CN108328599A - A method of nitrogen-doped porous carbon material is prepared based on citric acid transition/alkali metal complex salt - Google Patents
A method of nitrogen-doped porous carbon material is prepared based on citric acid transition/alkali metal complex salt Download PDFInfo
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Abstract
The present invention provides a kind of method preparing nitrogen-doped porous carbon material based on citric acid transition/alkali metal complex salt, and preparation method is：Using citric acid transition/alkali metal complex salt as carbon source, 1 is heat-treated in the atmosphere containing ammonia, at 500 1000 DEG C for 24 hours；Metal impurities are removed with acid elution after cooling, is washed with water and washs the extra acid solution of removal to neutrality, the porous carbon materials of N doping are obtained after dry.Preparation method of the present invention is simple, is not necessarily to pore-foaming agent, is easily operated, raw material sources are wide, environmentally protective, of low cost, it is advantageously implemented fairly large industrialized production, the nitrogen-doped porous carbon material of preparation has multi-stage pore structure, laminated structure containing hole and apparent graphite lattice fringe, large specific surface area, and contain abundant nitrogen hetero atom, oxygen reduction activity point is more, with good electrocatalytic oxidation reducing property and stability, it can be used for preparing electrocatalytic oxidation reducing electrode and other catalyst carriers.
Description
Technical field
The invention belongs to inorganic material to synthesize field, and in particular to one kind being based on citric acid transition/alkali metal complex salt
The method for preparing nitrogen-doped porous carbon material.
Background technology
Proton Exchange Membrane Fuel Cells is not generated pollution and is had received widespread attention due to its energy conversion rate height, when power generation.
However, since cell cathode oxygen reduction reaction is slow, the output power of fuel cell is constrained, needs catalyst to improve reaction
For rate to improve cell output, catalyst usually used at present is the PtC catalyst containing a large amount of platinum (Pt) metal.By
Pt metal abundancies are low in the earth's crust, expensive, and the shortcomings of easily poisoning, the commercial scale for seriously constraining fuel cell is answered
With.Solution mainly has following two approach：(1) it is reduced with lowpriced metal alloy and by area load by preparing Pt
Pt dosages.Such as the synthesis PtNi hollow Nanos alloy such as Shaofang Fu (Journal of Materials Chemistry
A,2016,4,8755)；Leyan Xiong etc. are in the surfaces WC/C deposition Pt (Journal of The Electr DEG C hemical S
℃iety,2015,162(4),F468).(2) non-Pt classes oxygen reduction electro-catalyst is developed.Common are transition metal carbide,
Nitride, chalcogen compound；Cobalt, Mn oxide, perovskite structure oxide, spinel strucutre oxides；Dopant impurity atoms
Carbon material (Angewandte Chemie International Edition, 2016,55,2650).In these solutions
In, since nitrogen-doping porous carbon materials have high-specific surface area, abundant pore passage structure, excellent electrocatalytic oxidation reproducibility
It can have received widespread attention.
The preparation method of nitrogen-doped porous carbon material is mainly the following method at present：(1) direct carborization.With nitrogenous
Organic compound is carbon source, under template action high temperature cabonization (Journal of Materials Chemistry A, 2017,
41,21709).This method is more demanding to presoma, needs synthesis or higher to purity requirement, of high cost, is unfavorable for scale
Metaplasia is produced.(2) chemical vapour deposition technique, by the organic matter of Nitrogen element, vapor deposition growth obtains the more of N doping in template
Hole carbon material (Microporous and Mesoporous Materials, 2016,225,224).This method is to equipment gas
Close property requires high, equipment costliness, and it is few to prepare sample size, it is difficult to realize fairly large production.(3) metal complexation reaction method,
Metal organic frame is synthesized by metal complexation reaction, be then carbonized (Applied Catalysis B- under an inert atmosphere
Environmental,2017,218,260).But the structure of metal complex and preparation process are generally complex, and match
Body is expensive, is difficult to be popularized in scale prepares use.
Citric acid metal salt is widely used in the fields such as food, medicine, chemical industry, herding, is a kind of chemical industry of cheap green
Raw material, preparing carbon material as carbon source using it has many advantages, such as environmentally protective, is produced on a large scale.
