CN114392732B - Composite material based on clay mineral and preparation method thereof - Google Patents
Composite material based on clay mineral and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000002734 clay mineral Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 107
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 22
- 239000002154 agricultural waste Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011246 composite particle Substances 0.000 claims abstract description 18
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000004005 microsphere Substances 0.000 claims abstract description 13
- 239000002070 nanowire Substances 0.000 claims abstract description 13
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims description 79
- 238000003756 stirring Methods 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 238000001816 cooling Methods 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 34
- 238000011010 flushing procedure Methods 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000011812 mixed powder Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 239000002028 Biomass Substances 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000010902 straw Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 8
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- CEKXZSQLUFQAOG-UHFFFAOYSA-N barium(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ba++] CEKXZSQLUFQAOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 10
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000005067 remediation Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 238000007873 sieving Methods 0.000 description 14
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 7
- 239000004927 clay Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 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 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
The invention discloses a clay mineral-based composite material and a preparation method thereof, belonging to the technical field of preparation of composite microsphere particles. The method comprises the steps of firstly synthesizing a substrate material by using clay minerals and agricultural wastes, then synthesizing composite particles of nano titanium dioxide and barium titanate nanowires doped with metal elements in a stepwise manner, and fixing the composite particles of nano titanium dioxide and barium titanate nanowires doped with metal elements on the surface of the substrate material to form microsphere particles. The composite material has the capability of adsorbing and catalyzing and degrading organic pollutants, has stronger renewable capability, and is suitable for the fields of wastewater treatment, environmental remediation and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of composite microsphere particles, and particularly relates to a clay mineral-based composite material and a preparation method thereof.
Background
The clay mineral and the biochar have the characteristics of large specific surface area, have good adsorption effect on heavy metals and organic pollutants in the environment, are low in price, have wide sources of raw materials, are ideal adsorption materials, and have wide application in environment restoration and water treatment. However, as a conventional adsorption material, it is necessary to regenerate it under severe conditions after reaching adsorption saturation, and the regeneration process is complicated and secondary pollution is easily caused. Therefore, there is a need to find an adsorbent material that has a strong adsorption capacity and is easily regenerated. The advanced oxidation method can effectively degrade organic pollutants, combines advanced oxidation with adsorption, and can effectively solve the regeneration problem of the adsorption material. A high-grade oxidation technology with wide application prospect is widely focused on by photocatalysis. Various photocatalytic materials are developed and popularized. The nano titanium dioxide is one of the most widely used photocatalysis materials at present, has a wider forbidden bandwidth, can only absorb ultraviolet light with the wavelength smaller than 387.5nm, therefore, the nano titanium dioxide can only generate photocatalysis reaction under the ultraviolet light, does not generate photocatalysis effect under visible light, however, only less than 5 percent of ultraviolet light in sunlight can be utilized, the utilization rate of pure titanium dioxide to sunlight is very low, the forbidden bandwidth of the nano titanium dioxide doped with metal elements is narrowed, the absorption wavelength moves towards the visible light direction, and the utilization rate of sunlight can be effectively improved. In order to improve the performance of nano titanium dioxide in catalyzing and degrading pollutants, researchers try to modify the nano titanium dioxide by using various methods, wherein doping metal elements has a remarkable effect on improving the photocatalytic performance of the titanium dioxide. In addition, the heterogeneous structure synthesized with other compounds can also effectively improve the photocatalysis performance of the nano titanium dioxide. In addition, the nano titanium dioxide and the piezoelectric material form a composite material, so that the photocatalysis performance of the composite material is remarkably improved, and meanwhile, the piezoelectric catalysis capability of the piezoelectric material is remarkably improved, and further, the stronger capability of catalyzing and degrading organic pollutants is obtained. The barium titanate nanowire is a nano material with excellent piezoelectric performance, and the doped metal element can effectively improve the piezoelectric performance of barium titanate. Therefore, it is needed to provide a metal doped barium titanate and titanium dioxide to obtain a composite material which has the advantages of strong removal of organic pollutants in water, regeneration capability, easy synthesis and wide application prospect.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a clay mineral-based composite material, wherein the composite material is microsphere particles formed by fixing nano titanium dioxide-barium titanate nanowire composite particles doped with metal elements on the surface of a substrate material;
