CN107866250B - Preparation method of carbon-coated noble metal nano catalyst - Google Patents
Preparation method of carbon-coated noble metal nano catalyst Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 98
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 89
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 105
- 238000001035 drying Methods 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000012266 salt solution Substances 0.000 claims abstract description 45
- 238000005406 washing Methods 0.000 claims abstract description 39
- 238000001914 filtration Methods 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000002791 soaking Methods 0.000 claims abstract description 17
- 229910021213 Co2C Inorganic materials 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 100
- 239000000243 solution Substances 0.000 claims description 86
- 238000004448 titration Methods 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 58
- 239000011261 inert gas Substances 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 46
- 238000003786 synthesis reaction Methods 0.000 claims description 35
- 239000012452 mother liquor Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000001556 precipitation Methods 0.000 claims description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 23
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052681 coesite Inorganic materials 0.000 claims description 20
- 229910052906 cristobalite Inorganic materials 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 229910052682 stishovite Inorganic materials 0.000 claims description 20
- 229910052905 tridymite Inorganic materials 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910021281 Co3O4In Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 description 55
- 239000002082 metal nanoparticle Substances 0.000 description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 26
- 229910017052 cobalt Inorganic materials 0.000 description 15
- 239000010941 cobalt Substances 0.000 description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 241001579016 Nanoa Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- -1 electroplating Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a carbon-coated noble metal nano catalyst, which at least comprises the following steps: 1) preparation of Co2C, a catalyst; 2) mixing the Co2Placing the C catalyst in a high-temperature reaction furnace and introducing inert gasCalcining, and taking out the calcined Co2C catalyst after a certain time; 3) providing a soluble noble metal salt solution, calcining the Co2And C, adding the catalyst into the soluble noble metal salt solution, soaking for a plurality of hours at a certain temperature, washing, filtering and drying to obtain the carbon-coated noble metal nano catalyst. The preparation method has the advantages of mild conditions, low cost, simple process, low energy consumption and high yield, and can obtain various carbon-coated noble metal nano catalysts.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a carbon-coated noble metal nano catalyst.
Background
The noble metal refers to gold, silver and platinum group (platinum, osmium, iridium, ruthenium, rhodium and palladium) elements, and has important strategic position in development at present, and particularly, the platinum group metal is regarded as the 'present industrial vitamin' in the middle of the 20 th century. Due to large specific surface area, high surface energy, high surface activity and high stability, the material is widely applied to the fields of catalysts, vessel devices, information sensing materials, high-technology materials (electrical contact materials, brazing filler metals, wrapping materials, electroplating, composite materials and sizing agents), energy materials, medical and environment-friendly materials and the like. 85% of the requirements for production, purification, oxidation, dehydrogenation, isomerization, synthesis, etc. in the chemical and petroleum industries depend on catalysts, more than half of which are noble metal-containing catalysts. Although the noble metal is widely used, it is expensive and a bottleneck in wide use, and thus it is necessary to stabilize the noble metal to improve the utilization of the noble metal.
The carbon-coated noble metal is a composite material with a nanocapsule structure, which is formed by taking noble metal nanoparticles as cores and coating concentric carbon structure layers outside the noble metal nanoparticles. The material with the structure not only shows a nanometer size effect, but also overcomes the defects of thermal instability, chemical instability and the like of the nanometer metal material due to overlarge surface energy, so that the carbon-coated noble metal material has good thermal stability and can improve the dispersity of the noble metal nanometer catalyst. Therefore, it is important to develop a method for preparing carbon-coated noble metal with mild conditions and simple operation.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention is directed to a method for preparing a carbon-coated noble metal nanocatalyst, which is used to solve the problems of large equipment load, high energy consumption, high cost, low yield, etc. in the prior art for preparing a carbon-coated noble metal nanocatalyst.
In order to achieve the above and other related objects, the present invention provides a method for preparing a carbon-coated noble metal nanocatalyst, the method at least comprising:
1) preparation of Co2C, a catalyst;
2) mixing the Co2Placing the catalyst C in a high-temperature reaction furnace, introducing inert gas for calcination, and after a certain time, calcining the Co2C, taking out the catalyst;
3) providing a soluble noble metal salt solution, calcining the Co2And C, adding the catalyst into the soluble noble metal salt solution, soaking for a plurality of hours at a certain temperature, washing, filtering and drying to obtain the carbon-coated noble metal nano catalyst.
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 1), the Co is prepared2The catalyst C comprises the following steps:
1-1) preparation of Co by precipitation or impregnation3O4;
1-2) reacting said Co3O4Placing the mixture in a reaction device, and introducing H into the reaction device at a certain temperature2And inert gas for a certain time;
1-3) introducing mixed gas of carbon monoxide and inert gas or mixed gas of synthesis gas and inert gas into the reaction device at a certain temperature for a certain time to obtain the Co2And C, a catalyst.
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 1-1), the Co prepared by adopting an impregnation method3O4Comprises a carrier, and adopts an impregnation method to prepare the Co3O4The method comprises the following steps:
1-1-1) according to Co3O4In an amount to provide a quantity of carrier;
1-1-2) according to Co3O4The loading amount and the composition ratio of the carrier are that the salt of all metal components except the alkali metal is configured into a uniform mixed salt solution with the same volume as the carrier;
1-1-3) adding the mixed salt solution into the carrier in a manner of dripping while stirring at a certain temperature;
1-1-4) after the titration is finished, keeping the temperature unchanged and dipping;
1-1-5) drying and roasting the dipped solution to obtain the Co3O4。
As a preferable embodiment of the method for preparing the carbon-coated noble metal nano catalyst of the present invention, in the step 1-1-1), the support includes ZrO2、TiO2、SiO2、Al2O3Or one or more of activated carbon.
