CN111450814B - Method for preparing zinc silicate catalyst by using natural attapulgite and application thereof - Google Patents
Method for preparing zinc silicate catalyst by using natural attapulgite and application thereof Download PDFInfo
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- 239000004110 Zinc silicate Substances 0.000 title claims abstract description 55
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 235000019352 zinc silicate Nutrition 0.000 title claims abstract description 55
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 36
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 47
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 39
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 35
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000011592 zinc chloride Substances 0.000 claims abstract description 15
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000002835 absorbance Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
- 235000010755 mineral Nutrition 0.000 abstract description 3
- 239000011707 mineral Substances 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- -1 ZnAl LDH Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the technical field of mineral modification, and particularly relates to a method for preparing a zinc silicate catalyst by using natural attapulgite and application thereof. The preparation method comprises the following steps: (1) Placing attapulgite and ammonium sulfate in a crucible, and treating the calcined product with hydrochloric acid solution; (2) Adding tetramethylammonium hydroxide into deionized water, adding the silicon dioxide prepared in the step (1) under vigorous stirring, then adding zinc chloride, and then transferring to a microwave hydrothermal kettle for hydrothermal reaction to obtain zinc silicate. The invention adopts the natural ore attapulgite as the silicon source for synthesizing the zinc silicate, the raw materials are cheap and easy to obtain, the preparation method is simple, and the synthesized two-dimensional ultrathin zinc silicate nanosheet has the advantages of large specific surface area, abundant active sites and the like, and simultaneously realizes the reduction of nitrogen into ammonia under mild conditions.
Description
Technical Field
The invention belongs to the technical field of mineral modification, and particularly relates to a method for preparing a two-dimensional ultrathin nanosheet zinc silicate photocatalyst by using attapulgite as a silicon source and application thereof.
Background
Ammonia is an important inorganic chemical product and plays a significant role in national economic production. However, in industrial production, ammonia is synthesized by the Haber-Bosh process under extreme conditions (673-873K, 20-40 MPa). The consumption of fossil fuel in the industrial ammonia synthesis process is extremely highLarge, inevitable, large amount of CO 2 And (5) discharging. Thus, nitrogen is reduced to ammonia (NH) under mild conditions 3 ) Is a problem to be solved urgently.
In recent years, solar energy is converted into chemical energy by using a solar photocatalytic technology, and the synthesis of ammonia by light-fixation nitrogen is receiving much attention. As a photocatalyst, solar energy must be efficiently absorbed to generate a large number of charge carriers (electron-hole pairs), rapidly separate these charge carriers to reduce recombination, strongly adsorb reactants to react with mobile carriers, and have valence and conduction bands suitable for oxidation and reduction reactions. At present, most of the widely applied optical nitrogen fixation materials have strict requirements on reaction conditions, higher cost and small photoresponse range.
Silicate mineral materials are typically inorganic materials and are widely used as catalyst supports and adsorbents due to their low cost and abundant reserves. However, the photocatalytic performance of silicate materials has been almost ignored to date. Attapulgite clay (ATP for short) is a water-rich magnesium aluminum silicate clay mineral, has a special fibrous crystal structure, and has the advantages of unique void structure, strong adsorption capacity and the like. However, the natural attapulgite has low photocatalytic efficiency, so that the attapulgite needs to be modified to improve the photocatalytic efficiency. At present, zinc-type layered double hydroxides (such as ZnAl LDH, znCr LDH and ZnTi LDH) are available, a known class of anionic clay has been used as a photocatalyst for degrading organic dyes and pesticides, but the zinc-type layered double hydroxides are white in color and have weak absorption of light.
Disclosure of Invention
Because most of the attapulgite is silicon dioxide, the attapulgite can be treated by acid dipping, calcining and other methods to be converted into silicon dioxide, so the invention utilizes the silicon dioxide in natural minerals to synthesize the zinc silicate photocatalyst.
In order to fully utilize natural silicon source, the invention uses attapulgite clay, hydrochloric acid, ammonium sulfate, zinc chloride and tetramethyl ammonium hydroxide as main raw materials, combines a calcining method and a microwave hydrothermal method, and utilizes silicon dioxide in the extracted attapulgite to synthesize the zinc silicate photocatalyst. And selecting proper calcination temperature and time, proper hydrochloric acid concentration and acid treatment time, microwave hydrothermal temperature and other technological parameters to obtain the zinc silicate photocatalyst.
