CN113479897B - Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof - Google Patents
Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof Download PDFInfo
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- CN113479897B CN113479897B CN202110806007.2A CN202110806007A CN113479897B CN 113479897 B CN113479897 B CN 113479897B CN 202110806007 A CN202110806007 A CN 202110806007A CN 113479897 B CN113479897 B CN 113479897B
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 43
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002135 nanosheet Substances 0.000 title claims abstract description 33
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000725 suspension Substances 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 17
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910015868 MSiO Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000010494 dissociation reaction Methods 0.000 abstract description 4
- 230000005593 dissociations Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000326 transition metal silicate Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 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
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
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Abstract
The application belongs to the technical field of new chemical materials, and particularly relates to a method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof, wherein the preparation process comprises the following steps: firstly, carrying out one-dimensional crystal beam dispersion and dissociation on the attapulgite powder, uniformly dispersing in an acid solution, washing and drying the precipitate to obtain a white precursor. Dispersing the white precursor in water to form suspension, ultrasonic dispersing, and dropping NH 4 NO 3 Transferring the suspension into a polytetrafluoroethylene reaction kettle for microwave hydrothermal reaction, centrifuging to separate out solid after the reaction is finished, washing, drying and grinding the solid into powder to obtain two-dimensional silicate, and applying the two-dimensional silicate to preparing methanol by photocatalytic carbon dioxide. Compared with the traditional noble metal catalyst, the photocatalyst for preparing methanol from carbon dioxide has the advantages of low raw material cost, simple and convenient synthesis method and the like, and is favorable for large-scale popularization.
Description
Technical Field
The application belongs to the technical field of new chemical materials, and particularly relates to a method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof.
Background
In recent years, in order to achieve the national strategic goals of "carbon peak", "carbon neutralization", the utilization of carbon dioxide resources has become a hot spot of research. Modern society development is extremely dependent on stable and reliable energy supplies, forcing people to tighten the development of sustainable and renewable energy to alleviate the dependence on fossil fuels. The photocatalytic reduction of carbon dioxide has been a great research direction for solar energy utilization and storage, and this path can directly hydrogenate carbon dioxide to convert the carbon dioxide into hydrocarbon fuel for people to use. Methanol is the simplest saturated alcohol, is widely used in industries such as organic synthesis, medicine, pesticides, paint, dye, automobile, national defense and the like, and is also an important chemical industry base material and clean liquid fuel. At present, the photocatalyst mostly adopts methods such as noble metal deposition or rare earth ion doping to improve the effect of reducing carbon dioxide, and has higher cost. In addition, part of the catalysts such as indium zinc sulfide and the like have serious influence on the photocatalytic performance due to the fact that flower-shaped spheres of the catalysts are too large and collapse easily. Thus, researchers have turned their view toward a natural mineral which is abundant, inexpensive and has a nano-size, and have been required to develop a novel catalyst capable of overcoming the above-mentioned disadvantages.
The attapulgite is used as a natural mineral clay material, has rich reserves in China, good dispersibility, larger specific surface area and unique one-dimensional nano rod-shaped structure, and is mostly used as a catalyst carrier. Modification of the attapulgite from physicochemical properties may include acidification, basification, surface functionalization, ion exchange, and the like. From the structure, the attapulgite is a hexacyclic base silicate mineral crystal, the special chain layer structure of the attapulgite consists of hexacyclic base silicon oxygen tetrahedrons, the vertexes of the hexacyclic base silicon oxygen tetrahedrons in the attapulgite are alternately turned up and down to form a chain structure, the geological condition formed by the ore itself takes on the chain layer structure due to the existence of metal magnesium atoms as support, the coordination number of cations between layers is usually 6, and under the condition of removing the original cation octahedrons, the space distribution of the attapulgite is remolded and transversely spread. The transition element in the attapulgite is usually Fe 2+ ,Fe 3+ But its content is higherLow, so that its absorptivity to light is low.
Disclosure of Invention
The application aims to provide a preparation and application of a photocatalysis carbon dioxide reduction material with low price, easily available raw materials and high photo-generated electron hole separation efficiency, in particular to a method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof. The preparation method is simple, the synthesis condition is mild, complex and expensive equipment is not needed, and the method is favorable for large-scale popularization.
In order to achieve the purpose of the application, the technical scheme adopted is as follows:
the two-dimensional nano sheet silicate material provided by the application has the following general formula: MSiO 3 Wherein M is any one of Fe, co, cu, ni.