As a preferable embodiment of the method for preparing the carbon-coated noble metal nano catalyst of the present invention, in the step 1-1-2), the salts of all metal components except for the alkali metal include a main metal cobalt salt, and the main metal cobalt salt includes one or more of chloride, nitrate, sulfate, carbonate, or acetate; the total molar concentration of the metal salt in the mixed salt solution is 0.01-5 mol/L.
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 1-1-4), the dipping temperature is 10-70 ℃, and the dipping time is 1-48 h.
As a preferred scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 1-1-5), the drying temperature is 20-200 ℃, and the drying time is 2-100 h; the roasting temperature is 200-600 ℃, and the roasting time is 0.5-24 h.
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 1-1), the Co is prepared by adopting a precipitation method3O4The method comprises the following steps:
1-1-1) according to Co3O4Preparing salt of all metal components except the alkali metal into a uniformly mixed salt solution, and preparing a precipitator solution;
1-1-2) providing mother liquor, and dripping the mixed salt solution and the precipitant solution into the mother liquor in a cocurrent manner at a certain temperature for precipitation;
1-1-3) after titration, keeping the temperature unchanged and aging;
1-1-4) separating, washing, drying and roasting the aged titration solution to obtain the Co3O4。
As a preferable embodiment of the method for preparing the carbon-coated noble metal nano catalyst of the present invention, in step 1-1-1), the salts of all metal components except for the alkali metal include a main metal cobalt salt, and the main metal cobalt salt includes one or more of chloride, nitrate, sulfate, carbonate, or acetate; the total molar concentration of the metal salt in the mixed salt solution is 0.01-5 mol/L.
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst of the present invention, in step 1-1-1), the precipitant in the precipitant solution includes one or more of potassium hydroxide, sodium carbonate, ammonium carbonate and sodium bicarbonate, and the molar concentration of the precipitant in the precipitant solution is 0.01mol/L to 5 mol/L.
As a preferable embodiment of the method for preparing the carbon-coated noble metal nano catalyst of the present invention, the Co is3O4The method comprises a carrier, and in the step 1-1-2), before the mixed salt solution and the precipitant solution are dripped into the mother liquor in a cocurrent mode at a certain temperature, the method also comprises a step of adding the carrier into the mother liquor.
As a preferable embodiment of the method for preparing the carbon-coated noble metal nano catalyst of the present invention, the support comprises ZrO2、TiO2、SiO2、Al2O3Or one or more of activated carbon.
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 1-1-2), the volume ratio of the precipitant solution and the mixed salt solution dropped into the mother liquor is 1: 5-5: 1; the precipitation temperature is 10-100 ℃; the pH of the precipitate is 5-14.
As a preferred scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 1-1-4), the drying temperature is 20-200 ℃, and the drying time is 2-100 h; the roasting temperature is 200-600 ℃, and the roasting time is 0.5-24 h.
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 1-2), H is introduced into the reaction device2The temperature of the mixed gas with inert gas is 150-500 ℃, and H2And H in a mixed gas of an inert gas2The volume percentage of (A) is 5-100%; introducing H into the reaction device2The time of the mixed gas of the inert gas and the inert gas is 0 to 48 hours.
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 1-3), the temperature of the mixed gas of carbon monoxide and inert gas or the mixed gas of synthesis gas and inert gas introduced into the reaction device is 150-400 ℃ in the step of introducing the mixed gas of carbon monoxide and inert gas into the reaction device, and the volume percentage of the carbon monoxide or the synthesis gas in the mixed gas is 5-100%; and introducing the mixed gas of carbon monoxide and inert gas or the mixed gas of synthesis gas and inert gas into the reaction device for 0.5-48 h.
As a preferable embodiment of the preparation method of the carbon-coated noble metal nano catalyst of the present invention, in the step 2), the inert gas is one or more of nitrogen, argon or helium, the purity of the inert gas is greater than or equal to 99.99%, and the space velocity is 100mlg-1h-1~20000mlg-1h-1。
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 2), the calcining temperature is 200-800 ℃, and the calcining time is 3-24 h.
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 3), the soluble noble metal salt solution comprises one or more of iridium nitrate, silver nitrate, rhodium nitrate, palladium nitrate, chloroplatinic acid, platinum nitrate, silver nitrate or chloroauric acid, and the molar concentration of the soluble noble metal salt solution is 0.01mol/L to 5 mol/L.
As a preferred scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 3), the soaking temperature is 20-80 ℃, and the soaking time is 0.5-5 h.
As a preferable scheme of the preparation method of the carbon-coated noble metal nano catalyst, in the step 3), the drying temperature is 20-200 ℃, and the drying time is 2-50 h.
As described above, the preparation method of the carbon-coated noble metal nano catalyst of the present invention has the following beneficial effects: the preparation method of the carbon-coated noble metal nano catalyst at least comprises the following steps: 1) preparation of Co2C, a catalyst; 2) mixing the Co2Placing the catalyst C in a high-temperature reaction furnace, introducing inert gas for calcination, and taking out the calcined Co2C catalyst after a certain time; 3) providing a soluble noble metal salt solution, calcining the Co2Adding a catalyst C into the soluble noble metal salt solution, soaking for a plurality of hours at a certain temperature, washing, filtering and drying to obtain the carbon-coated noble metal nanoA catalyst. The preparation method has the advantages of mild conditions, low cost, simple process, low energy consumption and high yield, and can obtain various carbon-coated noble metal nano catalysts.
