CN114797835B - ZnO/ZnCr 2 O 4 Preparation method of heterojunction photocatalyst and application of heterojunction photocatalyst in ammonia synthesis - Google Patents
ZnO/ZnCr 2 O 4 Preparation method of heterojunction photocatalyst and application of heterojunction photocatalyst in ammonia synthesis Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 88
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 67
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 13
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 13
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- 150000001844 chromium Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 238000001228 spectrum Methods 0.000 claims description 25
- 238000005286 illumination Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 30
- 239000011651 chromium Substances 0.000 description 29
- 239000002243 precursor Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 239000013078 crystal Substances 0.000 description 11
- 238000007036 catalytic synthesis reaction Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 8
- -1 chromium chloride nonahydrate Chemical compound 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- ICXVJVVYSULERR-UHFFFAOYSA-L dichlorozinc hexahydrate Chemical compound O.O.O.O.O.O.Cl[Zn]Cl ICXVJVVYSULERR-UHFFFAOYSA-L 0.000 description 7
- 238000004255 ion exchange chromatography Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001212 derivatisation Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 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
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
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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
- 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
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a ZnO/ZnCr 2 O 4 The preparation method of the heterojunction photocatalyst comprises the following steps: uniformly mixing zinc salt, chromium salt and water to obtain a solution A; providing an alkaline aqueous solution, denoted as solution B; adding the solution A and the solution B into pure water at the same time, and uniformly mixing to obtain a solution C; crystallizing, washing and drying the solution C to obtain hydrotalcite nano-sheets; calcining the hydrotalcite nano-sheet to obtain the ZnO/ZnCr 2 O 4 Heterojunction photocatalysts. The invention also provides ZnO/ZnCr prepared by the preparation method 2 O 4 Heterojunction photocatalyst and application thereof in photocatalytic synthesis of ammonia. The ZnO/ZnCr is prepared by topological transformation 2 O 4 The heterojunction photocatalyst effectively improves the photon-generated carrier transmission efficiency of the photocatalyst, thereby improving the photocatalytic ammonia synthesis performance. ZnO/ZnCr prepared by the invention 2 O 4 The heterojunction photocatalyst shows excellent photocatalytic performance in the reaction of photocatalytic synthesis of ammonia.
Description
Technical Field
The invention relates to the technical field of photocatalysts. And more particularly to a ZnO/ZnCr alloy 2 O 4 A preparation method of heterojunction photocatalyst and application of the heterojunction photocatalyst in photocatalytic synthesis of ammonia.
Background
Ammonia (NH) 3 ) Is one of the most important inorganic chemicals, which is not only an important component of agrochemicals and explosives, but also plays a key role in constructing macromolecules necessary for many life such as biological proteins, nucleic acids, and the like. Meanwhile, the ammonia synthesis industry plays an important role in national economy. Although nitrogen is the largest gas component in the earth's atmosphere, the volume is about 78%, but is defined byNitrogen activation and application have always presented serious challenges for tough nitrogen-nitrogen triple bonds. The natural nitrogen fixation process is a biological nitrogen fixation process by means of bacterial nitrogen fixation enzymes or a nitrogen fixation process completed in the atmosphere by means of lightning. In 1913, the catalytic reduction of nitrogen and hydrogen to ammonia by the Haber-Bosch process has been attracting attention successfully. However, industrial nitrogen fixation consumes 3-5% of world natural gas and 1-2% of world electric energy each year, and discharges a large amount of carbon dioxide, seriously hampering the development of ammonia synthesis. Therefore, finding a renewable and sustainable ammonia synthesis pathway has become a challenging task.
The method for fixing nitrogen by using inexhaustible and environment-friendly solar energy as the driving force of the reaction process is a synthesis approach with wide prospect. However, the current conversion efficiency of the photo-nitrogen fixation is far from meeting the actual industrial requirements. One of the intrinsic reasons is that the photoexcited carriers have low migration efficiency and short service life, and are easy to be compounded in the photocatalysis process, so that the generation efficiency of the photo-nitrogen fixation is reduced. Constructing semiconductor heterojunctions is considered an effective way to improve photogenerated electron hole transport, but how to prepare heterojunction photocatalysis for photosetting nitrogen by simple methods remains a work to be explored.
