CN110368978B - Titanium nitride hybrid carbon composite material and preparation method thereof - Google Patents
Titanium nitride hybrid carbon composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 229960003540 oxyquinoline Drugs 0.000 claims description 8
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000013110 organic ligand Substances 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 238000006722 reduction reaction Methods 0.000 abstract description 18
- 239000000446 fuel Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- CYKMNKXPYXUVPR-UHFFFAOYSA-N [C].[Ti] Chemical compound [C].[Ti] CYKMNKXPYXUVPR-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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 relates to a titanium nitride hybrid carbon composite material and a preparation method thereof, wherein a mixture consisting of an iron-organic complex, a titanium-containing compound and melamine is used as a precursor, and the precursor is subjected to high-temperature carbonization, acid washing and high-temperature nitridation treatment in sequence to prepare the titanium nitride hybrid carbon composite material, wherein carbon is iron and nitrogen co-doped porous carbon, titanium nitride nanoparticles are uniformly distributed in a porous carbon structure, the total doping amount of iron and nitrogen accounts for 0.5-5 wt% of the mass of the composite material, and the molar ratio of iron to nitrogen is 1: 2-8, the hybridized titanium nitride accounts for 3-15 wt% of the mass of the composite material. The invention has simple preparation process and cheap raw materials, shows high electrocatalytic activity when being used as a catalyst for the oxygen reduction reaction of the fuel cell, and has potential application value in the fields of low-temperature fuel cells and metal-air cells.
Description
Technical Field
The invention relates to a composite material and a preparation method thereof, in particular to a titanium nitride hybrid carbon composite material and a preparation method thereof.
Background
The energy crisis and environmental problems are increasingly prominent, the demand for fossil fuels and the emission of carbon dioxide are rapidly increasing, and the development of clean, efficient and low-carbon renewable energy sources is urgent. The hydrogen is used as a clean and high-energy secondary energy carrier, can be conveniently converted into heat and electricity, has high conversion efficiency, has wide sources, and is an important component of future energy.
The fuel cell has the characteristics of high energy conversion rate, low noise, high starting speed, simple and convenient structure and operation, no carbon dioxide emission, environmental friendliness and the like, and is one of important ways for realizing energy cleaning and low-carbon development. At present, widely used fuel cell catalysts are carbon-based catalysts, people utilize precursors of different carbons to form active sites of the catalysts by different doping or loading modes of active components, obtain various types of carbon composite materials, and the carbon composite materials can be used as fuel cell catalysts to obviously improve the electrocatalytic activity of the catalysts, but carbon carriers are easily oxidized and corroded in the fuel cell environment, so that the conductivity and the stability of the catalysts are reduced, and the performance of the fuel cells is reduced. Therefore, designing and preparing efficient, stable catalysts presents new challenges for fuel cell developers. Titanium nitride (TiN) has received much attention in the fuel cell field due to its high electrical conductivity and good oxidation resistance. A titanium nitride-graphene-carbon nanotube composite material is reported in an article J.Mater.chem.A,2013,1, 8007-one 8015, and is used as an oxygen reduction catalyst, wherein the composite material shows certain catalytic activity, but the oxygen reduction activity of the catalyst is low; a ChemSusChem 2013,6, 2016-2021 article reports a carbon-coated titanium nitride nanotube composite material, which has a unique one-dimensional hollow structure and higher conductivity, and the oxygen reduction catalytic activity of the composite material is obviously improved; the ChemElectrochem 2018,5, 2041-2049 article reports a cobalt-doped carbon-coated titanium nitride material, and the cobalt doping obviously improves the activity and stability of the catalyst. Although the carbon-titanium nitride composite materials reported above improve the oxygen reduction catalytic activity, the catalytic performance of the carbon-titanium nitride composite materials still has a certain difference from that of the commercial platinum-carbon catalyst, and needs to be further improved.
Disclosure of Invention
The invention aims to solve the problems and provides a titanium nitride hybrid carbon composite material, and the invention also aims to provide a preparation method of the titanium nitride hybrid carbon composite material. The composite material is prepared by compounding titanium nitride nanoparticles and carbon, and the titanium nitride hybrid carbon composite material is prepared by taking a mixture consisting of an iron-organic ligand, a titanium-containing compound and melamine as a precursor and sequentially carrying out high-temperature carbonization, acid pickling and high-temperature nitridation treatment processes, wherein the carbon is iron and nitrogen co-doped porous carbon, and the titanium nitride nanoparticles are uniformly distributed in a porous carbon structure. The invention has simple preparation process and cheap raw materials, shows high electrocatalytic performance when being used as a catalyst for the oxygen reduction reaction of the fuel cell, and has potential application value in the fields of low-temperature fuel cells and metal-air cells.
