CN105664835A - Batch preparation method of porous carbon nitride material under assistance of organic carboxylic acid - Google Patents
Batch preparation method of porous carbon nitride material under assistance of organic carboxylic acid Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 title abstract description 26
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title abstract description 25
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract 4
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 229910052799 carbon Inorganic materials 0.000 claims description 51
- 150000004767 nitrides Chemical class 0.000 claims description 50
- 239000011148 porous material Substances 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000877 Melamine resin Polymers 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 9
- 229940043267 rhodamine b Drugs 0.000 description 9
- 239000003125 aqueous solvent Substances 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- -1 wherein Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
-
- B01J35/613—
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- B01J35/615—
Abstract
The invention relates to a batch preparation method of a porous carbon nitride material under assistance of organic carboxylic acid. A hydrothermal-calcination two-step method is adopted, firstly organic carboxylic acid and melamine are uniformly mixed, then reaction is carried out under hydrothermal condition to obtain a porous carbon nitrogen hydrothermal precursor, and the hydrothermal precursor is calcined to obtain the porous carbon nitride material. By changing kind of the organic carboxylic acid and experimental conditions, controllable preparation of several kinds of porous carbon nitride materials with different structures, morphologies and specific surface areas can be realized. The batch preparation method provided by the invention has the advantages that raw materials are available, cost is low, a synthesis process is simple, operation is easy, repeatability is good, and mass preparation can be realized; and the prepared porous carbon nitride material has efficient organic pollutant adsorption degradation capacity and has a broad application prospect in the fields of treatment of environmental pollutants, hydrogen production through photocatalysis, drug loading and the like.
Description
Technical field
The present invention relates to the method that a kind of organic carboxyl acid auxiliary batch prepares nitride porous material with carbon element, belong to field of material preparation.
Background technology
Graphite phase carbon nitride has caused people to pay close attention to widely as a kind of novel metal-free semi-conducting material. Carbonitride has class graphite laminate structure, and interlayer is combined by Van der Waals force, is formed the conjugated system of height delocalization by nitrogen and two kinds of elements of carbon by hydridization in layer, and stability is high. Carbonitride has suitable band gap width (being about 2.7eV) as semi-conducting material, it is possible to absorbs major part visible ray, has again stronger oxidation and reducing power. Meanwhile, carbonitride is pollution-free to environmental and biological materials, toxicity is low. Therefore, carbonitride is with a wide range of applications in photocatalytic degradation environmental organic pollutant, photocatalysis hydrogen production, fluorescent material, sterilization material etc.
By improving technology of preparing, control pattern, and then the performance of Effective Regulation carbonitride is the target that people pursue. The preparation method of current carbonitride is mainly tripolycyanamide calcination method. The method mainly obtains block materials, it is impossible to effectively control pattern, performance of control. Nitride porous material with carbon element becomes the focus of people's research owing to having higher specific surface area. Hard template method is currently mainly adopted to prepare. As CN103861630A patent documentation discloses the graphite phase carbon nitride hollow ball visible light catalyst that a kind of combined polymerization is modified, the synthesis of its carbonitride hollow ball be with cyanamide and organic molecule monomer be predecessor, mesoporous silica spheres for template, by thermal polymerization with remove template and obtain. Wang et al. (J.Mater.Chem.A, 2015,3,5126-5131) utilizes calcium carbonate as template, is prepared for nitride porous material with carbon element. But hard template method experimental procedure is complicated, remove acid solution used by template easily causes pollution etc. and limits its extensive use.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides the method that a kind of organic carboxyl acid auxiliary batch prepares nitride porous material with carbon element, it is that organic carboxyl acid is added in tripolycyanamide by one, by the method for hydro-thermal-calcining two-step method controlled synthesis nitride porous material with carbon element.
