CN106179399A - Catalyst that nickel cobalt silver and carbon are combined and preparation method thereof - Google Patents
Catalyst that nickel cobalt silver and carbon are combined and preparation method thereof Download PDFInfo
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- CN106179399A CN106179399A CN201610521979.6A CN201610521979A CN106179399A CN 106179399 A CN106179399 A CN 106179399A CN 201610521979 A CN201610521979 A CN 201610521979A CN 106179399 A CN106179399 A CN 106179399A
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- silver
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- cobalt
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- QBCBTZZUMVZBLB-UHFFFAOYSA-N [Ag].[Co].[Ni] Chemical compound [Ag].[Co].[Ni] QBCBTZZUMVZBLB-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 49
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052709 silver Inorganic materials 0.000 claims abstract description 34
- 239000004332 silver Substances 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 31
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 30
- 239000010941 cobalt Substances 0.000 claims abstract description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- -1 washing is to pH=7 Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 230000005496 eutectics Effects 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910002058 ternary alloy Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- B01J35/391—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
Abstract
The present invention proposes a kind of nickel cobalt silver catalyst compound with carbon and preparation method thereof, under 25 80 DEG C of constant temperatures, uses reactor by material with carbon element powder and water mix homogeneously；Nickel, cobalt, the slaine of silver and reducing agent are simultaneously introduced to step S1 in the mixture obtained, metal ion mass fraction in a kettle. are controlled 0.001% 0.02%；And the mixture ph in reactor is controlled 7 10；Under the conditions of constant temperature 25～80 DEG C, the mixture in continuous stirred tank reactor 2 10 hours, obtain suspension；Described suspension is filtrated to get powder body material.Catalyst that the nickel cobalt silver provided in the present invention and carbon are combined and preparation method thereof, can reduce material cost, improves catalytic efficiency；Overcome that silver mixing is uneven, deposition of silver is uneven, powder body compacted density is little, particle size distribution width and the high defect of cost.
Description
Technical field
The present invention relates to new forms of energy and industrial catalyst field, particularly to the catalyst that a kind of nickel cobalt silver and carbon are compound
And preparation method thereof.
Background technology
At electrochemistry and catalytic field, metallic element is because of its special electronic structure, to the electro-catalysis such as hydrogen reduction, hydroxide
Reaction plays an important role.Wherein apply is noble metal and low transition metal element the most widely.Section in early days
Grinding in experiment, noble metal platinum, rhodium, palladium, silver etc. are electrochemical metal catalytic mechanism, lay the foundation.But noble metal reserves are non-
The fewest, the most expensive, it is applied only in military project national defense industry.Along with the demand of commercial market increases day by day, scientific research finds
Low transition metal is because of the outer-shell electron d track of its underfill, thus has electrochemical catalysis performance.Therefore, manganese, ferrum, cobalt, nickel,
The low transition metal element alternatively noble metal catalysts such as magnesium one of appropriately selected, has great market prospect.But
Single element, its catalysis is single, it is impossible to meet electrochemical catalysis demand in terms of practicality.Therefore, researcher
Sight is turned to the composite metal catalyst such as binary, ternary, to obtaining balance between catalytic performance and cost.
In traditional commercial production, argentum powder and material with carbon element is used to carry out the mixing of physical layer.Although simple possible, but
It is to expend a large amount of silver, causes production cost to remain high.In view of hybrid technique condition and the restriction of equipment, at macroscopically silver
Grain mixes with material with carbon element and is limited to equipment yardstick；On microcosmic, mixing does not reaches molecular scale.
Using roasting silver iodide, the method for silver nitrate to prepare air electrode powder body in prior art, effect is more mixed than machinery
Conjunction to be got well, but there is the shortcoming such as deposition of silver skewness, little, the particle size distribution width of powder body compacted density.
At present, the carbon nanotube loaded platinum being developed into and platinum-cobalt bimetallic catalyst, use cyclic voltammetry at fuel electricity
Pond is tested its electro catalytic activity, finds that the catalysis activity of platinum-cobalt/CNT duplex metal nano granule is higher than platinum/carbon nano
Pipe catalyst.This shows that binary metal catalyst activity is higher than unitary metallic catalyst.But platinum yield is rare, expensive,
Hard to carry on, need cheap metal to replace it.
