CN113479896B - Method for preparing calcium copper silicate material by using attapulgite and biomass and application of calcium copper silicate material - Google Patents

Method for preparing calcium copper silicate material by using attapulgite and biomass and application of calcium copper silicate material Download PDF

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CN113479896B
CN113479896B CN202110805500.2A CN202110805500A CN113479896B CN 113479896 B CN113479896 B CN 113479896B CN 202110805500 A CN202110805500 A CN 202110805500A CN 113479896 B CN113479896 B CN 113479896B
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attapulgite
calcium
silicate material
copper silicate
biomass
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CN113479896A (en
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李霞章
张海光
曹子文
姚超
朱劼
纪俊玲
陈群
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Changzhou University
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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
    • B01J35/39—
    • 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
    • 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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    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The application belongs to the technical field of novel material preparation and photocatalytic ammonia synthesis, and in particular relates to a method for preparing a calcium copper silicate material by utilizing attapulgite and biomass and application thereof, wherein attapulgite powder and ammonium sulfate are mixed and calcined, the obtained calcined product is uniformly dispersed into hydrochloric acid solution with a certain concentration, solid precipitate is washed, and SiO is obtained by drying 2 And (3) powder. SiO produced 2 Mixing and calcining the powder, the biomass containing calcium salt and basic copper carbonate to obtain a calcium copper silicate material, and applying the calcium copper silicate material to photocatalytic nitrogen fixation synthesis of ammonia. The method is characterized in that mineral attapulgite rich in nature is skillfully utilized as a raw material, the structure of the mineral attapulgite is recombined, and the calcium copper silicate catalyst with good nitrogen fixation effect is prepared by combining the mineral attapulgite with the rest of cheap biomass materials.

Description

Method for preparing calcium copper silicate material by using attapulgite and biomass and application of calcium copper silicate material
Technical Field
The application belongs to the technical field of novel material preparation and photocatalytic ammonia synthesis, and particularly relates to a method for preparing a calcium copper silicate material by using attapulgite and biomass and application thereof.
Background
The Haber-Bosch process using an iron-based catalyst has been widely used for industrial synthesis of ammonia, but the reaction needs to be performed at high temperature and high pressure, and the energy consumption is huge, and a new process for synthesizing ammonia is needed to be found in the present day of the increasing shortage of energy. In recent years, photocatalytic ammonia synthesis reaction has been widely focused, and the principle is to utilize sunlight to realize conversion from nitrogen to ammonia under the action of a catalyst. However, at present, noble metal deposition or ion doping and other methods are mostly adopted to improve the nitrogen fixation effect of the photocatalyst, so that the cost is high. In addition, part of the catalyst is such as TiO 2 And the photocatalytic performance of the light-emitting diode is seriously affected due to the fact that the light utilization rate of the light-emitting diode is not high due to the high bandwidth.
Disclosure of Invention
The application aims to overcome the problems in the prior art, and provides a preparation and application of a photocatalysis synthesis ammonia catalyst with low cost, easily available raw materials and high photo-generated electron hole separation efficiency, in particular to a method for preparing a calcium copper silicate 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 achieve the purpose of the application, the technical scheme adopted is as follows:
a method for preparing a calcium copper silicate material by using attapulgite and biomass comprises the following steps:
(1) Mixing attapulgite powder and ammonium salt at a mass ratio of 1:1 to the upper partMixing at a ratio of 1:5, placing the mixture in a ceramic crucible, placing the crucible in a muffle furnace, and raising the temperature to 400-700 ℃ at a speed of 1-8 ℃/min (SiO obtained beyond the range) 2 With more impurities, e.g. MgO, caO or Al 2 O 3 And the like, preferably heating to 500 ℃ at 2 ℃ per minute), then naturally cooling to room temperature, dispersing the obtained calcined product into an acid solution, hydrothermally stirring for 1-5 hours, separating out solids (preferably, hydrochloric acid concentration is 2mol/L, solid-to-liquid ratio of the calcined product to the hydrochloric acid is 1:20, and the temperature of the hydrothermally stirring is 80 ℃), washing and drying to obtain white SiO 2 And (3) powder.