Invention content
It is prepared based on citric acid transition/alkali metal complex salt in view of the above-mentioned problems, the object of the present invention is to provide one kind
The method of nitrogen-doped porous carbon material is prepared nitrogen through high temperature pyrolysis as carbon source using citric acid transition/alkali metal complex and mixes
Miscellaneous porous carbon materials, this method process conditions are simple, it is environmentally protective, of low cost, be easy to mass production.
To achieve the above object, the technical scheme is that：
A method of nitrogen-doped porous carbon material being prepared based on citric acid transition/alkali metal complex salt, including following
Step：It is hot at 500-1000 DEG C under the atmosphere containing ammonia using citric acid transition/alkali metal complex salt as carbon source
Solution reaction 1-24h, takes out, and metal impurities are removed with acid solution wash, then is freeze-dried after washing the extra acid of removal, finally obtains
Nitrogen-doped porous carbon material.
As a preferred embodiment of the above technical solution, the citric acid transition/alkali metal complex salt is ironic citrate, citric acid
Cobalt, citric acid nickel, copper citrate, zinc citrate, aluminium citrate, bismuth citrate, sodium citrate, potassium citrate, magnesium citrate, lemon
One or more mixtures of lemon acid calcium, barium citrate.
As a preferred embodiment of the above technical solution, the gas containing ammonia is that ammonia, ammonia argon mixture gas or ammonia nitrogen are mixed
Close gas.
As a preferred embodiment of the above technical solution, the heating rate of the pyrolytic reaction is 1-10 DEG C/min.
As a preferred embodiment of the above technical solution, the acid solution is hydrochloric acid, nitric acid or sulfuric acid.
As a preferred embodiment of the above technical solution, a concentration of 0.5-10mol/L of the acid solution.
As a preferred embodiment of the above technical solution, the nitrogen-doped porous carbon material is used as electrocatalytic oxidation reducing catalyst.
As a preferred embodiment of the above technical solution, described one kind preparing nitrogen based on citric acid transition/alkali metal complex salt
The method of doped porous carbon material, specifically includes following steps：
(1) by ironic citrate, citric acid cobalt, citric acid nickel, copper citrate, zinc citrate, aluminium citrate, bismuth citrate,
Sodium citrate, potassium citrate, magnesium citrate, calcium citrate, barium citrate one or more mixtures be placed in resistance tube furnace
Or in microwave tube type oven, under the atmosphere containing ammonia, it is warming up to 500-1000 DEG C with the rate of 1-10 DEG C/min, pyrolysis is anti-
1-24h is answered, after reaction, takes out, obtains intermediate product；
(2) intermediate product obtained by step (1) is washed in the hydrochloric acid, nitric acid or aqueous sulfuric acid of 0.5-10mol/L
Metal impurities are removed, then after the extra acid of washing removal, freeze-drying finally obtains nitrogen-doped porous carbon material.
Compared with prior art, the invention has the advantages that：
(1) present invention using citric acid transition/alkali metal complex salt prepares nitrogen-doped porous carbon material as raw material, and existing
Method compares, and citric acid transition/alkali metal complex salt produces corresponding gold during containing pyrolysis decomposition under ammonia atmosphere
Belong to oxide, metal nitride or metal impurities, abundant hole can be formed in situ after peracid solutions etch and remove these impurity
Hole structure need not add additional pore creating material or template compared with the conventional method, simplify production technology, and be prepared
Nitrogen-doped porous carbon material makes it have catalytic oxidation-reduction performance since the doping of nitrogen introduces oxygen reduction activity point,
And there is large surface area and relatively rich grade pore space structure, be conducive to coming into full contact with for electrolyte and active point, promote electric
Catalytic activity.
(2) nitrogen-doped porous carbon material that the present invention is prepared using citric acid transition/alkali metal complex salt as raw material as
Electrocatalytic oxidation reducing catalyst has excellent hydrogen reduction catalytic performance and stability, is better than the anti methanol toxication of PtC catalyst
Property, have broad application prospects in electrocatalytic oxidation reduction field, and raw material citric acid transition/alkali metal complex salt extensive use
In fields such as food, medicine, chemical industry, herdings, there is environmentally protective, cheap and easy to get feature, the use of citrate is presoma
It can simplify production technology as carbon source direct carbonization, reduce production cost and raw material are cheap and easy to get, be conducive to large-scale production,
Meanwhile using ammonia that can control the nitrogen content in intermediate product by adjusting atmosphere for nitrogen source, do not need nitrogenous forerunner
Body simplifies production technology.Therefore the preparation method preparation process of the present invention is simple, of low cost, is easy to large-scale production, has
There are good market prospects.
