CN113479896A - Method for preparing calcium silicate-copper material by using attapulgite and biomass and application thereof - Google Patents
Method for preparing calcium silicate-copper material by using attapulgite and biomass and application thereof Download PDFInfo
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- attapulgite
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- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 31
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 31
- 239000002028 Biomass Substances 0.000 title claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 title claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 title claims description 16
- 239000011575 calcium Substances 0.000 title claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims description 15
- 239000000843 powder Substances 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000378 calcium silicate Substances 0.000 claims abstract description 10
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 10
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 5
- VAELQCZFRATZQB-UHFFFAOYSA-N calcium copper silicate Chemical compound [Ca+2].[Cu+2].[O-][Si]([O-])([O-])[O-] VAELQCZFRATZQB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 102000002322 Egg Proteins Human genes 0.000 claims description 9
- 108010000912 Egg Proteins Proteins 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 210000003278 egg shell Anatomy 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-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
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 238000000227 grinding Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 241000907663 Siproeta stelenes Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal cation Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052882 wollastonite Inorganic materials 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
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention belongs to the technical field of novel material preparation and photocatalytic synthesis of ammonia, and particularly relates to a method for preparing calcium silicate copper material by using attapulgite and biomass and application thereof2And (3) powder. The SiO obtained2And mixing and calcining the powder, the calcium salt-containing biomass and the basic copper carbonate to obtain a calcium-silicate-copper material which is applied to photocatalytic nitrogen fixation for ammonia synthesis. The invention is characterized in that the attapulgite rich in the natural world is skillfully utilized as the raw material, the structure of the attapulgite is recombined, and the attapulgite and the rest cheap biomass materials are combined to prepare the calcium silicate copper catalyst with good nitrogen fixation effectThe noble metal catalyst has the advantages of low cost of raw materials, simple and convenient synthesis method and the like, and is beneficial to large-scale popularization.
Description
Technical Field
The invention belongs to the technical field of novel material preparation and ammonia photocatalytic synthesis, and particularly relates to a method for preparing a calcium silicate copper material by using attapulgite and biomass and application thereof.
Background
The Haber-Bosch method using an iron-based catalyst has been widely used for industrial synthesis of ammonia, but the reaction needs to be carried out at high temperature and high pressure, and the energy consumption is huge, and a new method for synthesizing ammonia is urgently needed today with increasing shortage of energy. The photocatalytic synthesis of ammonia reaction has attracted much attention in recent years, and its principle is to utilize sunlight to realize the conversion of nitrogen gas into ammonia gas under the action of catalyst. However, the existing photocatalyst mostly adopts methods such as noble metal deposition or ion doping to improve the nitrogen fixation effect, and the cost is high. In addition, part of the catalyst is, for example, TiO2And the photocatalytic performance of the photocatalyst is seriously influenced due to the high bandwidth and low light utilization rate.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide preparation and application of a photocatalytic synthesis ammonia catalyst which is low in price, easily available in raw materials and high in photoproduction electron hole separation efficiency, and particularly provides a method for preparing a calcium silicate copper material by using attapulgite and biomass 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 realize the purpose of the invention, the adopted technical scheme is as follows:
a method for preparing calcium silicate-copper material by using attapulgite and biomass comprises the following steps:
(1) mixing attapulgite powder and ammonium salt in a mass ratio of 1: 1-1: 5, placing the mixture in a ceramic crucible, and putting the crucible in a muffle furnace to rise at a speed of 1-8 ℃/minTo 400-700 deg.C (SiO obtained by exceeding the range)2With relatively high content of impurities such as MgO, CaO or Al2O3And the temperature is raised to 500 ℃ at the speed of 2 ℃/min preferably, then the temperature is naturally reduced to room temperature, the obtained calcined product is dispersed into an acid solution and is subjected to hydrothermal stirring for 1-5 h, then a solid is separated (preferably, the concentration of hydrochloric acid is 2mol/L, the solid-to-liquid ratio of the calcined product to the hydrochloric acid is 1:20, and the temperature of hydrothermal stirring is 80 ℃), washed and dried to obtain white SiO2And (3) powder.