The method for preparing the two-dimensional nano sheet silicate by using the attapulgite comprises the following steps of:
(1) Immersing the attapulgite powder into 3-7 mol/L hydrochloric acid solution, mixing and stirring for pretreatment for 0.5-4 h, wherein the solid-liquid ratio of the attapulgite powder to the hydrochloric acid solution is preferably 1:1. Too high a concentration of hydrochloric acid and too long a pretreatment time may result in dissociation of the hexacyclic based silicon oxygen tetrahedra, and too low a concentration of hydrochloric acid and too short a pretreatment time may result in incomplete removal of metal cations and limit dispersion of the hexacyclic based silicon oxygen tetrahedra. Then washing and drying to obtain pretreated attapulgite powder;
(2) Dispersing the attapulgite powder pretreated in the step (1) into an acid solution (the acid solution can be one of hydrochloric acid, nitric acid or sulfuric acid) with the concentration of less than 5mol/L, carrying out hydrothermal stirring for 4-16 h, separating out solid, washing, and drying to obtain the hexacyclic base type silicon oxygen tetrahedron white precursor. The solid-to-liquid ratio of the pretreated attapulgite powder to the hydrochloric acid solution in the step is preferably 1:10, and the concentration of the hydrochloric acid solution is 2mol/L. The time control of the step is key, the six-ring-shaped basic silicon oxygen tetrahedral unit can be dissociated when the time is too long, the morphology of the synthesized silicate is influenced, the metal ions can be incompletely removed when the time is too short, the purity of the subsequent silicate is influenced, and the morphology of the silicate structure is influenced.
(3) Dispersing the precursor prepared in the step (2)Forming suspension in water and dispersing with ultrasonic wave, then adjusting pH between 6-10 (preferably adding sodium hydroxide solution or dilute hydrochloric acid solution dropwise to adjust pH), dissolving transition metal nitrate in the suspension, and then NH 4 NO 3 Adding ammonia water into the suspension dropwise, and stirring uniformly to obtain a uniform suspension, wherein the molar ratio of silicon to transition metal element to ammonium ion is 1-2:1-4:1-12, and the transition metal nitrate is any one of Fe, co, cu, ni nitrate;
(4) Transferring the uniform suspension obtained in the step (3) into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out microwave reaction for 30-120 min at 120-220 ℃, then naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying to obtain the two-dimensional nano sheet silicate.
Preferably, the concentration of the hydrochloric acid solution in the step (1) is 5mol/L, and the pretreatment time is 2 hours. In the step (1), the purpose of preprocessing the attapulgite powder and hydrochloric acid is to peel off and remove a large amount of metal cations in the attapulgite body and impurities in the chain layer pore canal, and if the concentration of the hydrochloric acid is lower than 3mol/L, incomplete cation removal and uneven dispersion of six-ring-base type silicon oxygen tetrahedron units can be caused to influence the morphology of the subsequent silicate.
In order to ensure that the fully cleaned and incompletely removed cations are avoided, and at the same time, the dissociation of the hexacyclic base type silicon oxide tetrahedral units is avoided to form amorphous agglomerated silicon dioxide, the concentration of hydrochloric acid in the step (2) is not higher than 5mol/L, preferably, the concentration of hydrochloric acid is 2mol/L, the hydrothermal temperature is 80 ℃, and the hydrothermal stirring time is 6 hours. The use of 2mol/L hydrochloric acid in step (2) serves to clean the incompletely removed cations and to avoid dissociation of the hexacyclic silicon oxide tetrahedral units to form amorphous agglomerated silica.
Preferably, the ultrasonic dispersion time in step (3) is 30 minutes.
Preferably, the concentration of the sodium hydroxide solution in the step (3) is 0.5mol/L, and the concentration of the dilute hydrochloric acid solution is 0.1mol/L.
Preferably, in the step (3), the mass concentration of the ammonia water is 28%, and the stirring time is 10min.
Preferably, the vacuum drying temperature in step (4) is 60℃and the vacuum drying time is 2 hours.
The two-dimensional nano sheet silicate prepared by the method is used for photocatalytic carbon dioxide reduction.
The specific method comprises the following steps: dispersing the two-dimensional nano sheet silicate in deionized water, then adding the deionized water into a photocatalytic reaction device, and then adding CO 2 Introducing the mixture into a reaction device at a set flow rate, and then carrying out photocatalytic carbon dioxide reduction to obtain the methanol.
