CN115448266B - Preparation method of alpha and beta composite phase carbon nitride material combined by ferric oxide - Google Patents
Preparation method of alpha and beta composite phase carbon nitride material combined by ferric oxide Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 25
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 18
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 229940032296 ferric chloride Drugs 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229960004887 ferric hydroxide Drugs 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 239000004570 mortar (masonry) Substances 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- -1 carbon nitrides Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001659 ion-beam spectroscopy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The invention belongs to the field of functional materials, and in particular relates to a method for preparing super-hardness oxide by high-temperature calcination in a vacuum tube furnaceIron-bonded alpha and beta composite phase carbon nitride (C 3 N 4 ) The preparation method of the powder material mainly comprises dicyandiamide and ferric chloride hexahydrate (FeCl) 3 ·6H 2 O) is used as a raw material, after the water solution is frozen and dried to prepare a composite precursor, a crucible filled with the precursor is placed into a vacuum tube furnace, nitrogen is used as a protective gas, the temperature is kept for 4 hours at 550 ℃ at a heating rate of 2.5 ℃/min, and finally, a coarse product is obtained and is ground, washed and dried by an agate mortar, so that the ultra-hard alpha and beta composite phase carbon nitride powder material is obtained. The method takes the simple and easily-obtained pollution-free nitrogen-rich organic matters as the precursors, and prepares the super-hardness ferric oxide (Fe) through calcination 2 O 3 ) And combined alpha/beta composite phase carbon nitride. The invention has simple and effective process, low energy consumption, low price of the used raw materials and no pollution, and provides a new thought and a new way for designing and developing the alpha and beta composite carbon nitride.
Description
Technical Field
The invention relates to the field of functional materials, in particular to a method for preparing ferric oxide (Fe) by high-temperature calcination in a vacuum tube furnace 2 O 3 ) A method of combining alpha and beta composite phase carbon nitride materials.
Background
In 1989 A.L.Liu and M.L.Cohen predicted theoretically beta-carbon nitride (. Beta. -C) using the first principles pseudopotential energy band method 3 N 4 ) Such novel covalent compounds have not been found in nature. Subsequently, teter et al also calculated a structure based on the first principles to predict carbon nitride (C 3 N 4 ) There are five structures, namely, alpha-carbon nitride (alpha-C 3 N 4 ) Beta-carbon nitride (beta-C) 3 N 4 ) Cubic phase carbon nitride (C-C) 3 N 4 ) Quasi-cubic phase carbon nitride (p-C) 3 N 4 ) And graphite phase carbon nitride (g-C) 3 N 4 ). In these structures, α -carbon nitride (α -C 3 N 4 ) And beta-carbon nitride (beta-C) 3 N 4 ) Is similar to alpha-silicon nitride (alpha-Si) 3 N 4 ) And beta-silicon nitride (beta-Si) 3 N 4 ) The diamond-based high-speed integrated circuit has a plurality of excellent performances, and the most widely focused characteristics of ultra-high hardness, lower wear rate, better chemical stability, good infrared permeability, higher heat conductivity and the like are that the diamond-based high-speed integrated circuit can be applied to high-temperature and high-speed integrated circuits.
However, beta-carbon nitride (beta-C 3 N 4 ) Successful preparation of crystalline films was not achieved by laser sputtering technology at the university of harvard in the united states until 1993. After that, there is a lot of research work reporting how to obtain alpha-carbon nitride (alpha-C 3 N 4 ) Thin film or beta-carbon nitride (beta-C) 3 N 4 ) A film. Currently, there are mainly ion implantation, laser sputtering, ion beam sputtering, high temperature and high pressure, explosion impact synthesis, plasma chemical vapor deposition, solvothermal methods, and the like. However, these methods generally have the disadvantages of severe preparation conditions, high reaction and post-treatment temperatures, large equipment, poor crystallization of carbon-nitrogen films, and pure alpha-carbon nitride (alpha-C) 3 N 4 ) Or beta-carbon nitride (beta-C) 3 N 4 ) Only a few techniques have achieved a polycrystalline phase, limiting to some extent the investigation of the influence of the aggregation state structure of the molecules on the hardness of the material.