Therefore, the problem that presently, there are is: one, and mechanical mixture is uneven；Two, deposition of silver is uneven, powder body compacted density
Little, particle size distribution width；Three, platinum reserves are rare, expensive.For these reasons, metallic catalyst is absorbed in the condition of embarrassment,
Catalytic efficiency is low, or efficiency high price is expensive, it is difficult to the marketization.
Summary of the invention
Catalyst that the main object of the present invention is combined for providing nickel cobalt silver and carbon and preparation method thereof, reduces cost, carries
High catalytic efficiency；Overcome that silver mixing is uneven, deposition of silver is uneven, powder body compacted density is little, particle size distribution width and cost high
Defect.
The present invention proposes the catalyst that a kind of nickel cobalt silver is compound with carbon, and described catalyst is centered by carbon material particles,
Nickel, cobalt and three kinds of microcrystallines of silver are coated on the powder body material that described carbon material particles surface is formed, consisting of AgxCoyNiz/
C, and 0.1≤x≤0.5,0.1≤y≤0.3,0.1≤z≤0.2, x, y and z are respectively the mass ratio of silver, cobalt, nickel and material with carbon element.
Present invention also offers and a kind of prepare nickel cobalt silver and the compound catalyst method of carbon, comprise the following steps:
S1, under 25-80 DEG C of constant temperature, use reactor by material with carbon element powder and water mix homogeneously；
S2, nickel, cobalt, the slaine of silver and reducing agent are simultaneously introduced to step S1 in the mixture obtained, by metal from
Son mass fraction in a kettle. controls at 0.001%-0.02%；And the mixture ph in reactor is controlled at 7-
10；
S3, under the conditions of constant temperature 25～80 DEG C, the mixture in continuous stirred tank reactor 2-10 hour, obtain suspension；
S4, described suspension is filtrated to get powder body material.
Further, also include before described step S1:
S0, in agitator, add material with carbon element and acid, continuously mixing 1-3 hour；After being filtered by mixture, pH=is arrived in washing
7, obtain the material with carbon element powder of surface active.
Further, one during described material with carbon element includes carbon black, graphite, CNT, carbon fiber and Graphene or
The mixture of multiple composition.
Further, the acid in described step S0 includes in sulphuric acid, perchloric acid, nitric acid, oxalic acid, citric acid and hydrochloric acid
The mixture of one or more compositions.
Further, nickel in described step S2, cobalt, the slaine of silver include nitrate, sulfate, halide salt, oxalates,
Citrate and sulfate therein one or more.
Further, the reducing agent in described step S2 includes one or both in hydrazine hydrate and sulphite.
Further, described metal ion mass fraction in a kettle. is controlled the step at 0.001%-0.02%
Including:
The addition speed of regulation slaine, controls metal ion mass fraction in a kettle. at 0.001%-
0.02%.
Further, described mixture ph in reactor control includes in the step of 7-10:
The addition speed of regulation reducing agent, controls the mixture ph in reactor at 7-10.
Further, can also include after the step filtered in described step S4:
Wash, be dried, grind and sieve.
Compared with prior art, the nickel cobalt silver provided in the present invention and the compound catalyst of carbon and preparation method thereof have with
Lower beneficial effect:
Catalyst that the nickel cobalt silver provided in the present invention and carbon are combined and preparation method thereof, uses nickel, cobalt, three kinds of materials of silver
Mix catalyst, and three kinds of elements pollute nature rich reserves, moderate cost, many can the avoiding of recovery approach as far as possible
Environment；Silver has the function of oxygen-oxygen bond in activating oxygen molecule, and cobalt, nickel are widely used in Industrial Catalysis, and cobalt and nickel belong to transitionality together
Metal the 8th race, and atomic radius is close, easily forms eutectic, crystal hole and mistake occurs during eutectic is formed
Position, beneficially Ag doping is come in, thus is formed ternary alloy three-partalloy；When alloy is formed, addition material with carbon element is as nucleus, and this process is i.e.
For nonhomogen-ous nucleation；The advantage of nonhomogen-ous nucleation be time-consuming less, power consumption less, productivity is high, crystal development is complete；In crystal production mistake
Cheng Zhong, by addition speed and the addition speed of reducing agent of regulation slaine, can control the growth of crystal, control grain
Degree and compacted density；Molecular level is other to be mixed to use the method for preparing catalyst in the present invention to make silver nickel cobalt reach with material with carbon element；
Simultaneously because be combined with material with carbon element, therefore improve the electron transfer capacity of this composite, and then improve catalytic efficiency.
