then add 0.126g citric acid, 0.15g ethylene glycol, dropping mass fraction is the ammoniacal liquor adjustment pH value of solution of 1.5% is 6.7.3) colloidal sol: get 50ml step 1) obtained and 100ml.Step 2) obtain solution mixing after join in light irradiation apparatus, optical source wavelength is 200 ~ 800nm, and the intensity of light source is 200mW/cm
2, controlling reaction temperature is 25 DEG C, and illumination 15min, obtains AuCe after 45min, 2h
3+gel, its TEM photo as Fig. 2,3, shown in 4.4): by the gel that obtains after illumination 2h at the centrifugal 15min of 10000r/min, and by isolated gel dispersion in 2ml water, then repeatedly incipient impregnation to 0.17g SiO
2on carrier, after 100 DEG C of dry 12h with 5 DEG C/min heating rate from room temperature to 350 DEG C, calcining 4h after obtain 17nmAuCeO
2/ SiO
2support type nucleocapsid catalyst.
Catalyst TEM, XRD prepared by said method as illustrated in Figures 5 and 6, can find out thus clearly, the AuCeO after calcining
2core-shell nano is evenly distributed in SiO
2on carrier, do not occur reuniting and sintering phenomenon, Au micelle and shell thickness do not increase, and prove the good coated metal nano particle of oxide shell, make Au particle size analysis not have increase.By Fig. 2,3,4TEM photo is visible, and the thickness of shell increases with the time increase of illumination, and generates the reaction local of shell or its presoma in nano-metal particle surface, by controlled light time and then the thickness controlling shell, can reach the object of invention.
Two: get this Catalyst packing of 0.16g in fixed bed reactors, unstripped gas consists of 1vol.%CO, 1vol.%O
2, 98vol.%N
2as Balance Air, air speed is 15,000mLh
-1g
-1 cat.Raise with temperature, on this catalyst, the conversion ratio change of CO as shown in Figure 7.
Embodiment 2
1) natrium citricum (mass fraction 1%) measuring 4.7ml is dissolved in 45ml water, vigorous stirring 15min, then pour the 100ml round-bottomed flask that backflow cold flow pipe is housed into, when coming to life, injection adds the gold chloride (24.28 × 10 of 0.5ml
-3mol/l), reaction 30min, cool to room temperature, obtains 11nm Au nano particle for subsequent use.2) ammoniacal liquor: take 0.1736g cerous nitrate and be dissolved in 50ml water, then add 0.126g citric acid, 0.15g ethylene glycol, dripping 1.5% regulates pH value of solution to be 6.7.3) product: get 50ml step 1) obtained and 100ml step 2) obtain product mixing after add in light irradiation apparatus, optical source wavelength is 200 ~ 800nm, and the intensity of light source is 200mW/cm
2, controlling reacting liquid temperature is 25 DEG C, and light application time is set to 2h.4): by the product that finally obtains at the centrifugal 15min of 10000r/min, take out gel and to be dissolved in 2ml water then repeatedly incipient impregnation to 0.17g SiO
2on carrier, 100 DEG C of dry 12h are obtain support type nucleocapsid catalyst after 5 DEG C/min is warming up to 350 DEG C of calcining 4h with heating rate.
Embodiment 3
First in the round-bottomed flask that backflow cold flow pipe is housed, 0.5ml24.28 × 10 are added
-3the gold chloride of mol/l.Then vigorous stirring after adding hot reflux, when the 1.4ml natrium citricum (mass fraction 2%) added fast after solution boiling, stirs 30min in boiling situation, naturally cools to room temperature after removing thermal source, obtain 22nm Au nano particle for subsequent use.
Subsequent step is identical with embodiment 1.
Embodiment 4
First in the round-bottomed flask that backflow cold flow pipe is housed, 0.5ml24.28 × 10 are added
-3the gold chloride of mol/l.Then vigorous stirring after adding hot reflux, when the 0.5ml natrium citricum (mass fraction 1%) added fast after solution boiling, stirs 30min in boiling situation, naturally cools to room temperature for subsequent use after removing thermal source, obtain 32nm Au nano particle for subsequent use.Subsequent step is identical with embodiment 1 with condition.
Embodiment 5
Preparation and the subsequent step of 17nm Au nano particle are identical with embodiment 1, and difference is SiO
2carrier changes Al into
2o
3, baking temperature becomes 120 DEG C from 100 DEG C, prepares AuCeO
2/ Al
2o
3support type nucleocapsid catalyst.
Embodiment 6
The present embodiment oxide coated metal nucleocapsid structure is identical with embodiment 1 step, unlike carrier S iO
2quality be 0.4g.Catalyst test is with embodiment 1, and on catalyst, the conversion ratio of CO as shown in Figure 8.