SiO of six-ring base silicon oxygen tetrahedron structure 2 Plays an important role in the present application if SiO of six-ring-based silicon oxygen tetrahedral structure is not added 2 Then the transition metal nitrate is easy to be converted into the transition metal oxide nano-particles in the hydrothermal environment, and the transition metal oxide nano-particles are easier to be agglomerated into balls under the microwave hydrothermal condition, so that the obtained composite catalyst cannot achieve the ideal carbon dioxide reduction effect. The silicate of the two-dimensional nano sheet generated by the method can well overcome the problem, and meanwhile, the silicate of the two-dimensional nano sheet has abundant active sites on the surface and excellent photo-generated electron hole separation efficiency, so that the reaction can be effectively promoted.
The application adopts a microwave hydrothermal method, the molecular motion is changed from the original disordered state into ordered high-frequency vibration under the high-frequency energy field, so that the heating is more uniform, under the condition, smaller structural units forming a six-ring-based silicon oxygen tetrahedron structure can be self-assembled, and a new nano-layer sheet structure is formed under the participation of a complex formed by ammonium ions and transition metal cations.
The application has the advantages that: natural attapulgite clay mineral rich in nature is selected as raw material, and metallic elements of Fe, co, cu or Ni are introduced to replace Mg occupying the central position of cation octahedron 2+ ,Al 3+ The stable structure of the two-dimensional lamellar is synthesized by virtue of microwave hydrothermal reaction, and the silicon oxygen tetrahedron in the transition metal silicate is easy to distort and polarize, so that the migration rate of the photo-generated carriers is enhanced, and the photo-generated electrons are generatedThe hole separation efficiency is high, and the photocatalytic carbon dioxide reduction effect is good; meanwhile, the method has the advantages of rich raw material sources, low cost, environmental friendliness, simple and convenient preparation process and contribution to large-scale popularization.
Drawings
FIG. 1 is an XRD pattern of two-dimensional nanoplatelet silicates prepared in examples 1 to 4;
FIG. 2 is a CuSiO prepared in example 1 3 TEM image of the 50nm scale range of the sample;
FIG. 3 is a summary of methanol yields for examples 1-5 and comparative examples 1-2;
fig. 4 is the XRD pattern of comparative example 1 and comparative example 2 (upper curve corresponds to comparative example 1 and lower curve corresponds to comparative example 2).
Detailed Description
The present application is not limited to the following embodiments, and those skilled in the art can implement the present application in various other embodiments according to the present application, or simply change or modify the design structure and thought of the present application, which fall within the protection scope of the present application. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
The application is further described in detail below in connection with the examples:
examples preferred formulations and procedures are exemplified to further illustrate the application in detail, and to proceed under conventional conditions without specifying specific conditions therein. The raw materials, reagents or equipment used were conventional products commercially available without the manufacturer's knowledge.
Example 1
(1) Mixing attapulgite powder and 5mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 2h, washing, and drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to a solid-liquid ratio of 1:10, separating the solid after hydrothermal stirring for 6 hours at 80 ℃, washing and drying to obtain the hexacyclosiloxy tetrahedral white precursor.
(2) Dispersing 0.3g of the prepared precursor in waterAfter forming a suspension and dispersing with ultrasound for 30min, 0.5mol/L sodium hydroxide solution was added dropwise with stirring, ph=10 was adjusted, and then 10mmol Cu (NO 3 ) 2 ·3H 2 O and 20mmol NH 4 NO 3 An aqueous solution was prepared and added to the suspension, and 1mL of 28% strength aqueous ammonia was added dropwise to the suspension and stirred for 10min.
(3) Transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction at 220 ℃ for 60min, naturally cooling to room temperature, centrifuging to separate out solid, washing, and carrying out vacuum drying at 60 ℃ for 2h to obtain the two-dimensional nano-sheet CuSiO 3 。
For the two-dimensional nano-sheet CuSiO prepared in this example 3 X-ray powder diffraction experiments were performed and the morphology and structure thereof were observed under a transmission electron microscope.
XRD patterns are shown in FIG. 1 by comparison with CuSiO 3 The PDF card of (2) shows CuSiO at angles= 21.64 °, 30.70 °, 36.19 °, 62.26 °, etc 3 The characteristic diffraction characteristic peaks, combined with TEM photo FIG. 2, can prove that the two-dimensional nano-plate CuSiO 3 Is a successful synthesis of (a).
TEM pictures are shown in FIG. 2, from which it can be seen that the upper platelets grow uniformly and the band-like edges CuSiO 3 The film tends to grow into a sheet shape, and the film has uniform thickness and good dispersion.