Accompanying drawing explanation
Fig. 1 is the method for preparing catalyst schematic flow sheet that in the embodiment of the present invention, nickel cobalt silver and carbon are combined.
The realization of the object of the invention, functional characteristics and advantage will in conjunction with the embodiments, are described further referring to the drawings.
Detailed description of the invention
Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Proposing the catalyst that a kind of nickel cobalt silver is compound with carbon in the embodiment of the present invention, this catalyst is for carbon material particles to be
Center, the powder body material that nickel, cobalt and three kinds of microcrystallines of silver are coated on carbon material particles surface and are formed, consisting of
AgxCoyNiz/ C, wherein 0.1≤x≤0.5,0.1≤y≤0.3,0.1≤z≤0.2, x, y and z are respectively silver, cobalt, nickel and carbon material
The mass ratio of material.
In the present embodiment, nickel, cobalt, ag material are all excellent catalyst, and fit at nature rich reserves, cost
In, recovery approach many can avoid as far as possible pollute environment；Silver has the function of oxygen-oxygen bond in activating oxygen molecule, and cobalt, nickel are extensive
For Industrial Catalysis, cobalt and nickel belong to low transition metal the 8th race together, arrange in numerical order 27,28 on the periodic table of elements respectively, atomic radius
Close, easily form eutectic, during eutectic is formed, occur that crystal hole and dislocation, beneficially Ag doping are come in, thus
Form ternary alloy three-partalloy；When alloy is formed, addition material with carbon element is as nucleus, and this process is nonhomogen-ous nucleation；Nonhomogen-ous nucleation
Advantage be time-consuming less, power consumption less, productivity is high, crystal development is complete；Owing to being combined with material with carbon element, therefore improve this multiple
The electron transfer capacity of condensation material, and then improve catalytic efficiency；Therefore the catalyst catalytic performance in the embodiment of the present invention is good, becomes
This is low.
With reference to Fig. 1, for the method for preparing catalyst schematic flow sheet that nickel cobalt silver in the embodiment of the present invention and carbon are compound.
The embodiment of the present invention additionally provides and a kind of prepares nickel cobalt silver and the compound catalyst method of carbon, including following step
Rapid:
Step S0, in the agitator of glass lining, add material with carbon element and acid, continuously mixing 1-3 hour；Obtain surface to live
The material with carbon element powder changed；This step primarily serves the purpose of the surface of activated carbon material powder so that subsequent metal material is combined with carbon
Time be more prone to, compound more tight, catalytic effect is more preferably.
Can also include after above-mentioned steps S0 mixes the step of 1-3 hour continuously: wash after mixture is filtered and arrive
PH=7, in the present embodiment, is preferably used the mixture after deionized water wash filters.
Above-mentioned material with carbon element includes one or more compositions in carbon black, graphite, CNT, carbon fiber and Graphene
Mixture.Above-mentioned material with carbon element can be nonconducting material with carbon element, it is also possible to for the material with carbon element of conduction, preferably conduct electricity in the present embodiment
Material with carbon element；Above-mentioned agitator is not limited to glass lining.
In this step, the one or many during above-mentioned acid includes sulphuric acid, perchloric acid, nitric acid, oxalic acid, citric acid and hydrochloric acid
Plant the mixture of composition, one of which acid can be thought, it is also possible to mix for multiple acid.
Step S1, under 25-80 DEG C of constant temperature, use reactor by material with carbon element powder and water mix homogeneously；
Wherein, the material with carbon element powder in this step can be through the surface activation process of above-mentioned steps S0, to improve complex
Composite effect, promote end product catalytic performance.
Step S2, nickel, cobalt, the slaine of silver and reducing agent are simultaneously introduced to step S1 in the mixture obtained, control
Metal ion mass fraction in a kettle. is between 0.001%-0.02%；And by the mixture ph control in reactor
System is at 7-10；
Above-mentioned nickel, cobalt, the slaine of silver include nitrate, sulfate, halide salt, oxalates, citrate and sulphuric acid
Salt therein one or more；Above-mentioned reducing agent includes one or both in hydrazine hydrate and sulphite.