Description of the drawings
Attached drawing described herein is used to provide further understanding of the present invention, and is constituted part of this application, not
Inappropriate limitation of the present invention is constituted, in the accompanying drawings：
Attached drawing 1 is the flow for the method that nitrogen-doped porous carbon material is prepared based on citric acid transition/alkali metal complex salt
Schematic diagram.
Attached drawing 2 is the X ray diffracting spectrum of nitrogen-doped porous carbon material prepared by embodiment 1.
Attached drawing 3 is the electron scanning micrograph of intermediate product prepared by embodiment 1.
Attached drawing 4 is nitrogen-doped porous carbon material electron scanning micrograph prepared by embodiment 1.
Attached drawing 5 is transmission of the nitrogen-doped porous carbon material of the preparation of embodiment 1 under 200nm, 50nm and 5nm amplification factor
Electron micrograph.
Attached drawing 6 is the nitrogen adsorption desorption curve of nitrogen-doped porous carbon material prepared by embodiment 1.
Attached drawing 7 is the graph of pore diameter distribution of nitrogen-doped porous carbon material prepared by embodiment 1.
Attached drawing 8 is the x-ray photoelectron spectroscopy figure of nitrogen-doped porous carbon material prepared by embodiment 1.
Attached drawing 9 is nitrogen-doped porous carbon material prepared by embodiment 1 and commercialization PtC materials in 0.1mol/L potassium hydroxide oxygen
The comparison diagram of the LSV curves of 1600rpm in saturated solution.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1：
It weighs 5g ironic citrates to be put into aluminium oxide porcelain boat, then porcelain boat is put into resistance tube furnace, lead to after vacuumizing
Enter ammonia.5 DEG C/min of heating rate is set, and 600 DEG C keep the temperature 2 hours.After reaction by products therefrom 2.5mol/L hydrochloric acid
Aqueous solution etching removal metal impurities, are then washed to neutrality, nitrogen-doped porous carbon material are obtained after freeze-drying.
Embodiment 2
It weighs 5g ironic citrates to be put into aluminium oxide porcelain boat, then porcelain boat is put into tube furnace, ammonia is passed through after vacuumizing
Gas.10 DEG C/min of heating rate is set, and 900 DEG C keep the temperature 4 hours.After reaction by products therefrom 5mol/L aqueous hydrochloric acid solutions
Etching removal metal impurities, are then washed to neutrality, nitrogen-doped porous carbon material are obtained after freeze-drying.
Embodiment 3
It weighs 5g ironic citrates to be put into aluminium oxide porcelain boat, then porcelain boat is put into tube furnace, ammonia is passed through after vacuumizing
Nitrogen mixture gas.0.5 DEG C/min of heating rate is set, and 600 DEG C keep the temperature 4 hours.After reaction by products therefrom 2.5mol/
L aqueous hydrochloric acid solutions etching removal metal impurities, are then washed to neutrality, nitrogen-doped porous carbon material are obtained after freeze-drying.
Embodiment 4
It weighs 5g calcium citrates to be put into aluminium oxide porcelain boat, then porcelain boat is put into tube furnace, ammonia is passed through after vacuumizing
Gas.5 DEG C/min of heating rate is set, and 1000 DEG C keep the temperature 2 hours.It is after reaction that products therefrom is water-soluble with 10mol/L hydrochloric acid
Liquid etching removal metal impurities, are then washed to neutrality, nitrogen-doped porous carbon material are obtained after freeze-drying.
Embodiment 5
It weighs 5g potassium citrates to be put into aluminium oxide porcelain boat, then porcelain boat is put into tube furnace, ammonia is passed through after vacuumizing
It is argon-mixed.5 DEG C/min of heating rate is set, and 1000 DEG C keep the temperature 4 hours.After reaction by products therefrom 2.5mol/L nitre
Aqueous acid etching removal metal impurities, are then washed to neutrality, nitrogen-doped porous carbon material are obtained after freeze-drying.