(2) Mixing basic copper carbonate and calcium salt-containing biomass (preferably, calcium salt-containing biomass is eggshell powder and/or shell powder, in response: the selected biomass is mainly calcium element-containing) with the SiO prepared in step (1)2The powder is mixed according to a molar ratio of 0.5-1: 0.5-1: the calcium silicate copper material is obtained by mixing the raw materials according to a feeding ratio of 0.5-5, calcining the mixture for 1-5 hours at the temperature of 1000 ℃ below 800-.
Further, dispersing the calcined product obtained in the step (1) into a hydrochloric acid solution and carrying out hydrothermal stirring for 1-5 hours, wherein the hydrothermal stirring method is mechanical stirring or magnetic stirring.
Further, in the step (1), the ammonium salt is ammonium sulfate, ammonium nitrate or basic ammonium carbonate.
Further, the acid solution in the step (1) is hydrochloric acid, sulfuric acid or nitric acid solution.
The calcium silicate copper material prepared by the method is applied to photocatalytic synthesis of ammonia.
The specific application method is as follows: dispersing the calcium silicate copper material in deionized water, then adding the deionized water into a photocatalytic reaction device, and introducing N2And the ammonia is prepared by illumination catalysis.
In the invention, the attapulgite serving as a natural mineral clay material has abundant reserves in China, and has good dispersibility, larger specific surface area and unique one-dimensional nanorod structure. Because the attapulgite is rich in SiO2Can be prepared by completely destroying its octahedral structureTo obtain SiO2Raw materials, and ensures that the rod-shaped structure of the raw materials is not changed, and SiO in the transition metal cation silicate4The tetrahedra is susceptible to twisting and polarization, thereby enhancing the migration of photogenerated carriers. In addition, silicate-based photocatalysts have a wide prospect due to their low cost and abundant reserves. In addition, the main component of the calcium-containing biomass material such as egg shell powder, shell powder and the like is calcium carbonate, calcium ions and copper ions are introduced into the catalytic material through calcination, in the nitrogen fixation process, the catalytic material has a good adsorption and activation effect on nitrogen, the rapid reaction proceeding speed is determined, and the introduced calcium ions and copper ions can make defect positions in the material, so that the adsorption and activation on the nitrogen are realized. In addition, the introduction of calcium ions can also cause lattice distortion in the original silicate structure to generate oxygen vacancies, and the oxygen vacancies and defect sites can synergistically adsorb and activate nitrogen molecules, so that the photocatalytic nitrogen fixation efficiency is improved.
Therefore, compared with the prior art, the invention has the advantages that: the novel calcium silicate copper photocatalyst which has a stable structure, a two-dimensional lamellar structure, high separation efficiency of photo-generated electron holes and good effect of photo-catalytic synthesis of ammonia is synthesized by selecting minerals such as natural attapulgite, malachite and the like and calcium-containing biomass which are abundant in nature as raw materials and introducing metal elements of Ca and Cu through high-temperature solid-phase reaction; meanwhile, the method has the advantages of rich raw material sources, low cost, environmental friendliness, simple preparation process and contribution to large-scale popularization.
Drawings
FIG. 1 is the 800-CaCuSi prepared in example 14O10XRD pattern of (a) and corresponding PDF card;
FIG. 2 is the 800-CaCuSi prepared in example 14O10TEM image of the sample at scale range of 100 nm.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is described in more detail below with reference to the following examples:
example 1
(1) Mixing 5g of attapulgite powder and ammonium sulfate in a mass ratio of 1:1, placing the mixture in a ceramic crucible, putting the crucible in a muffle furnace, raising the temperature to 500 ℃ at the speed of 2 ℃/min, then naturally cooling the crucible to room temperature, and mixing the obtained calcined product according to the solid-to-liquid ratio of 1:20 is dispersed into 2mol/L hydrochloric acid solution, solid is separated after hydrothermal stirring for 6h at 80 ℃, and white SiO is obtained after washing and drying2And (3) powder.
