CN108906058B - Non-noble metal catalyst and preparation method thereof - Google Patents
Non-noble metal catalyst and preparation method thereof Download PDFInfo
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- CN108906058B CN108906058B CN201810757680.XA CN201810757680A CN108906058B CN 108906058 B CN108906058 B CN 108906058B CN 201810757680 A CN201810757680 A CN 201810757680A CN 108906058 B CN108906058 B CN 108906058B
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 49
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 42
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006722 reduction reaction Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 27
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 18
- 239000012876 carrier material Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002077 nanosphere Substances 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- 229940011182 cobalt acetate Drugs 0.000 claims description 10
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 abstract description 47
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 238000011946 reduction process Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 44
- 239000011259 mixed solution Substances 0.000 description 42
- 239000000047 product Substances 0.000 description 41
- 239000006227 byproduct Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 27
- 238000009210 therapy by ultrasound Methods 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 230000007062 hydrolysis Effects 0.000 description 20
- 238000006460 hydrolysis reaction Methods 0.000 description 20
- 239000012153 distilled water Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- 238000009777 vacuum freeze-drying Methods 0.000 description 13
- 238000000967 suction filtration Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
Images
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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/399—
-
- 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
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a preparation method of a non-noble metal catalyst, which comprises the following steps: mixing an ethanol-water solvent, a carrier material and non-noble metal salt to obtain non-noble metal salt dispersion liquid; and mixing the non-noble metal salt dispersion liquid with a sodium borohydride solution to perform a reduction reaction, and washing to obtain the non-noble metal catalyst. According to the preparation method, the solubility of the sodium metaborate generated in the reduction reaction process is controlled by adopting the ethanol-water solvent, the sodium metaborate is separated out along with the generation of non-noble metal in the reduction process, non-noble metal nano particles are isolated, the agglomeration growth of the non-noble metal nano particles is obviously inhibited, the particle size of the non-noble metal nano particles is effectively reduced, and meanwhile, the catalytic activity of the non-noble metal catalyst is greatly improved.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a non-noble metal catalyst and a preparation method thereof.
Background
The non-noble metal catalyst is the catalyst with the most application value due to the convenient preparation process, the excellent catalytic performance and the recyclability. By non-noble metal catalyst is meant that the active component of the catalyst is a pure metal or an alloy. Wherein the pure metal catalyst means that the component of the catalytic active substance is composed of a metal atom; the alloy catalyst refers to a catalyst with an active component composed of two or more metal atoms. The non-noble metal catalyst can be used independently or loaded on a carrier, has more using ways, and shows different catalytic performance along with different using modes.
The non-noble metal as solid catalyst has the main factors of affecting its adsorption-dissociation performance, namely the microscopic morphology and crystal structure characteristics of metal, because the exposed atoms on the surface of the metal crystal can provide a great deal of adsorption centers for adsorbing chemical molecules, the adsorbed molecules can simultaneously form adsorption bonds with a plurality of metal atoms on the surface, and if the possibility of the 2 nd layer atoms participating in adsorption is included, the adsorption bonding pattern provided by the metal catalyst is greatly increased. The distribution of the adsorption centers on the surface of the metal catalyst is influenced by the preparation method of the catalyst, the composition of the catalyst and the modification of the microstructure, so that different characteristics are shown. However, the non-noble metal nanoparticles are easy to agglomerate in the preparation process, so that the particle size of the generated non-noble metal particles is often larger, the subsequent application of the material is greatly influenced, and the performance of the non-noble metal is reduced.
Disclosure of Invention
The invention aims to provide a preparation method of non-noble metal, which can inhibit agglomeration of non-noble metal in the preparation process and effectively reduce the particle size of non-noble metal particles.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a non-noble metal catalyst, which comprises the following steps:
mixing an ethanol-water solvent, a carrier material and non-noble metal salt to obtain non-noble metal salt dispersion liquid;
and mixing the non-noble metal salt dispersion liquid with a sodium borohydride solution to perform a reduction reaction, and washing a reduction reaction product to obtain the non-noble metal catalyst.
Preferably, the volume ratio of ethanol to water in the ethanol-water solvent is (2-4): (1-3).
