CN103613087B - Method for preparing nitrogen carbon material by using animal waste, and application of nitrogen carbon material as oxygen reduction catalyst - Google Patents
Method for preparing nitrogen carbon material by using animal waste, and application of nitrogen carbon material as oxygen reduction catalyst Download PDFInfo
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- CN103613087B CN103613087B CN201310580946.5A CN201310580946A CN103613087B CN 103613087 B CN103613087 B CN 103613087B CN 201310580946 A CN201310580946 A CN 201310580946A CN 103613087 B CN103613087 B CN 103613087B
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- carbon material
- nitrogen
- nitrogen carbon
- oxygen reduction
- animal excrement
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- 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 provides a method for preparing a nitrogen carbon material by using animal waste, and belongs to the technical field of a novel material. The method comprises the following steps: by taking the animal waste as a raw material, carrying out primary carbonization treatment under protection of nitrogen after naturally airing, so as to obtain a carbon material; crushing the carbon material to be added in a salpeter solution; carrying out activating treatment for 20-24 hours under agitation; washing into a neutral state by using deionized water, baking, and then adding to an FeCl3/C2H5OH solution to agitate for 0.5-1 hour; further carrying out ball milling after directly drying; finally, carrying out secondary carbonization treatment under protection of nitrogen, so as to obtain the nitrogen carbon material. The material is high in nitrogen content, and displays better oxygen reduction performance when being applied to oxygen reduction reaction of a fuel cell as the oxygen reduction catalyst. Therefore, the nitrogen carbon material can be applied to the oxygen reduction reaction of the fuel cell as the oxygen reduction catalyst.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of preparation method of nitrogen carbon material, particularly relate to a kind of method utilizing animal excrement to prepare nitrogen carbon material; The invention still further relates to this nitrogen carbon material as oxygen reduction catalyst application in a fuel cell.
Background technology
In the face of day by day serious energy dilemma and problem of environmental pollution, research green is all being devoted to, continuable energy resource system in countries in the world.Fuel cell as a kind of be directly the power generation assembly of electric energy by the mode of electrochemical reaction by the chemical energy in fuel, there is the outstanding advantages such as environmental friendliness, structure is simple, energy transformation ratio is high, can effectively solve the problems such as current energy shortage and environmental pollution, thus studied widely and there is very wide application prospect.But fuel cell oxygen reduction catalyst directly affects performance and the life-span of fuel cell.Current carbon carries platinum and platinum alloy is widely used as low-temperature fuel cell oxygen reduction catalyst due to its superior catalytic activity and stability, but noble metal platinum is because it is expensive, scarcity of resources, the serious widespread use constraining fuel cell.Therefore, select cheap, be easy to get, free of contamination material is the problem that development fuel cell primarily solves as low-temperature fuel cell oxygen reduction catalyst material.
Animal excrement are swill movements of animal.Ight soil is unabsorbed swill part.For unabsorbed residue fraction, digestive tube then by large intestine, excretes from anus with stool form.Be protein mostly in animal excrement, inorganics, fat, indigested foodstuff fibre, dewatered Digestive system are remaining and the cell that comes off from enteron aisle and the bacterium died, and also have vitamin K, vitamins B etc.At present, the industrial applications for animal excrement mainly contains several direction below: one is make organic fertilizer, and two is make animal-feed, and three is fall as fuel consumption.Owing to containing a large amount of carbon, nitrogen element in animal excrement, therefore, using animal excrement as Carbon and nitrogen sources, through high-temperature calcination process, be made into the carbon material that nitrogen content is higher, can not only turn waste into wealth, but also solve Low-Temperature Fuel Cell Catalysts problem with high costs, the present situation alleviating our national resources shortage is had like a point important meaning.
Summary of the invention
The object of this invention is to provide a kind of method utilizing animal excrement to prepare nitrogen carbon material;
Another object of the present invention is to provide the application of a kind of nitrogen carbon material utilizing animal excrement to prepare as oxygen reduction catalyst.