The technical scheme of the invention is as follows: a titanium nitride hybrid carbon composite characterized by: the composite material is formed by compounding titanium nitride nanoparticles and iron and nitrogen co-doped porous carbon, wherein the titanium nitride nanoparticles are uniformly and stably dispersed in the porous carbon, the hybridized titanium nitride accounts for 3-15% of the mass of the composite material, the iron and nitrogen doped total amount accounts for 0.5-5% of the mass of the composite material, and the molar ratio of iron to nitrogen is 1: 2-8.
The invention also provides a method for preparing the titanium nitride hybrid carbon composite material, which comprises the following specific preparation steps:
(1) dissolving a certain amount of ferric salt in a solvent, then adding an organic ligand, uniformly stirring, sequentially adding melamine and a titanium-containing compound, continuously stirring to be in a gel state, drying, and grinding to obtain precursor powder;
(2) putting the precursor powder into a tube furnace, and carbonizing at high temperature in an inert atmosphere to obtain black powder;
(3) treating carbonized black powder with acid solution under heating condition, centrifuging, washing, and drying;
(4) and (3) putting the dried sample into a tubular furnace, and performing high-temperature nitridation treatment in an ammonia atmosphere to obtain the titanium nitride hybrid carbon composite material.
Preferably, the iron salt in the step (1) is one of ferric chloride, ferrous sulfate or ferric nitrate; the solvent is one of ethanol, water or methanol; the organic ligand is one of phenanthroline or 8-hydroxyquinoline; the titanium-containing compound is one of titanyl sulfate or titanium tetraisopropoxide.
Preferably, in the step (1), the molar ratio of the ferric salt to the organic ligand to the melamine to the titanium-containing compound to the solvent is 1: (1-6): (10-30): (2-10): (200-500).
The temperature of the high-temperature carbonization in the step (2) is preferably 700-1000 ℃, and the carbonization time is preferably 1-5 hours.
Preferably, the acid solution in the step (3) is sulfuric acid or hydrochloric acid solution; the concentration of the acid liquor is 0.5-2.0 mol/L; the mass ratio of the black powder to the acid liquor is 1 (80-120).
Preferably, the treatment temperature in the step (3) is 50 to 100 ℃ and the treatment time is 5 to 12 hours.
The temperature of the high-temperature nitridation in the step (4) is preferably 700-1000 ℃, and the nitridation time is preferably 1-5 hours.
Has the advantages that:
the preparation method is simple in preparation process and low in raw material cost, titanium compounds and high-nitrogen-content compounds are uniformly doped in the iron-organic metal complex, and the titanium nitride hybrid carbon composite material is obtained through carbonization, acid washing and nitridation treatment processes, wherein titanium nitride nanoparticles are uniformly distributed in an iron and nitrogen co-doped porous carbon structure and used as a fuel cell oxygen reduction reaction catalyst, so that the titanium nitride hybrid carbon composite material has high electrocatalysis performance and has potential application value in the fields of low-temperature fuel cells and metal-air cells.
Drawings
FIG. 1 Transmission Electron micrograph of catalyst A prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention: example 1
(1) Dissolving 0.55g of ferric chloride in 20.0g of ethanol, then adding 1.45g of 8-hydroxyquinoline, uniformly stirring, sequentially adding 3.78g of melamine and 1.60g of titanyl sulfate, continuously stirring until the mixture is gelatinous, drying, and grinding to obtain precursor powder; wherein the weight ratio of ferric chloride: 8-hydroxyquinoline: melamine: titanyl sulfate: the molar ratio of ethanol to ethanol is 1:5:15:5: 210;
(2) carbonizing the precursor powder in a tubular furnace at the high temperature of 850 ℃ for 2 hours in a nitrogen atmosphere to obtain black powder;
(3) treating 0.1g of the black powder with 9g of sulfuric acid solution (1.1M) at 80 deg.C for 8 hr, centrifuging, washing, and drying;
(4) and (2) putting the dried sample into a tube furnace, and carrying out nitridation treatment at the high temperature of 900 ℃ for 1 hour in an ammonia atmosphere to obtain a titanium nitride hybrid carbon composite material, wherein the titanium nitride hybrid carbon composite material is marked as a catalyst A, the total doping amount of iron and nitrogen is 1.9 wt% of the mass of the catalyst A, and the molar ratio of iron to nitrogen is 1: titanium nitride accounted for 5.8 wt.% of the mass of catalyst a. The transmission electron microscope image of the prepared catalyst a is shown in fig. 1, and it can be seen from the image that the titanium nitride nanoparticles are uniformly dispersed in the structure of the porous carbon.
(5) Testing the catalytic performance of oxygen reduction: the half-wave potential for oxygen reduction of catalyst a was 0.84V relative to the reversible hydrogen electrode.