Preferably, the carrier material is one or more of graphene oxide, carbon nanospheres and silica nanospheres.
Preferably, the volume ratio of the mass of the carrier material to the ethanol-water solvent is (1-2) g: (1-2) L.
Preferably, the non-noble metal salt is one or more of cobalt acetate, cobalt chloride, cobalt nitrate, cobalt acetate, nickel chloride, nickel nitrate, ferric acetate, ferric chloride and ferric nitrate.
Preferably, the volume ratio of the non-noble metal salt to the ethanol-water solvent is (1-2) mmol: (100-200) mL.
Preferably, the temperature of the reduction reaction is 4-6 ℃, and the time of the reduction reaction is 8-12 min.
Preferably, the concentration of the sodium borohydride solution is 0.125-0.25 mol/L.
Preferably, the mass ratio of the non-noble metal salt to the sodium borohydride is 1: (2-6).
The invention also provides a non-noble metal catalyst prepared by the preparation method, which comprises a carrier and non-noble metal nano particles loaded on the carrier, wherein the particle size of the non-noble metal nano particles is 4-10 nm.
The invention provides a preparation method of a non-noble metal catalyst, which comprises the following steps: mixing an ethanol-water solvent, a carrier material and non-noble metal salt to obtain non-noble metal salt dispersion liquid; and mixing the non-noble metal salt dispersion liquid with a sodium borohydride solution to perform a reduction reaction, and washing to obtain the non-noble metal catalyst. According to the preparation method, the solubility of the sodium metaborate generated in the reduction reaction process is controlled by adopting the ethanol-water solvent, the sodium metaborate is separated out along with the generation of non-noble metal in the reduction process, non-noble metal nano particles are isolated, the agglomeration growth of the non-noble metal nano particles is obviously inhibited, the particle size of the non-noble metal nano particles is effectively reduced, and meanwhile, the catalytic activity of the non-noble metal catalyst is greatly improved; the process is simple to operate, no pollution is caused to the environment, and according to the records of the embodiment, the particle size of non-noble metal nano particles in the non-noble metal catalyst is 4-10nm, the dispersing performance is good, and the agglomeration phenomenon is basically avoided; and the catalytic performance of the non-noble metal catalyst is obviously improved.
Drawings
FIG. 1 is a transmission plot of the C @ Co catalyst prepared in example 1;
FIG. 2 is a transmission plot of a C @ Co catalyst prepared from pure water;
FIG. 3 is a graph comparing the performance of the C @ Co catalyst prepared in example 1 and pure water to catalyze the hydrolysis of sodium borohydride.
Detailed Description
The invention provides a preparation method of a non-noble metal catalyst, which comprises the following steps:
mixing an ethanol-water solvent, a carrier material and non-noble metal salt to obtain non-noble metal salt dispersion liquid;
and mixing the non-noble metal salt dispersion liquid with a sodium borohydride solution to perform a reduction reaction, and washing a reduction product to obtain the non-noble metal catalyst.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
Mixing ethanol-water solvent, carrier material and non-noble metal salt to obtain non-noble metal salt dispersion liquid; in the invention, the volume ratio of ethanol to water in the ethanol-water solvent is preferably (2-4): (1-3), more preferably (2.5-3.5): (1.5-2.5), most preferably (2.8-3.2): (1.8-2.2).
In the invention, the carrier material is preferably one or more of graphene oxide, carbon nanospheres and silica nanospheres; when the carrier materials are two or more of the above specific choices, the present invention does not have any particular limitation on the ratio of the specific materials, and the specific materials may be mixed in any ratio.
In the present invention, the particle size of the support material is preferably from 100nm to 5 μm, more preferably from 200nm to 2 μm, most preferably from 300nm to 1 μm.
In the invention, the volume ratio of the mass of the carrier material to the ethanol-water solvent is preferably (1-2) g: (1-2) L, more preferably (1.2-1.8) g: (1.2-1.8) L, most preferably (1.4-1.6) g: (1.4-1.6) L.
In the invention, the non-noble metal salt is preferably one or more of cobalt acetate, cobalt chloride, cobalt nitrate, cobalt acetate, nickel chloride, nickel nitrate, ferric acetate, ferric chloride and ferric nitrate; when the non-noble metal salt is two or more of the above specific choices, the specific material ratio is not particularly limited, and the non-noble metal salt may be mixed at any ratio.