Embodiment 6
It weighs 5g bismuth citrates to be put into aluminium oxide porcelain boat, then porcelain boat is put into tube furnace, ammonia is passed through after vacuumizing
Gas.3 DEG C/min of heating rate is set, and 800 DEG C keep the temperature 2 hours.After reaction by products therefrom 6mol/L aqueous solution of nitric acid
Etching removal metal impurities, are then washed to neutrality, nitrogen-doped porous carbon material are obtained after freeze-drying.
Embodiment 7
It weighs 5g zinc citrates to be put into aluminium oxide porcelain boat, then porcelain boat is put into tube furnace, ammonia is passed through after vacuumizing
Gas.2 DEG C/min of heating rate is set, and 500 DEG C keep the temperature 2 hours.It is after reaction that products therefrom is water-soluble with 2.5mol/L sulfuric acid
Liquid etching removal metal impurities, are then washed to neutrality, nitrogen-doped porous carbon material are obtained after freeze-drying.
Embodiment 8
It weighs 5g citric acid cobalts to be put into aluminium oxide porcelain boat, then porcelain boat is put into tube furnace, ammonia is passed through after vacuumizing
Nitrogen mixture gas.5 DEG C/min of heating rate is set, and 700 DEG C keep the temperature 5 hours.After reaction by products therefrom 8mol/L salt
Aqueous acid etching removal metal impurities, are then washed to neutrality, nitrogen-doped porous carbon material are obtained after freeze-drying.
Nitrogen-doped porous carbon material prepared by embodiment 1 carries out X-ray diffraction test, as shown in Fig. 2, embodiment 1
Diffraction maximum of the nitrogen-doped porous carbon material of preparation at 2 θ=23.1o, 44.1o belongs to the diffraction maximum of carbon, without other impurity peaks,
Illustrate that metal impurities completely remove.
Intermediate product and nitrogen-doped porous carbon material prepared by embodiment 1 are scanned electron microscope observation, it is such as attached
Shown in Fig. 3 and attached drawing 4, by comparison it can be found that generating pore space structure after pickling, illustrate porous structure by removal metal impurities
It is in situ afterwards to generate.
Intermediate product and nitrogen-doped porous carbon material prepared by embodiment 1 carries out transmission electron microscope observation, such as attached
Shown in Fig. 5, it can be observed under 200nm and 50nm scales, N doping porous carbon is in the laminated structure containing hole, and in 5nm
Apparent graphite lattice fringe structure can be observed under scale.
Nitrogen-doped porous carbon material prepared by embodiment 1 carries out nitrogen adsorption desorption test, as shown in Fig. 6, the nitrogen of preparation
Doped porous carbon material specific surface area is 250.25m2/g, and carries out pore-size distribution test and find, as shown in Fig. 7, embodiment 1
The pore-size distribution of the nitrogen-doped porous carbon material of preparation shows it with hierarchical porous structure.
Nitrogen-doped porous carbon material prepared by embodiment 1 carries out x-ray photoelectron spectroscopy test, can be true from attached drawing 8
The carbon content for determining nitrogen-doped porous carbon material is 88.67at.%, and nitrogen content 3.14at.%, oxygen content 8.19at.% are said
Bright nitrogen-doping is into porous carbon materials.
Nitrogen-doped porous carbon material and commercialization PtC materials prepared by embodiment 1-8 is as the performance of oxygen reduction catalyst
It is characterized by electrochemistry linear potential sweep method (LSV).
Test condition is：Electrolyte uses 0.1M KOH aqueous solutions, and oxygen is blasted in test process, and working electrode is used and urged
The rotation glass-carbon electrode of agent modification, reference electrode use Ag/AgCl electrodes, and coated graphite rod electrrode is used to electrode.
The preparation method of working electrode：Nitrogen-doped porous carbon material prepared by 3mg is taken to be distributed to 100 μ L ethyl alcohol and 400 μ L
In the mixed solution of water, 30 μ L 5%Naifon solution, ultrasound 1 hour are added.5 μ L catalyst dispersions are taken to be added drop-wise to glass carbon
On electrode, after natural drying, the rotation glass-carbon electrode of catalyst modification is obtained, for use.