Compared with the traditional synthesis, the thermal polymerization method is a rapid, efficient, environment-friendly and low-cost preparation method, and is used for preparing graphite-phase carbon nitride (g-C) 3 N 4 ) A more common approach. The method is extended as rapid acquisition of alpha-carbon nitride (alpha-C) 3 N 4 ) And beta-carbon nitride (beta-C) 3 N 4 ) Is particularly important.
Disclosure of Invention
Aiming at the problems of harsh reaction conditions, complex process, high cost, long period, environment friendliness and almost pure alpha-carbon nitride (alpha-C) 3 N 4 ) Or beta-carbon nitride（β-C 3 N 4 ) The invention provides a preparation method of an alpha and beta composite phase carbon nitride material combined by ferric oxide.
The preparation operation steps of the alpha and beta composite phase carbon nitride material combined by ferric oxide are as follows:
(1) 1-2 g of ferric chloride hexahydrate (FeCl) 3 ·6H 2 O) is added into 6ml to 8ml of deionized water, and ultrasonic treatment is carried out at room temperature, thus obtaining completely dispersed ferric chloride (FeCl) 3 ) A solution;
(2) Adding 6-8 g dicyandiamide into 40-50 ml deionized water, continuously heating and stirring, heating to 90 ℃, and stirring until dicyandiamide is completely dissolved to obtain a completely dissolved dicyandiamide solution;
(3) Slowly dripping 40-50 ml dicyandiamide solution into 6-8 ml ferric chloride solution to make ferric ion (Fe 3+ ) Hydrolysis occurs to form ferric hydroxide (Fe (OH) 3 ) Obtaining a mixed solution; naturally cooling the mixed solution by standing under the condition of: the temperature is 25 ℃ and the time is 1h; filtering and collecting the aqueous solution; freeze-drying the aqueous solution to obtain a precursor;
(4) Placing the precursor in a vacuum tube furnace for high-temperature calcination under nitrogen atmosphere, wherein the calcination conditions are as follows: the temperature is 550 ℃, the heating rate is 2.5 ℃/min, and the calcination time is 4 hours, so that the blocky carbon nitride is prepared;
(5) Grinding, washing, alcohol washing and drying the blocky carbon nitride to prepare an alpha and beta composite phase carbon nitride material combined by ferric oxide;
the composite phase carbon nitride material is in a powder shape, the granularity is uniform, and the grain diameter is 2-6 mu m; wherein alpha carbon nitride (alpha-C 3 N 4 ) The content of the beta carbon nitride (beta-C) is 87 percent 3 N 4 ) The content is 13 percent, and the microhardness reaches 20GPa.
The further technical scheme is as follows:
in step (1), ultrasound conditions: the temperature is 40 ℃, the ultrasonic frequency is 40KHz, the ultrasonic treatment time is 0.5h, and the ultrasonic power is 480w.
In step (4), the freeze-drying conditions: firstly, freezing at the temperature of minus 10 ℃ for 24 hours; then drying under air cooling for 5h at 950w power and 8Pa vacuum degree and cooling temperature of-50deg.C.
In the step (5), the water washing is carried out for 3 times, and the alcohol washing is carried out for 1 time by absolute ethyl alcohol.
Compared with the background technology, the invention has the beneficial technical effects that:
1. in the step (3) of the invention, a thermally polymerized precursor is obtained by a freeze drying method, and after the solid state still keeps the molecular aggregation state of the precursor in the solution state, the precursor is put into a vacuum tube furnace for calcination, and finally the product of the invention is obtained. Because of the specific molecular aggregation state in the precursor, graphite-phase carbon nitride (g-C) is not obtained after calcination as in the conventional process 3 N 4 ) But rather alpha and beta complex phase carbon nitrides. The vacuum tube furnace equipment adopted in the invention has the characteristics of quick production and easy operation, and has the advantages of low operation cost and mild condition compared with large-scale laser sputtering equipment, ion beam sputtering equipment, high-temperature high-pressure furnace and the like.