In the present invention, the volume ratio of the amount of the non-noble metal salt to the ethanol-water solvent is preferably (1 to 2) mmol: (100 to 200) mL, more preferably (1.2 to 1.8) mmol: (120-180) mL, most preferably (1.4-1.6) mmol: (140-160) mL.
In the present invention, the mixing of the ethanol-water solvent, the support material and the non-noble metal salt preferably comprises the steps of:
mixing a carrier material with an ethanol-water solvent to obtain a mixed solution;
and mixing the mixed solution with non-noble metal salt to obtain non-noble metal salt dispersion liquid.
In the present invention, it is preferable to mix the carrier material with an ethanol-water solvent to obtain a mixed solution. In the present invention, the mixing is preferably performed by first performing ultrasound and then stirring; in the invention, the time of the ultrasonic treatment is preferably 40-70 min, more preferably 55-65 min, and most preferably 58-62 min; the present invention does not have any particular limitation on other parameters of the ultrasound, and the ultrasound may be performed using ultrasound parameters well known to those skilled in the art. In the invention, the stirring time is preferably 20-40 min, more preferably 25-35 min, and most preferably 28-32 min; the other parameters of the stirring are not particularly limited in the present invention, and the stirring may be performed by using stirring parameters known to those skilled in the art.
In the invention, the action of the first ultrasonic treatment and the second stirring treatment is to ensure that the bulk carrier material can be completely dispersed in the solvent and can be uniformly mixed in the solution.
After obtaining the mixed solution, the present invention preferably mixes the mixed solution with a non-noble metal salt to obtain a non-noble metal salt dispersion. In the present invention, the mixing is preferably performed by first performing ultrasound and then stirring; in the invention, the time of the ultrasonic treatment is preferably 25-50 min, more preferably 30-45 min, and most preferably 35-40 min; the present invention does not have any particular limitation on other parameters of the ultrasound, and the ultrasound may be performed using ultrasound parameters well known to those skilled in the art. In the invention, the stirring time is preferably 0.5-2.5 h, and more preferably 1-2 h; in the invention, the stirring temperature is preferably 4-6 ℃, and more preferably 5 ℃; the other parameters of the stirring are not particularly limited in the present invention, and the stirring may be performed by using stirring parameters known to those skilled in the art.
In the invention, the ultrasonic treatment and the stirring treatment have the functions of accelerating the dissolution of non-noble metal salts and uniformly dispersing non-noble metal ions in the mixed solution.
In the invention, the stirring temperature mainly creates a low-temperature environment for the reduction process, prevents the agglomeration phenomenon caused by excessively violent reaction at high temperature, and is beneficial to reducing catalyst particles.
After obtaining the non-noble metal salt dispersion liquid, mixing the non-noble metal salt dispersion liquid with a sodium borohydride solution to perform a reduction reaction, and washing a reduction product to obtain a non-noble metal catalyst; in the invention, the concentration of the sodium borohydride solution is preferably 0.125-0.25 mol/L, more preferably 0.15-0.22 mol/L, and most preferably 0.18-0.20 mol/L; in the present invention, the mass ratio of the non-noble metal salt to sodium borohydride is preferably 1: (2-6), more preferably 1: (3-5).
The mixing sequence of the non-noble metal salt dispersion liquid and the sodium borohydride solution is not limited by any special way, and the non-noble metal salt dispersion liquid and the sodium borohydride solution are mixed by adopting the mixing sequence well known by the technical personnel in the field; in the present invention, it can be specifically selected to add a sodium borohydride solution to the non-noble metal salt dispersion.
In the invention, the temperature of the reduction reaction is preferably 4-6 ℃, and more preferably 5 ℃; the time of the reduction reaction is preferably 8-12 min, and more preferably 9-11 min. In the present invention, the reduction reaction is preferably carried out under stirring, and the stirring in the present invention is not particularly limited, and may be carried out by stirring well known to those skilled in the art.