Embodiment 7
Preparation and the subsequent step of 17nm Au nano particle are identical with embodiment 1, and difference is that carrier is CNTs, and under vacuum condition, freeze drying 12h, prepares AuCeO
2/ CNTs support type nucleocapsid catalyst.
Embodiment 8
1): it is identical with embodiment 1 step that the present embodiment the 1st step prepares 17nm Au nano particle.2): 1.2076g cerous nitrate is dissolved in 50ml water, then add 0.5846g urea stirring and dissolving and become solution.3) product: get 50ml step 1) obtained and 100ml.Step 2) obtain product mixing after add in light irradiation apparatus, optical source wavelength is 200 ~ 800nm, and the intensity of light source is 200mW/cm
2, controlling reaction temperature is 45 DEG C, after illumination 4h, obtains AuCe (OH) through centrifugation
4core-shell nano, its TEM photo as shown in Figure 9.And by isolated gel dispersion in 2ml water, be then impregnated into 0.17g SiO
2on carrier, after 100 DEG C of dry 12h with 5 DEG C/min heating rate from room temperature to 350 DEG C, calcining 4h after obtain 17nm AuCeO
2/ SiO
2support type nucleocapsid catalyst.
Embodiment 9
1): it is identical with embodiment 1 step that the present embodiment the 1st step prepares 17nm Au nano particle.2) take 0.173g lanthanum nitrate and be dissolved in 50ml water, then add 0.126g citric acid, 0.15g ethylene glycol, the ammoniacal liquor dripping mass fraction 1.5% regulates pH value of solution to be 6.4.Subsequent step is identical with embodiment 1 with condition, obtains 17nm AuLa
2o
3/ SiO
2.
Embodiment 10
1): it is identical with embodiment 1 step that the present embodiment the 1st step prepares 17nm Au nano particle.2) take 0.117g cobalt nitrate and be dissolved in 50ml water, then add 0.126g citric acid, 0.15g ethylene glycol, the ammoniacal liquor dripping mass fraction 1.5% regulates pH value of solution to be 6.5.Subsequent step is identical with embodiment 1 with condition, then obtains 17nmAuCo
2o
3/ SiO
2support type nucleocapsid catalyst.
Embodiment 11
In the round-bottomed flask that backflow cold flow pipe is housed, add the glycerin solution (mass fraction is 40%) of 50ml.Vigorous stirring also, after being heated to 95 DEG C, adds 0.9ml58.87 × 10
-3mol/l silver nitrate, adds the natrium citricum that 1ml mass fraction is 3% after 1min, reaction is removed thermal source after stirring 1h and naturally cooled to room temperature, obtains 30nm Ag nano particle for subsequent use.Subsequent step is identical with embodiment 1 with condition, then obtains 30nm AgCeO
2/ SiO
2support type nucleocapsid catalyst.
Embodiment 12
In the 100ml round-bottomed flask that reflux condensing tube is housed, add 5ml58.87 × 10
-3mol/l silver nitrate and 0.25g mean molecule quantity are polyvinylpyrrolidone and the 20ml ethylene glycol solution (mass fraction 50%) of 55000, vigorous stirring is heated to 130 DEG C, remove thermal source after reaction 1h and naturally cool to room temperature, obtain 50nm Ag nano particle for subsequent use.Subsequent step is identical with embodiment 1 with condition, then obtains 50nm AgCeO
2/ SiO
2support type nucleocapsid catalyst.
Embodiment 13
1): it is identical with embodiment 12 step that the present embodiment the 1st step prepares 50nm Ag nano particle.2) take 0.117g cobalt nitrate and be dissolved in 50ml water, then add 0.126g citric acid, 0.15g ethylene glycol, the ammoniacal liquor dripping mass fraction 1.5% regulates pH value of solution to be 6.5.Subsequent step is identical with embodiment 7 with condition, then obtains 50nmAgCo
2o
3/ CNTs support type nucleocapsid catalyst.
Embodiment 14
In the 100ml round-bottomed flask that reflux condensing tube is housed, add 0.37ml17.49 × 10
-3the chloroplatinic acid of mol/l, 0.146g mean molecule quantity are polyvinylpyrrolidone and 56ml methanol-water (mass fraction 80%) solution of 10000, be heated to 100 DEG C of back flow reaction 3h after being uniformly mixed, after removing thermal source cool to room temperature, obtain 4nm Pt nano particle.Subsequent step is identical with embodiment 1 with condition, then obtains 4nm PtCeO
2/ SiO
2support type nucleocapsid catalyst.
Embodiment 15
1): it is identical with embodiment 14 step that the present embodiment the 1st step prepares 4nm Pt nano particle.2) take 0.117g cobalt nitrate and be dissolved in 50ml water, then add 0.126g citric acid, 0.15g ethylene glycol, the ammoniacal liquor dripping mass fraction 1.5% regulates pH value of solution to be 6.5.Subsequent step is identical with embodiment 1 with condition, then obtains 4nm PtCo
2o
3/ SiO
2support type nucleocapsid catalyst.