Drawings
Fig. 1 shows a flow chart of a preparation method of the carbon-coated noble metal nano-catalyst of the invention.
Fig. 2 shows a raman spectrum of a carbon-coated platinum metal nanoparticle prepared by the method for preparing a carbon-coated noble metal nanocatalyst provided in example 1 of the present invention.
Fig. 3 shows a transmission electron microscope image of carbon-coated platinum metal nanoparticles prepared by the method for preparing a carbon-coated noble metal nanocatalyst provided in example 1 of the present invention.
Fig. 4 shows an X-ray diffraction pattern of carbon-coated platinum metal nanoparticles prepared for the method of preparing a carbon-coated noble metal nanocatalyst provided in example 1 of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 4. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and although the drawings only show the components related to the present invention and are not drawn according to the number, shape and size of the components in actual implementation, the type, quantity and proportion of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
Referring to fig. 1, the present invention provides a method for preparing a carbon-coated noble metal nano-catalyst, which at least includes:
1) preparation of Co2C, a catalyst;
2) mixing the Co2Placing the catalyst C in a high-temperature reaction furnace, introducing inert gas for calcination, and after a certain time, calcining the Co2C, taking out the catalyst;
3) providing a soluble noble metal salt solution, calcining the Co2And C, adding the catalyst into the soluble noble metal salt solution, soaking for a plurality of hours at a certain temperature, washing, filtering and drying to obtain the carbon-coated noble metal nano catalyst.
In step 1), please refer to step S1 in FIG. 1, preparing Co2And C, a catalyst.
As an example, the Co was prepared2The catalyst C comprises the following steps:
1-1) preparation of Co by precipitation or impregnation3O4;
1-2) reacting said Co3O4Placing the mixture in a reaction device, and introducing H into the reaction device at a certain temperature2And inert gas for a certain time;
1-3) introducing mixed gas of carbon monoxide and inert gas or mixed gas of synthesis gas and inert gas into the reaction device at a certain temperature for a certain time to obtain the Co2And C, a catalyst.
As an example, in step 1-1), the Co may be prepared by a precipitation method or an impregnation method3O4。
In one example, the Co is prepared by an impregnation method3O4Comprises a carrier, and adopts an impregnation method to prepare the Co3O4The method comprises the following steps:
1-1-1) according to Co3O4In an amount to provide a quantity of carrier;
1-1-2) according to Co3O4The loading amount and the composition ratio of the carrier are that the salt of all metal components except the alkali metal is configured into a uniform mixed salt solution with the same volume as the carrier;
1-1-3) adding the mixed salt solution into the carrier in a manner of dripping while stirring at a certain temperature;
1-1-4) after the titration is finished, keeping the temperature unchanged and dipping;
1-1-5) drying and roasting the dipped solution to obtain the Co3O4。
As an example, the support comprises ZrO2、TiO2、SiO2、Al2O3Or one or more of activated carbon.
As an example, in step 1-1-2) of the impregnation method, the salts of all the metal components except the alkali metal include a main metal cobalt salt including one or more of chloride, nitrate, sulfate, carbonate, or acetate; the total molar concentration of the metal salts in the mixed salt solution is 0.01-5 mol/L, and preferably the total molar concentration of the metal salts in the mixed salt solution is 1-3 mol/L.
As an example, in step 1-1-4) of the impregnation method, the impregnation temperature is 10 ℃ to 70 ℃, preferably, the impregnation temperature is 20 ℃ to 40 ℃; the dipping time is 1 h-48 h, preferably, the dipping time is 5 h-12 h.
As an example, in the step 1-1-5) of the impregnation method, the drying temperature is 20 ℃ to 200 ℃ and the drying time is 2h to 100 h; preferably, the drying temperature is 40-120 ℃, and the drying time is 4-60 h; the roasting temperature is 200-600 ℃, and the roasting time is 0.5-24 h; preferably, the roasting temperature is 250-500 ℃, and the roasting time is 2-10 h.
As an example, the drying process in steps 1-1-5) of the impregnation method may be performed under vacuum conditions, an air atmosphere, and an inert atmosphere, and preferably, the drying process is performed under an air atmosphere.
In another example, the Co is prepared by precipitation3O4The method comprises the following steps:
1-1-1) according to Co3O4Preparing salt of all metal components except the alkali metal into a uniformly mixed salt solution, and preparing a precipitator solution;
1-1-2) providing mother liquor, and dripping the mixed salt solution and the precipitant solution into the mother liquor in a cocurrent manner at a certain temperature for precipitation;
1-1-3) after titration, keeping the temperature unchanged and aging;
1-1-4) separating, washing, drying and roasting the aged titration solution to obtain the Co3O4。
As an example, in step 1-1-1) of the precipitation method, the salts of all metal components except the alkali metal include a main metal cobalt salt including one or more of chloride, nitrate, sulfate, carbonate, or acetate; the total molar concentration of the metal salts in the mixed salt solution is 0.01-5 mol/L, and preferably the total molar concentration of the metal salts in the mixed salt solution is 1-3 mol/L.
As an example, in step 1-1-1) of the precipitation method, the precipitant in the precipitant solution includes one or more of potassium hydroxide, sodium carbonate, ammonium carbonate, and sodium bicarbonate, and the molar concentration of the precipitant in the precipitant solution is 0.01mol/L to 5mol/L, and preferably, the molar concentration of the precipitant in the precipitant solution is 1mol/L to 3 mol/L.
As an example, the Co3O4The method comprises a carrier, and in the step 1-1-2) of the precipitation method, before dropping the mixed salt solution and the precipitant solution into the mother liquor in a cocurrent manner at a certain temperature, the method also comprises a step of adding the carrier into the mother liquor. The carrier comprises ZrO2、TiO2、SiO2、Al2O3Or one or more of activated carbon.