In the reduction reaction process, the existence of ethanol can reduce the solubility of a reaction by-product sodium metaborate, so that the sodium metaborate is separated out together with non-noble metal, non-noble metal nano particles are isolated, and the agglomeration of the non-noble metal nano particles is reduced.
In the invention, the ratio of ethanol to water in the ethanol-water solvent can ensure the successful attachment of non-noble metal nanoparticles on the carrier, and the solubility of the by-product sodium metaborate can be strictly controlled, so that the by-product sodium metaborate and the non-noble metal are simultaneously separated out, the agglomeration of the non-noble metal is prevented, and finally the non-noble metal can achieve very good dispersibility on the carrier.
After the reduction reaction is finished, the precipitated product is preferably subjected to suction filtration, and the suction filtration is not limited in any way and can be carried out by adopting a suction filtration process well known to a person skilled in the art;
in the present invention, the number of washing with water is preferably 2 to 5, and more preferably 3 to 4.
In the present invention, the water wash functions to wash away sodium metaborate by-product.
After the water washing is completed, the present invention preferably dries the product after the water washing. In the present invention, the drying is preferably vacuum freeze-drying; in the present invention, the temperature of the vacuum freeze-drying is preferably-40 ℃ to-50 ℃, more preferably-42 ℃ to-48 ℃, and most preferably-44 ℃ to-46 ℃. The present invention does not have any particular limitation on other parameters of the vacuum freeze-drying, and the drying can be performed by using the parameters of the vacuum freeze-drying which are well known to those skilled in the art.
The invention also provides a non-noble metal catalyst prepared by the preparation method, which comprises a carrier and non-noble metal nano particles loaded on the carrier, wherein the particle size of the non-noble metal nano particles is 4-10 nm.
The following will describe a non-noble metal catalyst and its preparation method in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing ethanol and distilled water according to the volume ratio of 3:2 to obtain an ethanol-water solvent;
dissolving 0.1g of carbon nanospheres into 50mL of alcohol-water solvent, performing ultrasonic treatment for 60min, and stirring for 30min for dispersion to obtain a mixed solution;
dissolving 1mmol of cobalt acetate in the mixed solution, performing ultrasonic treatment for 30min, and stirring at 5 ℃ for 1h to obtain a cobalt acetate mixed solution;
adding 20mL of 0.2mol/L sodium borohydride solution into the cobalt acetate mixed solution, and continuously stirring for 10min at 5 ℃ until complete reduction is achieved, wherein the solubility of a by-product sodium metaborate generated in the reaction is reduced, and the by-product sodium metaborate and Co nanoparticles are simultaneously separated out;
carrying out suction filtration on the product, washing the product for 3-4 times by using distilled water, dissolving a by-product sodium metaborate in the water, and washing the by-product sodium metaborate to obtain a washed product;
and (3) carrying out vacuum freeze drying treatment on the washed product at-45 ℃ to obtain the C @ Co catalyst.
Fig. 1 is a transmission diagram of the C @ Co catalyst prepared by the above preparation method, and it can be seen from the diagram that cobalt nanoparticles are uniformly dispersed on the surface of the carbon nanospheres, and the particle size of the cobalt nanoparticles is distributed between 4 nm and 6 nm, and fig. 2 is a transmission diagram of the C @ Co catalyst prepared by pure water, and it can be seen from the diagram that the C @ Co catalyst prepared in example 1 is much smaller than the particle size of the C @ Co catalyst prepared by pure water.
FIG. 3 is a graph comparing the performance of the C @ Co catalyst prepared in example 1 and pure water in catalyzing the hydrolysis of sodium borohydride, and it can be seen that the catalytic performance of the C @ Co catalyst prepared in example 1 and the C @ Co catalyst prepared by pure water in the hydrolysis of 0.25mol/L sodium borohydride base solution (NaOH concentration is 0.25mol/L) in hydrogen production, which is tested at 30 ℃. The results show that the rate of hydrolysis of sodium borohydride by the C @ Co catalyst prepared in example 1 is increased by about 179% over the C @ Co catalyst prepared with pure water.