2. The invention has simple raw materials and low cost, and no reagent polluting the environment is required to be added in the preparation process.
3. By adjusting the amount of dicyandiamide in the precursor, alpha and beta composite phase carbon nitride materials with different composite ratios can be obtained, wherein alpha carbon nitride (alpha-C 3 N 4 ) The content of the beta carbon nitride (beta-C) is 87 percent 3 N 4 ) The content is 13 percent, and the microhardness reaches 20GPa.
Drawings
FIG. 1 is a FI-IR spectrum of the product obtained in example 1.
FIG. 2 is an X-ray diffraction pattern of the product obtained in example 1.
FIG. 3 is a scanning electron microscope image of the product obtained in example 1.
FIG. 4 is an XPS chart of the product obtained in example 1.
FIG. 5 is a hardness micro-indentation measurement of the product obtained in example 1.
Detailed Description
The invention is further described below with reference to the drawings and the specific preferred embodiments, but the scope of the invention is not limited thereby.
Unless otherwise indicated, all the experimental procedures described in the examples below were conventional, and all the raw materials and equipment used were commercially available.
Example 1
The preparation operation steps of the alpha and beta composite phase carbon nitride material combined by ferric oxide are as follows:
(1) 1g of ferric chloride hexahydrate (FeCl) was added to 6ml of deionized water 3 ·6H 2 O), ultrasound causes it to disperse completely. Ultrasonic conditions: the temperature is 40 ℃, the ultrasonic frequency is 40KHz, the ultrasonic treatment time is 0.5h, and the ultrasonic power is 480w.
(2) 6g of dicyandiamide was added to 40ml of deionized water, heated and stirred continuously until the dicyandiamide was completely dissolved.
(3) 40ml of dicyandiamide aqueous solution is heated to 90℃and 6ml of ferric chloride hexahydrate (FeCl) are slowly added dropwise 3 ·6H 2 O) in solution so as to promote Fe therein 3+ Hydrolysis occurs to form ferric hydroxide (Fe (OH) 3 ). Standing at 60deg.C for 1 hr, naturally cooling, filtering, collecting aqueous solution, lyophilizing to obtain product named precursor (FeCl) of ferric chloride and dicyanodiamine 3 /DCDA). Freeze-drying conditions: firstly, freezing at the temperature of minus 10 ℃ for 24 hours; then drying under the air cooling of the freezing mode for 5 hours at the power of 950w and the vacuum degree of 8Pa and the cooling temperature of-50 ℃ to obtain the precursor.
(4) The precursor was placed in a vacuum tube furnace under nitrogen (N 2 ) Under the atmosphere, the temperature is raised to 550 ℃ at a heating rate of 2.5 ℃/min, and the temperature is kept for 4 hours, so that the blocky carbon nitride is obtained. Finally grinding, washing with water, washing with alcohol and drying to obtain the composite phase carbon nitride material, namely the alpha and beta composite phase carbon nitride combined by ferric oxide.
The composite phase carbon nitride material is in powder shape, has uniform granularity and has the grain diameter of 2-6 mu m.
X-ray diffraction analysis (XRD) of the product obtained in this example 1 was performed using an XRD-6000 type X-ray powder diffractometer, with scanning rates and angles ranging from 10 DEG/min and from 5 DEG to 80 DEG; sample extra-magenta test (FT-IR) using a Nicolet 380 infrared spectrometer; morphology of the samples was observed with an EISS Sigma 300 Scanning Electron Microscope (SEM); determining the surface composition and the element chemical state of the material by using an ESCALAB 250Xi type X-ray photoelectron spectrometer (XPS); the hardness of the material was studied using a TI 980-bruk nanoindenter.