The two-dimensional nano-sheet CuSiO 3 The method is used for photocatalytic carbon dioxide reduction and comprises the following steps: weighing prepared two-dimensional nano-sheet CuSiO 3 0.05g of the mixture is dispersed in 100mL of deionized water, and then added into a photocatalysis reaction device, CO 2 Introducing CO into the reaction device at a flow rate of 30mL/min 2 After 60min, a 300W xenon lamp was used as a simulated light source to irradiate, 5mL samples were collected every 60min, centrifuged, and analyzed quantitatively using a gas chromatography external standard.
The methanol concentration after 6 hours reached 8.16. Mu. Mol.L as measured by the above method -1 。
Example 2
(1) Mixing attapulgite powder and 5mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 2h, washing, and drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to a solid-liquid ratio of 1:10, separating the solid after hydrothermal stirring for 6 hours at 80 ℃, washing and drying to obtain the hexacyclosiloxy tetrahedral white precursor.
(2) Dispersing 0.6g of the prepared precursor in water to form a suspension and dispersing with ultrasound for 30min, then, while stirring, dropwise adding 0.5mol/L sodium hydroxide solution, adjusting pH=9, and then, dispersing 10mmol Ni (NO 3 ) 2 ·3H 2 O and 40mmol NH 4 NO 3 An aqueous solution was prepared and added to the suspension, and 1mL of 28% strength aqueous ammonia was added dropwise to the suspension and stirred for 10min.
(3) Transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 120min at the temperature of 200 ℃, naturally cooling to room temperature, centrifuging to separate out solid, washing, and carrying out vacuum drying at the temperature of 60 ℃ for 2h. Obtaining the two-dimensional nano-sheet Ni 2 SiO 4 。
The subsequent detection method for photocatalytic carbon dioxide reduction is as in example 1, and the result shows that the methanol concentration reaches 3.68 mu mol L after 6 hours -1 。
Example 3
(1) Mixing attapulgite powder and 5mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 2h, washing, and drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to a solid-liquid ratio of 1:10, separating the solid after hydrothermal stirring for 6 hours at 80 ℃, washing and drying to obtain the hexacyclosiloxy tetrahedral white precursor.
(2) Dispersing 0.6g of the prepared precursor in water to form a suspension and dispersing with ultrasound for 30min, then dropwise adding 0.5mol/L sodium hydroxide solution while stirring, adjusting pH=8, and then dispersing 20mmol Co (NO 3 ) 2 ·3H 2 O and 30mmol NH 4 NO 3 An aqueous solution was prepared and added to the suspension, and 1mL of 28% strength aqueous ammonia was added dropwise to the suspension and stirred for 10min.
(3) Transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, and carrying out microwave reaction for 120min at 170 ℃ along withNaturally cooling to room temperature, centrifuging to separate out solid, washing, and vacuum drying at 60 ℃ for 2h. Obtaining the two-dimensional nano sheet Co 2 SiO 4 。
The subsequent detection method for photocatalytic carbon dioxide reduction is as in example 1, and the result shows that the methanol concentration reaches 2.74 mu mol.L after 6 hours -1 。
Example 4
(1) Mixing attapulgite powder and 5mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 2h, washing, and drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to a solid-liquid ratio of 1:10, separating the solid after hydrothermal stirring for 6 hours at 80 ℃, washing and drying to obtain the hexacyclosiloxy tetrahedral white precursor.
(2) Dispersing 0.9g of the prepared precursor in water to form a suspension and dispersing with ultrasound for 30min, then, while stirring, dropwise adding 0.5mol/L sodium hydroxide solution and 0.1mol/L dilute hydrochloric acid solution, adjusting pH=7, and subsequently, dispersing 30mmol Fe (NO 3 ) 2 ·6H 2 O and 60mmol NH 4 NO 3 An aqueous solution was prepared and added to the suspension, and 1mL of 28% strength aqueous ammonia was added dropwise to the suspension and stirred for 10min.
(3) Transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 60min at 150 ℃, naturally cooling to room temperature, centrifuging to separate out solid, washing, and carrying out vacuum drying at 60 ℃ for 2h. Obtaining the two-dimensional nano-sheet FeSiO 3 。
The subsequent detection method for photocatalytic carbon dioxide reduction is as in example 1, and the results show that the methanol concentration reaches 1.76. Mu. Mol.L after 6 hours -1 。
Example 5
(1) Mixing attapulgite powder and 3mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 4h, washing, and drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to a solid-to-liquid ratio of 1:10, separating the solid after hydrothermal stirring for 4 hours at 80 ℃, washing and drying to obtain the hexacyclic silicon oxide tetrahedron white precursor.
