CN113877621A - Red mud modified carbon nitride nano material and preparation method and application thereof - Google Patents
Red mud modified carbon nitride nano material and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- -1 iron ions Chemical class 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000003486 chemical etching Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000004131 Bayer process Methods 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- JAQXDZTWVWLKGC-UHFFFAOYSA-N [O-2].[Al+3].[Fe+2] Chemical compound [O-2].[Al+3].[Fe+2] JAQXDZTWVWLKGC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a red mud modified carbon nitride nano material and a preparation method and application thereof. The preparation method comprises the following steps: leaching red mud by acid to obtain red mud leachate; adjusting the pH value of the red mud leachate to 8-9 to obtain an active red mud precursor; calcining the active red mud precursor to obtain active red mud; the red mud modified carbon nitride nano material is obtained by carrying out heat treatment on an aqueous solution containing melamine and activated red mud. According to the invention, the reaction of iron ions in the activated red mud and cyano groups is utilized to regulate and control the layered and porous structures of the carbon nitride, the traditional chemical etching or stripping way is replaced, and the purpose of utilizing the red mud to modify the carbon nitride nano material and improving the additional value of the red mud resource utilization product is successfully realized; the layered red mud modified carbon nitride nano material prepared by the method has the advantages of uniform appearance, wide size regulation range and higher performance of hydrogen production by photocatalytic water decomposition.
Description
Technical Field
The invention relates to the technical field of red mud resource utilization, in particular to a red mud modified carbon nitride nano material and a preparation method and application thereof.
Background
The development of the comprehensive utilization of the red mud as the large comprehensive solid waste is increasingly sufferedAttention is paid to. The red mud is strong alkaline waste residue generated in the process of extracting aluminum oxide in aluminum production industry, and contains rich Fe2O3And appears reddish red. In China, more than 90% of alumina and aluminum hydroxide products are produced by a Bayer process, and 1-1.4 tons of red mud can be produced every 1 ton of alumina is produced on average. However, the red mud has strong alkalinity and complex components, and the comprehensive utilization rate of the red mud is less than 4 percent. At present, the main treatment mode of red mud is stockpiling and disposal in China and even the world. The red mud piling not only occupies a large amount of land and increases maintenance cost, but also causes environmental problems such as soil alkalization and groundwater pollution because strong alkaline substances and heavy metal ions in the red mud enter the soil and groundwater, and causes important harm to the local surrounding environment and society because the red mud piling site breaks the dam and other safety problems. How to properly dispose and utilize the red mud is a difficult problem which needs to be solved by sustainable development in the alumina industry at present, and has great significance for human beings and ecological environment.
The comprehensive utilization of the red mud at the present stage is mainly focused on the fields of building materials, road beds, valuable metal recovery, catalyst preparation and the like. The preparation process has low efficiency, high cost and low product added value, so the utilization rate of the red mud is low. Although a large number of patents disclose comprehensive utilization ways of red mud, researches on preparation of high value-added photocatalytic hydrogen production materials by directly taking solid waste red mud in the aluminum production industry as a raw material through a simple process method are rarely reported, so that improvement of the utilization efficiency of the red mud is limited.
Disclosure of Invention
In view of this, it is necessary to provide a red mud-modified carbon nitride nanomaterial, and a preparation method and an application thereof, so as to solve the technical problem of low red mud utilization rate in the prior art.
The first aspect of the invention provides a preparation method of a red mud modified carbon nitride nano material, which comprises the following steps:
leaching red mud by acid to obtain red mud leachate;
adjusting the pH value of the red mud leachate to 8-9 to obtain an active red mud precursor;
calcining the active red mud precursor to obtain active red mud;
the red mud modified carbon nitride nano material is obtained by carrying out heat treatment on an aqueous solution containing melamine and activated red mud.
The second aspect of the invention provides a red mud modified carbon nitride nanomaterial, which is obtained by the preparation method of the red mud modified carbon nitride nanomaterial provided by the first aspect of the invention.