the preparation process comprises the following steps:
1) Uniformly mixing agricultural waste biomass and clay minerals, wherein the mass ratio of the agricultural waste biomass is 20% -40%; mixing evenly mixed powder and urea according to the mass ratio of (3-40): 1, grinding, taking out and putting the materials into a tube furnace after finishing grinding, roasting the materials in a nitrogen atmosphere at 300-850 ℃ for 2-6 hours, and grinding the materials to obtain a material A, namely a substrate material, after cooling the materials to room temperature;
2) Uniformly mixing meta-titanic acid and barium hydroxide octahydrate, controlling the molar ratio of titanium to barium element to be 1:1, adding nitrate solution of metal element while stirring, wherein the molar ratio of metal element to titanium is 1:100, continuously stirring for 30-40 minutes, adding the mixed solution into a high-pressure reaction kettle, calcining for 85 minutes at 210 ℃, taking out a sample after cooling, grinding and crushing, washing sequentially with hydrochloric acid, deionized water, ethanol and deionized water, and drying and grinding the obtained product to obtain a material B, namely barium titanate nanowire doped with the metal element;
3) Mixing 24mL of absolute ethyl alcohol and 2mL of acetic acid with the mass fraction of 80% uniformly to form a mixed solution, adding 1-4 mL of tetrabutyl titanate into the mixed solution under the condition of magnetic stirring, continuously stirring for 30 minutes, adding 50wt% of ethanol solution and nitrate solution of metal elements into the mixed solution, mixing the obtained mixed solution with a material B, wherein the mass fraction of the material B is 10% -40%, continuously stirring for 12 hours, drying the obtained colloid at 80 ℃, placing the dried sample into a tube furnace, heating up to 300 ℃ at the heating rate of 5 ℃/min in an anoxic environment, preserving heat and calcining for 2 hours, cooling down to room temperature at the cooling rate of 5 ℃/min, taking out a calcined product, grinding to powder, washing for 4-6 times by deionized water, filtering, drying the filtered product under the condition of 80 ℃, growing metal element doped titanium dioxide on the metal element doped barium titanate nanowire, and grinding to obtain material C, namely metal element doped nano titanium dioxide-barium titanate nanowire composite particles;
4) Adding the material A into 20-60% hexadecyl trimethyl ammonium bromide solution, and magnetically stirring for 30 minutes to form a substrate material suspension; and (3) adding the material C into deionized water, stirring for 5 minutes, adding the mixture into a substrate material suspension while stirring, magnetically stirring for 3-6 hours, separating the mixture, washing the mixture with deionized water for 3-5 times, vacuum drying at 60 ℃, grinding, then placing the ground mixture into a tube furnace, heating to 300 ℃ in a nitrogen atmosphere, calcining at the temperature of 2-4 hours, naturally cooling to room temperature, and grinding to obtain the composite material.
Before the raw materials in the step 1) are used, the biomass of the agricultural waste is crushed and then passes through a 80-mesh sieve, and the clay mineral is crushed and then passes through the 80-mesh sieve;
the grinding process is to add the mixture into a ball mill for grinding for 6 hours;
the agricultural waste biomass comprises one or more of crop straw, rice hull or fallen leaves;
the clay mineral comprises one or more of attapulgite or montmorillonite.
In the flushing process in the step 2), flushing for 2-4 times each time; the concentration of the hydrochloric acid flushing agent is 0.2mol/L; the drying temperature was 80 ℃.
The nitrate solution of the metal element in the step 2) comprises a nitrate solution of transition metal and a nitrate solution of rare earth metal.
The nitrate solution of the metal element comprises a silver nitrate solution, a zinc nitrate solution or a cerium nitrate solution.
The adding amount of the nitrate solution of the metal element in the step 3) is 1-10% of the molar content of the tetrabutyl titanate.
The clay mineral based composite material obtained by the method.
The invention has the beneficial effects that:
1. according to the invention, the nano titanium dioxide-barium titanate composite particles modified by metal elements are grafted on the substrate material of the clay-based biochar, so that the photocatalysis and the immobilization of the piezoelectric material are realized, the photocatalysis performance and the piezoelectric catalysis performance of the nano composite material are improved, and the composite material is applied to the field of wastewater treatment.
2. Under illumination and ultrasonic conditions, the heterostructure formed by compounding the metal doped barium titanate and the metal doped titanium dioxide shows catalytic performance superior to that of pure barium titanate and titanium dioxide in a single configuration. The microsphere particles formed by fixing the titanium dioxide-barium titanate composite particles doped with metal elements on the surface of the clay-based biochar can remove organic pollutants in water through adsorption and catalysis, and can make use of the catalytic degradation characteristic of the material to enable the material to have a renewable function.