(2) Mixing basic cupric carbonate and calcium salt-containing biomass (preferably, eggshell powder and/or shell powder, and in response to selection of biomass mainly containing calcium element) with SiO obtained in step (1) 2 The molar ratio of the powder is 0.5-1: 0.5 to 1: calcining for 1-5 h at 800-1000 ℃ after mixing the materials with a feeding ratio of 0.5-5 (calcium copper silicate material can not be obtained after less than 1h, and the calcium copper silicate is in a lump shape and is not a two-dimensional sheet layer after more than 5h, preferably 2 h), naturally cooling to room temperature, grinding and drying to obtain the calcium copper silicate material.
Further, the obtained calcined product is dispersed into hydrochloric acid solution in the step (1) and is stirred for 1 to 5 hours in a hydrothermal mode, 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 N 2 And carrying out photocatalysis by illumination to obtain ammonia.
In the application, the attapulgite is used as a natural mineral clay material, has rich reserves in China, and has large specific surface area and unique one-dimensional nano rod-shaped structure due to good dispersibility. Because the attapulgite is rich in SiO 2 SiO can be produced by completely destroying its octahedral structure 2 Raw materials and ensure that the rod-shaped structure is unchanged, and SiO in transition metal cation silicate 4 Tetrahedra are susceptible to twisting and polarization, thereby enhancing migration of the photo-active carriers. In addition, silicate-based photocatalysts have broad prospects due to their low cost and abundant reserves. In addition, the main component of the calcium-containing biomass material such as eggshell powder, shell powder and the like is calcium carbonate, calcium ions and copper ions are introduced into the catalytic material through calcination, the calcium-containing biomass material has better adsorption and activation effects on nitrogen in the nitrogen fixation process, the faster reaction proceeding speed is determined, and the introduced calcium and copper metal ions can manufacture defect sites in the material, so that the adsorption and activation of 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 cooperatively adsorb and activate nitrogen molecules, so that the efficiency of photocatalytic nitrogen fixation is improved.
Therefore, compared with the prior art, the application has the advantages that: the method is characterized in that minerals such as natural attapulgite, malachite and the like rich in nature and calcium-containing biomass are selected as raw materials, metal elements Ca and Cu are introduced, and a novel calcium-copper silicate photocatalyst which has a stable structure, a two-dimensional lamellar structure, high photoproduction electron-hole separation efficiency and good photocatalytic ammonia synthesis effect is synthesized by means of high-temperature solid phase reaction; 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 a diagram of 800-CaCuSi prepared in example 1 4 O 10 An XRD pattern of (a) and a corresponding PDF card;
FIG. 2 is a diagram of 800-CaCuSi prepared in example 1 4 O 10 TEM image of the 100nm scale range of the sample.
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:
example 1
(1) 5g of attapulgite powder and ammonium sulfate are mixed according to the mass ratio of 1:1, mixing and placing the mixture into a ceramic crucible, placing the crucible into a muffle furnace, heating to 500 ℃ at a speed of 2 ℃/min, then naturally cooling to room temperature, and obtaining a calcined product according to a solid-to-liquid ratio of 1:20 are dispersed into 2mol/L hydrochloric acid solution, solid is separated out after being stirred for 6 hours under 80 ℃ in a hydrothermal mode, and white SiO is obtained after washing and drying 2 And (3) powder.
(2) 1.11g Cu 2 (OH) 2 CO 3 And 0.6g of prepared SiO from 1.0g of eggshell powder 2 Placing the powder and the mixture in a crucible, transferring to a muffle furnace, calcining for 2h at 800 ℃, naturally cooling to room temperature, grinding and drying to obtain a calcium silicate copper material, namely 800-CaCuSi 4 O 10 。
For 800-CaCuSi prepared in this example 4 O 10 The material is subjected to X-ray powder diffraction to analyze the phase, and the appearance and the structure of the material are observed under a transmission electron microscope.