The method that a kind of organic carboxyl acid auxiliary batch prepares nitride porous material with carbon element, its preparation process is as follows:
Adding water dissolution after tripolycyanamide and organic carboxyl acid being mixed according to mass ratio 1:1-1:20, wherein water is 1:1 with the mass ratio of organic carboxyl acid;Or tripolycyanamide and organic carboxyl acid are dissolved according to mass ratio 1:1-1:20 mixing; By the 80-180 DEG C of heating 1-16h in hydrothermal reaction kettle of the mixture after dissolving, obtain nitride porous carbon hydro-thermal predecessor; By nitride porous carbon hydro-thermal predecessor in tube furnace under nitrogen protection 450-650 DEG C calcining 1-6h, obtain nitride porous material with carbon element.
The kind of described organic carboxyl acid is acetic acid, oxalic acid, benzoic acid or salicylic acid;
Preferably, the mass ratio of described tripolycyanamide and organic carboxyl acid is 1:2-1:10;
Preferably, the 100-180 DEG C of heating 5-12h in hydrothermal reaction kettle of the mixture after described dissolving.
Preferably, described nitride porous carbon hydro-thermal predecessor in tube furnace under nitrogen protection 500-600 DEG C calcining 2-4h.
The present invention adopts organic carboxyl acid auxiliary and hydro-thermal-calcining two-step mode technique, by the change kind of organic carboxyl acid and addition, and the controlled synthesis nitride porous material with carbon element of multiple different-shape structure and specific surface area. Utilize organic carboxyl acid to decompose the feature producing gas, form loose structure; By changing organic carbochain or the size of benzene ring structure regulation and control pore structure. Increase the specific surface area of carbon nitride material, improve the mass transfer diffusion process in multiphase photocatalysis reaction, promoted the sharp separation of photo-generated carrier, significantly improved the degradation capability to organic pollution.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of ordered laminar nitride porous material with carbon element in the embodiment of the present invention 1;
It appeared that 13.7 ° and 27.6 ° two XRD diffraction maximums significantly belonging to graphite phase carbon nitride (100) and (002) crystal face occur from Fig. 1, it was demonstrated that prepared material is graphite phase carbon nitride material.
Fig. 2 is the stereoscan photograph (SEM) of different-shape nitride porous material with carbon element in the embodiment of the present invention 1,2,6;
Wherein a figure is the ordered laminar nitride porous material with carbon element that in embodiment 1, then acetic acid and tripolycyanamide hydro-thermal in aqueous solvent calcines preparation; B figure is the nitride porous material with carbon element that in embodiment 2, then acetic acid and tripolycyanamide hydro-thermal in anhydrous conditions calcines preparation; C figure is the tubular porous carbon nitride material that in embodiment 6, then benzoic acid and tripolycyanamide hydro-thermal in aqueous solvent calcines preparation;
It is observed that obvious layered porous structure from Fig. 2 a; It is observed that uniform loose structure in Fig. 2 b; It is observed that obvious tubular porous structure in Fig. 2 c.
Fig. 3 is the N of ordered laminar nitride porous material with carbon element in the embodiment of the present invention 12The comparison diagram of carbon nitride material prepared by adsorption/desorption curve and simple tripolycyanamide;
Fig. 3 finds out, the adsorption/desorption performance of ordered laminar nitride porous material with carbon element is substantially better than carbon nitride material prepared by tripolycyanamide, and it is 138m that BET method calculates the specific surface area of ordered laminar nitride porous material with carbon element2/ g, far above the specific surface area 31m of carbon nitride material prepared by simple tripolycyanamide2/g。
Fig. 4 is carbon nitride material that in the embodiment of the present invention 1 prepared by ordered laminar nitride porous material with carbon element and simple tripolycyanamide to rhodamine B catalysis activity comparison diagram under sunlight;
Fig. 4 is it will be seen that the photocatalytic degradation effect of rhodamine B is much better than carbon nitride material prepared by pure melamine by ordered laminar nitride porous material with carbon element.
Detailed description of the invention:
Below in conjunction with the drawings and specific embodiments, the particular content of the present invention is described in further detail.