3. In sunlight (100 mW/cm) 2 ) Under the condition of external pressure (ultrasonic 50W,27 kHz), the composite material has degradation capability superior to that of single titanium dioxide and barium titanate, and the removal rate of methylene blue, rhodamine B and the like in 4 hours can be close to 100 percent; the removal rate of the pollutants such as methyl orange and the like in 2 hours can be close to 100 percent. After the composite material is recycled for 9 times, the composite material can still keep a good removal effect on organic pollutants in water, the removal rate is kept above 95%, and good cycle performance is realized.
Drawings
FIG. 1 is a flow chart of the preparation of the composite material of the present invention.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and specific examples:
the preparation method of the composite material based on the clay mineral comprises the steps of firstly synthesizing a substrate material by using the clay mineral and agricultural wastes, then synthesizing composite particles of nano titanium dioxide and barium titanate nanowires doped with metal elements in a stepwise manner, and fixing the composite particles of the nano titanium dioxide and the barium titanate nanowires doped with the metal elements on the surface of the substrate material to form microsphere particles.
The method comprises the steps of obtaining metal element modified barium titanate by utilizing a hydrothermal synthesis method, obtaining metal element doped titanium dioxide-barium titanate composite particles by combining in-situ growth and hydrothermal synthesis, and grafting the composite particles onto a substrate material of clay-based biochar to synthesize the microsphere particle composite material capable of efficiently removing organic pollutants in water.
The doping of the metal elements can effectively improve the photocatalysis and piezocatalysis performance of the composite particles, and remarkably improve the pollutant degradation efficiency of the microsphere particles. In addition, in the process of fixing the composite particles on the clay-based biochar, defects are easily formed on the surface of the clay-based biochar, and the catalyst performance of the composite particles can be further improved by combining elements in the composite particles. Meanwhile, the clay-based biochar has the characteristic of large specific surface area, and provides a large number of adsorption sites for adsorbing organic matters in the process of removing the organic matters in water. Compared with the traditional adsorption material, the microsphere particles provided by the invention have the advantages that the surface-attached composite particles are utilized, and organic pollutants adsorbed on the surface of the microsphere particles are degraded through photocatalysis and piezocatalysis, so that the microsphere particles maintain higher adsorption performance, and further, the stronger regeneration capacity is obtained. The microsphere particles have the capability of adsorbing and catalyzing and degrading organic pollutants, have strong renewable capability, and are suitable for the fields of wastewater treatment, environmental remediation and the like.
The preparation process is shown in figure 1, and comprises the following steps:
1) Pulverizing agricultural waste biomass, sieving with an 80-mesh sieve, taking a screen residue for standby, sieving clay minerals with an 80-mesh sieve, taking a screen residue for standby, uniformly mixing the screened agricultural waste biomass powder and the screened clay mineral powder according to a certain proportion, wherein the mass ratio of the agricultural waste powder is 20% -40%, and mixing the uniformly mixed powder with urea according to the mass ratio of (3-40): 1, grinding for 6 hours in a ball mill, taking out mixed powder after grinding, putting the mixed powder into a tube furnace, roasting for 2-6 hours at 300-850 ℃ in a nitrogen atmosphere, and grinding to obtain a material A after cooling to room temperature;
2) Uniformly mixing 0.15 g of meta-titanic acid and 0.05mol/L of barium hydroxide octahydrate, wherein the molar ratio of titanium to barium is 1:1, adding a nitrate solution of a metal element while stirring, wherein the molar ratio of the metal element to titanium is 1:100, continuously stirring for 30 minutes, adding the mixed solution into a high-pressure reaction kettle, calcining for 85 minutes at 210 ℃, taking out a sample after cooling, grinding and crushing, flushing with 0.2mol/L hydrochloric acid solution for 2-4 times, flushing with deionized water for 2-3 times, flushing with ethanol solution for 2-3 times, flushing with deionized water for 3-4 times, and drying the obtained product at 80 ℃ to obtain a material B after grinding;
3) Mixing 24ml of absolute ethyl alcohol and 2ml of acetic acid with the mass fraction of 80% uniformly to form a mixed solution, adding 1-4 ml of tetrabutyl titanate into the mixed solution under the condition of magnetic stirring, continuously stirring for 30 minutes, adding 50% of ethanol solution and nitrate solution of filtered metal into the mixed solution, mixing the obtained mixed solution with a material B according to a certain proportion, drying the obtained colloid under the condition of 80 ℃ for 12 hours, placing the dried sample into a tube furnace, heating up to 300 ℃ at the heating rate of 5 ℃/min in an anoxic environment, preserving heat and calcining for 2 hours, cooling down to room temperature at the cooling rate of 5 ℃/min, taking out a calcined product, grinding to powder, washing for 4-6 times by deionized water, filtering, drying the filtered product under the condition of 80 ℃, and grinding to obtain a material C;
4) Adding the material A into 20-60% hexadecyl trimethyl ammonium bromide solution by mass fraction, magnetically stirring for 30 min to form a suspension A, adding the material C into deionized water, stirring for 5 min, adding the suspension A while stirring, magnetically stirring for 3-6 h, separating the mixture, washing with deionized water for 3-5 times, vacuum drying at 60 ℃, grinding, then placing into a tube furnace, heating to 300 ℃ under nitrogen atmosphere, calcining for 2-4 h at the temperature, naturally cooling to room temperature, and grinding to obtain the composite material.
