CN107282081A - A kind of preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst - Google Patents
A kind of preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst Download PDFInfo
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- CN107282081A CN107282081A CN201710399159.9A CN201710399159A CN107282081A CN 107282081 A CN107282081 A CN 107282081A CN 201710399159 A CN201710399159 A CN 201710399159A CN 107282081 A CN107282081 A CN 107282081A
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- 230000009467 reduction Effects 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 37
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 12
- 235000011160 magnesium carbonates Nutrition 0.000 claims abstract description 12
- 239000011592 zinc chloride Substances 0.000 claims abstract description 12
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 9
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 9
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 9
- 239000012498 ultrapure water Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000007654 immersion Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 24
- 230000007935 neutral effect Effects 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 22
- 239000011799 hole material Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UOVKYUCEFPSRIJ-UHFFFAOYSA-D hexamagnesium;tetracarbonate;dihydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O UOVKYUCEFPSRIJ-UHFFFAOYSA-D 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/618—
-
- B01J35/647—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst, belong to the synthesis technical field of porous carbon materials.Technical scheme main points are：A kind of preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst; carbon source, nitrogen source, zinc chloride and five hydrated basic magnesium carbonates are placed in glass mortar to grind 10 20min and be sufficiently mixed it and uniformly obtain material A; material A is transferred in porcelain boat and is positioned in tube furnace; then temperature programming is naturally cooling to room temperature and obtains material B to 800 1000 DEG C of holding 120min under inert gas shielding；Material B is transferred in container and acid solution immersion 18h is added, is then neutral with high-purity water washing to filtrate, then obtains bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst in 40 60 DEG C of dry 12 24h.Bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst specific surface area produced by the present invention is 1346 1976m2/ g, bore dia is 3.8nm or so, the performance with excellent hydrogen reduction catalytic performance and methanol tolerance and anthracemia.
Description
Technical field
The invention belongs to the synthesis technical field of porous carbon materials, and in particular to a kind of bulk multi-hole nitrogen-doped carbon hydrogen reduction
The preparation method of catalyst.
Background technology
Porous carbon materials turn into a kind of typical fuel with its high-specific surface area, abundant pore structure and good electric conductivity
Cell cathode oxygen reduction reaction catalyst.Heteroatom doping, which enters carbon material, can effectively improve the surface texture of carbon material, carry
The surface wettability of high-carbon material, strengthens the capacitive property and catalytic performance of carbon material（Peng, H.; Ma, G.; Sun,
K.; et al. Electrochim. Acta 2016, 190, 862-871.）.Nitrogen atom doping, which enters carbon material, following several
Plant existing way：Pyridine type nitrogen, pyrroles's type nitrogen, graphite mould nitrogen and oxidized form nitrogen.The reaction of nitrogen-doped carbon material catalytic oxidation-reduction
The essence of avtive spot needs to be continued to probe into, and some are scientific investigations showed that pyridine type nitrogen and graphite mould nitrogen all there is hydrogen reduction electricity to urge
Change activity.Nitrogen atom doping enters in carbon atom grid, because its stronger electronegativity causes the electron density of the carbon atom of surrounding to drop
It is low, be conducive to oxygen molecule absorption on the carbon atom of surrounding, weaken O -- O bond, promote oxygen reduction reaction.
At present, Publication No. CN104258892A patent discloses a kind of SiO synthesized with collosol and gel hydro-thermal method2Make
For hard template, multi-stage porous carbon block materials are prepared by nanometer casting method, nitrogen source is then added（Urea etc.）Nitrogen is prepared to mix
The method of miscellaneous mesopore/macropore multi-stage porous carbon oxygen reduction catalyst, although prepared nitrogen-doped carbon oxygen reduction catalyst than
Surface area is up to 1570-2480m2g-1, the macropore with three-dimensional communication, but this method program is complicated, it is not easy to operate.Publication number
For CN105186010A patent disclose one kind solid polymer is prepared by template of Eutectic molten salt, then high temperature solution hot preparation
Go out the method for nitrogen-doped carbon oxygen reduction catalyst, although the hierarchical porous structure nitrogen-doped carbon material pore structure prepared is abundant,
It is that the raw material that the method is used is various, cost is higher, complex process.Publication No. CN103435034A patent discloses one kind
Hetero atom is provided using ammoniacal liquor, vulcanized sodium, sodium borohydride, hydroiodic acid etc. and is used as reducing agent synthetic graphite base oxygen reduction catalyst
Method, this method technique is simple, wide using scope, but the performance of oxygen-reducing catalyst prepared is general, it is impossible to meet life
Produce the requirement living to oxygen reduction catalyst.