XRD patterns are shown in FIG. 1, by comparison with CaCuSi 4 O 10 The PDF card of (2) shows CaCuSi at 11.6 °, 23.2 °, 26.3 °, 39.6 °, etc 4 O 10 Characteristic diffraction characteristic peaks, and no impurity peaks, indicate that the 800-CaCuSi prepared by the method 4 O 10 Relatively pure, combined with TEM photograph FIG. 2, can prove 800-CaCuSi 4 O 10 Is a multi-layer stack of two-dimensional sheets.
The application also provides an application method of the photocatalyst for synthesizing ammonia by photocatalysis.
The application method comprises the following steps: weighing the prepared calcium copper silicate material 800-CaCuSi 4 O 10 0.04g was dissolved in 100mL deionized water,then adding the mixture into a photocatalysis reaction device, N 2 Introducing into a reaction device at a flow rate of 60mL/min, and introducing N 2 After 30min, a xenon lamp of 300W is used as a simulated light source for irradiation, 10mL of sample is collected every 30min, nahner reagent is added, supernatant liquid is extracted after full reaction, and absorbance is tested by an ultraviolet spectrometer at a wavelength of 420 nm.
800-CaCuSi was measured by the method described above 4 O 10 NH after 120min 4 + The production rate reaches 58.47 mu mol g -1 ·h -1 。
CaCuSi obtained when the calcination temperature in step (2) is 1000℃as measured by the above method 4 O 10 NH after 120min 4 + The production rate reaches 60.32 mu mol g -1 ·h -1 。
Example 2
(1) 5g of attapulgite powder and ammonium sulfate are mixed according to the mass ratio of 1:2 mixing and placing the mixture into a ceramic crucible, placing the crucible into a muffle furnace, heating to 500 ℃ at a speed of 2 ℃/min, naturally cooling to room temperature, and obtaining a calcined product according to a solid-to-liquid ratio of 1:20 are dispersed into 2mol/L hydrochloric acid solution, solid is separated out after being stirred for 6 hours under 80 ℃ in a hydrothermal mode, and white SiO is obtained after washing and drying 2 And (3) powder.
(2) 1.11g Cu 2 (OH) 2 CO 3 And 1.0g eggshell powder to obtain 1.2g SiO 2 Placing the powder and the mixture in a crucible, transferring the crucible into a muffle furnace, calcining for 2 hours at 850 ℃, naturally cooling to room temperature, grinding and drying to obtain 850-CaCuSi 4 O 10 。
Subsequent detection is as in example 1, NH after 120min 4 + The production rate reaches 86.88 mu mol g -1 ·h -1 。
Example 3
(1) 5g of attapulgite powder and ammonium sulfate are mixed according to the mass ratio of 1:3 mixing and placing the mixture in a ceramic crucible, placing the crucible in a muffle furnace, heating to 500 ℃ at a speed of 2 ℃/min, naturally cooling to room temperature, and obtaining a calcined product according to a solid-to-liquid ratio of 1:20 are dispersed into 2mol/L hydrochloric acid solution, and are subjected to hydrothermal stirring at 80 ℃ for 6 hours and then separatedSeparating out solid, washing and drying to obtain white SiO 2 And (3) powder.
(2) 1.11g Cu 2 (OH) 2 CO 3 And 1.8g of prepared SiO from 1.0g of eggshell powder 2 Placing the powder and the mixture in a crucible, transferring to a muffle furnace, calcining for 2h at 900 ℃, naturally cooling to room temperature, grinding and drying to obtain 900-CaCuSi 4 O 10 。
Subsequent detection is as in example 1, NH after 120min 4 + The production rate reaches 124.68 mu mol g -1 ·h -1
Example 4
(1) 5g of attapulgite powder and ammonium sulfate are mixed according to the mass ratio of 1:4 mixing and placing the mixture into a ceramic crucible, placing the crucible into a muffle furnace, heating to 500 ℃ at a speed of 2 ℃/min, naturally cooling to room temperature, and obtaining a calcined product according to a solid-to-liquid ratio of 1:20 are dispersed into 2mol/L hydrochloric acid solution, solid is separated out after being stirred for 6 hours under 80 ℃ in a hydrothermal mode, and white SiO is obtained after washing and drying 2 And (3) powder.