Example 2:
(1) dissolving 0.56g of ferrous sulfate in 10.8g of water, then adding 0.72g of phenanthroline, uniformly stirring, sequentially adding 3.02g of melamine and 0.96g of titanyl sulfate, continuously stirring to form gel, drying, and grinding to obtain precursor powder; wherein, the ferrous sulfate: phenanthroline: melamine: titanyl sulfate: the molar ratio of water to water is 1:2:12:3: 300;
(2) carbonizing the precursor powder in a tube furnace at 750 ℃ for 4 hours in an argon atmosphere to obtain black powder;
(3) treating 0.1g carbonized black powder with 10g sulfuric acid solution (0.6M) at 90 deg.C for 6 hr, centrifuging, washing, and drying;
(4) and (3) putting the dried sample into a tube furnace, and carrying out nitridation treatment at the high temperature of 850 ℃ for 2 hours in an ammonia atmosphere to obtain a titanium nitride hybrid carbon composite material, wherein the titanium nitride hybrid carbon composite material is marked as a catalyst B, the total doping amount of iron and nitrogen is 3.2 wt% of the mass of the catalyst B, and the molar ratio of iron to nitrogen is 1: titanium nitride accounted for 4.1 wt.% of the mass of catalyst B. From the transmission electron microscope image of the prepared catalyst, it can be seen that the titanium nitride nanoparticles are uniformly dispersed in the structure of the porous carbon.
(5) Testing the catalytic performance of oxygen reduction: the half-wave potential for oxygen reduction of catalyst B was 0.85V relative to the reversible hydrogen electrode.
Example 3:
(1) dissolving 0.81g of ferric nitrate in 26.9g of methanol, then adding 0.87g of 8-hydroxyquinoline, uniformly stirring, sequentially adding 5.04g of melamine and 3.98g of titanium tetraisopropoxide, continuously stirring until the mixture is gelatinous, drying, and grinding to obtain precursor powder; wherein the weight ratio of ferric nitrate: 8-hydroxyquinoline: melamine: titanium tetraisopropoxide: the molar ratio of methanol to methanol is 1:3:20:7: 420;
(2) carbonizing the precursor powder in a tubular furnace at a high temperature of 950 ℃ for 3 hours in a nitrogen atmosphere to obtain black powder;
(3) treating 0.1g carbonized black powder with 11g hydrochloric acid solution (1.6M) at 60 deg.C for 11 hr, centrifuging, washing, and drying;
(4) and (3) putting the dried sample into a tube furnace, and carrying out nitridation treatment at 800 ℃ for 3 hours in an ammonia atmosphere to obtain a titanium nitride hybrid carbon composite material, wherein the titanium nitride hybrid carbon composite material is marked as a catalyst C, the total doping amount of iron and nitrogen is 4.7 wt% of the mass of the catalyst C, and the molar ratio of iron to nitrogen is 1: and 7, the titanium nitride accounts for 7.7 wt% of the mass of the catalyst C. From the transmission electron micrograph of the prepared catalyst, it can be seen that the titanium nitride nanoparticles are uniformly dispersed in the structure of the porous carbon.
(5) Testing the catalytic performance of oxygen reduction: the half-wave potential for oxygen reduction of catalyst C was 0.84V versus the reversible hydrogen electrode.
Example 4:
(1) dissolving 0.56g of ferrous sulfate in 44.2g of ethanol, then adding 1.44g of phenanthroline, uniformly stirring, sequentially adding 6.80g of melamine and 2.88g of titanyl sulfate, continuously stirring to form gel, drying, and grinding to obtain precursor powder; wherein, the ferrous sulfate: phenanthroline: melamine: titanyl sulfate: the molar ratio of ethanol to ethanol is 1:4:27:9: 480;
(2) carbonizing the precursor powder in a tube furnace at 900 ℃ in an argon atmosphere for 2.5 hours to obtain black powder;
(3) treating 0.1g carbonized black powder with 10g hydrochloric acid solution (1.8M) at 70 deg.C for 7 hr, centrifuging, washing, and drying;
(4) and (3) putting the dried sample into a tube furnace, and carrying out nitriding treatment at the high temperature of 750 ℃ for 4 hours in an ammonia atmosphere to obtain a titanium nitride hybrid carbon composite material, wherein the titanium nitride hybrid carbon composite material is marked as a catalyst D, the total doping amount of iron and nitrogen is 0.8 wt% of the mass of the catalyst D, and the molar ratio of iron to nitrogen is 1: titanium nitride accounted for 9.3 wt.% of the mass of catalyst D. From the transmission electron microscope image of the prepared catalyst, it can be seen that the titanium nitride nanoparticles are uniformly dispersed in the structure of the porous carbon.