(2) 1.11g of Cu2(OH)2CO3And 1.0g of eggshell powder 0.6g of SiO2Mixing the powder and the mixture, placing the mixture in a crucible, transferring the mixture to a muffle furnace, calcining the mixture for 2 hours at the temperature of 800 ℃, naturally cooling the mixture to room temperature, grinding the mixture, and drying the ground mixture to obtain calcium-silicate-copper material, which is marked as 800-CaCuSi4O10。
For the 800-CaCuSi prepared in this example4O10The material is subjected to X-ray powder diffraction analysis to analyze the phase thereof, and the appearance and the structure of the material are observed under a transmission electron microscope.
The XRD pattern is shown in figure 1 by comparing CaCuSi4O10The PDF card can know that CaCuSi appears at 11.6 degrees, 23.2 degrees, 26.3 degrees, 39.6 degrees and the like4O10The characteristic diffraction characteristic peak is not existed, and there is no impurity peak, which indicates that 800-CaCuSi prepared by the method is4O10Is relatively pure, and can prove that 800-CaCuSi is combined with a TEM photograph 24O10The structure of (a) is a multi-layer stack of two-dimensional lamellae.
The invention also provides an application method of the photocatalyst for photocatalytic synthesis of ammonia.
The application method comprises the following steps: weighing the prepared calcium silicate copper material 800-CaCuSi4O100.04g of the solution is dissolved in 100mL of deionized water and then added into a photocatalytic reaction device, N2The reaction was fed at a flow rate of 60mL/minDevice, let in N2After 30min, a 300W xenon lamp is used as a simulated light source for irradiation, 10mL of samples are collected every 30min, a Nashin reagent is added, after full reaction, supernatant is extracted, and the absorbance of the supernatant is tested by an ultraviolet spectrometer at the wavelength of 420 nm.
800-CaCuSi measured by the above method4O10NH after 120min4 +The generation rate reaches 58.47 mu mol g-1·h-1。
The CaCuSi obtained when the calcination temperature in the step (2) is 1000 ℃ is measured by the method4O10NH after 120min4 +The generation rate reaches 60.32 mu mol g-1·h-1。
Example 2
(1) Mixing 5g of attapulgite powder and ammonium sulfate in a mass ratio of 1:2 and placing the mixture in a ceramic crucible, putting the crucible in a muffle furnace, raising the temperature to 500 ℃ at the speed of 2 ℃/min, then naturally cooling the crucible to room temperature, and mixing the obtained calcined product according to the solid-liquid ratio of 1:20 is dispersed into 2mol/L hydrochloric acid solution, solid is separated after hydrothermal stirring for 6h at 80 ℃, and white SiO is obtained after washing and drying2And (3) powder.
(2) 1.11g of Cu2(OH)2CO3And 1.0g of eggshell powder 1.2g of SiO2Mixing the powder and the mixture, placing the mixture in a crucible, transferring the mixture to a muffle furnace, calcining the mixture for 2 hours at 850 ℃, naturally cooling the mixture to room temperature, grinding the mixture, and drying the ground mixture to obtain 850-CaCuSi4O10。
Subsequent detection as in example 1, NH after 120min4 +The generation rate reaches 86.88 mu mol g-1·h-1。
Example 3
(1) Mixing 5g of attapulgite powder and ammonium sulfate in a mass ratio of 1: 3, mixing and placing in a ceramic crucible, putting the crucible in a muffle furnace, raising the temperature to 500 ℃ at the speed of 2 ℃/min, then naturally cooling to room temperature, and mixing the obtained calcined product according to the solid-to-liquid ratio of 1:20 is dispersed into 2mol/L hydrochloric acid solution, solid is separated after hydrothermal stirring for 6h at 80 ℃, and white SiO is obtained after washing and drying2And (3) powder.