Example 2
Mixing ethanol and distilled water according to the volume ratio of 1:1 to obtain an ethanol-water solvent;
dissolving 0.1g of graphene oxide in 100mL of alcohol-water solvent, performing ultrasonic treatment for 30min, stirring for 30min, and dispersing to obtain a mixed solution;
dissolving 1mmol of cobalt chloride in the mixed solution, performing ultrasonic treatment for 30min, and stirring at 5 ℃ for 1h to obtain a uniform cobalt chloride mixed solution;
adding 20mL of 0.125mol/L sodium borohydride solution into the cobalt acetate mixed solution, and continuously stirring for 10min at 5 ℃ until complete reduction is achieved, wherein the solubility of a by-product sodium metaborate generated in the reaction is reduced, and the by-product sodium metaborate and Co nanoparticles are simultaneously separated out;
carrying out suction filtration on the product, washing the product for 3-4 times by using distilled water, dissolving a by-product sodium metaborate in the water, and washing the by-product sodium metaborate to obtain a washed product;
and (3) carrying out vacuum freeze drying treatment on the washed product at-45 ℃ to obtain GO @ Co.
The GO @ Co is characterized, the test result is basically consistent with that of the embodiment 1, the fact that the cobalt simple substance is uniformly dispersed on the surface of graphene, the particle size of cobalt particles is distributed between 5 and 8 nanometers and is far smaller than that of the cobalt simple substance prepared by the conventional method is shown, GO @ C is used as a catalyst, the catalytic performance of the catalyst on hydrolysis hydrogen production of 0.25mol/L sodium borohydride alkali solution (NaOH:0.25mol/L) is tested at 30 ℃, and the hydrolysis speed of the catalyst on sodium borohydride is improved by about 138.4% compared with that of GO @ Co prepared by using pure water as a solvent.
Example 3
Mixing ethanol and distilled water according to the volume ratio of 7:3 to obtain an ethanol-water solvent;
dissolving 0.1g of silicon dioxide nanospheres into 100mL of ethanol-water solvent, performing ultrasonic treatment for 60min, stirring for 30min, and dispersing to obtain a mixed solution;
dissolving 2mmol of cobalt nitrate in the mixed solution, performing ultrasonic treatment for 45min, and stirring at 5 ℃ for 1h to obtain a uniform cobalt nitrate mixed solution;
adding 20mL of 0.25mol/L sodium borohydride solution into the cobalt nitrate mixed solution, and continuously stirring for 10min at 5 ℃ until complete reduction is achieved, wherein the solubility of a by-product sodium metaborate generated in the reaction is reduced, and the by-product sodium metaborate and Co nanoparticles are simultaneously separated out;
carrying out suction filtration on the product, washing the product for 3-4 times by using distilled water, dissolving a by-product sodium metaborate in the water, and washing the by-product sodium metaborate to obtain a washed product;
carrying out vacuum freeze drying treatment on the washed product at-45 ℃ to obtain SiO2@CAnd (c) a catalyst.
For the SiO2The characterization is carried out on @ Co, the test result of the method is basically consistent with that of the embodiment 1, the result shows that the cobalt simple substance is uniformly dispersed on the surface of the silicon dioxide nanosphere, the particle size of cobalt particles is distributed between 6-9 nanometers and is far smaller than that of the cobalt simple substance prepared by the conventional method, and SiO is added2The catalyst of @ Co is tested at 30 ℃ for the catalytic performance of the catalyst on 0.25mol/L ammonia borane hydrolysis hydrogen production, and the hydrolysis speed of the catalyst on sodium borohydride is higher than that of SiO prepared by using pure water as a solvent2@ Co is an improvement of about 84.6%.
Example 4
Mixing ethanol and distilled water according to the volume ratio of 2:3 to obtain an ethanol-water solvent;
dissolving 0.2g of graphene oxide in 100mL of ethanol-water solvent, performing ultrasonic treatment for 45min, stirring for 30min, and dispersing to obtain a mixed solution;
dissolving 2mmol of nickel nitrate in the mixed solution, performing ultrasonic treatment for 30min, and stirring at 5 ℃ for 2h to obtain a uniform nickel nitrate mixed solution;
adding 30mL of 0.2mol/L sodium borohydride solution into the nickel nitrate mixed solution, and continuously stirring for 10min at 5 ℃ until complete reduction is achieved, wherein the solubility of a by-product sodium metaborate generated in the reaction is reduced, and the by-product sodium metaborate and Ni nano-particles are separated out simultaneously;
carrying out suction filtration on the product, washing the product for 3-4 times by using distilled water, dissolving a by-product sodium metaborate in the water, and washing the by-product sodium metaborate to obtain a washed product;
and (3) carrying out vacuum freeze drying treatment on the washed product at-45 ℃ to obtain the GO @ Ni catalyst.