The third aspect of the invention provides an application of the red mud modified carbon nitride nano material, and the red mud modified carbon nitride nano material is applied to photocatalytic hydrolysis hydrogen production.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the reaction of iron ions in the activated red mud and cyano groups is utilized to regulate and control the layered and porous structures of the carbon nitride, the traditional chemical etching or stripping way is replaced, and the purpose of utilizing the red mud to modify the carbon nitride nano material and improving the additional value of the red mud resource utilization product is successfully realized;
the layered red mud modified carbon nitride nano material prepared by the method has the advantages of uniform appearance, wide size regulation range and higher performance of hydrogen production by photocatalytic water decomposition.
Drawings
FIG. 1 is an XRD pattern of the product obtained in example 1 of the present invention;
FIG. 2 is an SEM photograph of a product obtained in example 2 of the present invention;
FIG. 3 is an XRD pattern of the product obtained in example 3 of the present invention;
FIG. 4 is an SEM photograph of a product obtained in example 3 of the present invention;
FIG. 5 is a graph showing the photocatalytic water splitting hydrogen production performance of the product obtained in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first aspect of the invention provides a preparation method of a red mud modified carbon nitride nano material, which comprises the following steps:
s1, carrying out acid leaching on the red mud to obtain a red mud leachate;
s2, adjusting the pH value of the red mud leachate to 8-9 to obtain an active red mud precursor;
s3, calcining the active red mud precursor to obtain active red mud;
s4, carrying out heat treatment on the aqueous solution containing melamine and activated red mud to obtain the red mud modified carbon nitride nano material.
The innovation of the method is that the carbon nitride is modified by extracting useful components from the red mud and removing useless components. The activated red mud or iron-aluminum oxide obtained by the method contains unsaturated iron ions, and can react with melamine under the condition of water content to generate porous carbon nitride. Specifically, an acid leaching method is adopted to dissociate iron and aluminum elements in the red mud into a liquid phase, iron ions and aluminum ions are precipitated into a solid phase by adjusting the pH value, and then the active red mud is obtained by calcining treatment; then mixing the activated red mud and melamine, carrying out heat treatment in the presence of water, and carrying out stripping and pore-forming on carbon nitride through the reaction of iron ions in the activated red mud and cyano-groups in the melamine to obtain thin-layer porous carbon nitride; finally, compounding the red mud with active red mud to obtain the red mud modified carbon nitride nano material. The method can effectively increase the added value of the red mud resource product and improve the comprehensive utilization rate of the red mud; the method adopts the means and processes of acid leaching, activation, heat treatment and the like, has the advantages of simple preparation process, low cost and environmental friendliness, and does not need to use complex process flow and equipment.
In step S1 of the present invention, the red mud may be directly leached by acid, or may be leached by acid after dealkalization, which is not limited in the present invention.
In some embodiments of the invention, the red mud is dealkalized and then leached with acid. Further, the dealkalization process specifically comprises the following steps: washing the red mud with water to remove alkali until the red mud is neutral, and then carrying out suction filtration to obtain the dealkalized red mud.
In step S1 of the present invention, the acid used is an inorganic acid. Further, the inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid.
In step S1, the inorganic acid has a molar concentration of 1 to 20mol/L, and further 5 to E
15mol/L, and further 6-12 mol/L; the liquid-solid ratio of the inorganic acid to the red mud is 5-30 mL/g, and further 6-10 mL/g.
In step S1, the temperature in the leaching process is 60-100 ℃, and further 80 ℃; the time is 5-24 hours, further 12-18 hours, and the leaching process is carried out under the condition of stirring.
In step S2, the step of adjusting the pH of the red mud leachate to 8 to 9 to obtain an activated red mud precursor includes: and adjusting the pH value of the red mud leachate to 8-9, centrifuging to obtain a precipitate, and then washing and drying with ethanol to obtain an active red mud precursor.