(2) 1.11g of Cu2(OH)2CO3And 1.0g of eggshell powder 1.8g of SiO2Mixing the powder and the mixture, placing the mixture in a crucible, transferring the mixture to a muffle furnace, calcining the mixture for 2 hours at 900 ℃, naturally cooling the mixture to room temperature, grinding the mixture, and drying the ground mixture to obtain 900-CaCuSi4O10。
Subsequent detection as in example 1, NH after 120min4 +The generation rate reaches 124.68 mu mol g-1·h-1
Example 4
(1) Mixing 5g of attapulgite powder and ammonium sulfate in a mass ratio of 1: 4, mixing and placing in a ceramic crucible, putting the crucible in a muffle furnace, raising the temperature to 500 ℃ at the speed of 2 ℃/min, then naturally cooling to room temperature, and mixing the obtained calcined product according to the solid-liquid ratio of 1:20 is dispersed into 2mol/L hydrochloric acid solution, solid is separated after hydrothermal stirring for 6h at 80 ℃, and white SiO is obtained after washing and drying2And (3) powder.
(2) 1.11g of Cu2(OH)2CO3And 1.0g of eggshell powder and 2.4g of prepared SiO2Mixing the powder and the mixture, placing the mixture in a crucible, transferring the mixture to a muffle furnace, calcining the mixture for 2 hours at 950 ℃, naturally cooling the mixture to room temperature, grinding the mixture, and drying the ground mixture to obtain 950-CaCuSi4O10。
Subsequent detection as in example 1, NH after 120min4 +The generation rate reaches 107.96 mu mol g-1·h-1。
Example 5
(1) Mixing 5g of attapulgite powder and ammonium sulfate in a mass ratio of 1:5, mixing and placing in a ceramic crucible, putting the crucible in a muffle furnace, raising the temperature to 500 ℃ at the speed of 2 ℃/min, then naturally cooling to room temperature, and mixing the obtained calcined product according to the solid-liquid ratio of 1:20 is dispersed into 2mol/L hydrochloric acid solution, solid is separated after hydrothermal stirring for 6h at 80 ℃, and white SiO is obtained after washing and drying2And (3) powder.
(2) 1.11g of Cu2(OH)2CO3And 1.0g of eggshell powder and 3.0g of prepared SiO2Mixing the powders, placing in a crucible, transferring to a muffle furnace, and cutting at 1000 deg.CCalcining for 2 hours, naturally cooling to room temperature, grinding and drying to obtain 1000-CaCuSi4O10。
Subsequent detection as in example 1, NH after 120min4 +The generation rate reaches 78.45 mu mol g-1·h-1。
Comparative example 1
(1) Mixing 5g of attapulgite powder and ammonium sulfate in a mass ratio of 1:1, placing the mixture in a ceramic crucible, putting the crucible in a muffle furnace, raising the temperature to 500 ℃ at the speed of 2 ℃/min, then naturally cooling the crucible to room temperature, and mixing the obtained calcined product according to the solid-to-liquid ratio of 1:20 is dispersed into 2mol/L hydrochloric acid solution, solid is separated after hydrothermal stirring for 6h at 80 ℃, and white SiO is obtained after washing and drying2And (3) powder.
(2) 2.4g of the SiO obtained are taken2Powder with 1.11g Cu2(OH)2CO3Mixing, placing in a crucible, transferring into a muffle furnace, transferring into the muffle furnace, calcining at 800 deg.C for 2h, naturally cooling to room temperature, grinding, and oven drying to obtain CuSiO3。
Subsequent detection as in example 1, NH after 120min4 +The production rate only reaches 27.36 mu mol g-1·h-1So there is no photoresponse in the near infrared region, resulting in CuSiO under the same conditions3The photocatalysis nitrogen fixation effect is weaker than that of CaCuSi4O10。
Comparative example 2
(1) Mixing 5g of attapulgite powder and ammonium sulfate in a mass ratio of 1:1, placing the mixture in a ceramic crucible, putting the crucible in a muffle furnace, raising the temperature to 500 ℃ at the speed of 2 ℃/min, then naturally cooling the crucible to room temperature, and mixing the obtained calcined product according to the solid-to-liquid ratio of 1:20 is dispersed into 2mol/L hydrochloric acid solution, solid is separated after hydrothermal stirring for 6h at 80 ℃, and white SiO is obtained after washing and drying2And (3) powder.