(2) Dispersing 0.6g of the prepared precursor in water to form suspension, performing ultrasonic dispersion for 30min, and stirringWhile stirring, a dilute hydrochloric acid solution of 0.1mol/L was added dropwise, pH=6 was adjusted, and then 20mmol Cu (NO 3 ) 2 ·3H 2 O and 60mmol NH 4 NO 3 An aqueous solution was prepared and added to the suspension, and 1mL of 28% strength aqueous ammonia was added dropwise to the suspension and stirred for 10min.
(3) Transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 90min at the temperature of 120 ℃, naturally cooling to room temperature, centrifuging to separate out solid, washing, and carrying out vacuum drying at the temperature of 60 ℃ for 2h. Obtaining the two-dimensional nano-sheet CuSiO 3 。
The subsequent detection method for photocatalytic carbon dioxide reduction is as in example 1, and the results show that the methanol concentration reaches 1.62. Mu. Mol.L after 6 hours -1 。
Example 6
(1) Mixing attapulgite powder and 7mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 0.5h, washing, and drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to a solid-liquid ratio of 1:10, separating the solid after hydrothermal stirring for 16 hours at 80 ℃, washing and drying to obtain the hexacyclosiloxy tetrahedral white precursor.
(2) Dispersing 0.3g of the prepared precursor in water to form a suspension and dispersing with ultrasound for 30min, then, while stirring, dropwise adding 0.5mol/L sodium hydroxide solution, adjusting pH=10, and then, dispersing 10mmol Cu (NO 3 ) 2 ·3H 2 O and 20mmol NH 4 NO 3 An aqueous solution was prepared and added to the suspension, and 1mL of 28% strength aqueous ammonia was added dropwise to the suspension and stirred for 10min.
(3) Transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 120min at the temperature of 200 ℃, naturally cooling to room temperature, centrifuging to separate out solid, washing, and carrying out vacuum drying at the temperature of 60 ℃ for 2h. Obtaining two-dimensional CuSiO 3 A nano-sheet.
The subsequent detection method for photocatalytic carbon dioxide reduction is as in example 1, and the results show that the methanol concentration reaches 1.38. Mu. Mol.L after 6 hours -1 。
Comparative example 1
(1) 0.3g of commercialized SiO 2 Dispersing in water to form a suspension, and dispersing with ultrasound for 30min, then dropwise adding 0.5mol/L sodium hydroxide solution with stirring, adjusting pH=10, and then adding 10mmol Cu (NO 3 ) 2 ·3H 2 O and 20mmol NH 4 NO 3 An aqueous solution was prepared and added to the suspension, and 1mL of 28% strength aqueous ammonia was added dropwise to the suspension and stirred for 10min.
(3) Transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 120min at 220 ℃, naturally cooling to room temperature, centrifuging to separate out solid, washing, and carrying out vacuum drying at 60 ℃ for 2h to obtain solid-1.
XRD patterns are shown in FIG. 4 by comparison of CuO and SiO 2 The PDF card of (2) shows that diffraction characteristic peaks peculiar to CuO appear at angles of 35.45 degrees, 28.73 degrees, 48.76 degrees, 61.57 degrees and the like, and CuSiO is not obtained 3 A large number of micron-sized spherical copper oxides were observed from the TEM images.
The subsequent detection method for photocatalytic carbon dioxide reduction is as in example 1, and the results show that the methanol concentration after 6 hours only reaches 0.24 mu mol L -1 。
Comparative example 2
(1) 10mmol of Na 2 SiO 4 ·9H 2 O was dispersed in water to form a suspension and ultrasonically dispersed for 30min, then, 0.5mol/L sodium hydroxide solution was added dropwise with stirring, pH=10 was adjusted, and then 10mmol Cu (NO 3 ) 3 ·3H 2 O and 20mmol NH 4 NO 3 An aqueous solution was prepared and added to the suspension, and 1mL of 28% strength aqueous ammonia was added dropwise to the suspension and stirred for 10min.
(3) Transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 120min at 220 ℃, naturally cooling to room temperature, centrifuging to separate out solid, washing, and carrying out vacuum drying at 60 ℃ for 2h to obtain solid-2.
XRD patterns are shown in FIG. 4, and CuSiO is not obtained 3 The sample, presented with an amorphous shape.
The subsequent detection method for photocatalytic carbon dioxide reduction is as in example 1, and the results show that the methanol concentration after 6 hours only reaches 0.27. Mu. Mol.L -1 。
As can be seen from the above examples, siO obtained by the process according to the application 2 Still maintains the hexacyclic base type silicon oxygen tetrahedral structure, and the SiO is sold in the market 2 The shape of the microsphere is mostly microsphere with smooth surface, and the microsphere does not have a six-ring-based silicon oxygen tetrahedron structure, so that the SiO can not be converted by the attapulgite in application 2 Is effective in (1).