As an example, in step 1-1-2) of the precipitation method, the volume ratio of the precipitant solution to the mixed salt solution dropped into the mother liquor is 1:5 to 5: 1; the precipitation temperature is 10-100 ℃, preferably, the precipitation temperature is 20-80 ℃; the precipitation pH is 5-14, preferably, the precipitation pH is 7-11.
As an example, in the step 1-1-4) of the precipitation method, the drying temperature is 20 ℃ to 200 ℃, and the drying time is 2h to 100 h; preferably, the drying temperature is 40-120 ℃, and the drying time is 4-60 h; the roasting temperature is 200-600 ℃, and the roasting time is 0.5-24 h; preferably, the roasting temperature is 250-500 ℃, and the roasting time is 2-10 h.
As an example, the drying process in steps 1-1-4) in the precipitation method may be performed under vacuum conditions, an air atmosphere, and an inert atmosphere, preferably, the drying process is performed under an air atmosphere; the calcination process in steps 1-1-4) in the precipitation method may be performed in a vacuum condition, an air atmosphere, a nitrogen atmosphere, or a helium atmosphere, and preferably, the calcination process is performed in a nitrogen atmosphere and an air atmosphere.
As an example, in the step 1-2), H is introduced into the reaction apparatus2The temperature of the mixed gas with inert gas is 150-500 ℃, and H2And H in a mixed gas of an inert gas2The volume percentage of (A) is 5-100%; introducing H into the reaction device2The time of the mixed gas with the inert gas is 0 to 48 hours; preferably, H is introduced into the reaction device2The temperature of the mixed gas with inert gas is 250-350 ℃, H2And H in a mixed gas of an inert gas2The volume percentage of (A) is 10-100%; introducing H into the reaction device2The time of the mixed gas of the inert gas and the inert gas is 0 to 10 hours.
As an example, in the step 1-3), when the mixed gas of carbon monoxide and inert gas or the mixed gas of synthesis gas and inert gas is introduced into the reaction device, the temperature is 150 ℃ to 400 ℃, and the volume percentage of the carbon monoxide or the synthesis gas in the mixed gas is 5% to 100%; the time for introducing the mixed gas of carbon monoxide and inert gas or the mixed gas of synthesis gas and inert gas into the reaction device is 0.5 to 48 hours; preferably, the temperature of the mixed gas of carbon monoxide and inert gas or the mixed gas of synthesis gas and inert gas introduced into the reaction device is 180-250 ℃ when the mixed gas of carbon monoxide and inert gas or the mixed gas of synthesis gas and inert gas is introduced into the reaction device, and the volume percentage of the carbon monoxide or the synthesis gas in the mixed gas is 10-100%; and introducing the mixed gas of carbon monoxide and inert gas or the mixed gas of synthesis gas and inert gas into the reaction device for 5-10 hours.
In step 2), please refer to step S2 in fig. 1, the Co is mixed2Placing the catalyst C in a high-temperature reaction furnace, introducing inert gas for calcination, and after a certain time, calcining the Co2And C, taking out the catalyst.
Illustratively, the inert gas is one or more of nitrogen, argon or helium, the purity of the inert gas is greater than or equal to 99.99%, and the space velocity is 100mlg-1h-1~20000mlg-1h-1Preferably, the space velocity is 1000mlg-1h-1~10000mlg-1h-1。
As an example, the calcination temperature is 200 ℃ to 800 ℃, preferably, the calcination temperature is 300 ℃ to 450 ℃; the calcination time is 3-24 h, preferably 5-10 h.
In step 3), please refer to step S3 in FIG. 1, a soluble noble metal salt solution is provided, and the Co after calcination is added2And C, adding the catalyst into the soluble noble metal salt solution, soaking for a plurality of hours at a certain temperature, washing, filtering and drying to obtain the carbon-coated noble metal nano catalyst.
By way of example, the soluble precious metal salt solution comprises one or more of iridium nitrate, silver nitrate, rhodium nitrate, palladium nitrate, chloroplatinic acid, platinum nitrate, silver nitrate or chloroauric acid, and the molar concentration of the soluble precious metal salt solution is 0.01mol/L to 5mol/L, preferably 0.5mol/L to 3 mol/L.
As an example, the soaking temperature is 20 ℃ to 80 ℃, preferably, the soaking temperature is 20 ℃ to 30 ℃; the soaking time is 0.5 h-5 h, preferably 0.5 h-2 h.
By way of example, the drying temperature is 20 ℃ to 200 ℃, preferably 60 ℃ to 120 ℃; the drying time is 2-50 h, preferably 4-10 h.
The following specific examples are illustrative of Co-based compositions of the present invention2And C, a method for preparing the graphitized hollow nano structure is introduced in detail.
Example 1
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 65 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing for 5H at 400 ℃, then cooling to 220 ℃, switching gas to H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of Fischer-Tropsch reaction, and the space velocity is 8000mlg-1h-1Raising the temperature to 400 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the carbon-coated platinum metal nanoparticles. As can be seen from fig. 2 to 4, the carbon-coated platinum metal nanoparticles prepared in this example only contain platinum simple substance and have no residual cobalt, a raman spectrum of the carbon-coated platinum metal nanoparticles is shown in fig. 2, a transmission electron microscope image is shown in fig. 3, and an X-ray diffraction pattern is shown in fig. 4.
Example 2
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 25 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 25 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing for 5H at 400 ℃, then cooling to 220 ℃, switching gas to H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 400 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the carbon-coated platinum metal nanoparticles.