The kind of heretofore described organic carboxyl acid can be acetic acid, oxalic acid, benzoic acid or salicylic acid, but is not limited to this several organic carboxyl acids;Used by the present embodiment, organic carboxyl acid is analytical pure. The used noble gas of the present embodiment can use nitrogen.
Embodiment 1.
Tripolycyanamide and analytical pure acetic acid being mixed according to mass ratio 1:10, be scattered in aqueous solvent, wherein, the volume ratio of water and acetic acid is 1:1, by above-mentioned solution 160 DEG C of heating 10h in hydrothermal reaction kettle, obtains nitride porous carbon hydro-thermal predecessor; Calcine 2h by lower for above-mentioned hydro-thermal predecessor nitrogen protection in tube furnace 550 DEG C, obtain ordered laminar nitride porous material with carbon element, as shown in Fig. 1, Fig. 2 a. The specific surface area of ordered laminar nitride porous material with carbon element is 138m2g-1, far above the specific surface area 31m of carbon nitride material prepared by simple tripolycyanamide2/ g, as shown in Figure 3.
Embodiment 2.
Tripolycyanamide and acetic acid are mixed according to mass ratio 1:10, under anhydrous condition, by above-mentioned solution 180 DEG C of heating 16h in hydrothermal reaction kettle, obtains nitride porous carbon hydro-thermal predecessor; Calcine 6h by lower for above-mentioned hydro-thermal predecessor inert gas shielding in tube furnace 500 DEG C, obtain nitride porous material with carbon element, as shown in Figure 2 b. The specific surface area of even porous carbon nitride material is 76m2/g。
Embodiment 3.
Tripolycyanamide and oxalic acid being mixed according to mass ratio 1:5, be scattered in aqueous solvent, wherein, the mass ratio of water and oxalic acid is 1:1, by above-mentioned solution 180 DEG C of heating 5h in hydrothermal reaction kettle, obtains nitride porous carbon hydro-thermal predecessor; Calcine 2h by lower for above-mentioned hydro-thermal predecessor inert gas shielding in tube furnace 600 DEG C, obtain nitride porous material with carbon element. The specific surface area of nitride porous material with carbon element is 106m2/g。
Embodiment 4.
Tripolycyanamide and oxalic acid being mixed according to mass ratio 1:20, be scattered in aqueous solvent, wherein, the mass ratio of water and oxalic acid is 1:1, by above-mentioned solution 150 DEG C of heating 10h in hydrothermal reaction kettle, obtains nitride porous carbon hydro-thermal predecessor; Calcine 4h by lower for above-mentioned hydro-thermal predecessor inert gas shielding in tube furnace 500 DEG C, obtain nitride porous material with carbon element. The specific surface area of nitride porous material with carbon element is 112m2/g。
Embodiment 5.
Tripolycyanamide and butanoic acid being mixed according to mass ratio 1:1, be scattered in aqueous solvent, wherein, the mass ratio of water and butanoic acid is 1:1, by above-mentioned solution 80 DEG C of heating 16h in hydrothermal reaction kettle, obtains nitride porous carbon hydro-thermal predecessor; Calcine 6h by lower for above-mentioned hydro-thermal predecessor inert gas shielding in tube furnace 450 DEG C, obtain nitride porous material with carbon element. The specific surface area of nitride porous material with carbon element is 86m2/g。
Embodiment 6.
Tripolycyanamide and benzoic acid being mixed according to mass ratio 1:1, be scattered in aqueous solvent, wherein, water and benzoic mass ratio are 1:1, by above-mentioned solution 180 DEG C of heating 16h in hydrothermal reaction kettle, obtain nitride porous carbon hydro-thermal predecessor; Calcine 6h by lower for above-mentioned hydro-thermal predecessor inert gas shielding in tube furnace 550 DEG C, obtain tubular porous carbon nitride material, as shown in Figure 2 c. The specific surface area of tubular porous carbon nitride material is 68m2/g。
Embodiment 7.