In step S3, the calcination temperature is 200-700 ℃, further 400-500 ℃, and the calcination time is 1-6 hours, further 2-4 hours, further 2 hours. According to the invention, hydroxide in the precursor can be partially converted into oxide through calcination, so that a small amount of unsaturated iron ions in the activated red mud react with melamine to promote the formation of porous carbon nitride, and the porous carbon nitride is modified by using the activated red mud. If the calcining temperature is too low, incomplete reaction is caused, and the generation of oxides is influenced; if the temperature of calcination is too high, the particles will agglomerate, and the catalytic performance will be affected.
In step S4, in an aqueous solution containing melamine and activated red mud, the mass concentration of the melamine is 0.1-1 g/mL, and further 0.4-0.7 g/mL; the mass ratio of the activated red mud to the melamine is (0.005-0.5): 1, if the mass ratio is too high, the porous structure is destroyed, so that the porous carbon nitride material cannot be formed, and if the mass ratio is too low, the modification effect of the red mud on the carbon nitride is poor. Further (0.025-0.5): 1, and more preferably 0.05.
In step S4, the heat treatment temperature is 450 to 600 ℃, further 500 to 550 ℃, further 550 ℃, and the heat treatment time is 1 to 8 hours, further 2 to 6 hours, further 5.5 hours. If the temperature of the heat treatment is too high, the carbon nitride structure is completely crushed into a small-size nanosheet structure, so that the specific surface area of the nanosheet structure is reduced, and the heterogeneous structure between the activated red mud and the carbon nitride is damaged due to the too high temperature, so that the catalytic performance of the activated red mud and the carbon nitride is influenced; if the temperature of the heat treatment is too low, the forbidden band width of the carbon nitride is larger, and the carbon nitride forms an irregular blocky fault structure, so that the catalytic activity is lower.
In some preferred embodiments of the present invention, the heat treatment process is divided into two stages, wherein the temperature of the first stage is 450-600 ℃, further 500-550 ℃, further 550 ℃, and the heat treatment time is 1-8 hours, further 2-6 hours, further 4 hours; the temperature of the second stage heat treatment is 450-600 ℃, further 500-550 ℃, further 550 ℃, and the time of the heat treatment is 0.5-4 h, further 1-3 h. Further, before the second stage of the heat treatment is started, the first stage product is also cooled to room temperature and ground, so as to obtain thinner nanosheets.
In the invention, the red mud is one or more of sintering process red mud, Bayer process red mud and mixed process red mud.
The second aspect of the invention provides a red mud modified carbon nitride nanomaterial, which is obtained by the preparation method of the red mud modified carbon nitride nanomaterial provided by the first aspect of the invention.
In the invention, the size of the red mud modified carbon nitride nano material is 0.1-1 mu m, and the specific surface area reaches 300-700 m2/g。
The third aspect of the invention provides an application of the red mud modified carbon nitride nano material, and the red mud modified carbon nitride nano material is applied to photocatalytic hydrolysis hydrogen production.
Example 1
A preparation method of a red mud modified carbon nitride nano material comprises the following steps:
(1) washing the original Bayer red mud with water to remove alkali until the red mud is neutral, and then performing reduced pressure suction filtration to obtain the dealkalized red mud;
(2) mixing dried dealkalized red mud 5g with concentrated hydrochloric acid 50mL to obtain mixed slurry, heating to 80 ℃, carrying out leaching reaction under stirring for 12h to obtain a leaching material, and then separating to obtain a supernatant and a residue;
(3) adjusting the pH value of the supernatant to 8.0, centrifuging to obtain a precipitate, washing with ethanol, and drying to obtain an active red mud precursor;
(4) calcining the activated red mud precursor in a tubular furnace for 2 hours at the calcining temperature of 400 ℃ to obtain activated red mud;
(5) mixing 2.0g of melamine, 0.05g of activated red mud and 3mL of deionized water to obtain a uniform suspension solution; and then carrying out heat treatment on the suspension for 4h at 550 ℃ in an air atmosphere, cooling to room temperature, taking out and grinding, and then continuously carrying out heat treatment for 1.5h at 550 ℃ in the air atmosphere to obtain the red mud modified carbon nitride nano material powder.