One, the preparation of nitrogen carbon material
The present invention utilizes animal excrement to prepare the method for nitrogen carbon material, is by after animal excrement natural air drying, and first carrying out a carbonizing treatment under nitrogen protection obtains carbon material; Carbon material ball mill joins in salpeter solution after pulverizing, and stirs lower activation treatment 20 ~ 24h, washes into neutral, oven dry with deionized water; Then FeCl is joined
3/ C
2h
5stir process 0.5 ~ 1 h in OH solution, continues ball milling 6 ~ 8 h, finally carries out secondary carbonizing treatment under nitrogen protection, obtain nitrogen carbon material after convection drying.
The temperature of a described carbonizing treatment is at 500 ~ 1000 DEG C, and calcination time is 6 ~ 8 h.
The concentration of described salpeter solution is 1 ~ 2 mol/L; The mass volume ratio of a carbonization gained carbon material and salpeter solution is 1:20 ~ 1:400 g/mL.
Described FeCl
3/ C
2h
5the concentration of OH solution is 0.5 ~ 3 mol/L; A carbonization gained carbon material and FeCl
3/ C
2h
5the mass volume ratio of OH solution is 1:5 ~ 1:100 g/mL.
Described secondary carbonizing treatment calcines 2 ~ 6 h at 500 ~ 1000 DEG C.
Described drying carries out in air dry oven at 50 ~ 80 DEG C.
The animal waste that animal excrement of the present invention are mainly collected, the i.e. ight soil of the domestic animal such as ox, sheep, horse, pig, chicken, duck.
Two, the stuctures and properties of nitrogen carbon material
Fig. 1 be the nitrogen carbon material prepared of the present invention with the Raman comparison diagram of business XC-72 carbon dust.As can be seen from Figure 1, at 1304 cm
-1with 1595 cm
-1having there is the characteristic peak of carbon material in place, illustrates that this carbon material exists with greying state respectively.
Fig. 2 is the scanning electron microscope (SEM) photograph of nitrogen carbon material prepared by the present invention.As can be seen from Figure 2, the nitrogen carbon material that prepared by the present invention presents bulk morphologies.
Fig. 3 hydrogen reduction graphic representation that to be the nitrogen carbon material prepared of the present invention react as the catalytic oxidation-reduction of oxygen reduction catalyst and business XC-72 carbon dust.As can be seen from Figure 3, this nitrogen carbon material as catalyzer compared with business XC-72 carbon dust, take-off potential and half-wave potential have been shuffled 148 mV and 95 mV respectively, illustrate that this nitrogen carbon material is significantly improved than traditional commerce XC-72 carbon dust half-wave potential and take-off potential, show better hydrogen reduction performance.Therefore, can be used as oxygen reduction catalyst to be applied in the hydrogen reduction catalyzed reaction of fuel cell.
Accompanying drawing explanation
Fig. 1 is the Raman comparison diagram of the nitrogen carbon material prepared of the present invention and business XC-72 carbon dust;
Fig. 2 is the scanning electron microscope (SEM) photograph of nitrogen carbon material prepared by the present invention;
Fig. 3 is the hydrogen reduction graphic representation that the catalytic oxidation-reduction of the nitrogen carbon material prepared of the present invention and business XC-72 carbon dust reacts.
Embodiment
Below by specific embodiment, the preparation of nitrogen carbon material of the present invention and hydrogen reduction catalytic performance are described further.
embodiment 1
By the cow dung natural air drying at normal temperatures collected, in tube furnace, nitrogen protection, 700 DEG C of high-temperature calcination 2h, put into ball mill ball milling 6 h to pulverizing.Take 1g sample, add 20 mL salpeter solutions (2mol/L), magnetic agitation 24 h, washes into neutrality with deionized water, dries in the bellows of 60 DEG C; Then the FeCl of 5mL is added
3/ C
2h
5oH solution (3mol/L), stirs 0.5 ~ 1 h, in the bellows of 60 DEG C, continues ball milling after drying; Last in tube furnace, nitrogen protection, 700 DEG C of pyroprocessing 2 h, obtain nitrogen carbon material.