In the present embodiment, in above-mentioned steps, control metal ion mass fraction in a kettle. at 0.001%-
Step between 0.02% includes: can be existed by metal ion by plant equipment or the artificial addition speed regulating slaine
Mass fraction in reactor controls at 0.001%-0.02%；Above-mentioned mixture ph in reactor is controlled 7-10's
Step includes: can be by plant equipment or the artificial addition speed regulating reducing agent, by the mixture ph control in reactor
System is at 7-10.
The present embodiment can control crystalline substance by the addition speed of regulation slaine and the addition speed of regulation reducing agent
The growth of body, comes Control granularity and compacted density；The addition speed of reasonable adjusting slaine and reducing agent, controls metal ion
Mass fraction in a kettle. and control mixture pH value so that compacted density is little, particle size distribution width, promote catalysis effect
Rate.
Step S3, under the conditions of constant temperature 25～80 DEG C, the mixture in continuous stirred tank reactor 2-10 hour, obtain suspended
Liquid；
Step S4, above-mentioned suspension filtered, wash, be dried, grind, sieving obtains powder body material；This powder body material
Material is the catalyst that nickel cobalt silver is compound with carbon.
In above-mentioned steps S4, suspension i.e. can obtain this powder body material, in actual applications, powder body material through filtering
Surface often doped with water, slaine or reducing agent etc., there is also the phenomenon of powder body material caking simultaneously, therefore can enter
Row subsequent wash, the process being dried, grind or sieving；Further, the step washed, be dried, grind or sieve can root
Carry out selecting collocation according to being actually needed, the most in actual applications, a step therein or multistep can be carried out.
In the present embodiment, above-mentioned preparation method is liquid phase method, and nickel, cobalt, silver can be made to reach molecule rank with material with carbon element
Mixing, promote catalytic efficiency etc..It should be understood that use solid phase method can also obtain equally in the present embodiment propose urge
Agent.
For the ease of understanding, the embodiment of the present invention provides catalyst and preparation method thereof, propose specific examples below and enter
Row further illustrates.
Specific embodiment 1, it is provided that the catalyst that a kind of nickel, cobalt, silver and carbon are compound, consisting of: Ag0.1Co0.1Ni0.1/ C,
I.e. x=0.1, y=0.1, z=0.1, its preparation method specifically includes following steps:
S10, in the agitator of glass lining, adding 1000g carbon black materials and 5000g mass fraction is that 20% nitric acid is molten
Liquid, continuously mixing 1 hour；By mixture through filtering, it is washed with deionized pH=7, obtains the hydrocarbon black powder of surface active.
S11, under the conditions of constant temperature 25 DEG C, use reactor by the hydrocarbon black powder in step S10 and 5L water mix homogeneously.
S12, the slaine and the 97g hydrazine hydrate that 312g nickel nitrate, 311g cobalt nitrate, 158g silver nitrate are mixed are simultaneously introduced
In the mixture of step S11, its concentration in whole reactor is controlled to divide in quality by the addition speed of regulation slaine
Number is 0.001%；PH value in whole reactor is controlled 7 by the addition speed of regulation hydrazine hydrate.
S13, under the conditions of constant temperature 25 DEG C, continuous stirring 2 hours, obtain suspension.
S14, suspension filtered, wash, be dried, grind, the powder body material obtained that sieves is that nickel, cobalt, silver and carbon are combined
Catalyst, i.e. Ag0.1Co0.1Ni0.1/C。
Specific embodiment 2, the catalyst that a kind of nickel, cobalt, silver and carbon are compound, consisting of: Ag0.5Co0.3Ni0.2/ C, i.e. x
=0.5, y=0.3, z=0.2.Its preparation method comprises the steps:
S20, in the agitator of glass lining, adding 1000g graphite and 5000g mass fraction is 10% sulfuric acid solution,
Mixing 3 hours continuously；By mixture through filtering, it is washed with deionized pH=7, obtains the powdered graphite of surface active.
S21, under the conditions of constant temperature 80 DEG C, use reactor by the powdered graphite in step S20 and 5L water mix homogeneously.
S22, the slaine and the 270g hydrazine hydrate that 528g nickel sulfate, 792g cobaltous sulfate, 790g silver nitrate are mixed add simultaneously
Entering in the mixture of step S21, its concentration in whole reactor is controlled in quality by the addition speed of regulation slaine
Mark is 0.02%；PH value in whole reactor is controlled 10 by the addition speed of regulation precipitant.