Example 1
1) Crushing crop straws, sieving with an 80-mesh sieve, taking a screen residue for later use, sieving clay minerals with an 80-mesh sieve, taking a screen residue for later use, uniformly mixing the screened agricultural waste biomass powder and the screened clay mineral powder according to a certain proportion, wherein the agricultural waste powder accounts for 20% of the mass ratio, and mixing the uniformly mixed powder with urea according to the mass ratio of 10:1, grinding for 6 hours in a ball mill, taking out mixed powder after grinding, putting the mixed powder into a tube furnace, roasting for 3 hours at 800 ℃ in a nitrogen atmosphere, and grinding to obtain a material A after cooling to room temperature;
2) Uniformly mixing 0.15 g of meta-titanic acid and 0.05mol/L of barium hydroxide octahydrate, wherein the molar ratio of titanium to barium is 1:1, adding a cerium nitrate solution while stirring, wherein the molar ratio of cerium to titanium is 1:100, continuously stirring for 30 minutes, adding the mixed solution into a high-pressure reaction kettle, calcining for 85 minutes at 210 ℃, taking out a sample after cooling, grinding and crushing, flushing with 0.2mol/L hydrochloric acid solution for 4 times, flushing with deionized water for 2=3 times, flushing with ethanol solution for 3 times, flushing with deionized water for 4 times, and drying the obtained product at 80 ℃ to obtain a material B after grinding;
3) Mixing 24ml of absolute ethyl alcohol and 2ml of acetic acid with the mass fraction of 80% uniformly to form a mixed solution, adding 1-4 ml of tetrabutyl titanate into the mixed solution under the condition of magnetic stirring, continuously stirring for 30 minutes, adding 50% of ethanol solution and cerium nitrate solution into the mixed solution, mixing the obtained mixed solution with a material B according to a proportion, wherein the mass fraction of the material B is 10%, continuously stirring for 12 hours, drying the obtained colloid at 80 ℃, placing the dried sample into a tube furnace, heating to 300 ℃ at the heating rate of 5 ℃/min in an anoxic environment, preserving heat and calcining for 2 hours, cooling to room temperature at the cooling rate of 5 ℃/min, taking out a calcined product, grinding to powder, washing for 4-6 times by deionized water, filtering, drying the filtered product at 80 ℃, and grinding to obtain a material C;
4) Adding the material A into 40% hexadecyl trimethyl ammonium bromide solution, magnetically stirring for 30 min to form suspension A, adding the material C into deionized water, stirring for 5 min, adding the mixture into the suspension A while stirring, magnetically stirring for 5 h, separating the mixture, washing the mixture with deionized water for 5 times, vacuum drying at 60 ℃, grinding, putting the ground mixture into a tube furnace, heating to 300 ℃ under nitrogen atmosphere, calcining for 3 h at the temperature, naturally cooling to room temperature, and grinding to obtain the composite material.