Tripolycyanamide and salicylic acid being mixed according to mass ratio 1:5, be scattered in aqueous solvent, wherein, water and salicylic mass ratio are 1:1, by above-mentioned solution 180 DEG C of heating 16h in hydrothermal reaction kettle, obtain nitride porous carbon hydro-thermal predecessor; Calcine 6h by lower for above-mentioned hydro-thermal predecessor inert gas shielding in tube furnace 550 DEG C, obtain tubular porous carbon nitride material. The specific surface area of tubular porous carbon nitride material is 66m2/g。
Checking example:
Ordered laminar nitride porous material with carbon element prepared in the embodiment of the present invention 1 is used for the photocatalytic degradation experiment of organic dyestuff rhodamine B, and detailed process and step are as follows:
50mg ordered laminar nitride porous material with carbon element is scattered in the rhodamine B solution of 50mL50mg/L, under dark condition, stir 30min reach adsorption equilibrium, then solution is placed under sunlight, every 5min with in liquid-transfering gun absorption 1mL solution to centrifuge tube, centrifugal collection supernatant, utilize ultraviolet-visible spectrophotometer to measure absorbance, draw out under different light application time the photocatalytic degradation curve chart to 50mg/L rhodamine B solution according to the absorbance of rhodamine B solution under maximum absorption wavelength 553nm wavelength.
Fig. 4 is carbon nitride material that in the embodiment of the present invention 1 prepared by ordered laminar nitride porous material with carbon element and simple tripolycyanamide to rhodamine B catalysis activity comparison diagram under sunlight, it can be seen that, rhodamine B degradation rate is basically reached 100% by ordered laminar nitride porous material with carbon element after sunlight 20min, and the degradation rate of rhodamine B is only 4.1% by the carbon nitride material that merely prepared by tripolycyanamide after sunlight 20min, it was shown that the photocatalysis performance that prepared ordered laminar nitride porous material with carbon element is excellent.
The explanation of above case study on implementation can be used to help to understand principles of the invention and method. But above case study on implementation is not unique, should not be construed as limitation of the present invention. With present inventive concept without the various process programs of substantial differences all within protection scope of the present invention.
Claims (4)
1. the method that an organic carboxyl acid auxiliary batch prepares nitride porous material with carbon element, it is characterised in that its preparation process is as follows:
Adding water dissolution after tripolycyanamide and organic carboxyl acid being mixed according to mass ratio 1:1-1:20, wherein water is 1:1 with the mass ratio of organic carboxyl acid; Or tripolycyanamide and organic carboxyl acid are dissolved according to mass ratio 1:1-1:20 mixing; By the 80-180 DEG C of heating 1-16h in hydrothermal reaction kettle of the mixture after dissolving, obtain nitride porous carbon hydro-thermal predecessor; By nitride porous carbon hydro-thermal predecessor in tube furnace under nitrogen protection 450-650 DEG C calcining 1-6h, obtain nitride porous material with carbon element;
Described organic carboxyl acid is acetic acid, oxalic acid, benzoic acid or salicylic acid.
2. the method that a kind of organic carboxyl acid as claimed in claim 1 auxiliary batch prepares nitride porous material with carbon element, it is characterised in that the mass ratio of described tripolycyanamide and organic carboxyl acid is 1:2-1:10.
3. the method that a kind of organic carboxyl acid as claimed in claim 1 auxiliary batch prepares nitride porous material with carbon element, it is characterised in that the mixture after described dissolving is 100-180 DEG C of heating 5-12h in hydrothermal reaction kettle.
4. a kind of organic carboxyl acid as claimed in claim 1 auxiliary batch prepare nitride porous material with carbon element method, it is characterised in that described nitride porous carbon hydro-thermal predecessor in tube furnace under nitrogen protection 500-600 DEG C calcining 2-4h.
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