S23, under the conditions of constant temperature 80 DEG C, continuous stirring 10 hours, obtain suspension.
S24, this suspension filtered, wash, be dried, grind, the powder body material obtained that sieves is that nickel, cobalt, silver and carbon are multiple
The catalyst closed, i.e. Ag0.5Co0.3Ni0.2/C。
Specific embodiment 3, the catalyst that a kind of nickel, cobalt, silver and carbon are compound, consisting of: Ag0.25Co0.2Ni0.15/ C, i.e. x
=0.25, y=0.2, z=0.15.Its preparation method comprises the steps:
S30, in the agitator of glass lining, adding 1000g CNT and 5000g mass fraction is 20% hydrochloric acid,
Incorporation time 2 hours continuously；By mixture through filtering, it is washed with deionized pH=7, obtains the carbon nanometer of surface active
Pipe.
S31, under the conditions of constant temperature 57 DEG C, use reactor by the CNT in step S30 and 5L water mix homogeneously.
S32, slaine 332g Nickel dichloride., 443g cobaltous chloride, 395g silver nitrate mixed and sodium sulfite 895g are simultaneously
Joining in the mixture of step S31, its concentration in whole reactor is controlled in matter by the addition speed of regulation slaine
Amount mark is 0.01%；PH value in whole reactor is controlled 8.5 by the addition speed of regulation reducing agent.
S33, under the conditions of constant temperature 57 DEG C, continuous stirring 6 hours, obtain suspension.
S34, this suspension filtered, wash, be dried, grind, the powder body material obtained that sieves is that nickel, cobalt, silver and carbon are multiple
The catalyst closed, i.e. Ag0.25Co0.2Ni0.15/C。
In sum, for catalyst that the nickel cobalt silver provided in the embodiment of the present invention and carbon are compound and preparation method thereof, make
Form catalyst by nickel, cobalt, three kinds of material mixing of silver, and three kinds of elements are in nature rich reserves, moderate cost, recovery approach
How can avoid polluting environment as far as possible；Silver has the function of oxygen-oxygen bond in activating oxygen molecule, and cobalt, nickel are widely used in industry and urge
Changing, cobalt and nickel belong to low transition metal the 8th race together, and atomic radius is close, easily forms eutectic, in the process that eutectic is formed
In occur that crystal hole and dislocation, beneficially Ag doping are come in, thus form ternary alloy three-partalloy；When alloy is formed, add carbon material
Material is as nucleus, and this process is nonhomogen-ous nucleation；The advantage of nonhomogen-ous nucleation be time-consuming less, power consumption less, productivity is high, crystal is sent out
Educate complete；During crystal production, by addition speed and the addition speed of reducing agent of regulation slaine, can control
The growth of crystal, comes Control granularity and compacted density；The method for preparing catalyst in the present invention is used to make silver nickel cobalt and material with carbon element
Reach the other mixing of molecular level；Simultaneously because be combined with material with carbon element, therefore improve the electron transfer energy of this composite
Power, and then improve catalytic efficiency.
The foregoing is only the preferred embodiments of the present invention, not thereby limit the scope of the claims of the present invention, every utilization
Equivalent structure or equivalence flow process that description of the invention and accompanying drawing content are made convert, or it is relevant to be directly or indirectly used in other
Technical field, be the most in like manner included in the scope of patent protection of the present invention.
Claims (10)
1. the catalyst that a nickel cobalt silver and carbon are combined, it is characterised in that described catalyst is centered by carbon material particles,
Nickel, cobalt and three kinds of microcrystallines of silver are coated on the powder body material that described carbon material particles surface is formed, consisting of AgxCoyNiz/
C, and 0.1≤x≤0.5,0.1≤y≤0.3,0.1≤z≤0.2, x, y and z are respectively the mass ratio of silver, cobalt, nickel and material with carbon element.
2. the method preparing catalyst described in claim 1, it is characterised in that comprise the following steps:
S1, under 25-80 DEG C of constant temperature, use reactor by material with carbon element powder and water mix homogeneously；
S2, nickel, cobalt, the slaine of silver and reducing agent are simultaneously introduced to step S1 in the mixture obtained, metal ion is existed
Mass fraction in reactor controls at 0.001%-0.02%；And the mixture ph in reactor is controlled at 7-10；
S3, under the conditions of constant temperature 25～80 DEG C, the mixture in continuous stirred tank reactor 2-10 hour, obtain suspension；
S4, described suspension is filtrated to get powder body material.