(2) 1.11g Cu 2 (OH) 2 CO 3 And 1.0g eggshell powder 2.4g of the obtained SiO 2 Placing the powder and the mixture in a crucible, transferring the crucible into a muffle furnace, calcining for 2h at 950 ℃, naturally cooling to room temperature, grinding and drying to obtain 950-CaCuSi 4 O 10 。
Subsequent detection is as in example 1, NH after 120min 4 + The production rate reaches 107.96 mu mol g -1 ·h -1 。
Example 5
(1) 5g of attapulgite powder and ammonium sulfate are mixed according to the mass ratio of 1:5 mixing and placing the mixture in a ceramic crucible, placing the crucible in a muffle furnace, heating to 500 ℃ at a speed of 2 ℃/min, naturally cooling to room temperature, and obtaining a calcined product according to a solid-to-liquid ratio of 1:20 are dispersed into 2mol/L hydrochloric acid solution, solid is separated out after being stirred for 6 hours under 80 ℃ in a hydrothermal mode, and white SiO is obtained after washing and drying 2 And (3) powder.
(2) 1.11g Cu 2 (OH) 2 CO 3 And 1.0g eggshell powder to obtain 3.0g SiO 2 Placing the powder and the mixture in a crucible, transferring to a muffle furnace, calcining for 2h at 1000 ℃, naturally cooling to room temperature, grinding and drying to obtain 1000-CaCuSi 4 O 10 。
Subsequent detection is as in example 1, NH after 120min 4 + The production rate reaches 78.45 mu mol g -1 ·h -1 。
Comparative example 1
(1) 5g of attapulgite powder and ammonium sulfate are mixed according to the mass ratio of 1:1, mixing and placing the mixture into a ceramic crucible, placing the crucible into a muffle furnace, heating to 500 ℃ at a speed of 2 ℃/min, then naturally cooling to room temperature, and obtaining a calcined product according to a solid-to-liquid ratio of 1:20 are dispersed into 2mol/L hydrochloric acid solution, solid is separated out after being stirred for 6 hours under 80 ℃ in a hydrothermal mode, and white SiO is obtained after washing and drying 2 And (3) powder.
(2) 2.4g of the prepared SiO was taken 2 Powder and 1.11g Cu 2 (OH) 2 CO 3 Mixing, 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 CuSiO 3 。
Subsequent detection is as in example 1, NH after 120min 4 + The production rate is only 27.36 mu mol g -1 ·h -1 So there is no photo-response in the near infrared region, resulting in CuSiO in the same case 3 The photocatalytic nitrogen fixation effect is weaker than CaCuSi 4 O 10 。
Comparative example 2
(1) 5g of attapulgite powder and ammonium sulfate are mixed according to the mass ratio of 1:1, mixing and placing the mixture into a ceramic crucible, placing the crucible into a muffle furnace, heating to 500 ℃ at a speed of 2 ℃/min, then naturally cooling to room temperature, and obtaining a calcined product according to a solid-to-liquid ratio of 1:20 are dispersed into 2mol/L hydrochloric acid solution, solid is separated out after being stirred for 6 hours under 80 ℃ in a hydrothermal mode, and white SiO is obtained after washing and drying 2 And (3) powder.
(2) 2.4g of the prepared SiO was taken 2 The powder was mixed with 1.0g eggshell powder and placed in a crucible and transferred to a muffle furnaceCalcining at 800 deg.c for 2 hr, cooling naturally to room temperature, grinding and stoving to obtain CaSiO 3 。
Subsequent detection is as in example 1, NH after 120min 4 + The production rate only reaches 33.42 mu mol g -1 ·h -1 。
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 (9)

1. The application of the calcium copper silicate material prepared by using attapulgite and biomass is characterized in that:
the preparation of the calcium silicate copper material by using the 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 into a ceramic crucible, placing the crucible into a muffle furnace, heating to 400-700 ℃ at a speed of 1-8 ℃/min, naturally cooling to room temperature, dispersing the obtained calcined product into an acid solution, hydrothermally stirring for 1-5 h, separating out solids, washing, and drying to obtain white SiO 2 A powder;
(2) Mixing basic cupric carbonate and biomass containing calcium salt with SiO prepared in step (1) 2 The powder is prepared from the following components in percentage by mole (0.5-1): 0.5-1: mixing the materials according to a feeding ratio of 0.5-5, calcining for 1-5 h at 800-1000 ℃, naturally cooling to room temperature, grinding and drying to obtain the calcium copper silicate material;
the application refers to the use for photocatalytic synthesis of ammonia.