(2) 2.4g of the SiO obtained are taken2Mixing the powder with 1.0g egg shell powder, placing in a crucible, transferring into a muffle furnace, calcining at 800 deg.C for 2 hr, naturally cooling to room temperature, grinding, and oven drying to obtain CaSiO3。
Subsequent detection as in example 1, NH after 120min4 +The formation rate only reaches 33.42 mu mol g-1·h-1。
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
Claims (10)
1. A method for preparing calcium silicate-copper material by using attapulgite and biomass is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing attapulgite powder and ammonium salt in a mass ratio of 1: 1-1: 5, placing the mixture in a ceramic crucible, placing the crucible in a muffle furnace, heating to 400-700 ℃ at a speed of 1-8 ℃/min, naturally cooling to room temperature, dispersing the obtained calcined product in an acid solution, carrying out hydrothermal stirring for 1-5 h, separating out a solid, washing, and drying to obtain white SiO2Powder;
(2) mixing basic copper carbonate and calcium salt-containing biomass with the SiO prepared in step (1)2The powder is mixed according to a molar ratio of 0.5-1: 0.5-1: mixing the materials according to a feeding ratio of 0.5-5, calcining the mixture for 1-5 hours at the temperature of 800-.
2. The method for preparing calcium silicate-copper material by using attapulgite and biomass according to claim 1, which is characterized in that: the temperature rise speed in the step (1) is 2 ℃/min and is increased to 500 ℃.
3. The method for preparing calcium silicate-copper material by using attapulgite and biomass according to claim 1, which is characterized in that: the concentration of the hydrochloric acid solution in the step (1) is 2mol/L, the solid-to-liquid ratio of the calcined product to the hydrochloric acid is 1:20, and the hydrothermal stirring temperature is 80 ℃.
4. The method for preparing calcium silicate-copper material by using attapulgite and biomass according to claim 1, which is characterized in that: the biomass containing calcium salt in the step (2) is egg shell powder and/or shell powder.
5. The method for preparing calcium silicate-copper material by using attapulgite and biomass according to claim 1, which is characterized in that: the calcination time in the step (2) is 2 h.
6. The application of the calcium-silicate-copper material prepared by the method for preparing the calcium-silicate-copper material by using the attapulgite and the biomass as claimed in any one of claims 1 to 5 is characterized in that: used for photocatalytic synthesis of ammonia.
7. The application of the calcium silicate-copper material prepared by the method for preparing the calcium silicate-copper material by using the attapulgite and the biomass as claimed in claim 6 is characterized in that: the method comprises the following steps: dispersing the calcium silicate copper material in deionized water, then adding the deionized water into a photocatalytic reaction device, and introducing N2And the ammonia is prepared by illumination catalysis.
8. The method for preparing calcium silicate-copper material by using attapulgite and biomass according to claim 1, which is characterized in that: dispersing the calcined product obtained in the step (1) into a hydrochloric acid solution, and carrying out hydrothermal stirring for 1-5 h, wherein the hydrothermal stirring method is mechanical stirring or magnetic stirring.
9. The method for preparing calcium silicate-copper material by using attapulgite and biomass according to claim 1, which is characterized in that: in the step (1), the ammonium salt is ammonium sulfate, ammonium nitrate or basic ammonium carbonate.
10. The method for preparing calcium silicate-copper material by using attapulgite and biomass according to claim 1, which is characterized in that: the acid solution in the step (1) is hydrochloric acid, sulfuric acid or nitric acid solution.
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