Comparative example 1
1) Crushing crop straws, sieving with an 80-mesh sieve, taking a screen residue for later use, sieving clay minerals with an 80-mesh sieve, taking a screen residue for later use, uniformly mixing the screened agricultural waste biomass powder and the screened clay mineral powder according to a certain proportion, wherein the agricultural waste powder accounts for 20% of the mass ratio, and mixing the uniformly mixed powder with urea according to the mass ratio of 10:1, grinding for 6 hours in a ball mill, taking out mixed powder after grinding, putting the mixed powder into a tube furnace, roasting for 3 hours at 800 ℃ in a nitrogen atmosphere, and grinding to obtain a material A after cooling to room temperature;
2) Uniformly mixing 0.15 g of meta-titanic acid and 0.05mol/L of barium hydroxide octahydrate, wherein the molar ratio of titanium to barium is 1:1, adding a cerium nitrate solution while stirring, wherein the molar ratio of cerium to titanium is 1:100, continuously stirring for 30 minutes, adding the mixed solution into a high-pressure reaction kettle, calcining for 85 minutes at 210 ℃, taking out a sample after cooling, grinding and crushing, flushing with 0.2mol/L hydrochloric acid solution for 4 times, flushing with deionized water for 2=3 times, flushing with ethanol solution for 3 times, flushing with deionized water for 4 times, and drying the obtained product at 80 ℃ to obtain a material B after grinding;
3) Adding the material A into 40% hexadecyl trimethyl ammonium bromide solution, magnetically stirring for 30 min to form suspension A, adding the material B into deionized water, stirring for 5 min, adding the mixture into the suspension A while stirring, magnetically stirring for 5 h, separating the mixture, washing the mixture with deionized water for 5 times, vacuum drying at 60 ℃, grinding, then placing the mixture into a tube furnace, heating to 300 ℃ under nitrogen atmosphere, calcining for 3 h at the temperature, naturally cooling to room temperature, and grinding to obtain the material.
Comparative example 2
1) Crushing crop straws, sieving with an 80-mesh sieve, taking a screen residue for later use, sieving clay minerals with an 80-mesh sieve, taking a screen residue for later use, uniformly mixing the screened agricultural waste biomass powder and the screened clay mineral powder according to a certain proportion, wherein the agricultural waste powder accounts for 20% of the mass ratio, and mixing the uniformly mixed powder with urea according to the mass ratio of 10:1, grinding for 6 hours in a ball mill, taking out mixed powder after grinding, putting the mixed powder into a tube furnace, roasting for 3 hours at 800 ℃ in a nitrogen atmosphere, and grinding to obtain a material A after cooling to room temperature;
3) Mixing 24ml of absolute ethyl alcohol and 2ml of acetic acid with the mass fraction of 80% uniformly to form a mixed solution, adding 1-4 ml of tetrabutyl titanate into the mixed solution under the condition of magnetic stirring, continuously stirring for 30 minutes, adding 50% of ethanol solution and cerium nitrate solution into the mixed solution, continuously stirring for 12 hours, drying the obtained colloid at 80 ℃, placing the dried sample into a tube furnace, heating to 300 ℃ at the heating rate of 5 ℃/min in an anoxic environment, preserving heat and calcining for 2 hours, cooling to room temperature at the cooling rate of 5 ℃/min, taking out a calcined product, grinding to powder, washing for 4-6 times by deionized water, filtering, drying the filtered product at 80 ℃ and obtaining a material C after grinding;
4) Adding the material A into 40% hexadecyl trimethyl ammonium bromide solution, magnetically stirring for 30 min to form suspension A, adding the material C into deionized water, stirring for 5 min, adding the mixture into the suspension A while stirring, magnetically stirring for 5 h, separating the mixture, washing the mixture with deionized water for 5 times, vacuum drying at 60 ℃, grinding, then placing the mixture into a tube furnace, heating to 300 ℃ under nitrogen atmosphere, calcining for 3 h at the temperature, naturally cooling to room temperature, and grinding to obtain the material.
Comparative example 3
1) Uniformly mixing 0.15 g of meta-titanic acid and 0.05mol/L of barium hydroxide octahydrate, wherein the molar ratio of titanium to barium is 1:1, adding a cerium nitrate solution while stirring, wherein the molar ratio of cerium to titanium is 1:100, continuously stirring for 30 minutes, adding the mixed solution into a high-pressure reaction kettle, calcining for 85 minutes at 210 ℃, taking out a sample after cooling, grinding and crushing, flushing with 0.2mol/L hydrochloric acid solution for 2-4 times, flushing with deionized water for 2-3 times, flushing with ethanol solution for 2-3 times, flushing with deionized water for 3-4 times, and drying the obtained product at 80 ℃ to obtain a material B after grinding;
2) Adding the material A into 40% hexadecyl trimethyl ammonium bromide solution, magnetically stirring for 30 min to form suspension A, adding the material B into deionized water, stirring for 5 min, adding the mixture into the suspension A while stirring, magnetically stirring for 3-6 h, separating the mixture, washing the mixture with deionized water for 5 times, vacuum drying at 60 ℃, grinding, then placing the mixture into a tube furnace, heating to 300 ℃ in nitrogen atmosphere, calcining for 3 h at the temperature, naturally cooling to room temperature, and grinding to obtain the material.