In addition, the SiO2 crystals prepared by a precipitation method (the SiO2 crystals which are loose, finely dispersed and precipitated in a flocculent structure are obtained by acidification of silicate) in the prior art exist in the form of silicon oxygen tetrahedra, but are scattered and unordered, do not have units derived from the six-ring-base silicon oxygen tetrahedra in attapulgite, and do not have structural advantages in the process of synthesizing lamellar silicic acid.
The foregoing is only a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art, who is within the scope of the present application, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present application, and should be covered by the scope of the present application.
Claims (10)
1. A method for preparing two-dimensional nano sheet silicate by using attapulgite comprises the following steps: MSiO 3 Wherein, M is any one of Fe, co, cu, ni, its characterized in that: the method comprises the following steps:
(1) Immersing attapulgite powder into 3-7 mol/L hydrochloric acid solution, mixing and stirring for pretreatment for 0.5-4 h, then washing and drying to obtain pretreated attapulgite powder;
(2) Dispersing the attapulgite powder pretreated in the step (1) into an acid solution with the concentration of less than 5mol/L, carrying out hydrothermal stirring for 4-16 hours, separating out solids, washing and drying to obtain a hexacyclic basic silicon oxygen tetrahedron white precursor;
(3) Dispersing the precursor prepared in the step (2) in waterForming suspension, ultrasonic dispersing, regulating pH to 6-10, dissolving transition metal nitrate in the suspension, and NH-dispersing 4 NO 3 Adding ammonia water into the suspension dropwise, and stirring uniformly to obtain a uniform suspension, wherein the molar ratio of silicon to transition metal element to ammonium ion is 1-2:1-4:1-12, and the transition metal nitrate is any one of Fe, co, cu, ni nitrate;
(4) Transferring the uniform suspension obtained in the step (3) into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out microwave reaction for 30-120 min at 120-220 ℃, then naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying to obtain the two-dimensional nano sheet silicate.
2. The method for preparing two-dimensional nano sheet silicate by using attapulgite according to claim 1, wherein the method comprises the following steps: in the step (1), the solid-to-liquid ratio of the attapulgite powder to the hydrochloric acid solution is 1:1, the concentration of the hydrochloric acid solution is 5mol/L, and the pretreatment time is 2 hours.
3. The method for preparing two-dimensional nano sheet silicate by using attapulgite according to claim 1, wherein the method comprises the following steps: the solid-to-liquid ratio of the pretreated attapulgite powder to the hydrochloric acid solution in the step (2) is 1:10, the concentration of the hydrochloric acid solution is 2mol/L, the hydrothermal temperature is 80 ℃, and the hydrothermal stirring time is 6h.
4. The method for preparing two-dimensional nano sheet silicate by using attapulgite according to claim 1, wherein the method comprises the following steps: in the step (3), the pH is adjusted by dropwise adding 0.5mol/L of sodium hydroxide solution or 0.1mol/L of hydrochloric acid solution.
5. The method for preparing two-dimensional nano sheet silicate by using attapulgite according to claim 1, wherein the method comprises the following steps: the ultrasonic dispersion time in the step (3) is 30min.
6. The method for preparing two-dimensional nano sheet silicate by using attapulgite according to claim 1, wherein the method comprises the following steps: in the step (3), the mass concentration of the ammonia water is 28%, and the stirring time is 10min.
7. The method for preparing two-dimensional nano sheet silicate by using attapulgite according to claim 1, wherein the method comprises the following steps: the vacuum drying temperature in the step (4) is 60 ℃, and the vacuum drying time is 2 hours.
8. The method for preparing two-dimensional nano sheet silicate by using attapulgite according to claim 1, wherein the method comprises the following steps: the acid solution in the step (2) is one of hydrochloric acid, sulfuric acid or nitric acid.
9. Use of a two-dimensional nanosheet silicate prepared by a method as claimed in any of claims 1-8, wherein: is used for preparing methanol by photocatalytic reduction of carbon dioxide.
10. Use of two-dimensional nanosheet silicate according to claim 9, wherein: comprises dispersing the two-dimensional nano sheet silicate in deionized water, adding into a photocatalysis reaction device, and adding CO 2 Introducing the mixture into a reaction device at a set flow rate, and then carrying out photocatalytic carbon dioxide reduction to obtain the methanol.