ZnO is used as a semiconductor photocatalyst with a forbidden bandwidth of 3.3eV, and is widely applied in the field of photocatalysis by virtue of the characteristics of fluorescence, absorption, ultraviolet scattering and the like. ZnCr 2 O 4 As a spinel photocatalyst, the gap width is about 3.4eV, and the photocatalyst also has good photocatalytic performance. ZnO/ZnCr composed of ZnO and ZnO 2 O 4 Heterojunction photocatalyst has been reported for many times in the field of photocatalytic pollutant degradation, however, no related literature report yet provides a new preparation method for ZnO/ZnCr prepared 2 O 4 Heterojunction photocatalysts and expand their use.
Disclosure of Invention
Based on this, a first object of the present invention is to provide a ZnO/ZnCr 2 O 4 A preparation method of heterojunction photocatalyst. In the method, the hydrotalcite is firstly derivatized in situThe heterojunction photocatalyst is prepared and ZnO/ZnCr obtained by the method 2 O 4 Heterojunction photocatalysts are particularly useful in photocatalytic ammonia synthesis reactions.
A second object of the present invention is to provide ZnO/ZnCr particles prepared by the method of the first object 2 O 4 Heterojunction photocatalysts.
A third object of the present invention is to provide ZnO/ZnCr as described in the second object above 2 O 4 The application of heterojunction photocatalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
ZnO/ZnCr 2 O 4 The preparation method of the heterojunction photocatalyst comprises the following steps:
uniformly mixing zinc salt, chromium salt and water to obtain a solution A;
providing an alkaline aqueous solution, denoted as solution B;
adding the solution A and the solution B into pure water at the same time, and uniformly mixing to obtain a solution C;
crystallizing, washing and drying the solution C to obtain hydrotalcite nano-sheets;
calcining the hydrotalcite nano-sheet to obtain the ZnO/ZnCr 2 O 4 Heterojunction photocatalysts.
The invention takes hydrotalcite nano-sheets as precursors to prepare ZnO/ZnCr by in-situ derivatization 2 O 4 Heterojunction photocatalyst, thereby enabling ZnO/ZnCr 2 O 4 The heterojunction photocatalyst has stronger interaction and higher transmission efficiency of photo-generated carriers.
Further, in the alkaline aqueous solution, the alkaline substance comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Further, the amount of pure water C is 15-25mL.
Further, the crystallization temperature is 60-80 ℃ and the crystallization time is 12-18 hours.
Further, in order to provide a suitable environment for crystal growth, the crystallization is performed by using an oil bath; the washing and drying are preferably carried out in a forced air drying oven.
Further, the calcined atmosphere is air; the calcination temperature is 300-600 ℃ and the time is 2-4 hours. By controlling the calcination conditions, the catalyst with higher activity can be prepared to catalyze the synthesis of ammonia.
Further, the drying temperature is 60-80 ℃ and the drying time is 12-24 hours.
Further, in the solution A, the concentration of the zinc salt is 0.9375-2.5 mol.L -1 The concentration of the chromium salt is 0.625-1.25mol.L -1 . By controlling the addition ratio of zinc and chromium in the solution A, the catalyst with higher activity can be prepared to catalyze the synthesis of ammonia. Most preferably, the concentration of zinc salt in the solution A is 1.25 mol.L -1 The concentration of the chromium salt was 0.625 mol.L -1 。
Further, the zinc salt is selected from one of zinc chloride, zinc sulfate and the like.
Further, the chromium salt is selected from one of chromium chloride, chromium sulfate, and the like.
Further, the pH of the alkaline solution B is maintained at 10-14.
In order to achieve the second object, the invention provides ZnO/ZnCr prepared by the preparation method according to the first object 2 O 4 Heterojunction photocatalysts.
To achieve the third object, the present invention provides ZnO/ZnCr as described in the second object 2 O 4 The application of the heterojunction photocatalyst in the photocatalytic synthesis of ammonia.
Further, the photocatalytic synthetic ammonia is synthetic ammonia by reacting photocatalytic nitrogen with water.