Attached drawing 9 is nitrogen-doped porous carbon material prepared by embodiment 1 and commercialization PtC materials in 0.1mol/L potassium hydroxide oxygen
The LSV curves of 1600rpm in saturated solution, hydrogen reduction take-off potential are that -0.115V illustrates its tool close to commercialization PtC materials
There is preferable electrocatalytic oxidation reducing property.Electrochemical Characterization is carried out to nitrogen-doped porous carbon material prepared by embodiment 2-8,
The result shows that it is with oxygen reduction reaction catalytic activity.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (8)
1. a kind of method preparing nitrogen-doped porous carbon material based on citric acid transition/alkali metal complex salt, which is characterized in that
Include the following steps：Using citric acid transition/alkali metal complex salt as carbon source, under the atmosphere containing ammonia, in 500-
Pyrolytic reaction 1-24h at 1000 DEG C takes out, and metal impurities are removed with acid solution wash, then wash after the extra acid of removal freeze it is dry
It is dry, finally obtain nitrogen-doped porous carbon material.
2. one kind as described in claim 1 prepares nitrogen-doped porous carbon material based on citric acid transition/alkali metal complex salt
Method, it is characterised in that：Citric acid transition/alkali metal complex the salt be ironic citrate, citric acid cobalt, citric acid nickel,
Copper citrate, zinc citrate, aluminium citrate, bismuth citrate, sodium citrate, potassium citrate, magnesium citrate, calcium citrate, lemon
One or more mixtures of sour barium.
3. one kind as described in claim 1 prepares nitrogen-doped porous carbon material based on citric acid transition/alkali metal complex salt
Method, it is characterised in that：The gas containing ammonia is ammonia, ammonia argon mixture gas or ammonia nitrogen mixed gas.
4. one kind as described in claim 1 prepares nitrogen-doped porous carbon material based on citric acid transition/alkali metal complex salt
Method, it is characterised in that：The heating rate of the pyrolytic reaction is 1-10 DEG C/min.
5. one kind as described in claim 1 prepares nitrogen-doped porous carbon material based on citric acid transition/alkali metal complex salt
Method, it is characterised in that：The acid solution is hydrochloric acid, nitric acid, sulfuric acid or their mixture.
6. one kind as described in claim 1 prepares nitrogen-doped porous carbon material based on citric acid transition/alkali metal complex salt
Method, it is characterised in that：A concentration of 0.5-10mol/L of the acid solution.
7. it is porous that one kind as described in claim 1 to 6 is any being based on citric acid transition/alkali metal complex salt prepares N doping
The method of carbon material, it is characterised in that：Nitrogen-doped porous carbon material is used as electrocatalytic oxidation reducing catalyst.
8. it is porous that one kind as described in claim 1 to 6 is any being based on citric acid transition/alkali metal complex salt prepares N doping
The method of carbon material, which is characterized in that specifically include following steps：
(1) by ironic citrate, citric acid cobalt, citric acid nickel, copper citrate, zinc citrate, aluminium citrate, bismuth citrate, lemon
Sour sodium, potassium citrate, magnesium citrate, calcium citrate, barium citrate one or more mixtures be placed in resistance tube furnace or micro-
In wave tube furnace, under the atmosphere containing ammonia, it is warming up to 500-1000 DEG C with the rate of 1-10 DEG C/min, pyrolytic reaction 1-
For 24 hours, after reaction, it takes out, obtains intermediate product；
(2) intermediate product obtained by step (1) is washed into removal in the hydrochloric acid, nitric acid or aqueous sulfuric acid of 0.5-10mol/L
Metal impurities, then after the extra acid of washing removal, freeze-drying finally obtains nitrogen-doped porous carbon material.
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| CN108996486A (en) * | 2018-08-21 | 2018-12-14 | 中国科学院南京土壤研究所 | A kind of classifying porous charcoal and its preparation method and application |
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| CN109019559A (en) * | 2018-09-27 | 2018-12-18 | 中国科学院化学研究所 | A kind of three-dimensional porous carbon material of element doping and the preparation method and application thereof |
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| CN112028052B (en) * | 2020-09-18 | 2022-03-29 | 西北大学 | Preparation method and application of biomass carbon-based Fe monatomic-N doped porous carbon material |
| CN115072698A (en) * | 2022-05-09 | 2022-09-20 | 中国空间技术研究院 | Heteroatom-doped aperture-controllable two-dimensional carbon material and preparation method thereof |
| CN114918426A (en) * | 2022-05-27 | 2022-08-19 | 上海大学 | Block bismuth-carbon composite and preparation method and application thereof |
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Application publication date: 20180727 |