CN109718822A - Method for preparing metal-carbon composite catalytic material and application thereof - Google Patents
Method for preparing metal-carbon composite catalytic material and application thereof Download PDFInfo
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- CN109718822A CN109718822A CN201811483981.4A CN201811483981A CN109718822A CN 109718822 A CN109718822 A CN 109718822A CN 201811483981 A CN201811483981 A CN 201811483981A CN 109718822 A CN109718822 A CN 109718822A
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- metal
- carbon
- ball milling
- carbon composite
- catalytic material
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052786 argon Inorganic materials 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims abstract 2
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229920001864 tannin Polymers 0.000 claims description 5
- 239000001648 tannin Substances 0.000 claims description 5
- 235000018553 tannin Nutrition 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- AFSDNFLWKVMVRB-UHFFFAOYSA-N Ellagic acid Chemical compound OC1=C(O)C(OC2=O)=C3C4=C2C=C(O)C(O)=C4OC(=O)C3=C1 AFSDNFLWKVMVRB-UHFFFAOYSA-N 0.000 claims description 3
- 229920002079 Ellagic acid Polymers 0.000 claims description 3
- ATJXMQHAMYVHRX-CPCISQLKSA-N Ellagic acid Natural products OC1=C(O)[C@H]2OC(=O)c3cc(O)c(O)c4OC(=O)C(=C1)[C@H]2c34 ATJXMQHAMYVHRX-CPCISQLKSA-N 0.000 claims description 3
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 claims description 3
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 235000004132 ellagic acid Nutrition 0.000 claims description 3
- 229960002852 ellagic acid Drugs 0.000 claims description 3
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- FAARLWTXUUQFSN-UHFFFAOYSA-N methylellagic acid Natural products O1C(=O)C2=CC(O)=C(O)C3=C2C2=C1C(OC)=C(O)C=C2C(=O)O3 FAARLWTXUUQFSN-UHFFFAOYSA-N 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 229960001285 quercetin Drugs 0.000 claims description 3
- 235000005875 quercetin Nutrition 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims 1
- 229960000355 copper sulfate Drugs 0.000 claims 1
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 12
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000002082 metal nanoparticle Substances 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 26
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 16
- 239000002086 nanomaterial Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 12
- 229910001928 zirconium oxide Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 6
- 239000001263 FEMA 3042 Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920002258 tannic acid Polymers 0.000 description 6
- 235000015523 tannic acid Nutrition 0.000 description 6
- 229940033123 tannic acid Drugs 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CHUYYOSIZBKMJD-UHFFFAOYSA-N acetic acid;gold Chemical compound [Au].CC(O)=O CHUYYOSIZBKMJD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229920002824 gallotannin Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- 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
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- Catalysts (AREA)
Abstract
The invention belongs to the technical field of preparation of carbon-based materials, and relates to a method for preparing a metal-carbon composite catalytic material and application thereof, wherein the preparation method comprises the following steps: (1) mixing 0.5-5g of carbon source and 0.02-1g of metal salt, placing the mixture in a ball milling tank made of 50mL of zirconia, carrying out ball milling for 30-60min, then adding 1-20g of nitrogen source, and carrying out ball milling for 30-60min to obtain ball-milled powder; (2) and (3) placing the powder subjected to ball milling in the step (1) into a tubular furnace, and roasting at high temperature for 1-2 hours under the protection of argon to obtain the metal-carbon composite catalytic material. The metal-carbon composite material prepared by the method has the advantages of small size of metal nanoparticles, less impurities, high catalytic activity, stable active substances and the like, has great application potential in the field of catalysis, and researches the catalytic activity of the composite material in water decomposition and carbon dioxide reduction reactions. The method has the advantages of simple process, short production period, low cost and environmental protection.
Description
Technical field
The present invention relates to a kind of method and its application for preparing metal-carbon composite catalyzing material, belong to carbon-based material preparation
Technical field.