Further, the application comprises the steps of:
ZnO/ZnCr in a light-permeable reaction device 2 O 4 Mixing heterojunction photocatalyst and ultrapure water to obtain a mixed solution, introducing high-purity nitrogen under the condition of avoiding light, opening a condensed water device, and carrying out full spectrum illumination for 10 minutes to 1 hour.
Further, the mixingZnO/ZnCr in solution 2 O 4 The concentration of the heterojunction photocatalyst is 0.33-0.5g.L -1 。
Further, the time period of introducing high-purity nitrogen in the dark is 0.5-1 hour.
Further, the ultrapure water is water with a resistivity of 18mΩ×cm at room temperature of 25 ℃.
Further, the high-purity nitrogen is nitrogen with a volume fraction of not less than 99.999 vol%.
Further, the method further comprises centrifuging the reaction solution after full spectrum illumination, and detecting the ammonia content by ion chromatography.
Any range recited in the present invention includes any numerical value between the endpoints and any sub-range of any numerical value between the endpoints or any numerical value between the endpoints unless specifically stated otherwise.
The preparation method in the invention is a conventional method unless otherwise specified. All materials used, unless otherwise indicated, are commercially available from published sources or are prepared according to the prior art, and all percentages, such as by mass, are percentages unless otherwise indicated.
The beneficial effects of the invention are as follows:
ZnO/ZnCr prepared by different preparation methods 2 O 4 The heterojunction photocatalysts have different catalytic performances, and in the invention, the ZnO/ZnCr is prepared by hydrotalcite in-situ derivatization and topology transformation for the first time 2 O 4 The heterojunction photocatalyst effectively improves the photon-generated carrier transmission efficiency of the photocatalyst, so that the performance of photocatalytic synthesis of ammonia is improved, and the prepared catalyst can be well applied to catalytic synthesis of ammonia.
In the preparation method of the invention, znCr-hydrotalcite nano-sheets are prepared and used as precursors, and ZnO/ZnCr is prepared by calcining and in-situ derivatization by a one-step method 2 O 4 The heterojunction photocatalyst enables two semiconductor components in the heterojunction to be fully contacted, interaction is enhanced, and therefore the transfer of photon-generated carriers is facilitated.
ZnO/ZnCr prepared by the preparation method of the invention 2 O 4 The heterojunction photocatalyst has low preparation cost, simple and convenient preparation, simple process and easy mass production, and ZnO/ZnCr is firstly prepared 2 O 4 Heterojunction photocatalysts are used for photocatalytic synthesis of ammonia reactions, and excellent properties are obtained.
The main path for preparing ammonia from hydrogen and nitrogen in the prior art is to use noble metal Ru and Fe oxide catalysts, and the preparation is carried out in a high-temperature high-pressure system; compared with the prior art, the invention adopts the light-driven ammonia synthesis reaction, is more environment-friendly and energy-saving than the prior art system, and prepares ZnO/ZnCr by in-situ derivatization by taking hydrotalcite as a precursor for the first time 2 O 4 Heterojunction photocatalyst and application thereof in photocatalytic synthesis of ammonia. The invention is expected to be amplified in industry and applied practically.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Figure 1 shows XRD patterns of the products obtained in examples 1-4 of the present invention.
FIG. 2 shows the ZnO/ZnCr compositions obtained in examples 1-4 of the present invention 2 O 4 The heterojunction photocatalyst is used for photocatalytic synthesis of ammonia under the same reaction condition.
Figure 3 shows XRD patterns of the products obtained in comparative examples 1-2 and example 2 of the present invention.
FIG. 4 shows the photocatalytic synthesis of ammonia under the same reaction conditions for the photocatalysts obtained in comparative examples 1 to 4 and example 2 according to the present invention.