2. The use of the calcium copper silicate material prepared from attapulgite and biomass according to claim 1, wherein: the temperature rising speed in the step (1) is 2 ℃/min, and the temperature rises to 500 ℃.
3. The use of the calcium copper silicate material prepared from attapulgite and biomass according to claim 1, wherein: the acid solution in the step (1) is hydrochloric acid solution, the concentration of the hydrochloric acid solution 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 ℃.
4. The use of the calcium copper silicate material prepared from attapulgite and biomass according to claim 1, wherein: the biomass containing calcium salt in the step (2) is eggshell powder and/or shell powder.
5. The use of the calcium copper silicate material prepared from attapulgite and biomass according to claim 1, wherein: the calcination time described in step (2) was 2 h.
6. The use of the calcium copper silicate material prepared from attapulgite and biomass according to claim 1, wherein: 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 N 2 And carrying out photocatalysis by illumination to obtain ammonia.
7. The use of the calcium copper silicate material prepared from attapulgite and biomass according to claim 1, wherein: and (3) dispersing the obtained calcined product in the step (1) into hydrochloric acid solution and carrying out hydrothermal stirring for 1-5 h, wherein the hydrothermal stirring method is mechanical stirring or magnetic stirring.
8. The use of the calcium copper silicate material prepared from attapulgite and biomass according to claim 1, wherein: the ammonium salt in the step (1) is ammonium sulfate, ammonium nitrate or basic ammonium carbonate.
9. The use of the calcium copper silicate material prepared from attapulgite and biomass according to claim 1, wherein: the acid solution in the step (1) is hydrochloric acid, sulfuric acid or nitric acid solution.
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Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2748634A1 (en) * 1976-11-01 1978-05-03 Mitsubishi Chem Ind METHOD FOR THE CATALYTIC REDUCTION OF NITROGEN OXIDES
US4329328A (en) * 1979-10-19 1982-05-11 National Research Development Corporation Method of synthesizing zincosilicate or stannosilicate or titanosilicate material
CA1184739A (en) * 1981-04-23 1985-04-02 Yoshinori Yoshida Crystalline silicate compounds and process for preparing hydrocarbons or unsaturated alcohols by using said silicate compounds as catalyst
JPH04182312A (en) * 1990-11-15 1992-06-29 Tosoh Corp Crystalline copper silicate and it production
CN101745387A (en) * 2009-12-25 2010-06-23 华东理工大学 Catalyst for ammonia synthesis and ammonia decomposition, preparation method and application thereof
JP2011195376A (en) * 2010-03-19 2011-10-06 Fukui Prefecture Metal-doped calcium silicate mesoporous powder and method for producing the same
CN103237599A (en) * 2010-12-07 2013-08-07 国立大学法人东京工业大学 Ammonia synthesis catalyst and ammonia synthesis method
WO2014040220A1 (en) * 2012-09-11 2014-03-20 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method thereof
CN105071215A (en) * 2015-08-27 2015-11-18 浙江大学 Purpose of CaCuSi4O10 two-dimensional crystal, and saturation absorber device composed of the crystal
CN105236430A (en) * 2015-08-20 2016-01-13 浙江大学 Method for preparing CaCuSi4O10 two-dimensional crystals
CN106379906A (en) * 2016-08-12 2017-02-08 陕西科技大学 Preparation method for archaistic blue pigments
CN108479777A (en) * 2018-03-28 2018-09-04 常州大学 A kind of preparation method and applications of attapulgite composite photo-catalyst