Example 3
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 45 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at the temperature of 45 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is transferred to a muffle furnace to be heated to 330 ℃ by a program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing for 5H at 400 ℃, then cooling to 220 ℃, switching gas to H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 400 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the carbon-coated platinum metal nanoparticles.
Example 4
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 65 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L aluminum platinic acid, stirring at room temperature for 1h, washing, and filteringFiltering, and drying in a drying oven at 100 ℃ for 5h to obtain the carbon-coated platinum metal nanoparticles.
Example 5
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 65 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L silver nitrate solution, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the carbon-coated platinum metal nanoparticles.
Example 6
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 65 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L silver nitrate solution, stirring and stirring at 40 ℃ for 0.5h, washing, filtering, and drying in a 100 ℃ drying oven for 5h to obtain the carbon-coated silver metal nanoparticles.
Example 7
C is to beo(NO3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 65 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 15mL of 2mol/L silver nitrate solution, stirring and stirring at 30 ℃ for 0.5h, washing, filtering, and drying in a 100 ℃ drying oven for 5h to obtain the carbon-coated silver metal nanoparticles.
Example 8
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 25 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 25 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing for 5H at 400 ℃, then cooling to 220 ℃, switching gas to H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 400 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L silver nitrate solution, stirring and soaking at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the carbon-coated silver metal nanoparticles.
Example 9
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 25 ℃ and a pH of 8. Dripping deviceAfter the determination is finished, the mixture is aged for 2h at 25 ℃, is dried for 12h in a 100 ℃ oven after being centrifuged and washed for 6 times, and is transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 h. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing for 5H at 400 ℃, then cooling to 220 ℃, switching gas to H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 400 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L silver nitrate solution, stirring and soaking at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the carbon-coated silver metal nanoparticles.
Example 10
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 45 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at the temperature of 45 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is transferred to a muffle furnace to be heated to 330 ℃ by a program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing for 5H at 400 ℃, then cooling to 220 ℃, switching gas to H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 400 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L silver nitrate solution, stirring and stirring at 30 ℃ for 0.5h, washing, filtering, and drying in a 100 ℃ drying oven for 5h to obtain the carbon-coated silver metal nanoparticles.
Example 11
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 65 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. Taking 1.5g to roastThe catalyst (2) was placed in a reaction tube and 10% H was introduced2Reducing for 5H at 400 ℃, then cooling to 220 ℃, switching gas to H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 400 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L palladium nitrate solution, stirring and stirring at 30 ℃ for 0.5h, washing, filtering, and drying in a 100 ℃ drying oven for 5h to obtain the carbon-coated palladium metal nanoparticles.
Example 12
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 65 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing at 300 deg.C for 5H, cooling to 220 deg.C, and switching gas to H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L palladium nitrate solution, stirring and stirring at 30 ℃ for 0.5h, washing, filtering, and drying in a 100 ℃ drying oven for 5h to obtain the carbon-coated palladium metal nanoparticles.
Example 13
Mixing Co (NO)3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 65 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L rhodium nitrate solution, stirring and stirring at 30 ℃ for 0.5h, washing, filtering, and drying in a 100 ℃ drying oven for 5h to obtain the carbon-coated rhodium metal nanoparticles.
Example 14
Mixing Co (NO)3)2·6H2O and Na2CO3All are prepared into a solution with the concentration of 2 mol/L. Adding mother liquor into a beaker, and adding a certain amount of SiO into the mother liquor2The two solutions were co-precipitated in a stirred mother liquor in a cocurrent manner by adjusting the cobalt loading to 10%, the titration temperature to 65 ℃ and controlling the titration pH to-8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of calcined 10% Co/SiO2The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the SiO supported catalyst2The carbon-coated platinum metal nanoparticles above.
Example 15
Mixing Co (NO)3)2·6H2O and Na2CO3All are prepared into a solution with the concentration of 2 mol/L. Adding mother liquor into a beaker, and adding a certain amount of SiO into the mother liquor2The two solutions were co-precipitated in a stirred mother liquor in a cocurrent manner by adjusting the cobalt loading to 20%, the titration temperature to 65 ℃ and controlling the titration pH to-8. Aging at 65 deg.C for 2 hr after titration, centrifuging, washing for 6 times, oven drying at 100 deg.C for 12 hr, and dryingThen transferring the mixture to a muffle furnace to be heated to 330 ℃ in a programmed way and roasted for 3 h. 1.5g of calcined 10% Co/SiO2The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the SiO supported catalyst2The carbon-coated platinum metal nanoparticles above.
Example 16
Mixing Co (NO)3)2·6H2O and Na2CO3All are prepared into a solution with the concentration of 2 mol/L. Adding mother liquor into a beaker, and adding a certain amount of TiO into the mother liquor2The two solutions were co-precipitated in a stirred mother liquor in a cocurrent manner by adjusting the cobalt loading to 10%, the titration temperature to 65 ℃ and controlling the titration pH to-8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of calcined 10% Co/TiO was taken2The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the supported TiO2The carbon-coated platinum metal nanoparticles above.
Example 17
Mixing Co (NO)3)2·6H2O and Na2CO3All are prepared into a solution with the concentration of 2 mol/L. Adding mother liquor into a beaker, adding the mother liquorAdding a certain amount of TiO2The two solutions were co-precipitated in a stirred mother liquor in a cocurrent manner by adjusting the cobalt loading to 10%, the titration temperature to 65 ℃ and controlling the titration pH to-8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of calcined 10% Co/TiO was taken2The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L silver nitrate solution, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the supported TiO2The carbon-coated silver metal nanoparticles above.