The invention relates to a preparation method of a zinc silicate photocatalyst, which comprises the following specific steps:
(1) Weighing a certain amount of attapulgite and ammonium sulfate, placing the attapulgite and ammonium sulfate in a crucible, calcining for 1-3 h at 550 ℃ in a muffle furnace, and then placing the crucible in a 3mol/L hydrochloric acid solution for treatment for 2-4 h;
wherein the mass ratio of the attapulgite to the ammonium sulfate is 1.33-1:3; the hydrochloric acid solution was diluted to 3mol/L with 35% analytical pure hydrochloric acid.
(2) Adding a small amount of tetramethylammonium hydroxide into deionized water, adding the silicon dioxide prepared in the step (1) under vigorous stirring, then adding a certain amount of zinc chloride, and then transferring the mixture into a microwave hydrothermal kettle for hydrothermal reaction for 60-90 min at the hydrothermal temperature of 140-180 ℃ to obtain the zinc silicate.
The tetramethylammonium hydroxide used in the experiment was 25% aqueous tetramethylammonium hydroxide having a concentration of about 2.38mol/L.
The adding amount of the tetramethylammonium hydroxide corresponding to the silicon dioxide is as follows: 2.6 ml.
The addition amount of zinc chloride relative to silicon dioxide is 0.5-4:1.
The invention also provides a photocatalytic application of the zinc silicate, and the zinc silicate photocatalyst is used for synthesizing ammonia through photocatalysis.
The application method comprises the following steps: weighing 0.04g of prepared zinc silicate photocatalyst, dissolving in 100mL of deionized water, and adding into a photocatalytic reaction device, N 2 The reaction apparatus was then charged at a flow rate of 60 mL/min. After 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.
Compared with the prior art, the invention has the beneficial effects that
(1) The invention adopts the attapulgite which is natural ore as the silicon source for synthesizing the zinc silicate, and the raw materials are cheap and easy to obtain, thereby reducing the production cost, saving the energy consumption and realizing the reduction of nitrogen into ammonia under mild conditions.
(2) According to the invention, the rod-shaped attapulgite is converted into two-dimensional ultrathin nanosheet zinc silicate by a liquid phase growth method, the zinc silicate prepared by the method has the advantages of stable structure, uniform particle size and thickness, less impurities and controllability, the ultrathin structure solves the problem of electron-hole recombination, the high reduction potential of the material is ensured, and the nitrogen fixation reaction is more favorably carried out.
(3) The method for preparing the zinc silicate is simpler, and the synthesized zinc silicate with the ultrathin sheet structure has rich active sites and is beneficial to the adsorption of nitrogen.
The invention is further illustrated with reference to the following figures and examples.
Drawings
FIG. 1 is an XRD spectrum of attapulgite, silica and zinc silicate;
FIG. 2 is a TEM image of zinc silicate prepared in example 1, taken on a scale of 100 nm;
FIG. 3 is an XRD spectrum of attapulgite, silica and zinc silicate prepared in comparative example 4;
fig. 4 is a TEM picture of zinc silicate prepared in comparative example 4.
Detailed Description
Example 1
(1) Firstly weighing 2g of attapulgite, 6g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, putting the calcined attapulgite in 3mol/L salt solution at 80 ℃, treating for 2h in water bath, centrifuging, washing for multiple times until the solution is neutral, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of the silicon dioxide prepared in the step (1) under vigorous stirring, adding 0.5g of zinc chloride after the silicon dioxide is dissolved, then transferring the solution into a microwave hydrothermal kettle, setting the microwave frequency to be 2450MHz and 2450MHz, carrying out hydrothermal reaction for 90min, and obtaining the zinc silicate at the hydrothermal temperature of 160 ℃.
The zinc silicate prepared in this example was subjected to an X-ray diffraction experiment, and the structure and morphology thereof were observed under a transmission electron microscope, and the XRD spectrum of the silica and attapulgite is shown in fig. 1: the calcined and acid-treated attapulgite is completely converted into silicon dioxide, and the silicon dioxide is completely converted into zinc silicate after hydrothermal reaction, so that almost no other impurities are generated.