The GO @ Ni is characterized, the test result is basically consistent with that of the GO @ Ni in example 1, the nickel elementary substance is uniformly dispersed on the surface of graphene oxide, the particle size of nickel particles is distributed between 8 and 10 nanometers and is far smaller than that of the nickel elementary substance prepared by the conventional method, GO @ Ni is used as a catalyst, the catalytic performance of GO @ Ni on hydrolysis hydrogen production of 0.25mol/L sodium borohydride alkali solution (NaOH:0.25mol/L) is tested at 30 ℃, and the hydrolysis speed of GO @ Ni on sodium borohydride is improved by about 133.2% compared with that of GO @ Ni prepared by using pure water as a solvent.
Example 5
Mixing ethanol and distilled water according to the volume ratio of 3:2 to obtain an ethanol-water solvent;
dissolving 0.1g of graphene oxide in 100mL of ethanol-water solvent, performing ultrasonic treatment for 45min, stirring for 30min, and dispersing to obtain a mixed solution;
dissolving 1mmol of nickel chloride in the mixed solution, performing ultrasonic treatment for 30min, and stirring at 5 ℃ for 2h to obtain a uniform nickel chloride mixed solution;
adding 20mL of 0.15mol/L sodium borohydride solution into the nickel chloride mixed solution, and continuously stirring for 10min at 5 ℃ until complete reduction is achieved, wherein the solubility of a by-product sodium metaborate generated in the reaction is reduced, and the by-product sodium metaborate and Ni nano-particles are separated out simultaneously;
carrying out suction filtration on the product, washing the product for 3-4 times by using distilled water, dissolving a by-product sodium metaborate in the water, and washing the by-product sodium metaborate to obtain a washed product;
and (3) carrying out vacuum freeze drying treatment on the washed product at-45 ℃ to obtain the GO @ Ni catalyst.
The GO @ Ni is characterized, the test result is basically consistent with that of the GO @ Ni in example 1, the nickel elementary substance is uniformly dispersed on the surface of graphene oxide, the particle size of nickel particles is distributed between 5 and 7 nanometers and is far smaller than that of the nickel elementary substance prepared by the conventional method, GO @ Ni is used as a catalyst, the catalytic performance of GO @ Ni on hydrolysis hydrogen production of 0.2mol/L sodium borohydride alkali solution (NaOH:0.25mol/L) is tested at 30 ℃, and the hydrolysis speed of GO @ Ni on sodium borohydride is improved by about 146.8% compared with that of GO @ Ni prepared by using pure water as a solvent.
Example 6
Mixing ethanol and distilled water according to the volume ratio of 4:1 to obtain an ethanol-water solvent;
dissolving 0.2g of carbon nanospheres into 200mL of ethanol-water solvent, performing ultrasonic treatment for 60min, stirring for 30min, and dispersing to obtain a mixed solution;
dissolving 2mmol of nickel acetate in the mixed solution, performing ultrasonic treatment for 45min, and stirring at 5 ℃ for 2h to obtain a uniform nickel acetate mixed solution;
adding 20mL of 0.25mol/L sodium borohydride solution into the nickel acetate mixed solution, and continuously stirring for 10min at 5 ℃ until complete reduction is achieved, wherein the solubility of a by-product sodium metaborate generated in the reaction is reduced, and the by-product sodium metaborate and Ni nano-particles are separated out simultaneously;
carrying out suction filtration on the product, washing the product for 3-4 times by using distilled water, dissolving a by-product sodium metaborate in the water, and washing the by-product sodium metaborate to obtain a washed product;
and (3) carrying out vacuum freeze drying treatment on the washed product at-45 ℃ to obtain the C @ Ni catalyst.