Background technique
C-based nanomaterial because it has excellent electric conductivity and thermal conductivity, good mechanical property and high-specific surface area,
Many advantages, such as price of the structure and active site abundant and relative moderate that are easy to regulate and control, in recent years in energy storage,
Heterogeneous catalysis and environmental protection etc. get more and more people's extensive concerning.Importantly, having unique physicochemical property and being easy to
The carbon nanomaterial of regulation easily can adjust its superficiality by introducing intrinsic defect, foreign atom and functional group
Matter, this provides opportunity further to rationally design advanced c-based nanomaterial, and will be helpful to more fully understand structure-performance
Between relationship.Recent research indicate that the research emphasis for adulterating carbon material is mainly mixed with nitrogen-doped carbon (N-C material) and metal nitrogen
Based on miscellaneous carbon (M-N-C).Especially this kind of metal-carbon composite (M-N-C) has both many excellent of metal and nitrogen-doped carbon material
Point and the " MN containing catalytic activityX" site, with corproporphyrin structure, monometallic site therein can also be directly as work
Property site, this kind of material has maximum atom utilization, homogeneous catalyst active site, lower metal ligancy and vulnerable to tune
The advantages such as the electronic structure of control show the catalytic property dramatically different with corresponding block materials, in water-splitting, metal-air
Battery and conventional multiphase catalytic field show biggish application prospect.However, the system of this kind of metal-carbon composite nano materials
It is standby, it usually needs using metal organic framework compound or organic micromolecule compound and organic polymer as presoma, to lead to
Cross high-temperature roasting preparation；Or it is obtained using the reduction of wet chemistry method dipping.So during the preparation process, inevitably needing phase
When the solvent (such as the auxiliary agents such as the organic agents such as alcohol or acid-base reagent and surfactant) of quantity, no matter using organic molten
Agent/auxiliary agent reagent or acid-base reagent, this will necessarily generate a large amount of waste liquids, will increase environmental pressure and manufacturing cost, seriously violate
Green chemical concept greatly limits its prepare with scale and industrial application prospect.Therefore, it is necessary to a kind of green is developed,
Low cost, convenient and large-scale production method prepare the high-quality metal-carbon composite with good form to meet
Following application demand.
Summary of the invention
In order to overcome the deficiencies in the prior art, metal-carbon composite catalyzing is prepared it is an object of the present invention to provide a kind of
The method and its application of material.This method simple process, it is with short production cycle, at low cost, environmentally protective, be capable of large scale preparation
Category-carbon composite.Using this method preparation metal-carbon composite have metal nanoparticle size is small, impurity is less,
The advantages that catalytic activity is high, active material is stablized has biggish application potential in catalytic field, and has probed into composite material and existed
Catalytic activity in water decomposition and carbon dioxide reduction reaction.
In order to achieve the above-mentioned object of the invention, in the presence of solving the problems, such as prior art, technical solution that the present invention takes
It is: a method of preparing metal-carbon composite catalyzing material, comprising the following steps:
Step 1, by 0.5-5g carbon source and 0.02-1g metal salt, mixing is placed in the ball grinder of 50mL zirconium oxide material, ball
30-60min is ground, 1-20g nitrogen source, then ball milling 30-60min, the powder after obtaining ball milling are then added；The carbon source is selected from single
One of peaceful acid, ellagic acid, Gallotannin, quercetin or ellagic tannin, the metal salt is selected from nickel acetate, sulphur
One of sour copper, cobalt acetate, ferric nitrate, zinc chloride, manganese nitrate, silver acetate, acetic acid gold or palladium acetate, the nitrogen source is selected from double
Cyanamide, one of urea or melamine；
Step 1 is obtained the powder after ball milling by step 2, is placed in tube furnace, under protection of argon gas, 600-1000 DEG C of roasting
1-2h is burnt, metal-carbon composite catalyzing material is made.
The metal-carbon composite catalyzing material of the method preparation is catalyzed reaction in water decomposition and in carbon dioxide electrification
Learn the application in reduction catalysts reaction.
The medicine have the advantages that a kind of method and its application for preparing metal-carbon composite catalyzing material, wherein the side of preparation
Method is the following steps are included: 0.5-5g carbon source and 0.02-1g metal salt are mixed the ball grinder for being placed in 50mL zirconium oxide material by (1)
In, then ball milling 30-60min adds 1-20g nitrogen source, then ball milling 30-60min, the powder after obtaining ball milling；(2) by step
1 obtains the powder after ball milling, is placed in tube furnace, and under protection of argon gas, it is multiple that metal-carbon is made in 600-1000 DEG C of roasting 1-2h
Close catalysis material.Using the metal-carbon composite of this method preparation with metal nanoparticle size is small, impurity is less, urges
Change the advantages that activity is high, active material is stablized, there is biggish application potential in catalytic field, and probed into composite material in water
It decomposes and the catalytic activity in carbon dioxide reduction reaction.It is the method for the present invention simple process, with short production cycle, at low cost, green
Environmental protection, being capable of large scale preparation metal-carbon composite catalyzing material.