The content of the invention
Present invention solves the technical problem that there is provided a kind of simple and with low cost bulk multi-hole nitrogen-doped carbon of technique
The preparation method of oxygen reduction catalyst.
The present invention adopts the following technical scheme that a kind of bulk multi-hole nitrogen-doped carbon hydrogen reduction is urged to solve above-mentioned technical problem
The preparation method of agent, it is characterised in that concretely comprise the following steps：
（1）Carbon source, nitrogen source, zinc chloride and five hydrated basic magnesium carbonates are placed in into grinding 10-20min in glass mortar makes its abundant
Well mixed to obtain material A, wherein carbon source is the one or more in glucose, fructose or cellulose, and nitrogen source is urea or three
One or more in poly cyanamid；
（2）Material A is transferred in porcelain boat and is positioned in tube furnace, under inert gas shielding, 60min liters are passed through by room temperature
Temperature is to 300 DEG C, and 300 DEG C keep 120min, then are warming up to 800-1000 DEG C of holding 120min with 10 DEG C/min heating rate, so
After be naturally cooling to room temperature and obtain material B；
（3）Material B is transferred in container and acid solution immersion 18h is added, is then neutrality with high-purity water washing to filtrate,
Then bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst is obtained in 40-60 DEG C of dry 12-24h.
Further preferably, the mass ratio that feeds intake of described carbon source, nitrogen source, zinc chloride and five hydrated basic magnesium carbonates is 1.1:
0.297-1.16:3.3:1.1-2.2。
Further preferably, described inert gas is the one or more in nitrogen or argon gas.
Further preferably, described acid solution is molar concentration 2mol/L hydrochloric acid solution.
The present invention has following beneficial effect compared with prior art：
1st, present invention introduces zinc chloride as activator, the specific surface area and pore volume of carbon material, the more activity of exposure are increased
Site, the oxygen reduction catalytic activity of reinforcing material；
2nd, the pore volume for further increasing carbon material present invention introduces five hydrated basic magnesium carbonates generates the carbon materials of bulk multi-hole
Material, enhances the electric conductivity of carbon material, and with the increase of five hydrated basic magnesium carbonate amounts, the ratio surface of prepared carbon material
Product and pore volume gradually increase；
3rd, more avtive spots are formed present invention introduces nitrogen source, enhances the chemical property of prepared carbon material；
4th, bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst specific surface area produced by the present invention is 1346-1976m2/ g, bore dia
For 3.8nm or so, the performance with excellent hydrogen reduction catalytic performance and methanol tolerance and anthracemia.
Brief description of the drawings
Fig. 1 is the field emission scanning electron microscope figure of bulk multi-hole nitrogen-doped carbon material C 2 prepared by the embodiment of the present invention 2；
Fig. 2 is the transmission electron microscope picture of bulk multi-hole nitrogen-doped carbon material C 2 prepared by the embodiment of the present invention 2；
Fig. 3 is the X ray diffracting spectrum of bulk multi-hole nitrogen-doped carbon material prepared by 1-6 of the embodiment of the present invention；
Fig. 4 is the Raman spectrograms of bulk multi-hole nitrogen-doped carbon material prepared by 1-6 of the embodiment of the present invention；
Fig. 5 is the graph of pore diameter distribution of bulk multi-hole nitrogen-doped carbon material prepared by 1-3 of the embodiment of the present invention；
Fig. 6 is the cyclic voltammetry curve of bulk multi-hole nitrogen-doped carbon material prepared by 1-3 of the embodiment of the present invention.