Embodiment 16
Preparation and the subsequent step of 4nm Pt nano particle are identical with embodiment 15, and difference is that carrier is CNTs, and freeze drying 12h under vacuum condition, prepares 4nm PtCo
2o
3/ CNTs support type nucleocapsid catalyst.
Claims (10)
1. a carried oxide clad metal nucleocapsid catalyst; It is characterized in that shell is evenly oxide coated, kernel is the catalyst with core-casing structure of metal nanoparticle.
2. the preparation method of the carried oxide clad metal nucleocapsid catalyst of claim 1, is characterized in that step is:
(1) configure metal-sol, the mol ratio of reducing agent and soluble metal salt is (1 ~ 1 × 10
6): 1;
(2) configuring concentration of metal ions is 1 × 10
-3~ 100 × 10
-3the metal oxide shell precursor solution of mol/l;
(3) the metal oxide shell precursor solution of metal-sol step (1) obtained and step (2) is (0.02 ~ 2) according to volume ratio: 1 mix after, join in built-in light irradiation apparatus, be under the condition of 25 ~ 50 DEG C in reaction temperature, photo-irradiation treatment 15min ~ 5h;
(4) by the product obtained in step (3) at rotating speed be 8000 ~ 10000r/min centrifuge on be separated, the whole ultrasonic disperse of gel of gained is in water, incipient impregnation is on solid carrier several times, and the product after dipping obtains load metal oxide nucleocapsid catalyst through super-dry, calcining.
3. method as claimed in claim 2, it is characterized in that in described step (1), is 10 × 10 by molar concentration
-3~ 100 × 10
-3the soluble metal salt solution of mol/l, through stirring and heat be back to solution boiling after, add the reductant solution that mass fraction is 1 ~ 100%, described mass fraction is the mass fraction of reducing agent in the reducing agent aqueous solution; Or be first the reductant solution of 1 ~ 100% by mass fraction, after agitating heating is back to boiling, then to add molar concentration be 10 × 10
-3~ 100 × 10
-3the soluble metal salt solution of mol/l.Continue back flow reaction 5 ~ 60min after solution mixing, be cooled to room temperature, obtain metal-sol.
4. method as claimed in claim 2, is characterized in that described step (2) metal oxide shell precursor solution: be 1:(0.5 ~ 3 according to the mol ratio of soluble metal salt, citric acid and chelating agent): (2 ~ 12) preparing metal ion concentration is 1 × 10
-3~ 100 × 10
-3the mixed solution of mol/l, then adjusting pH value of solution with the alkali lye that mass fraction is 1 ~ 10% is 6 ~ 7, obtains metal oxide shell precursor solution.
5. method as claimed in claim 2, is characterized in that described step (2) metal oxide shell precursor solution: be 1:(1 ~ 10 according to the mol ratio of soluble salt and urea), configuration concentration of metal ions is 1 × 10
-3~ 100 × 10
-3the metal oxide shell precursor solution of mol/l.
6. method as claimed in claim 2, is characterized in that described step (4) baking temperature is 60 ~ 120 DEG C; Drying time is 6 ~ 24; Then load metal oxide nucleocapsid catalyst is obtained after calcining 3 ~ 5h with the heating rate of 1 ~ 10 DEG C/min from room temperature to 300 ~ 750 DEG C.
7. method as claimed in claim 2, is characterized in that described step (1) soluble metal salt cation is the one in Au, Pt, Ag, Cu, Pd, Mg or Al; Anion is a kind of in gold chloride root, chloroplatinic acid root, nitrate anion, chlorion or sulphion; Described reducing agent is the one in natrium citricum, tannic acid, ascorbic acid, white phosphorus, sodium borohydride, glycerine, polyvinylpyrrolidone, ethanol, ethylene glycol, citric acid, glucose or hydrazine hydrate.
8. method as claimed in claim 2, is characterized in that the described soluble metal salt cation of described step (2) is the one in Ce, La, Al, Ti, Mn, Fe, Co, Ni or Zn; Anion is a kind of in nitrate anion, chlorion; Described chelating agent is ethylene glycol or ethylenediamine tetra-acetic acid (EDTA); Described alkali lye is the one in ammoniacal liquor, NaOH or potassium hydroxide.
9. method as claimed in claim 2, it is characterized in that described step (3) optical source wavelength is 200 ~ 800nm, intensity of illumination is 10 ~ 500mW/cm
2.
10. method as claimed in claim 2, is characterized in that described step step (4) carrier is SiO
2, graphite, CNT (CNTs), A1
2o
3or TiO
2in one or more.
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