TEM representation of the zinc silicate prepared in the embodiment shows that the zinc silicate is a two-dimensional ultrathin nanosheet with a large specific surface area, and the specific surface area of the obtained zinc silicate is about 238m 2 /g。
The invention also provides a method for synthesizing ammonia by photocatalysis by using the material, which comprises the following steps: weighing 0.04g of the prepared composite material, dissolving the composite material in 100mL of deionized water, and then adding the mixture into a photocatalytic reaction device, wherein N is 2 Introducing into a reaction device at a flow rate of 60mL/min, and introducing N 2 Irradiating by using a 300W xenon lamp as a simulated light source after 30min, collecting 10mL of samples every 30min, adding a Nashin reagent, extracting supernatant after full reaction, and testing the absorbance of the supernatant by using an ultraviolet spectrometer at the wavelength of 420nm, wherein the ammonia generation rate of the samples is measured as follows: the generation of ammonia gas from zinc silicate is about 134 mu mol.L -1 ·h -1 The ammonia generated by attapulgite is about 21 mu mol.L -1 ·h -1 。
Example 2
(1) Firstly weighing 2g of attapulgite, placing 2g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, placing in 3mol/L salt solution after calcining, carrying out water bath treatment for 3h at 80 ℃, then centrifuging, washing for multiple times until the solution is neutral, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of silicon dioxide prepared in the step (1) under vigorous stirring, adding 0.25g of zinc chloride after the silicon dioxide is dissolved, then transferring the solution into a microwave hydrothermal kettle, setting the microwave frequency to be 2450MHz, carrying out hydrothermal reaction for 60min, and obtaining zinc silicate with the hydrothermal temperature of 140 ℃ and the specific surface area of about 219m 2 (ii) in terms of/g. Subsequent measurements were made as in example 1, with ammonia gas generation at a rate of about 123. Mu. Mol. L -1 ·h -1 。
Example 3
(1) Firstly weighing 2g of attapulgite, 4g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, placing in 3mol/L salt solution at 80 ℃ after calcining, treating for 3h in water bath, centrifuging, washing for multiple times until the solution is neutral, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of the silicon dioxide prepared in the step (1) under vigorous stirring, adding 0.75g of zinc chloride after the silicon dioxide is dissolved, then transferring the solution into a microwave hydrothermal kettle, setting the microwave frequency to be 2450MHz, carrying out hydrothermal reaction for 70min, and carrying out hydrothermal reaction at the temperature of 150 ℃ to obtain the zinc silicate with the specific surface area of about 189m 2 (ii) in terms of/g. Subsequent measurements were made as in example 1, with ammonia gas generation at a rate of about 119. Mu. Mol. Multidot.L -1 ·h -1 。
Example 4
(1) Firstly weighing 2g of attapulgite, 1g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, putting the calcined attapulgite in 3mol/L salt solution at 80 ℃, treating for 2h in water bath, centrifuging, washing for multiple times until the solution is neutral, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of silicon dioxide prepared in the step (1) under vigorous stirring, adding 1g of zinc chloride after the silicon dioxide is dissolved, then transferring the solution into a microwave hydrothermal kettle, setting the microwave frequency to be 2450MHz, carrying out hydrothermal reaction for 80min, and obtaining zinc silicate with the hydrothermal temperature of 170 ℃ and the specific surface area of about 220m 2 (ii) in terms of/g. Subsequent measurements were made as in example 1, with ammonia gas generation at a rate of about 126. Mu. Mol. Multidot.L -1 ·h -1 。
Example 5
(1) Firstly weighing 3g of attapulgite, placing 1g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, placing in a 3mol/L salt solution after calcining, treating for 4h in water bath at 80 ℃, centrifuging, washing for many times to neutrality, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) 2.6mL of tetramethylammonium hydroxide was added to 50mL of deionized water with vigorous stirringAdding 0.25g of silicon dioxide prepared in the step (1) under stirring, adding 0.125g of zinc chloride after the silicon dioxide is dissolved, then transferring the solution into a microwave hydrothermal kettle, setting the microwave frequency at 2450MHz, carrying out hydrothermal reaction for 90min, and carrying out hydrothermal reaction at 180 ℃ to obtain the zinc silicate with the specific surface area of about 229m 2 (iv) g. The subsequent measurement was carried out as in example 1, generating ammonia gas at a rate of 114. Mu. Mol. Multidot.L -1 ·h -1 。
Comparative example 1
Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of commercial silicon dioxide under vigorous stirring, adding 0.5g of zinc chloride after the silicon dioxide is dissolved, then transferring the solution into a microwave hydrothermal kettle, setting the microwave frequency to be 2450MHz, carrying out hydrothermal reaction for 90min, and obtaining zinc silicate with the specific surface area of about 89m at the hydrothermal temperature of 160 DEG C 2 (ii) in terms of/g. The subsequent measurement was carried out as in example 1, with the ammonia gas generation rate being 24. Mu. Mol. Multidot.L -1 ·h -1 。