Found by hydrogen reduction test, this nitrogen carbon material, as the oxygen reduction catalyst of fuel cell electrode, have been shuffled 30 mV and 34 mV respectively compared with the take-off potential of business XC-72 carbon dust oxygen reduction reaction and half-wave potential.
embodiment 2
By the cow dung natural air drying at normal temperatures collected, being placed in tube furnace, nitrogen protection, 800 DEG C of high-temperature calcination 2h, putting into ball mill ball milling 6 h to pulverizing.Take 1g sample, add 50 mL salpeter solutions (2mol/L), magnetic agitation 24 h, washes into neutrality with deionized water, dries in the bellows of 60 DEG C; Then the FeCl of 10mL is added
3/ C
2h
5oH solution (2mol/L), stirs 0.5 ~ 1 h, in the bellows of 60 DEG C, continues ball milling after drying; Last in tube furnace, nitrogen protection, 800 DEG C of pyroprocessing 2 h, obtain nitrogen carbon material.
Found by hydrogen reduction test, this nitrogen carbon material, as the oxygen reduction catalyst of fuel cell electrode, have been shuffled 96 mV and 88 mV respectively compared with the take-off potential of business XC-72 carbon dust oxygen reduction reaction and half-wave potential.
embodiment 3
By the cow dung natural air drying at normal temperatures collected, being placed in tube furnace, nitrogen protection, 900 DEG C of high-temperature calcination 2h, putting into ball mill ball milling 6 h to pulverizing.Take 1g sample, add 100 mL salpeter solutions (1mol/L), magnetic agitation 24 h, washes into neutrality with deionized water, dries in the bellows of 60 DEG C; Then the FeCl of 40mL is added
3/ C
2h
5oH solution (0.5mol/L), stirs 0.5 ~ 1 h, in the bellows of 60 DEG C, continues ball milling after drying; Last in tube furnace, nitrogen protection, 900 DEG C of pyroprocessing 2 h, obtain nitrogen carbon material.
Found by hydrogen reduction test, this nitrogen carbon material, as the oxygen reduction catalyst of fuel cell electrode, have been shuffled 46 mV and 58 mV respectively compared with the take-off potential of business XC-72 carbon dust oxygen reduction reaction and half-wave potential.
embodiment 4
By the cow dung natural air drying at normal temperatures collected, being placed in tube furnace, nitrogen protection, 1000 DEG C of high-temperature calcination 2h, putting into ball mill ball milling 6 h to pulverizing.Take 1g sample, add 100 mL salpeter solutions (1.5mol/L), magnetic agitation 24 h, washes into neutrality with deionized water, dries in the bellows of 60 DEG C; Then the FeCl of 80mL is added
3/ C
2h
5oH solution (2mol/L), stirs 0.5 ~ 1 h, in the bellows of 60 DEG C, continues ball milling after drying; Last in tube furnace, nitrogen protection, 1000 DEG C of pyroprocessing 2 h, obtain nitrogen carbon material.
Found by hydrogen reduction test, this nitrogen carbon material, as the oxygen reduction catalyst of fuel cell electrode, have been shuffled 36 mV and 18 mV respectively compared with the take-off potential of business XC-72 carbon dust oxygen reduction reaction and half-wave potential.
embodiment 5
By the sheep excrement natural air drying at normal temperatures collected, being placed in tube furnace, nitrogen protection, 800 DEG C of high-temperature calcination 2h, putting into ball mill ball milling 6 h to pulverizing.Take 1g sample, add 50 mL salpeter solutions (2mol/L), magnetic agitation 24 h, washes into neutrality with deionized water, dries in the bellows of 60 DEG C; Then the FeCl of 10mL is added
3/ C
2h
5oH solution (2mol/L), stirs 0.5 ~ 1 h, in the bellows of 60 DEG C, continues ball milling after drying; Last in tube furnace, nitrogen protection, 800 DEG C of pyroprocessing 2 h, obtain nitrogen carbon material.