The product obtained in this example was analyzed by X-ray diffraction, and the results are shown in FIG. 1, in which the characteristic peaks and C of the product obtained3N4The standard spectra are consistent, and no impurity peak appears, which indicates that the obtained product is a layered red mud modified carbon nitride nano material.
Example 2
A preparation method of a red mud modified carbon nitride nano material comprises the following steps:
(1) washing the original Bayer red mud with water to remove alkali until the red mud is neutral, and then performing reduced pressure suction filtration to obtain the dealkalized red mud;
(2) mixing dried 5g dealkalized red mud with 30mL sulfuric acid (6mol/L) to obtain mixed slurry, heating to 80 ℃, carrying out leaching reaction under the stirring condition for 12h to obtain a leaching material, and then separating to obtain a supernatant and a residue;
(3) adjusting the pH value of the supernatant to 8.0, centrifuging to obtain a precipitate, washing with ethanol, and drying to obtain an active red mud precursor;
(4) calcining the activated red mud precursor in a tubular furnace for 2 hours at the calcining temperature of 400 ℃ to obtain activated red mud;
(5) mixing 2.0g of melamine, 0.2g of activated red mud and 4mL of deionized water to obtain a uniform suspension solution; and then carrying out heat treatment on the suspension for 4h at 550 ℃ in an air atmosphere, cooling to room temperature, taking out and grinding, and then continuously carrying out heat treatment for 1h at 550 ℃ in the air atmosphere to obtain the red mud modified carbon nitride nano material powder.
Fig. 2 is an SEM image of the red mud-modified carbon nitride nanomaterial obtained in this example, and it can be seen from the SEM image that the obtained product is flaky in morphology and 1 μm in size.
Example 3
A preparation method of a red mud modified carbon nitride nano material comprises the following steps:
(1) washing the original Bayer red mud with water to remove alkali until the red mud is neutral, and then performing reduced pressure suction filtration to obtain the dealkalized red mud;
(2) mixing dried dealkalized red mud 5g with concentrated hydrochloric acid 50mL to obtain mixed slurry, heating to 80 ℃, carrying out leaching reaction under stirring for 12h to obtain a leaching material, and then separating to obtain a supernatant and a residue;
(3) adjusting the pH value of the supernatant to 8.0, centrifuging to obtain a precipitate, washing with ethanol, and drying to obtain an active red mud precursor;
(4) calcining the activated red mud precursor in a tubular furnace for 2 hours at the calcining temperature of 500 ℃ to obtain activated red mud;
(5) mixing 2.0g of melamine, 0.1g of activated red mud and 4mL of deionized water to obtain a uniform suspension solution; and then carrying out heat treatment on the suspension for 4h at 550 ℃ in an air atmosphere, cooling to room temperature, taking out and grinding, and then continuously carrying out heat treatment for 1.5h at 550 ℃ in the air atmosphere to obtain the red mud modified carbon nitride nano material powder.
Fig. 3 and 4 are an XRD chart and an SEM chart, respectively, of the product obtained in example 3 of the present invention. As can be seen from fig. 3 and 4, the characteristic peak and C of the red mud-modified carbon nitride nanomaterial obtained in this embodiment3N4The standard spectra are consistent, no impurity peak appears, and the obtained product is flaky.
Example 4
A preparation method of a red mud modified carbon nitride nano material comprises the following steps:
(1) washing the original Bayer red mud with water to remove alkali until the red mud is neutral, and then performing reduced pressure suction filtration to obtain the dealkalized red mud;
(2) mixing dried dealkalized red mud 5g with concentrated hydrochloric acid 50mL to obtain mixed slurry, heating to 80 ℃, carrying out leaching reaction under stirring for 18h to obtain a leaching material, and then separating to obtain a supernatant and a residue;
(3) adjusting the pH value of the supernatant to 9.0, centrifuging to obtain a precipitate, washing with ethanol, and drying to obtain an active red mud precursor;
(4) calcining the activated red mud precursor in a tubular furnace for 2 hours at the calcining temperature of 500 ℃ to obtain activated red mud;
(5) mixing 2.0g of melamine, 1.0g of activated red mud and 5mL of deionized water to obtain a uniform suspension solution; and then carrying out heat treatment on the suspension for 4h at 550 ℃ in an air atmosphere, cooling to room temperature, taking out and grinding, and then continuously carrying out heat treatment for 3h at 550 ℃ in the air atmosphere to obtain the red mud modified carbon nitride nano material powder.