The C @ Ni is characterized, the test result is basically consistent with that of the embodiment 1, the nickel simple substance is uniformly dispersed on the surface of the carbon nanosphere, the particle size of nickel particles is distributed between 6 and 9 nanometers and is far smaller than that of the nickel simple substance prepared by the conventional method, the C @ Ni is used as a catalyst, the catalytic performance of the C @ Ni on the hydrogen production by hydrolysis of 0.25mol/L sodium borohydride alkali solution (NaOH:0.25mol/L) is tested at 30 ℃, and the hydrolysis speed of the C @ Ni on sodium borohydride is improved by about 96.5 percent compared with that of the C @ Ni prepared by using pure water as a solvent.
Example 7
Mixing ethanol and distilled water according to the volume ratio of 4:1 to obtain an ethanol-water solvent;
dissolving 0.2g of silicon dioxide nanospheres into 200mL of ethanol-water solvent, performing ultrasonic treatment for 60min, stirring for 30min, and dispersing to obtain a mixed solution;
dissolving 2mmol of ferric chloride in the mixed solution, performing ultrasonic treatment for 30min, and stirring at 5 ℃ for 2h to obtain a uniform ferric chloride mixed solution;
adding 40mL of 0.125mol/L sodium borohydride solution into the ferric chloride mixed solution, and continuously stirring for 10min at 5 ℃ until complete reduction is achieved, wherein the solubility of a by-product sodium metaborate generated in the reaction is reduced, and the by-product sodium metaborate and Fe nano-particles are separated out simultaneously;
carrying out suction filtration on the product, washing the product for 3-4 times by using distilled water, dissolving a by-product sodium metaborate in the water, and washing the by-product sodium metaborate to obtain a washed product;
carrying out vacuum freeze drying treatment on the washed product at-45 ℃ to obtain SiO2@ Fe catalyst.
To what is neededThe SiO2The characterization is carried out on the @ Fe, the test result of the @ Fe is basically consistent with that of the embodiment 1, the situation that the iron simple substance is uniformly dispersed on the surface of the silicon dioxide nanosphere, the particle size of iron particles is distributed between 6-9 nanometers and is far smaller than that of the iron simple substance prepared by the conventional method is shown, and SiO is added2@ Fe is used as a catalyst, the catalytic performance of the catalyst on 0.25mol/L ammonia borane hydrolysis hydrogen production is tested at the temperature of 30 ℃, and the hydrolysis speed of the catalyst on sodium borohydride is higher than that of SiO prepared by using pure water as a solvent2@ Fe increased by about 88.5%.
Example 8
Mixing ethanol and distilled water according to the volume ratio of 3:2 to obtain an ethanol-water solvent;
dissolving 0.2g of carbon nanospheres into 150mL of ethanol-water solvent, performing ultrasonic treatment for 60min, stirring for 30min, and dispersing to obtain a mixed solution;
dissolving 1mmol of ferric acetate in the mixed solution, performing ultrasonic treatment for 30min, and stirring at 5 ℃ for 2h to obtain a uniform ferric acetate mixed solution;
adding 15mL of 0.2mol/L sodium borohydride solution into the ferric acetate mixed solution, and continuously stirring for 10min at 5 ℃ until complete reduction is achieved, wherein the solubility of a by-product sodium metaborate generated in the reaction is reduced, and the by-product sodium metaborate and Fe nano-particles are simultaneously separated out;
carrying out suction filtration on the product, washing the product for 3-4 times by using distilled water, dissolving a by-product sodium metaborate in the water, and washing the by-product sodium metaborate to obtain a washed product;
and (3) carrying out vacuum freeze drying treatment on the washed product at-45 ℃ to obtain the C @ Fe catalyst.
The C @ Fe is characterized, the test result is basically consistent with that of the embodiment 1, the iron simple substance is uniformly dispersed on the surface of the carbon nanosphere, the particle size of iron particles is distributed between 4 and 7 nanometers and is far smaller than that of the iron simple substance prepared by the conventional method, the C @ Fe is used as a catalyst, the catalytic performance of the C @ Fe on the hydrogen production by hydrolysis of 0.25mol/L sodium borohydride alkali solution (NaOH:0.25mol/L) is tested at 30 ℃, and the hydrolysis speed of the C @ Fe on sodium borohydride is improved by about 124 percent compared with that of the C @ Fe prepared by using pure water as a solvent.