Comparative example 4
1) Crushing crop straws, sieving with an 80-mesh sieve, taking a screen residue for later use, sieving clay minerals with an 80-mesh sieve, taking a screen residue for later use, uniformly mixing the screened agricultural waste biomass powder and the screened clay mineral powder according to a certain proportion, wherein the agricultural waste powder accounts for 20% of the mass ratio, and mixing the uniformly mixed powder with urea according to the mass ratio of 10:1, grinding for 6 hours in a ball mill, taking out mixed powder after grinding, putting the mixed powder into a tube furnace, roasting for 3 hours at 800 ℃ in a nitrogen atmosphere, and grinding to obtain a material after cooling to room temperature.
Performance testing
In the above examples 1 and comparative examples 1 to 4, the composite material prepared in the method of example 1 was designated as material a, undoped titanium dioxide was designated as material B, undoped barium titanate was designated as material C, composite particles of titanium dioxide and barium titanate prepared in the same manner as in the present invention were designated as material D, and clay-based biochar without supporting nano composite particles was designated as material E. 0.01g of each of the above 5 materials was taken, and the weighed materials were added to 50mL of methylene blue solution having a concentration of 10ppm under dark conditions, and after 12 hours of shaking under dark conditions, each was subjected to separate light (100 mW/cm 2 ) In the environment, the environment of single ultrasonic (50W, 27 kHz) and the environment of simultaneous illumination and ultrasonic, the reaction time is recorded, and the reaction is detected to be differentAfter the interval, the methylene blue removal rate was as shown in table 1 below.
TABLE 1 removal of different materials in different reaction environments
In addition, the regeneration performance of the material A was tested, 0.01g of the material A was put into 50mL (10 ppm) of methylene blue solution, after shaking for 12 hours in the dark, the material A was subjected to the conditions of light and ultrasound, after the reaction for 6 hours, the removal rate of methylene blue was measured, and was used as the removal rate at the 1 st cycle, the material A was separated, dried, and then put into 50mL (10 ppm) of methylene blue solution again, the above reaction procedure was repeated to obtain the removal rate 2, and as the removal rate at the 2 nd cycle, and the repeated use effects of the material A were obtained by analogy, as shown in Table 2 below.
Table 2 cyclic test experiments for composite removal effect
Therefore, after repeated use, the material A still has high removal effect on methylene blue.
Example 2
1) Crushing crop straws, sieving with a 80-mesh sieve, taking a screen lower material for later use, crushing attapulgite, sieving with a 80-mesh sieve, taking a screen lower material for later use, uniformly mixing the screened crop straws with the screened attapulgite powder according to a proportion, wherein the crop straw powder accounts for 20% of the mass ratio, and mixing the uniformly mixed powder with urea according to a mass ratio of 10:1, grinding for 6 hours in a ball mill, taking out mixed powder after grinding, putting the mixed powder into a tube furnace, roasting for 3 hours at 800 ℃ in a nitrogen atmosphere, and grinding to obtain a material A after cooling to room temperature;
2) Uniformly mixing 0.15 g of metatitanic acid and 0.05mol/L of barium hydroxide octahydrate, wherein the molar ratio of titanium to barium is 1:1, adding a zinc nitrate solution while stirring, wherein the molar ratio of zinc to titanium is 1:100, continuously stirring for 30 minutes, adding the mixed solution into a high-pressure reaction kettle, calcining for 85 minutes at 210 ℃, taking out a sample after cooling, grinding and crushing, flushing with 0.2mol/L hydrochloric acid solution for 4 times, flushing with deionized water for 2=3 times, flushing with ethanol solution for 3 times, flushing with deionized water for 4 times, and drying the obtained product at 80 ℃ to obtain a material B after grinding;
3) Mixing 24ml of absolute ethyl alcohol and 2ml of acetic acid with the mass fraction of 80% uniformly to form a mixed solution, adding 1-4 ml of tetrabutyl titanate into the mixed solution under the condition of magnetic stirring, continuously stirring for 30 minutes, adding 50% of ethanol solution and zinc nitrate solution into the mixed solution, mixing the obtained mixed solution with a material B according to a proportion, wherein the mass fraction of the material B is 15%, continuously stirring for 12 hours, drying the obtained colloid at 80 ℃, placing the dried sample into a tube furnace, heating to 300 ℃ at the heating rate of 5 ℃/min in an anoxic environment, preserving heat and calcining for 2 hours, cooling to room temperature at the cooling rate of 5 ℃/min, taking out a calcined product, grinding to powder, washing for 4-6 times by deionized water, filtering, drying the filtered product at 80 ℃, and grinding to obtain a material C;
4) Adding the material A into 40% hexadecyl trimethyl ammonium bromide solution, magnetically stirring for 30 min to form suspension A, adding the material C into deionized water, stirring for 5 min, adding the mixture into the suspension A while stirring, magnetically stirring for 5 h, separating the mixture, washing the mixture with deionized water for 5 times, vacuum drying at 60 ℃, grinding, putting the ground mixture into a tube furnace, heating to 300 ℃ under nitrogen atmosphere, calcining for 3 h at the temperature, naturally cooling to room temperature, and grinding to obtain the composite material.