Application example
The layered red mud modified carbon nitride nano material obtained in the embodiment 3 is applied to a hydrogen production experiment by photolysis, and specifically comprises the following steps:
50mg of the red mud modified carbon nitride nano material obtained in the embodiment is weighed and dispersed in 100mL of aqueous solution, then 10mL of methanol is added, and the mixture is placed in a hydrogen production reactor and magnetically stirred in a dark place. Meanwhile, the reaction system is vacuumized to remove air in the reactor. Under the irradiation condition of 200W xenon lamp, commercial product C was used3N4As a comparative experiment, data in the gas chromatography are read at regular intervals to obtain a hydrogen concentration time-varying curve, so that the water decomposition efficiency of the photocatalyst is evaluated.
FIG. 4 shows the red mud-modified carbon nitride nanomaterial prepared in example 3 and a commercial product C3N4The performance comparison chart of decomposing water to produce hydrogen shows that the performance of the obtained red mud modified carbon nitride nano material for producing hydrogen by decomposing water to produce hydrogen is higher than that of the commercialized C3N4The concentration of generated hydrogen at 180min reaches about 5290 mu mol/g, compared with the commercial C3N4Improved by 8.3 times and photocatalytic efficiencyIs obviously enhanced.
The results show that the preparation process is simple and environment-friendly, and the efficiency of the prepared red mud modified carbon nitride nano material for decomposing water to generate hydrogen under simulated sunlight is obviously superior to that of the commercial C3N4。
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. The preparation method of the red mud modified carbon nitride nano material is characterized by comprising the following steps of:
leaching red mud by acid to obtain red mud leachate;
adjusting the pH value of the red mud leachate to 8-9 to obtain an active red mud precursor;
calcining the active red mud precursor to obtain active red mud;
the red mud modified carbon nitride nano material is obtained by carrying out heat treatment on the aqueous solution containing melamine and the activated red mud.
2. The method for preparing the red mud-modified carbon nitride nanomaterial according to claim 1, wherein an acid used in the leaching process is an inorganic acid.
3. The method for preparing the red mud-modified carbon nitride nanomaterial according to claim 2, wherein the inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid in a leaching process.
4. The preparation method of the red mud modified carbon nitride nanomaterial according to claim 2, wherein in a leaching process, the molar concentration of the inorganic acid is 1-20 mol/L, and the liquid-solid ratio of the inorganic acid to the red mud is 5-30 mL/g.
5. The preparation method of the red mud modified carbon nitride nanomaterial according to claim 1, wherein in the leaching process, the leaching temperature is 60-100 ℃ and the leaching time is 5-24 hours.
6. The preparation method of the red mud-modified carbon nitride nanomaterial according to claim 1, wherein the calcination temperature is 200-700 ℃ and the calcination time is 1-6 hours.
7. The preparation method of the red mud-modified carbon nitride nanomaterial according to claim 1, wherein the mass concentration of melamine in an aqueous solution containing melamine and activated red mud is 0.1-1 g/mL; the mass ratio of the activated red mud to the melamine is (0.005-0.5): 1.
8. the preparation method of the red mud modified carbon nitride nanomaterial according to claim 1, wherein the heat treatment temperature is 450-600 ℃, and the heat treatment time is 1-8 hours.
9. The red mud modified carbon nitride nanomaterial is characterized in that the red mud modified carbon nitride nanomaterial is obtained by the preparation method of the red mud modified carbon nitride nanomaterial according to any one of claims 1 to 8.
10. The application of the red mud-modified carbon nitride nanomaterial of claim 9, wherein the red mud-modified carbon nitride nanomaterial is applied to photocatalytic hydrolysis to produce hydrogen.
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