In figure：The pore structure of 1- bulk multi-hole nitrogen-doped carbon materials, the fluff structure of 2- bulk multi-hole nitrogen-doped carbon materials.
Embodiment
The above to the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
（1）1.1g glucose, 3.3g zinc chloride, the hydrated basic magnesium carbonates of 1.1g five and 0.297g urea are placed in glass mortar
Grinding 10min is sufficiently mixed it uniformly to obtain material A 1；
（2）Material A 1 is transferred in porcelain boat and is positioned in tube furnace, is protected in flow velocity for 100mL/min nitrogen gas
Under, 300 DEG C are warming up to by 60min by room temperature, 300 DEG C keep 120min, then are warming up to 900 with 10 DEG C/min heating rate
DEG C keep 120min, be then naturally cooling to room temperature and obtain material B1；
（3）Material B1 is transferred in 100mL beakers and adds the hydrochloric acid solution that 80mL molar concentrations are 2mol/L and soaks 18h,
Then it is neutral with high-purity water washing to filtrate, then obtains bulk multi-hole N doping in 40 DEG C of dry 12h in air dry oven
Carbon oxygen reduction catalyst C1.
Embodiment 2
（1）1.1g glucose, 3.3g zinc chloride, the hydrated basic magnesium carbonates of 1.1g five and 0.594g urea are placed in glass mortar
Grinding 10min is sufficiently mixed it uniformly to obtain material A 2；
（2）Material A 2 is transferred in porcelain boat and is positioned in tube furnace, is protected in flow velocity for 100mL/min nitrogen gas
Under, 300 DEG C are warming up to by 60min by room temperature, 300 DEG C keep 120min, then are warming up to 900 with 10 DEG C/min heating rate
DEG C keep 120min, be then naturally cooling to room temperature and obtain material B2；
（3）Material B2 is transferred in 100mL beakers and adds the hydrochloric acid solution that 80mL molar concentrations are 2mol/L and soaks 18h,
Then it is neutral with high-purity water washing to filtrate, then obtains bulk multi-hole N doping in 40 DEG C of dry 12h in air dry oven
Carbon oxygen reduction catalyst C2.
Embodiment 3
（1）1.1g glucose, 3.3g zinc chloride, the hydrated basic magnesium carbonates of 1.1g five and 1.16g urea are placed in glass mortar
Grinding 10min is sufficiently mixed it uniformly to obtain material A 3；
（2）Material A 3 is transferred in porcelain boat and is positioned in tube furnace, is protected in flow velocity for 100mL/min nitrogen gas
Under, 300 DEG C are warming up to by 60min by room temperature, 300 DEG C keep 120min, then are warming up to 900 with 10 DEG C/min heating rate
DEG C keep 120min, be then naturally cooling to room temperature and obtain material B3；
（3）Material B3 is transferred in 100mL beakers and adds the hydrochloric acid solution that 80mL molar concentrations are 2mol/L and soaks 18h,
Then it is neutral with high-purity water washing to filtrate, then obtains bulk multi-hole N doping in 40 DEG C of dry 24h in air dry oven
Carbon oxygen reduction catalyst C3.
Embodiment 4
（1）1.1g glucose, 3.3g zinc chloride, the hydrated basic magnesium carbonates of 1.1g five and 0.594g urea are placed in glass mortar
Grinding 20min is sufficiently mixed it uniformly to obtain material A 4；
（2）Material A 4 is transferred in porcelain boat and is positioned in tube furnace, is protected in flow velocity for 100mL/min nitrogen gas
Under, 300 DEG C are warming up to by 60min by room temperature, 300 DEG C keep 120min, then are warming up to 800 with 10 DEG C/min heating rate
DEG C keep 120min, be then naturally cooling to room temperature and obtain material B4；
（3）Material B4 is transferred in 100mL beakers and adds the hydrochloric acid solution that 80mL molar concentrations are 2mol/L and soaks 18h,
Then it is neutral with high-purity water washing to filtrate, then obtains bulk multi-hole N doping in 40 DEG C of dry 12h in air dry oven
Carbon oxygen reduction catalyst C4.