The composite material obtained in example 2 was used to remove rhodamine B according to the performance test procedure described above. Adding 0.01g of the composite material into 50mL of rhodamine B solution with the concentration of 10ppm under the dark condition, oscillating for 12 hours under the dark condition, and then placing the composite material in light (100 mW/cm) 2 ) Under the condition of +ultrasound (50W, 27 kHz)After 4 hours, the removal rate of rhodamine B is higher than 98 percent.
Example 3
1) Pulverizing fallen leaves, sieving with a 80-mesh sieve, taking undersize for later use, sieving montmorillonite clay mineral with a 80-mesh sieve, taking undersize for later use, uniformly mixing the sieved fallen leaf biomass powder and the sieved clay mineral powder according to a proportion, wherein the fallen leaf powder accounts for 30% of the mass ratio, and mixing the uniformly mixed powder with urea according to a mass ratio of 20:1, grinding for 6 hours in a ball mill, taking out mixed powder after grinding, putting the mixed powder into a tube furnace, roasting for 5 hours at 700 ℃ in a nitrogen atmosphere, and grinding to obtain a material A after cooling to room temperature;
2) Uniformly mixing 0.15 g of metatitanic acid and 0.05mol/L of barium hydroxide octahydrate, wherein the molar ratio of titanium to barium is 1:1, adding a zinc nitrate solution while stirring, wherein the molar ratio of zinc to titanium is 1:100, continuously stirring for 30 minutes, adding the mixed solution into a high-pressure reaction kettle, calcining for 85 minutes at 210 ℃, taking out a sample after cooling, grinding and crushing, flushing with 0.2mol/L hydrochloric acid solution for 4 times, flushing with deionized water for 2=3 times, flushing with ethanol solution for 3 times, flushing with deionized water for 4 times, and drying the obtained product at 80 ℃ to obtain a material B after grinding;
3) Mixing 24ml of absolute ethyl alcohol and 2ml of acetic acid with the mass fraction of 80% uniformly to form a mixed solution, adding 1-4 ml of tetrabutyl titanate into the mixed solution under the condition of magnetic stirring, continuously stirring for 30 minutes, adding 50% of ethanol solution and zinc nitrate solution into the mixed solution, mixing the obtained mixed solution with a material B according to a proportion, wherein the mass fraction of the material B is 20%, continuously stirring for 12 hours, drying the obtained colloid at 80 ℃, placing the dried sample into a tube furnace, heating to 300 ℃ at the heating rate of 5 ℃/min in an anoxic environment, preserving heat and calcining for 2 hours, cooling to room temperature at the cooling rate of 5 ℃/min, taking out a calcined product, grinding to powder, washing for 4-6 times by deionized water, filtering, drying the filtered product at 80 ℃, and grinding to obtain a material C;
4) Adding the material A into 40% hexadecyl trimethyl ammonium bromide solution, magnetically stirring for 30 min to form suspension A, adding the material C into deionized water, stirring for 5 min, adding the mixture into the suspension A while stirring, magnetically stirring for 5 h, separating the mixture, washing the mixture with deionized water for 5 times, vacuum drying at 60 ℃, grinding, putting the ground mixture into a tube furnace, heating to 300 ℃ under nitrogen atmosphere, calcining for 3 h at the temperature, naturally cooling to room temperature, and grinding to obtain the composite material.