Example 18
Mixing Co (NO)3)2·6H2O and Na2CO3All are prepared into a solution with the concentration of 2 mol/L. Adding mother liquor into a beaker, and adding a certain amount of Al into the mother liquor2O3The two solutions were co-precipitated in a stirred mother liquor in a cocurrent manner by adjusting the cobalt loading to 10%, the titration temperature to 65 ℃ and controlling the titration pH to-8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of calcined 10% Co/Al are taken2O3The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid solution, stirring at room temperature for 1h, washing, filtering, and then putting into a 100 ℃ oven to be driedDrying for 5h to obtain the loaded Al2O3The carbon-coated platinum metal nanoparticles above.
Example 19
Mixing Co (NO)3)2·6H2O and Na2CO3All are prepared into a solution with the concentration of 2 mol/L. Adding mother liquor into a beaker, and adding a certain amount of Al into the mother liquor2O3The two solutions were co-precipitated in a stirred mother liquor in a cocurrent manner by adjusting the cobalt loading to 10%, the titration temperature to 65 ℃ and controlling the titration pH to-8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of calcined 10% Co/Al are taken2O3The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing the mixture for 5 hours at 350 ℃, then cooling the mixture to 220 ℃, and switching the gas into H22/CO-synthesis gas at a space velocity of 2000mlg-1h-1. He is introduced after 10h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L rhodium nitrate solution, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the Al-loaded catalyst2O3The carbon-coated rhodium metal nanoparticles above.
Example 20
Weighing 10g of SiO2Placing into a beaker according to SiO2So that the cobalt loading was 10%, the amount of Co (NO) was determined3)2·6H2O is prepared into 10gSiO with the concentration of 2mol/L and the volume of2Water-absorbing capacity of the solution. The above solution was added dropwise to the carrier at 25 ℃ with stirring. After titration, the mixture is soaked for 12 hours at 25 ℃, then is placed in a 100 ℃ oven for drying for 12 hours, and then is transferred to a muffle furnace for roasting for 3 hours by temperature programming to 330 ℃. 1.5g of calcined 10% Co/SiO2The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing for 5h at 400 ℃, then cooling to 220 ℃, switching the gas to pure CO, and controlling the space velocity to 2000mlg-1h-1. After being treated for 20h, the mixture is led toHe, space velocity 8000mlg-1h-1Raising the temperature to 400 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the SiO supported catalyst2The carbon-coated platinum metal nanoparticles above.
Example 21
Weighing 10g of SiO2Placing into a beaker according to SiO2So that the cobalt loading was 20%, the amount of Co (NO) was determined3)2·6H2O is prepared into 10gSiO with the concentration of 2mol/L and the volume of2Water-absorbing capacity of the solution. The above solution was added dropwise to the carrier at 25 ℃ with stirring. After titration, the mixture is soaked for 12 hours at 25 ℃, then is placed in a 100 ℃ oven for drying for 12 hours, and then is transferred to a muffle furnace for roasting for 3 hours by temperature programming to 330 ℃. 1.5g of calcined 20% Co/SiO2The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing for 5h at 350 ℃, then cooling to 220 ℃, switching the gas to pure CO, and controlling the space velocity to 2000mlg-1h-1. He is introduced after 20h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the SiO supported catalyst2The carbon-coated platinum metal nanoparticles above.
Example 22
Weighing 10g of SiO2Placing into a beaker according to SiO2So that the cobalt loading was 20%, the amount of Co (NO) was determined3)2·6H2O is prepared into 10gSiO with the concentration of 2mol/L and the volume of2Water-absorbing capacity of the solution. The above solution was added dropwise to the carrier at 25 ℃ with stirring. After titration, the mixture is soaked for 12 hours at 25 ℃, then is placed in a 100 ℃ oven for drying for 12 hours, and then is transferred to a muffle furnace for roasting for 3 hours by temperature programming to 330 ℃. 1.5g of calcined 20% Co/SiO2The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing for 5h at 350 ℃, then cooling to 220 ℃, switching the gas to pure CO, and controlling the space velocity to 2000mlg-1h-1. He is introduced after 20h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L silver nitrate solution, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the SiO supported catalyst2The carbon-coated silver metal nanoparticles above.
Example 23
Weighing 10g of SiO2Placing into a beaker according to SiO2So that the cobalt loading was 20%, the amount of Co (NO) was determined3)2·6H2O is prepared into 10gSiO with the concentration of 2mol/L and the volume of2Water-absorbing capacity of the solution. The above solution was added dropwise to the carrier at 25 ℃ with stirring. After titration, the mixture is soaked for 12 hours at 25 ℃, then is placed in a 100 ℃ oven for drying for 12 hours, and then is transferred to a muffle furnace for roasting for 3 hours by temperature programming to 330 ℃. 1.5g of calcined 20% Co/SiO2The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing for 5h at 350 ℃, then cooling to 220 ℃, switching the gas to pure CO, and controlling the space velocity to 2000mlg-1h-1. He is introduced after 20h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L palladium nitrate solution, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the SiO supported catalyst2The carbon-coated palladium metal nanoparticles.
Example 24
Weighing 10g of TiO2Placing into a beaker according to TiO2So that the cobalt loading was 20%, the amount of Co (NO) was determined3)2·6H2O is prepared into 10g TiO with the concentration of 2mol/L2Water-absorbing capacity of the solution. The above solution was added dropwise to the carrier at 25 ℃ with stirring. Soaking at 25 deg.C for 12h after titration, oven drying at 100 deg.C for 12h, and dryingTransferring the mixture into a muffle furnace, and carrying out roasting for 3 hours by temperature programming to 330 ℃. 1.5g of calcined 20% Co/TiO was taken2The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing for 5h at 350 ℃, then cooling to 220 ℃, switching the gas to pure CO, and controlling the space velocity to 2000mlg-1h-1. He is introduced after 20h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L palladium nitrate solution, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the supported TiO2The carbon-coated palladium metal nanoparticles.