CN111215068A (en) * 2018-11-26 2020-06-02 启东市兴腾贸易有限公司 Preparation of Cu/SiO2Method for preparing catalyst
CN111228484A (en) * 2018-11-12 2020-06-05 中国科学院上海硅酸盐研究所 Application of xonotlite and composite biological material containing xonotlite
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
CN111994914A (en) * 2020-08-10 2020-11-27 苏州鼎安科技有限公司 Ion co-doped beta-dicalcium silicate powder, preparation method and application
WO2021113927A1 (en) * 2019-12-13 2021-06-17 The University Of Sydney Doped calcium silicate-based ceramic materials and the use thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9028957B2 (en) * 2012-09-12 2015-05-12 University Of Georgia Research Foundation, Inc. Metal silicate nanosheets, methods of making metal silicate nanosheets, and methods of use

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2748634A1 (en) * 1976-11-01 1978-05-03 Mitsubishi Chem Ind METHOD FOR THE CATALYTIC REDUCTION OF NITROGEN OXIDES
US4329328A (en) * 1979-10-19 1982-05-11 National Research Development Corporation Method of synthesizing zincosilicate or stannosilicate or titanosilicate material
CA1184739A (en) * 1981-04-23 1985-04-02 Yoshinori Yoshida Crystalline silicate compounds and process for preparing hydrocarbons or unsaturated alcohols by using said silicate compounds as catalyst
JPH04182312A (en) * 1990-11-15 1992-06-29 Tosoh Corp Crystalline copper silicate and it production
CN101745387A (en) * 2009-12-25 2010-06-23 华东理工大学 Catalyst for ammonia synthesis and ammonia decomposition, preparation method and application thereof
JP2011195376A (en) * 2010-03-19 2011-10-06 Fukui Prefecture Metal-doped calcium silicate mesoporous powder and method for producing the same
CN103237599A (en) * 2010-12-07 2013-08-07 国立大学法人东京工业大学 Ammonia synthesis catalyst and ammonia synthesis method
WO2014040220A1 (en) * 2012-09-11 2014-03-20 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method thereof
CN105236430A (en) * 2015-08-20 2016-01-13 浙江大学 Method for preparing CaCuSi4O10 two-dimensional crystals
CN105071215A (en) * 2015-08-27 2015-11-18 浙江大学 Purpose of CaCuSi4O10 two-dimensional crystal, and saturation absorber device composed of the crystal
CN106379906A (en) * 2016-08-12 2017-02-08 陕西科技大学 Preparation method for archaistic blue pigments
CN108479777A (en) * 2018-03-28 2018-09-04 常州大学 A kind of preparation method and applications of attapulgite composite photo-catalyst
CN111228484A (en) * 2018-11-12 2020-06-05 中国科学院上海硅酸盐研究所 Application of xonotlite and composite biological material containing xonotlite
CN111215068A (en) * 2018-11-26 2020-06-02 启东市兴腾贸易有限公司 Preparation of Cu/SiO2Method for preparing catalyst
WO2021113927A1 (en) * 2019-12-13 2021-06-17 The University Of Sydney Doped calcium silicate-based ceramic materials and the use thereof
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
CN111994914A (en) * 2020-08-10 2020-11-27 苏州鼎安科技有限公司 Ion co-doped beta-dicalcium silicate powder, preparation method and application

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Flux growth and characterization of cuprorivaite: the influence of temperature, flux, and silica source;A. Bloise，等;Appl. Phys. A;第650页 *
Nanoscience of an Ancient Pigment;Darrah Johnson-McDaniel，等;JACS;第1677−1679页 *
Production and characterization of Egyptian blue and Egyptian green frit，Pierluigi Bianchetti;Pierluigi Bianchetti，等;Journal of Cultural Heritage;第179-188页 *
掺铜硅酸钙生物陶瓷的制备与表征及其促血 管化性能的研究;孔妮;中国优秀硕士学位论文全文数据库 工程科技I辑;全文 *
生物陶瓷在组织工程中的应用;王晓亚;常江;;生命科学(03);全文 *

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