Embodiment 5
（1）1.1g glucose, 3.3g zinc chloride, the hydrated basic magnesium carbonates of 1.1g five and 0.594g urea are placed in glass mortar
Grinding 10min is sufficiently mixed it uniformly to obtain material A 5；
（2）Material A 5 is transferred in porcelain boat and is positioned in tube furnace, is protected in flow velocity for 100mL/min nitrogen gas
Under, 300 DEG C are warming up to by 60min by room temperature, 300 DEG C are kept 120min, then are warming up to 10 DEG C/min heating rate
1000 DEG C of holding 120min, are then naturally cooling to room temperature and obtain material B5；
（3）Material B5 is transferred in 100mL beakers and adds the hydrochloric acid solution that 80mL molar concentrations are 2mol/L and soaks 18h,
Then it is neutral with high-purity water washing to filtrate, then obtains bulk multi-hole N doping in 40 DEG C of dry 12h in air dry oven
Carbon oxygen reduction catalyst C5.
Embodiment 6
（1）1.1g glucose, 3.3g zinc chloride, the hydrated basic magnesium carbonates of 2.2g five and 0.594g urea are placed in glass mortar
Grinding 10min is sufficiently mixed it uniformly to obtain material A 6；
（2）Material A 6 is transferred in porcelain boat and is positioned in tube furnace, is protected in flow velocity for 100mL/min nitrogen gas
Under, 300 DEG C are warming up to by 60min by room temperature, 300 DEG C keep 120min, then are warming up to 900 with 10 DEG C/min heating rate
DEG C keep 120min, be then naturally cooling to room temperature and obtain material B6；
（3）Material B6 is transferred in 100mL beakers and adds the hydrochloric acid solution that 80mL molar concentrations are 2mol/L and soaks 18h,
Then it is neutral with high-purity water washing to filtrate, then obtains bulk multi-hole N doping in 60 DEG C of dry 12h in air dry oven
Carbon oxygen reduction catalyst C6.
Embodiment above describes general principle, principal character and the advantage of the present invention, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (4)
1. a kind of preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst, it is characterised in that concretely comprise the following steps：
（1）Carbon source, nitrogen source, zinc chloride and five hydrated basic magnesium carbonates are placed in into grinding 10-20min in glass mortar makes its abundant
Well mixed to obtain material A, wherein carbon source is the one or more in glucose, fructose or cellulose, and nitrogen source is urea or three
One or more in poly cyanamid；
（2）Material A is transferred in porcelain boat and is positioned in tube furnace, under inert gas shielding, 60min liters are passed through by room temperature
Temperature is to 300 DEG C, and 300 DEG C keep 120min, then are warming up to 800-1000 DEG C of holding 120min with 10 DEG C/min heating rate, so
After be naturally cooling to room temperature and obtain material B；
（3）Material B is transferred in container and acid solution immersion 18h is added, is then neutrality with high-purity water washing to filtrate,
Then bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst is obtained in 40-60 DEG C of dry 12-24h.
2. the preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst according to claim 1, it is characterised in that：Institute
The mass ratio that feeds intake for carbon source, nitrogen source, zinc chloride and five hydrated basic magnesium carbonates stated is 1.1:0.297-1.16:3.3:1.1-
2.2。
3. the preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst according to claim 1, it is characterised in that：Institute
The inert gas stated is the one or more in nitrogen or argon gas.
4. the preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst according to claim 1, it is characterised in that：Institute
The acid solution stated is molar concentration 2mol/L hydrochloric acid solution.