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Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1359367A (en) * | 1970-08-31 | 1974-07-10 | Exxon Research Engineering Co | Layered complex metal silicate composition their preparation and use in hydrocarbon conversion reactions |
| NL7613957A (en) * | 1976-12-16 | 1978-06-20 | Shell Int Research | CRYSTALLINE SILICATES. |
| JPH05245A (en) * | 1991-06-24 | 1993-01-08 | Kiyohisa Ota | Conversion of carbon dioxide, carbonic ion or hydrocarbonic ion to high value added substance by photocatalytic action |
| AU8324698A (en) * | 1997-07-15 | 1999-02-10 | University Of Queensland, The | Catalytic conversion of gases via cation-exchangeable alumino-silicate materials |
| JP2005145800A (en) * | 2003-11-19 | 2005-06-09 | National Institute Of Advanced Industrial & Technology | Method of manufacturing layered silicate compound |
| WO2011156971A1 (en) * | 2010-06-18 | 2011-12-22 | 海洋王照明科技股份有限公司 | Halosilicate luminescent materials and preparation methods and uses thereof |
| CN102666387A (en) * | 2009-12-22 | 2012-09-12 | 东曹株式会社 | Novel metal silicate and method for producing the same, nitrogen oxide removing catalyst and method for producing the same, and nitrogen oxide removing method using the catalyst |
| CN105802282A (en) * | 2016-02-29 | 2016-07-27 | 中国科学院兰州化学物理研究所 | Method for preparing red hybridized pigment from red attapulgite clay |
| WO2016123711A1 (en) * | 2015-02-04 | 2016-08-11 | Pc-Cups Ltd. | Metallo-silicate catalyst (msc) compositions, methods of preparation and methods of use in partial upgrading of hydrocarbon feedstocks |
| CN107804854A (en) * | 2017-11-27 | 2018-03-16 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | The method that cupric silicate nanotube is prepared using low-grade attapulgite clay |
| CN108238605A (en) * | 2018-04-08 | 2018-07-03 | 吉林大学 | A kind of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon and preparation method thereof |
| CN108479777A (en) * | 2018-03-28 | 2018-09-04 | 常州大学 | A kind of preparation method and applications of attapulgite composite photo-catalyst |
| KR101920897B1 (en) * | 2017-06-09 | 2018-11-21 | 골든비엔씨 (주) | Method of manufacturing for silica composite using coal ash |
| JP2018202411A (en) * | 2017-05-31 | 2018-12-27 | 古河電気工業株式会社 | Carbon dioxide reduction catalyst structure and method for producing the same, and carbon dioxide reduction device having the carbon dioxide reduction catalyst structure |
| CN109569580A (en) * | 2018-11-29 | 2019-04-05 | 南昌航空大学 | A kind of composite photocatalyst and its preparation method and application |
| CN109911908A (en) * | 2019-03-26 | 2019-06-21 | 中国科学院兰州化学物理研究所 | The method for preparing various structures nano material using the low-grade clay mineral of rich iron |
| CN110603097A (en) * | 2017-04-04 | 2019-12-20 | 沙特基础工业全球技术公司 | Nano zeolite catalyst with high silicon-aluminium ratio |
| CN111437809A (en) * | 2020-04-29 | 2020-07-24 | 江苏纳欧新材料有限公司 | Preparation method and application of rare earth element doped bismuth silicate photocatalyst |
| CN111450814A (en) * | 2020-04-29 | 2020-07-28 | 江苏纳欧新材料有限公司 | Method for preparing zinc silicate catalyst by using natural attapulgite and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005049362A1 (en) * | 2005-10-12 | 2007-04-19 | Basf Ag | Process for the preparation of a silicate |
| JP7090278B2 (en) * | 2018-03-07 | 2022-06-24 | 日立造船株式会社 | CHA type titanosilicate separation membrane and its manufacturing method, and gas separation method |
-
2021
- 2021-07-16 CN CN202110806007.2A patent/CN113479897B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1359367A (en) * | 1970-08-31 | 1974-07-10 | Exxon Research Engineering Co | Layered complex metal silicate composition their preparation and use in hydrocarbon conversion reactions |
| NL7613957A (en) * | 1976-12-16 | 1978-06-20 | Shell Int Research | CRYSTALLINE SILICATES. |
| JPH05245A (en) * | 1991-06-24 | 1993-01-08 | Kiyohisa Ota | Conversion of carbon dioxide, carbonic ion or hydrocarbonic ion to high value added substance by photocatalytic action |