The resulting composite was used to remove methyl orange according to the performance test procedure described above. 0.01g of the composite material was taken, added to 50mL (10 ppm) of methyl orange solution under dark conditions, and after 12 hours of shaking under dark conditions, each was placed under light (100 mW/cm) 2 ) After 2 hours of reaction under +ultrasound (50W, 27 kHz), the removal rate of methyl orange exceeded 95%.
Claims (5)
1. The preparation method of the clay mineral-based composite material is characterized in that the composite material is microsphere particles formed by fixing nano titanium dioxide-barium titanate nanowire composite particles doped with metal elements on the surface of a substrate material;
the preparation process comprises the following steps:
1) Uniformly mixing agricultural waste biomass and clay minerals, wherein the mass ratio of the agricultural waste biomass is 20% -40%; mixing evenly mixed powder and urea according to the mass ratio of (3-40): 1, grinding, taking out and putting the materials into a tube furnace after finishing grinding, roasting the materials in a nitrogen atmosphere at 300-850 ℃ for 2-6 hours, and grinding the materials to obtain a material A, namely a substrate material, after cooling the materials to room temperature;
the agricultural waste biomass is one or more of crop straw, rice hull or fallen leaves;
the clay mineral is one or two of attapulgite and montmorillonite;
2) Uniformly mixing meta-titanic acid and barium hydroxide octahydrate, controlling the molar ratio of titanium to barium element to be 1:1, adding nitrate solution of metal element while stirring, wherein the metal element is cerium or zinc, the molar ratio of the metal element to titanium is 1:100, continuously stirring for 30-40 minutes, adding the mixed solution into a high-pressure reaction kettle, calcining for 85 minutes at 210 ℃, taking out a sample after cooling, grinding and crushing, washing sequentially with hydrochloric acid, deionized water, ethanol and deionized water, and drying and grinding an obtained product to obtain a material B, namely the barium titanate nanowire doped with the metal element;
3) Mixing 24mL of absolute ethyl alcohol and 2mL of acetic acid with the mass fraction of 80% uniformly to form a mixed solution, adding 1-4 mL of tetrabutyl titanate into the mixed solution under the condition of magnetic stirring, continuously stirring for 30 minutes, adding 50wt% of ethanol solution and nitrate solution of metal elements into the mixed solution, mixing the obtained mixed solution with a material B, wherein the mass fraction of the material B is 10% -40%, continuously stirring for 12 hours, drying the obtained colloid at 80 ℃, placing the dried sample into a tube furnace, heating up to 300 ℃ at the heating rate of 5 ℃/min in an anoxic environment, preserving heat and calcining for 2 hours, cooling down to room temperature at the cooling rate of 5 ℃/min, taking out a calcined product, grinding to powder, washing for 4-6 times by deionized water, filtering, drying the filtered product under the condition of 80 ℃, enabling the metal element doped barium titanate to grow on the metal element doped nanowire, and grinding to obtain a material C, namely the metal element doped nanowire titanium dioxide-nanowire composite particles;
4) Adding the material A into 20% -60% hexadecyl trimethyl ammonium bromide solution by mass fraction, and magnetically stirring for 30 minutes to form a substrate material suspension; and (3) adding the material C into deionized water, stirring for 5 minutes, adding the mixture into a substrate material suspension while stirring, magnetically stirring for 3-6 hours, separating the mixture, washing the mixture with deionized water for 3-5 times, vacuum drying at 60 ℃, grinding, then placing the ground mixture into a tube furnace, heating to 300 ℃ in a nitrogen atmosphere, calcining at the temperature of 2-4 hours, naturally cooling to room temperature, and grinding to obtain the composite material.
2. The method for preparing the clay mineral-based composite material according to claim 1, wherein the step 1) is that before the raw materials are used, the agricultural waste biomass is crushed and then passes through a 80-mesh sieve, and the clay mineral is crushed and then passes through the 80-mesh sieve;
the grinding process is to add into a ball mill for grinding for 6 hours.
3. The method for preparing the clay mineral-based composite material according to claim 1, wherein in the step 2), each time of washing is 2-4 times; the concentration of the hydrochloric acid flushing agent is 0.2mol/L; the drying temperature was 80 ℃.
4. The method for preparing the clay mineral-based composite material according to claim 1, wherein the nitrate solution of the metal element in the step 3) is added in an amount of 1% -10% of the molar content of tetrabutyl titanate.
5. A clay mineral-based composite material obtainable by the process according to any one of claims 1 to 4.
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