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| CN201710399159.9A CN107282081A (en) | 2017-05-31 | 2017-05-31 | A kind of preparation method of bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097228A (en) * | 2017-12-11 | 2018-06-01 | 河南师范大学 | A kind of universality method that abundant Jie/macropore carbon oxygen reduction catalyst is prepared with single pore-foaming agent |
| CN108163854A (en) * | 2017-12-25 | 2018-06-15 | 河南师范大学 | For the universality preparation method of the porous C catalyst of organic pollutants in water body degradation |
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| CN108321403A (en) * | 2018-01-22 | 2018-07-24 | 厦门大学 | A kind of oxidation reduction catalyst and preparation method thereof |
| CN108469483A (en) * | 2018-03-23 | 2018-08-31 | 福州大学 | A kind of ultra-thin two-dimension carbonoxide nitrogen nanometer sheet and its preparation and application |
| CN109012729A (en) * | 2018-08-13 | 2018-12-18 | 河南师范大学 | A kind of preparation method of porous nitrogen fluorine codope carbon oxygen reduction catalyst |
| CN110690464A (en) * | 2019-10-22 | 2020-01-14 | 陕西科技大学 | Preparation method of transition metal and nitrogen co-doped porous carbon electrocatalyst |
| CN112678819A (en) * | 2021-01-27 | 2021-04-20 | 中南林业科技大学 | High-nitrogen-doped lignin-based porous carbon and preparation method thereof |
| CN113241452A (en) * | 2021-04-15 | 2021-08-10 | 国家电投集团氢能科技发展有限公司 | Three-dimensional porous platinum catalyst and preparation method thereof |
| CN113277509A (en) * | 2021-05-26 | 2021-08-20 | 中国科学技术大学 | Porous carbon nano material and preparation method thereof |
| CN113522334A (en) * | 2021-06-29 | 2021-10-22 | 河南师范大学 | Method for synthesizing shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst |
| CN114892196A (en) * | 2022-06-14 | 2022-08-12 | 南京大学 | Hierarchical pore material and preparation method and application thereof |
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| CN108097228A (en) * | 2017-12-11 | 2018-06-01 | 河南师范大学 | A kind of universality method that abundant Jie/macropore carbon oxygen reduction catalyst is prepared with single pore-foaming agent |
| CN108163854A (en) * | 2017-12-25 | 2018-06-15 | 河南师范大学 | For the universality preparation method of the porous C catalyst of organic pollutants in water body degradation |
| CN108321403A (en) * | 2018-01-22 | 2018-07-24 | 厦门大学 | A kind of oxidation reduction catalyst and preparation method thereof |
| CN108273538A (en) * | 2018-01-30 | 2018-07-13 | 中南民族大学 | A method of reduction N- heteroaryl hydrocarbon compounds prepare N- heterocycle compounds |
| CN108469483A (en) * | 2018-03-23 | 2018-08-31 | 福州大学 | A kind of ultra-thin two-dimension carbonoxide nitrogen nanometer sheet and its preparation and application |
| CN109012729A (en) * | 2018-08-13 | 2018-12-18 | 河南师范大学 | A kind of preparation method of porous nitrogen fluorine codope carbon oxygen reduction catalyst |
| CN110690464A (en) * | 2019-10-22 | 2020-01-14 | 陕西科技大学 | Preparation method of transition metal and nitrogen co-doped porous carbon electrocatalyst |
| CN110690464B (en) * | 2019-10-22 | 2022-07-29 | 陕西科技大学 | Preparation method of transition metal and nitrogen co-doped porous carbon electrocatalyst |
| CN112678819A (en) * | 2021-01-27 | 2021-04-20 | 中南林业科技大学 | High-nitrogen-doped lignin-based porous carbon and preparation method thereof |
| CN113241452A (en) * | 2021-04-15 | 2021-08-10 | 国家电投集团氢能科技发展有限公司 | Three-dimensional porous platinum catalyst and preparation method thereof |
| CN113277509A (en) * | 2021-05-26 | 2021-08-20 | 中国科学技术大学 | Porous carbon nano material and preparation method thereof |
| CN113522334A (en) * | 2021-06-29 | 2021-10-22 | 河南师范大学 | Method for synthesizing shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst |
| CN114892196A (en) * | 2022-06-14 | 2022-08-12 | 南京大学 | Hierarchical pore material and preparation method and application thereof |
| CN114892196B (en) * | 2022-06-14 | 2024-02-09 | 南京大学 | Hierarchical porous material and preparation method and application thereof |
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