Example 25
Weighing 10g of TiO2Placing into a beaker according to TiO2So that the cobalt loading was 20%, the amount of Co (NO) was determined3)2·6H2O is prepared into 10g TiO with the concentration of 2mol/L2Water-absorbing capacity of the solution. The above solution was added dropwise to the carrier at 25 ℃ with stirring. After titration, the mixture is soaked for 12 hours at 25 ℃, then is placed in a 100 ℃ oven for drying for 12 hours, and then is transferred to a muffle furnace for roasting for 3 hours by temperature programming to 330 ℃. 1.5g of calcined 20% Co/TiO was taken2The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing for 5h at 350 ℃, then cooling to 220 ℃, switching the gas to pure CO, and controlling the space velocity to 2000mlg-1h-1. He is introduced after 20h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid solution, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the supported TiO2The carbon-coated platinum metal nanoparticles above.
Example 26
Weighing 10g of Al2O3Placing into a beaker according to TiO2So that the cobalt loading was 20%, the amount of Co (NO) was determined3)2·6H2O is prepared into 10g of Al with the concentration of 2mol/L and the volume2O3Of water absorption capacityAnd (3) solution. The above solution was added dropwise to the carrier at 25 ℃ with stirring. After titration, the mixture is soaked for 12 hours at 25 ℃, then is placed in a 100 ℃ oven for drying for 12 hours, and then is transferred to a muffle furnace for roasting for 3 hours by temperature programming to 330 ℃. 1.5g of calcined 20% Co/Al are taken2O3The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing for 5h at 350 ℃, then cooling to 220 ℃, switching the gas to pure CO, and controlling the space velocity to 2000mlg-1h-1. He is introduced after 20h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid solution, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the Al-loaded catalyst2O3The carbon-coated platinum metal nanoparticles above.
Example 27
Weighing 10g of Al2O3Placing into a beaker according to TiO2So that the cobalt loading was 20%, the amount of Co (NO) was determined3)2·6H2O is prepared into 10g of Al with the concentration of 2mol/L and the volume2O3Water-absorbing capacity of the solution. The above solution was added dropwise to the carrier at 25 ℃ with stirring. After titration, the mixture is soaked for 12 hours at 25 ℃, then is placed in a 100 ℃ oven for drying for 12 hours, and then is transferred to a muffle furnace for roasting for 3 hours by temperature programming to 330 ℃. 1.5g of calcined 20% Co/Al are taken2O3The catalyst was loaded into a reaction tube and 10% H was introduced2Reducing for 5h at 350 ℃, then cooling to 220 ℃, switching the gas to pure CO, and controlling the space velocity to 2000mlg-1h-1. He is introduced after 20h of treatment, and the space velocity is 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 10 hours, and then cooling and taking out. Putting the taken catalyst into a beaker, adding 20mL of 1mol/L chloroplatinic acid solution, stirring and stirring at 40 ℃ for 0.5h, washing, filtering, and drying in a 100 ℃ drying oven for 5h to obtain the Al-loaded catalyst2O3The carbon-coated platinum metal nanoparticles above.
Example 28
Mixing Co (N)O3)2·6H2O and Na2CO3A solution having a concentration of 2mol/L was prepared, and titration was carried out at a temperature of 65 ℃ and a pH of 8. After titration, the mixture is aged for 2 hours at 65 ℃, is dried for 12 hours in a 100 ℃ oven after being centrifuged and washed for 6 times, and is then transferred to a muffle furnace to be heated to 330 ℃ by program and roasted for 3 hours. 1.5g of the calcined catalyst was placed in a reaction tube and H was introduced2Treating the synthesis gas with/CO 2 at 250 deg.C for 20h, introducing He, and setting the space velocity at 8000mlg-1h-1Raising the temperature to 350 ℃, maintaining the temperature for 15h, and then cooling and taking out. And putting the taken catalyst into a beaker, adding 20mL of 1mol/L silver nitrate solution, stirring at room temperature for 1h, washing, filtering, and drying in an oven at 100 ℃ for 5h to obtain the carbon-coated platinum metal nanoparticles.
In summary, the present invention provides a method for preparing a carbon-coated noble metal nano-catalyst, which at least comprises: 1) preparation of Co2C, a catalyst; 2) mixing the Co2Placing the catalyst C in a high-temperature reaction furnace, introducing inert gas for calcination, and taking out the calcined Co2C catalyst after a certain time; 3) providing a soluble noble metal salt solution, calcining the Co2And C, adding the catalyst into the soluble noble metal salt solution, soaking for a plurality of hours at a certain temperature, washing, filtering and drying to obtain the carbon-coated noble metal nano catalyst. The preparation method has the advantages of mild conditions, low cost, simple process, low energy consumption and high yield, and can obtain various carbon-coated noble metal nano catalysts.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (17)
1. A preparation method of a carbon-coated noble metal nano catalyst is characterized by at least comprising the following steps:
1) preparation of Co2C catalyst, preparation of said Co2The catalyst C comprises the following steps: 1-1) preparation of Co by precipitation or impregnation3O4(ii) a 1-2) reacting said Co3O4Placing the mixture in a reaction device, and introducing H into the reaction device at a certain temperature2And inert gas for a certain time; 1-3) introducing mixed gas of carbon monoxide and inert gas or mixed gas of synthesis gas and inert gas into the reaction device at a certain temperature for a certain time to obtain the Co2C, a catalyst, wherein the temperature in the step 1-3) is 150-400 ℃, and the volume percentage of carbon monoxide or synthesis gas in the mixed gas is 5-100%; the time for introducing the mixed gas of carbon monoxide and inert gas or the mixed gas of synthesis gas and inert gas into the reaction device is 0.5 to 48 hours;
2) mixing the Co2Placing the catalyst C in a high-temperature reaction furnace, introducing inert gas for calcination, and after a certain time, calcining the Co2C, taking out the catalyst, wherein the inert gas is one or more of nitrogen, argon or helium, the purity of the inert gas is greater than or equal to 99.99%, and the space velocity is 100mlg-1h-1~20000mlg-1h-1The calcination temperature is 200-800 ℃, and the calcination time is 3-24 h;
3) providing a soluble noble metal salt solution, calcining the Co2And C, adding the catalyst into the soluble noble metal salt solution, soaking for a plurality of hours at a certain temperature, washing, filtering and drying to obtain the carbon-coated noble metal nano catalyst.
2. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 1, wherein: in step 1-1), the Co prepared by an immersion method3O4Comprises a carrier, and adopts an impregnation method to prepare the Co3O4The method comprises the following steps:
1-1-1) according to Co3O4In an amount to provide a quantity of carrier;
1-1-2) according to Co3O4The loading amount and the composition ratio of the carrier are that all metal salts of non-alkali metals are configured into a uniform mixed salt solution with the same volume as the carrier;
1-1-3) adding the mixed salt solution into the carrier in a manner of dripping while stirring at a certain temperature;
1-1-4) after the titration is finished, keeping the temperature unchanged and dipping;
1-1-5) drying and roasting the dipped solution to obtain the Co3O4。
3. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 2, wherein: in step 1-1-1), the support comprises ZrO2、TiO2、SiO2、Al2O3Or one or more of activated carbon.
4. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 2, wherein: in the step 1-1-2), all metal salts of non-alkali metals comprise main metal cobalt salts, and the main metal cobalt salts comprise one or more of chloride, nitrate, sulfate, carbonate or acetate; the total molar concentration of the metal salt in the mixed salt solution is 0.01-5 mol/L.
5. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 2, wherein: in the step 1-1-4), the dipping temperature is 10-70 ℃, and the dipping time is 1-48 h.
6. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 2, wherein: in the step 1-1-5), the drying temperature is 20-200 ℃, and the drying time is 2-100 h; the roasting temperature is 200-600 ℃, and the roasting time is 0.5-24 h.
7.The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 1, wherein: in step 1-1), the Co is prepared by a precipitation method3O4The method comprises the following steps:
1-1-1) according to Co3O4Preparing a main metal cobalt salt into a uniformly mixed salt solution and preparing a precipitator solution;
1-1-2) providing mother liquor, and dripping the mixed salt solution and the precipitant solution into the mother liquor in a cocurrent manner at a certain temperature for precipitation;
1-1-3) after titration, keeping the temperature unchanged and aging;
1-1-4) separating, washing, drying and roasting the aged titration solution to obtain the Co3O4。
8. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 7, wherein: in the step 1-1-1), the main metal cobalt salt comprises one or more of chloride, nitrate, sulfate, carbonate or acetate; the total molar concentration of the metal salt in the mixed salt solution is 0.01-5 mol/L.
9. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 7, wherein: in the step 1-1-1), the precipitant in the precipitant solution comprises one or more of potassium hydroxide, sodium carbonate, ammonium carbonate and sodium bicarbonate, and the molar concentration of the precipitant in the precipitant solution is 0.01 mol/L-5 mol/L.
10. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 7, wherein: the Co3O4The method comprises a carrier, and in the step 1-1-2), before the mixed salt solution and the precipitant solution are dripped into the mother liquor in a cocurrent mode at a certain temperature, the method also comprises a step of adding the carrier into the mother liquor.
11. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 10, wherein: the carrier comprises ZrO2、TiO2、SiO2、Al2O3Or one or more of activated carbon.
12. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in any one of claims 7, 10 or 11, wherein: in the step 1-1-2), the volume ratio of the precipitant solution to the mixed salt solution dropped into the mother liquor is 1: 5-5: 1; the precipitation temperature is 10-100 ℃; the pH value of the precipitate is 5-14.
13. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 7, wherein: in the step 1-1-4), the drying temperature is 20-200 ℃, and the drying time is 2-100 h; the roasting temperature is 200-600 ℃, and the roasting time is 0.5-24 h.
14. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 1, wherein: in the step 1-2), H is introduced into the reaction device2The temperature of the mixed gas with inert gas is 150-500 ℃, and H2And H in a mixed gas of an inert gas2The volume percentage of (A) is 5-100%; introducing H into the reaction device2The time of the mixed gas of the inert gas and the inert gas is 0 to 48 hours.
15. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 1, wherein: in the step 3), the soluble precious metal salt comprises one or more of iridium nitrate, silver nitrate, rhodium nitrate, palladium nitrate, chloroplatinic acid, platinum nitrate, silver nitrate or chloroauric acid, and the molar concentration of the soluble precious metal salt solution is 0.01-5 mol/L.
16. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 1, wherein: in the step 3), the soaking temperature is 20-80 ℃, and the soaking time is 0.5-5 h.
17. The method for preparing a carbon-coated noble metal nanocatalyst as claimed in claim 1, wherein: in the step 3), the drying temperature is 20-200 ℃, and the drying time is 2-50 h.
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