Found by hydrogen reduction test, this nitrogen carbon material, as the oxygen reduction catalyst of fuel cell electrode, have been shuffled 96 mV and 88 mV respectively compared with the take-off potential of business XC-72 carbon dust oxygen reduction reaction and half-wave potential.
Claims (7)
1. utilizing animal excrement to prepare the method for nitrogen carbon material, is by after animal excrement natural air drying, and first carrying out a carbonizing treatment under nitrogen protection obtains carbon material; Carbon material ball mill joins in salpeter solution after pulverizing, and stirs lower activation treatment 20 ~ 24h, washes into neutral, oven dry with deionized water; Then FeCl is joined
3/ C
2h
5stir process 0.5 ~ 1 h in OH solution, continues ball milling 6 ~ 8 h, finally carries out secondary carbonizing treatment under nitrogen protection, obtain nitrogen carbon material after convection drying.
2. utilize animal excrement to prepare the method for nitrogen carbon material as claimed in claim 1, it is characterized in that: a carbonizing treatment calcines 6 ~ 8 h at 500 ~ 1000 DEG C.
3. utilize animal excrement to prepare the method for nitrogen carbon material as claimed in claim 1, it is characterized in that: the concentration of described salpeter solution is 1 ~ 2 mol/L.
4. as described in claim 1, utilize animal excrement to prepare the method for nitrogen carbon material, it is characterized in that: the mass volume ratio of a carbonization gained carbon material and salpeter solution is 1:20 ~ 1:400 g/mL.
5. utilize animal excrement to prepare the method for nitrogen carbon material as claimed in claim 1, it is characterized in that: FeCl
3/ C
2h
5the concentration of OH solution is 0.5 ~ 3 mol/L.
6. utilize animal excrement to prepare the method for nitrogen carbon material as claimed in claim 1, it is characterized in that: a carbonization gained carbon material and FeCl
3/ C
2h
5the mass volume ratio of OH solution is 1:5 ~ 1:100 g/mL.
7. utilize animal excrement to prepare the method for nitrogen carbon material as claimed in claim 1, it is characterized in that: secondary carbonizing treatment calcines 2 ~ 6 h at 500 ~ 1000 DEG C.
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| CN103613087B true CN103613087B (en) | 2015-04-08 |
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| CN103992144B (en) * | 2014-05-20 | 2016-03-30 | 中国科学技术大学 | A kind of method being prepared nitrogenous carbon material by biomass pyrolytic carbonization |
| CN108545716A (en) * | 2018-06-28 | 2018-09-18 | 普定县信义农业开发有限公司 | A kind of carbon nano-particle material |
| CN108892120A (en) * | 2018-06-28 | 2018-11-27 | 普定县石阶农业开发有限公司 | The method that one boar factory discards excrement green circulatory |
| CN110801855A (en) * | 2018-08-06 | 2020-02-18 | 北京大学深圳研究生院 | Preparation method and application of transition metal and nitrogen co-doped carbon material |
| CN112062120A (en) * | 2020-09-18 | 2020-12-11 | 中国石油大学(华东) | Preparation method and application of hard carbon |
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| US7524795B1 (en) * | 2004-02-20 | 2009-04-28 | The United States Of America As Represented By The Secretary Of The Agriculture | Activated carbons from animal manure |
| CN102614904B (en) * | 2012-01-12 | 2014-04-09 | 西北师范大学 | Graphitized nitrogen-containing carbon material and application of same as electrocatalyst carrier |
| CN103007975B (en) * | 2012-12-04 | 2014-07-02 | 西北师范大学 | Preparation of nitrogen-containing carbon material and application thereof as oxygen-reduction electrocatalyst in fuel cell |
| CN103212430B (en) * | 2013-04-08 | 2015-04-08 | 西北师范大学 | Method for synthesizing nitrogen-carbon nonmetal reducing catalyst by utilizing concentrated sulfuric acid carbonization |
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