(5) Testing the catalytic performance of oxygen reduction: the half-wave potential for oxygen reduction of catalyst D was 0.85V relative to the reversible hydrogen electrode.
Comparative example 1:
(1) dissolving 0.55g of ferric chloride in 20.0g of ethanol, then adding 1.45g of 8-hydroxyquinoline, uniformly stirring to form gel, drying, and grinding to obtain precursor powder; wherein the weight ratio of ferric chloride: 8-hydroxyquinoline: the molar ratio of ethanol is 1:5: 210;
(2) carbonizing the precursor powder in a tubular furnace at a high temperature of 850 ℃ for 2 hours in a nitrogen atmosphere to obtain black powder;
(3) treating 0.1g carbonized black powder with 9g sulfuric acid solution (1.1M) at 80 deg.C for 8 hr, centrifuging, washing, and drying;
(4) and (2) putting the dried sample into a tube furnace, and carrying out nitridation treatment at the high temperature of 900 ℃ for 1 hour in the atmosphere of ammonia gas to obtain a titanium nitride hybrid carbon composite material, wherein the titanium nitride hybrid carbon composite material is marked as a catalyst X, the total doping amount of iron and nitrogen is 3.2 wt% of the mass of the catalyst C, and the molar ratio of iron to nitrogen is 1: 3.5.
(5) testing the catalytic performance of oxygen reduction: the half-wave potential for oxygen reduction of the catalyst X was 0.52V with respect to the reversible hydrogen electrode.
The half-wave potentials of the electrocatalytic oxygen reduction reactions of the catalysts prepared in the above examples and comparative examples are shown in table 1:
TABLE 1 half-wave potential of the catalyst electrocatalytic oxygen reduction reaction
| Catalyst and process for preparing same | A | B | C | D | X |
| Half-wave potential (V) | 0.84 | 0.85 | 0.84 | 0.85 | 0.52 |
Claims (8)
1. A titanium nitride hybrid carbon composite characterized by: the composite material is formed by compounding titanium nitride nanoparticles with iron and nitrogen codoped porous carbon, the titanium nitride nanoparticles are uniformly and stably dispersed in the porous carbon, wherein hybridized titanium nitride accounts for 3-15% of the mass of the composite material, the iron and nitrogen doping total amount accounts for 0.5-5% of the mass of the composite material, and the molar ratio of iron to nitrogen is 1: 2-8.
2. A method for preparing the titanium nitride hybrid carbon composite material of claim 1, which comprises the following specific steps:
(1) dissolving a certain amount of ferric salt in a solvent, then adding an organic ligand, uniformly stirring, sequentially adding melamine and a titanium-containing compound, continuously stirring to be in a gel state, drying, and grinding to obtain precursor powder;
(2) putting the precursor powder into a tube furnace, and carbonizing at high temperature in an inert atmosphere to obtain black powder;
(3) treating carbonized black powder with acid solution under heating condition, centrifuging, washing, and drying;
(4) and (3) putting the dried sample into a tubular furnace, and performing high-temperature nitridation treatment in an ammonia atmosphere to obtain the titanium nitride hybrid carbon composite material.
3. The method according to claim 2, wherein the iron salt in step (1) is one of ferric chloride, ferrous sulfate or ferric nitrate; the solvent is one of ethanol, water or methanol; the organic ligand is one of phenanthroline or 8-hydroxyquinoline; the titanium-containing compound is one of titanyl sulfate or titanium tetraisopropoxide.
4. The process according to claim 2, wherein the molar ratio of the iron salt, the organic ligand, the melamine, the titanium-containing compound and the solvent in step (1) is 1: (1-6): (10-30): (2-10): (200-500).
5. The method as set forth in claim 2, wherein the temperature of the high-temperature carbonization in the step (2) is 700 ℃ and 1000 ℃ and the carbonization time is 1 to 5 hours.
6. The method according to claim 2, wherein the acid solution in the step (3) is sulfuric acid or hydrochloric acid solution; the concentration of the acid liquor is 0.5-2.0 mol/L; the mass ratio of the black powder to the acid liquor is 1 (80-120).
7. The method according to claim 2, wherein the treatment temperature in the step (3) is 50 to 100 ℃ and the treatment time is 5 to 12 hours.
8. The method as claimed in claim 2, wherein the temperature of the high temperature nitridation in step (4) is 700 ℃ and 1000 ℃, and the nitridation time is 1-5 hours.
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| CN115367726A (en) * | 2021-05-19 | 2022-11-22 | 北京化工大学 | Oxygen-doped titanium nitride hybridized and nitrogen-doped porous carbon material and preparation method and application thereof |
| CN112820885A (en) * | 2020-12-31 | 2021-05-18 | 昆明理工大学 | Preparation method of nitrogen-doped carbon-coated titanium nitride nanoparticle composite material |
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