Detailed description of the invention
Fig. 1 is the X-ray diffraction analysis figure of the Ni-N-C catalyst prepared in embodiment 1.
Fig. 2 is the transmission electron microscope photo figure of the Ni-N-C catalyst prepared in embodiment 2.
In figure: (a) high power that scale is 50nm projects electron microscope, and (b) high power that scale is 20nm projects electron microscope.
Fig. 3 is the X-ray diffraction analysis figure of the Pd-N-C catalyst prepared in embodiment 10.
Fig. 4 is the performance map of Carbon dioxide electrochemical reduction described in embodiment 11.
Fig. 5 is (0.5M H in acid condition described in embodiment 122SO4) liberation of hydrogen polarization curve.
Fig. 6 is (0.5M H in acid condition described in embodiment 132SO4) analysis oxygen polarization curve.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
0.5g tannic acid and 0.1g nickel acetate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball milling
Then 30min adds 1g melamine, then ball milling 30min.Then the powder that will be obtained after above-mentioned ball milling, is placed in tube furnace
In, under protection of argon gas, 700 DEG C of roasting 1h can be prepared by Ni-N-C c-based nanomaterial catalyst.From the XRD diagram (figure of sample
1) it will be clear that (002) characteristic diffraction peak of carbon, does not occur the characteristic diffraction peak of apparent elemental nickel in.
Embodiment 2
1g ellagic acid and 0.5g nickel acetate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball milling
Then 30min adds 3g dicyandiamide, then ball milling 30min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnace
In, under protection of argon gas, 800 DEG C of roasting 2h can be prepared by Ni-N-C c-based nanomaterial catalyst.From the transmission electron microscope of sample
It can be seen that material has pore structure abundant in photo figure (Fig. 2), it is applied to electrochemically reducing carbon dioxide and shows
Excellent catalytic activity.
Embodiment 3
5g tannic acid and 1g copper sulphate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball milling
Then 60min adds 20g dicyandiamide, then ball milling 60min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnace
In, under protection of argon gas, 800 DEG C of roasting 2h can be prepared by Cu-N-C c-based nanomaterial catalyst.
Embodiment 4
2g Gallotannin and 0.3g cobalt acetate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball
30min is ground, 5g urea, then ball milling 30min are then added.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnace
In, under protection of argon gas, 600 DEG C of roasting 1h can be prepared by Co-N-C c-based nanomaterial catalyst.It is applied to acid item
Electrolysis water liberation of hydrogen under part shows relatively excellent catalytic activity.
Embodiment 5
1g tannic acid and 0.1g ferric nitrate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball milling
Then 30min adds 10g melamine, then ball milling 40min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tubular type
In furnace, under protection of argon gas, 900 DEG C of roasting 1h can be prepared by Fe-N-C c-based nanomaterial catalyst.It is applied to acidity
Under the conditions of be electrolysed elutriation oxygen, show relatively excellent catalytic activity.
Embodiment 6
3g quercetin and 1g zinc chloride are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball milling
Then 45min adds 6g melamine, then ball milling 45min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnace
In, under protection of argon gas, 1000 DEG C of roasting 1.5h can be prepared by Zn-N-C c-based nanomaterial catalyst.
Embodiment 7
2g tannic acid and 0.5g manganese nitrate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball milling
Then 45min adds 6g melamine, then ball milling 45min.Then, by the obtained powder after above-mentioned ball milling, it is placed in tubular type
In furnace, under protection of argon gas, 850 DEG C of roasting 2h can be prepared by Mn-N-C c-based nanomaterial catalyst.
Embodiment 8
0.5g tannic acid and 0.03g silver acetate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball milling
Then 50min adds 8g melamine, then ball milling 30min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnace
In, under protection of argon gas, 800 DEG C of roasting 1h can be prepared by Ag-N-C c-based nanomaterial catalyst.