Referring to fig. 1, an FT-IR spectrum of a composite phase carbon nitride sample was prepared. At 808, 1200-1700 and 3100-3500 cm -1 There was a distinct absorption peak, indicating that the product synthesized in this example 1 was carbon nitride. Located at 808 cm -1 The absorption peak at this point is due to bending vibration of the triazine ring, 1200-1700 cm -1 The absorption peak at this point is due to the tensile vibrations of c=n and C-N, 3100-3500 cm -1 Broadband with-NH 2 And = NH stretching vibration.
Referring to fig. 2, an XRD spectrum of a composite phase carbon nitride sample was prepared in example 1. As can be seen from fig. 2, the diffraction pattern mainly comprises five diffraction peaks, d values of 0.4694 nm (18.89 °), 0.2826 nm (31.63 °), 0.2711 nm (33.02 °), 0.2346 nm (38.34 °) and 0.1635 nm (56.21 °), respectively. Corresponding to the alpha- (001), alpha- (002), beta- (200), alpha- (002) and beta- (220) crystal planes. Thus, the XRD analysis results are consistent with the theoretical calculated values of crystal plane parameters of the a-phase and beta-phase superhard carbon nitrides reported by S.Matsumoto et al. Wherein alpha carbon nitride (alpha-C 3 N 4 ) The content of the beta carbon nitride (beta-C) is 87 percent 3 N 4 ) The content was 13%.
Referring to fig. 3, the carbon nitride product prepared in this example 1 consisted of a large number of random fragments, and had a size of about 10 μm.
Referring to fig. 4, XPS diagram of a composite phase carbon nitride sample prepared in example 1. As shown in fig. 4a, XPS spectroscopy confirmed the presence of C, N, O and Fe elements in the prepared carbon nitride sample. FIG. 4b shows a C1 s spectrum of a sample comprising three deconvoluted peaks corresponding to material C-C bonds (284.80 eV), sp, respectively 2 C=n bond (286.33 eV) and sp 3 Type C-N bond (288.53 eV). Two main spectra of N1 s (FIG. 4 c)The reflection of the peaks is concentrated at binding energies 397.75 and 399.15eV due to sp, respectively 2 C=n bond and sp 3 Type C-N bond. The high resolution XPS spectrum of Fe 2p is shown in FIG. 4 d. The 710.29 eV and 723.55 eV peaks in the Fe 2p spectrum correspond to Fe 2p, respectively 3/2 And Fe 2p 1/2 Is Fe 2 O 3 This indicates that the material prepared is made of Fe 2 O 3 And alpha/beta complex phase C 3 N 4 And is composed of the components.
Referring to fig. 5, ferric oxide (Fe 2 O 3 ) The combined alpha and beta composite phase carbon nitride has higher microhardness reaching 20GPa.
Example 2
The preparation operation steps of the alpha beta composite phase carbon nitride material combined by ferric oxide are as follows:
(1) 1g of ferric chloride hexahydrate (FeCl) was added to 6ml of deionized water 3 ·6H 2 O), ultrasound causes it to disperse completely. Ultrasonic conditions: the temperature is 40 ℃, the ultrasonic frequency is 40KHz, the ultrasonic treatment time is 0.5h, and the ultrasonic power is 480w.
(2) 5g of dicyandiamide are added to 40ml of deionized water, heated and stirred continuously until the dicyandiamide is completely dissolved.