Method the most according to claim 2, it is characterised in that also include before described step S1:
S0, in agitator, add material with carbon element and acid, continuously mixing 1-3 hour；After being filtered by mixture, washing is to pH=7,
Material with carbon element powder to surface active.
The most according to the method in claim 2 or 3, it is characterised in that described material with carbon element include carbon black, graphite, CNT,
The mixture of one or more compositions in carbon fiber and Graphene.
Method the most according to claim 3, it is characterised in that the acid in described step S0 includes sulphuric acid, perchloric acid, nitre
The mixture of one or more compositions in acid, oxalic acid, citric acid and hydrochloric acid.
The most according to the method in claim 2 or 3, it is characterised in that in described step S2, nickel, cobalt, the slaine of silver include
Nitrate, sulfate, halide salt, oxalates, citrate and sulfate therein one or more.
The most according to the method in claim 2 or 3, it is characterised in that the reducing agent in described step S2 include hydrazine hydrate with
And one or both in sulphite.
The most according to the method in claim 2 or 3, it is characterised in that described metal ion quality in a kettle. is divided
Numerical control system includes in the step of 0.001%-0.02%:
The addition speed of regulation slaine, controls metal ion mass fraction in a kettle. at 0.001%-0.02%.
The most according to the method in claim 2 or 3, it is characterised in that described mixture ph in reactor is controlled
The step of 7-10 includes:
The addition speed of regulation reducing agent, controls the mixture ph in reactor at 7-10.
The most according to the method in claim 2 or 3, it is characterised in that all right after the step filtered in described step S4
Including:
Wash, be dried, grind and sieve.
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| PCT/CN2017/091851 WO2018006829A1 (en) | 2016-07-05 | 2017-07-05 | Nickel-cobalt-silver-carbon composite catalyst and preparation method therefor |
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| CN106944057A (en) * | 2017-03-31 | 2017-07-14 | 深圳市国创新能源研究院 | A kind of preparation method of monoatomic metal carbon composite catalytic agent for electrocatalytic reaction |
| WO2018006829A1 (en) * | 2016-07-05 | 2018-01-11 | 深圳市知赢科技有限公司 | Nickel-cobalt-silver-carbon composite catalyst and preparation method therefor |
| CN111638254A (en) * | 2020-05-29 | 2020-09-08 | 广州钰芯传感科技有限公司 | Nano-porous cobalt-nickel composite electrode capable of simultaneously detecting sulfite and nitrite and preparation method thereof |
| CN112774691A (en) * | 2021-01-27 | 2021-05-11 | 宁波方太厨具有限公司 | Preparation method of aldehyde-removing catalyst |
| CN116082915A (en) * | 2022-12-08 | 2023-05-09 | 湖南碳峰材料科技有限公司 | Composite carbon-silicon nanofiber coating material and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018006829A1 (en) * | 2016-07-05 | 2018-01-11 | 深圳市知赢科技有限公司 | Nickel-cobalt-silver-carbon composite catalyst and preparation method therefor |
| CN106944057A (en) * | 2017-03-31 | 2017-07-14 | 深圳市国创新能源研究院 | A kind of preparation method of monoatomic metal carbon composite catalytic agent for electrocatalytic reaction |
| CN111638254A (en) * | 2020-05-29 | 2020-09-08 | 广州钰芯传感科技有限公司 | Nano-porous cobalt-nickel composite electrode capable of simultaneously detecting sulfite and nitrite and preparation method thereof |
| CN111638254B (en) * | 2020-05-29 | 2022-07-12 | 广州钰芯传感科技有限公司 | Electrochemical method for simultaneously detecting sulfite and nitrite based on nano porous cobalt-nickel composite electrode |
| CN112774691A (en) * | 2021-01-27 | 2021-05-11 | 宁波方太厨具有限公司 | Preparation method of aldehyde-removing catalyst |
| CN116082915A (en) * | 2022-12-08 | 2023-05-09 | 湖南碳峰材料科技有限公司 | Composite carbon-silicon nanofiber coating material and preparation method and application thereof |
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