Embodiment 9
0.5g tannic acid and 0.02g acetic acid gold are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball milling
Then 40min adds 8g melamine, then ball milling 50min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnace
In, under protection of argon gas, 950 DEG C of roasting 1h can be prepared by Au-N-C c-based nanomaterial catalyst.
Embodiment 10
0.5g ellagic tannin and 0.03g palladium acetate are weighed respectively, and mixing is placed in the ball milling of 50mL zirconium oxide material
In tank, then ball milling 35min adds 5g melamine, then ball milling 55min.Then, the powder that will be obtained after above-mentioned ball milling,
It is placed in tube furnace, under protection of argon gas, 800 DEG C of roasting 2h can be prepared by Pd-N-C c-based nanomaterial catalyst.From sample
XRD diagram (Fig. 3) in it will be clear that carbon (002) characteristic diffraction peak, do not occur the feature diffraction of apparent simple substance palladium
Peak.
Embodiment 11
Electrochemically reducing carbon dioxide performance test, electrochemistry used are carried out to prepared metal-carbon composite catalyst
Work station is Shanghai Chen Hua CHI660E.Electrolytic cell is H-type, is proton exchange membrane, 0.1M NaHCO with nafion 1173As
Electrolyte is to electrode, using the conductive carbon paper that catalyst loads as work with platinized platinum using silver/silver chloride electrode as reference electrode
Make electrode, constitutes three-electrode system.Electrochemically reducing carbon dioxide performance test is carried out with catalyst prepared by embodiment 2,
Catalyst prepared by 5mg is taken, is dissolved in 1mL ethyl alcohol, is then added 30 μ L nafion binders, after ultrasonic 30min, takes 100
μ L is coated on 1cm-2On carbon paper, excellent carbon dioxide reduction performance is shown after drying at room temperature as working electrode ,-
Under 0.86V voltage, carbon monoxide faradic efficiency is up to 94.8%, shows excellent performance as shown in figure 4, current density
Up to 18.2mA cm-2, and have excellent stability, it can be steady testing 25 hours.
Embodiment 12
Carrying out electrolysis water liberation of hydrogen to prepared metal-carbon composite catalyst can test, and electrochemical workstation used is upper
Hai Chenhua CHI660E.Electrolytic cell is there-necked flask shape, 0.5M H2SO4As electrolyte, using silver/silver chloride electrode as reference electrode,
It is that using the conductive carbon paper that catalyst loads as working electrode, three-electrode system is constituted to electrode with carbon-point.With 4 institute of embodiment
The catalyst of preparation, which carries out electrolysis water liberation of hydrogen, to be tested, and take catalyst prepared by 2mg, be dissolved in 1mL ethyl alcohol, be then added 30
μ L nafion binder after ultrasonic 30min, takes 20 μ L to be coated on 0.2cm-2On carbon paper, after drying at room temperature as working electrode into
The test of row Hydrogen Evolution Performance, shows relatively excellent performance, can obtain from its liberation of hydrogen polarization curve (LSV, Fig. 5), reach 10mA
cm-2Its overpotential of current density is only 34mV.
Embodiment 13
Electrolysis elutriation oxygen performance test is carried out to prepared metal-carbon composite catalyst, electrochemical workstation used is
Shanghai Chen Hua CHI660E.Electrolytic cell is there-necked flask shape, 0.5M H2SO4As electrolyte, using silver/silver chloride electrode as reference electricity
Pole is, using the conductive carbon paper that catalyst loads as working electrode, to constitute three-electrode system to electrode with carbon-point.With embodiment 5
Prepared catalyst, which carries out electrolysis elutriation oxygen, to be tested, and take catalyst prepared by 2mg, be dissolved in 1mL ethyl alcohol, be then added
30 μ L nafion binders after ultrasonic 30min, take 20 μ L to be coated on 0.2cm-2On carbon paper, working electrode is used as after drying at room temperature
Analysis oxygen performance test is carried out, relatively excellent performance is shown, analysing oxygen polarization curve (LSV, Fig. 6) from it can obtain, and reach 10mA
cm-2Its overpotential of current density is 480mV.
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