(3) 40ml of dicyandiamide aqueous solution is heated to 90℃and 6ml of ferric chloride hexahydrate (FeCl) are slowly added dropwise 3 ·6H 2 O) in solution so as to promote Fe therein 3+ Hydrolysis occurs to form ferric hydroxide (Fe (OH) 3 ). Standing the above mixed solution at 60deg.C for 1 hr, naturally cooling, filtering, collecting aqueous solution, lyophilizing to obtain product called precursor (FeCl) of ferric chloride and dicyanodiamine 3 /DCDA). Freeze-drying, freeze-drying conditions: firstly, freezing at the temperature of minus 10 ℃ for 24 hours; then drying under the air cooling of the freezing mode for 5 hours at the power of 950w and the vacuum degree of 8Pa and the cooling temperature of-50 ℃ to obtain the precursor.
(4) The precursor was placed in a vacuum tube furnace under nitrogen (N 2 ) Under the atmosphere, the temperature is raised to 570 ℃ at a heating rate of 2.5 ℃/min and is continued for 4 hours, so that the blocky carbon nitride is obtained. Most preferably, the first to fourthFinally grinding, washing with water, washing with alcohol and drying to obtain the alpha and beta composite phase carbon nitride combined by ferric oxide.
Characterization analysis by adopting X-ray diffraction, an X-ray photoelectron spectrometer and the like in the example 1 proves that the obtained product is the alpha and beta composite phase carbon nitride combined by ferric oxide. Wherein alpha carbon nitride (alpha-C 3 N 4 ) The content of the beta carbon nitride (beta-C) is 80 percent 3 N 4 ) The content is 20%.
Claims (4)
1. The preparation method of the alpha and beta composite phase carbon nitride material combined by ferric oxide is characterized by comprising the following operation steps:
(1) Adding 1-2 g of ferric chloride hexahydrate into 6-8 ml of deionized water, and performing ultrasonic treatment at room temperature to obtain a completely dispersed ferric chloride solution;
(2) Adding 6-8 g dicyandiamide into 40-50 ml deionized water, continuously heating and stirring, heating to 90 ℃, and stirring until the dicyandiamide is completely dissolved to obtain a completely dissolved dicyandiamide solution;
(3) Slowly dripping 40-50 ml dicyandiamide solution into 6-8 ml ferric chloride solution to hydrolyze ferric ions to generate ferric hydroxide, thus obtaining mixed solution; naturally cooling the mixed solution by standing under the condition of: the temperature is 25 ℃ and the time is 1h; filtering and collecting the aqueous solution; freeze-drying the aqueous solution to obtain a precursor;
(4) Placing the precursor in a vacuum tube furnace for high-temperature calcination under nitrogen atmosphere, wherein the calcination conditions are as follows: the temperature is 550 ℃, the heating rate is 2.5 ℃/min, and the calcination time is 4 hours, so that a block sample is prepared;
(5) Grinding the block sample, washing with water, washing with alcohol, and drying to obtain the alpha and beta composite phase carbon nitride material combined by ferric oxide;
the composite phase carbon nitride material is in a powder shape, the granularity is uniform, and the grain diameter is 2-6 mu m; wherein the alpha carbon nitride content is 87 percent, the beta carbon nitride content is 13 percent, and the microhardness reaches 20GPa.
2. The method for preparing the iron oxide-bonded alpha and beta composite phase carbon nitride material according to claim 1, wherein the method comprises the following steps: in step (1), ultrasound conditions: the temperature is 40 ℃, the ultrasonic frequency is 40KHz, the ultrasonic treatment time is 0.5h, and the ultrasonic power is 480W.
3. The method for preparing the iron oxide-bonded alpha and beta composite phase carbon nitride material according to claim 1, wherein the method comprises the following steps: in step (3), the freeze-drying conditions: firstly, freezing at the temperature of minus 10 ℃ for 24 hours; then drying under air cooling at 950W power, 8Pa vacuum degree, cooling temperature of-50deg.C and freezing mode for 5 hr.
4. The method for preparing the iron oxide-bonded alpha and beta composite phase carbon nitride material according to claim 1, wherein the method comprises the following steps: in the step (5), the water washing is carried out for 3 times, and the alcohol washing is carried out for 1 time by absolute ethyl alcohol.
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