Comparative example 2
(1) Preparation of silica as in example 1;
(2) Adding 2.6mL of prepared NaOH solution (about 2.8 mol/L) into 50mL of deionized water, adding 0.25g of silicon dioxide prepared in the step (1) under vigorous stirring, adding 0.5g of zinc chloride after the silicon dioxide is dissolved, then transferring the solution into a microwave hydrothermal kettle, setting the microwave frequency to be 2450MHz, carrying out hydrothermal reaction for 90min, obtaining zinc silicate at the hydrothermal temperature of 160 ℃, wherein the specific surface area is about 129m 2 (iv) g. The subsequent measurement was carried out as in example 1, with the ammonia gas generation rate being 32. Mu. Mol. Multidot.L -1 ·h -1 。
Comparative example 3
(1) Preparation of silica as in example 1;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of silicon dioxide prepared in the step (1) under vigorous stirring, adding 0.5g of zinc chloride after the silicon dioxide is dissolved, then transferring the solution into a hydrothermal kettle, carrying out hydrothermal reaction for 24 hours at a hydrothermal temperature of 160 ℃ to obtain zinc silicate with the specific surface area of about 108m 2 (ii) in terms of/g. The subsequent measurement was carried out as in example 1, with the ammonia gas generation rate being 27. Mu. Mol. Multidot.L -1 ·h -1 。
Comparative example 4
(1) Silica was prepared as in example 1;
(2) Adding 1.8mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of silicon dioxide prepared in the step (1) under vigorous stirring, observing that the silicon dioxide is not completely dissolved by naked eyes, adding 0.5g of zinc chloride, transferring the solution into a microwave hydrothermal kettle, setting the microwave frequency to be 2450MHz, carrying out hydrothermal reaction for 90min, and obtaining zinc silicate with the hydrothermal temperature of 160 ℃ and the specific surface area of about 89m 2 (ii) in terms of/g. And the product was subjected to XRD and TEM analysis. Other subsequent measurements were made as in example 1, with ammonia gas generation rate of 14. Mu. Mol. Multidot.L -1 ·h -1 。
The zinc silicate prepared in the comparative example is subjected to an X-ray diffraction experiment, the structure and the morphology of the zinc silicate are observed under a transmission electron microscope, and the XRD spectrogram of the zinc silicate and the attapulgite and the silicon dioxide is shown in figure 3: the calcined and acid-treated attapulgite is completely converted into silicon dioxide, and the silicon dioxide is not completely converted into zinc silicate after hydrothermal reaction.
TEM characterization of the zinc silicate prepared in this example, as shown in FIG. 4, it can be seen that the silica is not completely converted to zinc silicate, but has a partially rod-like structure.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (5)
1. A zinc silicate catalyst for photocatalytic synthesis of ammonia prepared from natural attapulgite is characterized in that the catalyst is two-dimensional ultrathin nanosheet zinc silicate;
the preparation method of the catalyst comprises the following steps:
(1) Weighing attapulgite and ammonium sulfate, placing the attapulgite and ammonium sulfate in a crucible, calcining for 1-3 h at 550 ℃ in a muffle furnace, and then placing in 3mol/L hydrochloric acid solution for treatment for 2-4 h to prepare silicon dioxide;
(2) Adding tetramethylammonium hydroxide into deionized water, adding the silicon dioxide prepared in the step (1) under vigorous stirring, then adding zinc chloride, and then transferring to a microwave hydrothermal kettle for hydrothermal reaction to obtain zinc silicate;
the mass ratio of the tetramethylammonium hydroxide to the silicon dioxide is 2.25;
the microwave frequency is set to 2450MHz;
the hydrothermal reaction time is 60-90 min, and the hydrothermal temperature is 140-180 ℃.
2. The zinc silicate catalyst of claim 1, wherein the mass ratio of attapulgite to ammonium sulfate in step (1) is 1.33-1:3; the hydrochloric acid solution was diluted to 3mol/L with 35% analytical pure hydrochloric acid.
3. The zinc silicate catalyst of claim 1, wherein the tetramethylammonium hydroxide of step (2) is added to deionized water to form a 25% aqueous solution of tetramethylammonium hydroxide.
4. The zinc silicate catalyst of claim 1, wherein the mass ratio of zinc chloride to silica in step (2) is 0.5 to 4:1.
5. The zinc silicate catalyst of claim 1, wherein the process for the photocatalytic synthesis of ammonia is: weighing the prepared zinc silicate catalyst, dissolving the zinc silicate catalyst in deionized water, and then adding the zinc silicate catalyst into a photocatalytic reaction device, N 2 Introducing into a reaction device at a flow rate of 60mL/min, irradiating for 30min by using a 300W xenon lamp as a simulated light source, collecting 10mL of samples every 30min, adding a Nashin reagent, extracting supernatant after full reaction, and testing the absorbance of the supernatant by using an ultraviolet spectrometer at a wavelength of 420 nm.
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