| AU8324698A (en) * | 1997-07-15 | 1999-02-10 | University Of Queensland, The | Catalytic conversion of gases via cation-exchangeable alumino-silicate materials |
| JP2005145800A (en) * | 2003-11-19 | 2005-06-09 | National Institute Of Advanced Industrial & Technology | Method of manufacturing layered silicate compound |
| CN102666387A (en) * | 2009-12-22 | 2012-09-12 | 东曹株式会社 | Novel metal silicate and method for producing the same, nitrogen oxide removing catalyst and method for producing the same, and nitrogen oxide removing method using the catalyst |
| WO2011156971A1 (en) * | 2010-06-18 | 2011-12-22 | 海洋王照明科技股份有限公司 | Halosilicate luminescent materials and preparation methods and uses thereof |
| WO2016123711A1 (en) * | 2015-02-04 | 2016-08-11 | Pc-Cups Ltd. | Metallo-silicate catalyst (msc) compositions, methods of preparation and methods of use in partial upgrading of hydrocarbon feedstocks |
| CA3147965A1 (en) * | 2015-02-04 | 2016-08-11 | Pc-Cups Ltd. | Metallo-silicate catalyst (msc) compositions, methods of preparation and methods of use in partial upgrading of hydrocarbon feedstocks |
| CN105802282A (en) * | 2016-02-29 | 2016-07-27 | 中国科学院兰州化学物理研究所 | Method for preparing red hybridized pigment from red attapulgite clay |
| CN110603097A (en) * | 2017-04-04 | 2019-12-20 | 沙特基础工业全球技术公司 | Nano zeolite catalyst with high silicon-aluminium ratio |
| JP2018202411A (en) * | 2017-05-31 | 2018-12-27 | 古河電気工業株式会社 | Carbon dioxide reduction catalyst structure and method for producing the same, and carbon dioxide reduction device having the carbon dioxide reduction catalyst structure |
| KR101920897B1 (en) * | 2017-06-09 | 2018-11-21 | 골든비엔씨 (주) | Method of manufacturing for silica composite using coal ash |
| CN107804854A (en) * | 2017-11-27 | 2018-03-16 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | The method that cupric silicate nanotube is prepared using low-grade attapulgite clay |
| CN108479777A (en) * | 2018-03-28 | 2018-09-04 | 常州大学 | A kind of preparation method and applications of attapulgite composite photo-catalyst |
| CN108238605A (en) * | 2018-04-08 | 2018-07-03 | 吉林大学 | A kind of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon and preparation method thereof |
| CN109569580A (en) * | 2018-11-29 | 2019-04-05 | 南昌航空大学 | A kind of composite photocatalyst and its preparation method and application |
| CN109911908A (en) * | 2019-03-26 | 2019-06-21 | 中国科学院兰州化学物理研究所 | The method for preparing various structures nano material using the low-grade clay mineral of rich iron |
| CN111437809A (en) * | 2020-04-29 | 2020-07-24 | 江苏纳欧新材料有限公司 | Preparation method and application of rare earth element doped bismuth silicate photocatalyst |
| CN111450814A (en) * | 2020-04-29 | 2020-07-28 | 江苏纳欧新材料有限公司 | Method for preparing zinc silicate catalyst by using natural attapulgite and application thereof |
Non-Patent Citations (8)
| Title |
|---|
| Efficient hydrogen generation over a novel Ni phyllosilicate photocatalyst;Imane Ghiat，等;Journal of Photochemistry & Photobiology A: Chemistry;第111952页 * |
| F. Gonzalez,等.Thermal investigation of acid-activated attapulgites: influence of isomorphic substitution in the octahedral sheet.Thermochimica Acta.1992,第239-246页. * |
| Mesoporous hybrid Zn-silicate derived from red palygorskite clay as a high-efficient adsorbent for antibiotics;Wenbo Wang，等;Microporous and Mesoporous Materials;第317-325页 * |
| Robust nickel silicate catalysts with high Ni loading for CO2 methanation;Lin Liao,等;Chem Asian J.;第678 –689页 * |
| Two-Dimensional Layered Zinc Silicate Nanosheets with Excellent Photocatalytic Performance for Organic Pollutant Degradation and CO2 Conversion;Lan Wang，等;Angew. Chem.;第8187 –8192页 * |
| 光催化还原CO_2材料的研究进展;鲁冰倩;张长明;朱天瑜;陈艳;周文伟;黄晨峰;张小超;;化工新型材料(06);全文 * |
| 活化凹凸棒石对多级孔分子筛合成种类和孔道结构的影响;李红玑;王发良;李享;杨靖;宋经华;李波;;材料工程(04);全文 * |
| 硅酸盐纳米材料的制备及光催化性能探索;乔峥;中国优秀硕士论文全文数据库;全文 * |
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