Example 9
Mixing ethanol and distilled water according to the volume ratio of 1:1 to obtain an ethanol-water solvent;
dissolving 0.1g of graphene oxide in 100mL of ethanol-water solvent, performing ultrasonic treatment for 60min, stirring for 30min, and dispersing to obtain a mixed solution;
dissolving 1mmol of ferric nitrate in the mixed solution, performing ultrasonic treatment for 30min, and stirring at 5 ℃ for 2h to obtain a uniform ferric nitrate mixed solution;
adding 20mL of 0.125mol/L sodium borohydride solution into the ferric nitrate mixed solution, and continuously stirring for 10min at 5 ℃ until complete reduction is achieved, wherein the solubility of a by-product sodium metaborate generated in the reaction is reduced, and the by-product sodium metaborate and Fe nano-particles are separated out simultaneously;
carrying out suction filtration on the product, washing the product for 3-4 times by using distilled water, dissolving a by-product sodium metaborate in the water, and washing the by-product sodium metaborate to obtain a washed product;
and (3) carrying out vacuum freeze drying treatment on the washed product at-45 ℃ to obtain the GO @ Fe catalyst.
The GO @ Fe is characterized, the test result is basically consistent with that of the embodiment 1, the iron simple substance is uniformly dispersed on the surface of graphene oxide, the particle size of iron particles is distributed between 5 and 9 nanometers and is far smaller than that of the iron simple substance prepared by the conventional method, the GO @ Fe is used as a catalyst, the catalytic performance of the GO @ Fe on hydrolysis hydrogen production of 0.25mol/L sodium borohydride alkali solution (NaOH:0.25mol/L) is tested at 30 ℃, and the hydrolysis speed of GO @ Fe on sodium borohydride is improved by about 95.7% compared with that of GO @ Fe prepared by using pure water as a solvent.
According to the embodiment, the solubility of the sodium metaborate generated in the reduction reaction process is controlled by adopting the ethanol-water solvent, the sodium metaborate is separated out along with the generation of the non-noble metal in the reduction process, the non-noble metal nano particles are isolated, the agglomeration growth of the non-noble metal particles in the preparation process is obviously inhibited, the particle size of the non-noble metal is effectively reduced, the catalytic activity of the non-noble metal catalyst is greatly improved, the process is simple to operate, and the environment is not polluted.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of a non-noble metal catalyst comprises the following steps:
mixing an ethanol-water solvent, a carrier material and non-noble metal salt to obtain non-noble metal salt dispersion liquid;
mixing the non-noble metal salt dispersion liquid with a sodium borohydride solution to perform a reduction reaction, and washing a reduction reaction product to obtain a non-noble metal catalyst;
the temperature of the reduction reaction is 4-6 ℃, and the time of the reduction reaction is 8-12 min;
the volume ratio of ethanol to water in the ethanol-water solvent is (2-4): (1-3);
the volume ratio of the amount of the non-noble metal salt to the ethanol-water solvent is (1-2) mmol: (100-200) mL;
the concentration of the sodium borohydride solution is 0.125-0.25 mol/L.
2. The preparation method of claim 1, wherein the carrier material is one or more of graphene oxide, carbon nanospheres and silica nanospheres.
3. The method according to any one of claims 1 to 2, wherein the ratio of the mass of the carrier material to the volume of the ethanol-water solvent is (1 to 2) g: (1-2) L.
4. The method according to claim 1, wherein the non-noble metal salt is one or more selected from the group consisting of cobalt acetate, cobalt chloride, cobalt nitrate, cobalt acetate, nickel chloride, nickel nitrate, iron acetate, iron chloride, and iron nitrate.
5. The method of claim 1, wherein the mass ratio of the non-noble metal salt to the sodium borohydride is 1: (2-6).
6. The non-noble metal catalyst prepared by the preparation method of any one of claims 1 to 5, which comprises a carrier and non-noble metal nanoparticles supported on the carrier, wherein the particle size of the non-noble metal nanoparticles is 4-10 nm.
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