Fig. 5 shows XRD patterns of precursor hydrotalcite nanoplatelets obtained in comparative example 6 and example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
ZnO/ZnCr 2 O 4 The preparation method of the heterojunction photocatalyst comprises the following steps:
1) Preparing a mixed metal precursor solution: dissolving 0.0375mol of zinc chloride hexahydrate and 0.025mol of chromium chloride nonahydrate in 40mL of water, and fully and uniformly dispersing to obtain a uniform solution;
2) Preparing a mixed alkali solution: dissolving 0.12mol of sodium hydroxide and 0.1mol of sodium carbonate in 80mL of water, and fully and uniformly dispersing to obtain a uniform solution;
3) Slowly dripping the uniform solution obtained in the step 1) and the step 2) into 20mL of pure water at the same time, and uniformly mixing to obtain a solution C;
4) Heating the solution C in an oil bath, crystallizing at 60deg.C for 18 hr to obtain a product, and naming the product as Zn 1.5 Cr 1 -LDH；
5) Obtaining the Zn product from the step 4) 1.5 Cr 1 Washing LDH with deionized water for 4 times, drying at 60deg.C for 24 hr, and grinding to obtain precursor Zn 1.5 Cr 1 -LDH；
6) Precursor Zn 1.5 Cr 1 Placing the-LDH into a muffle furnace, and calcining at 500 ℃ for 2 hours to obtain a product ZnO/ZnCr 2 O 4 Heterojunction photocatalyst and named Zn 1.5 Cr 1 -5。
ZnO/ZnCr obtained in this example 2 O 4 As can be seen from the graph in FIG. 1, the XRD spectrum of the heterojunction photocatalyst is shown in FIG. 1, and under this condition, the synthesized Zn 1.5 Cr 1 -5 the photocatalyst forms distinct ZnO with distinct peaks of (101), (100), (002) and (311) crystal planes. At the same time, znCr 2 O 4 The (111) and (220) crystal face characteristic peaks of (C) are obviously present.
ZnO/ZnCr is added into a light-permeable reaction device 2 O 4 10mg of heterojunction photocatalyst and 30mL of ultrapure water, namely water with the resistivity reaching 18MΩ cm at the room temperature of 25 ℃, and under the condition of avoiding light, high-purity nitrogen with the volume fraction of 99.999vol% is introduced, and a condensed water device is opened to carry out full spectrum illumination for 1 hour. And centrifuging the reaction solution after the completion of the photoreaction, taking out 2mL, and detecting the ammonia content by using ion chromatography.
This example shows the ammonia yield at 1 hour of full spectrum irradiation as shown in FIG. 2, and the catalytic synthesis of ammonia performance reaches 13.6. Mu. Mol. G -1 ·h -1 。
Example 2
ZnO/ZnCr 2 O 4 The preparation method of the heterojunction photocatalyst comprises the following steps:
1) Preparing a mixed metal precursor solution: dissolving 0.05mol of zinc chloride hexahydrate and 0.025mol of chromium chloride nonahydrate in 40mL of water, and fully and uniformly dispersing to obtain a uniform solution;
2) Preparing a mixed alkali solution: dissolving 0.12mol of sodium hydroxide and 0.1mol of sodium carbonate in 80mL of water, and fully and uniformly dispersing to obtain a uniform solution;
3) Slowly dripping the uniform solution obtained in the step 1) and the step 2) into 20mL of pure water at the same time, and uniformly mixing to obtain a solution C;
4) Heating the solution C in an oil bath, crystallizing at 60deg.C for 18 hr to obtain a product, and naming the product as Zn 2 Cr 1 -LDH；
5) Obtaining the Zn product from the step 4) 2 Cr 1 Washing LDH with deionized water for 4 times, drying at 60deg.C for 24 hr, and grinding to obtain precursor Zn 2 Cr 1 -LDH；
6) Precursor Zn 2 Cr 1 Placing the-LDH into a muffle furnace, and calcining at 500 ℃ for 2 hours to obtain a product ZnO/ZnCr 2 O 4 Heterojunction photocatalyst and named Zn 2 Cr 1 -5。
ZnO/ZnCr obtained in this example 2 O 4 As can be seen from the graph in FIG. 1, the XRD spectrum of the heterojunction photocatalyst is shown in FIG. 1, and under this condition, the synthesized Zn 2 Cr 1 -5 the photocatalyst forms distinct ZnO with distinct peaks of (101), (100), (002) and (311) crystal planes. At the same time, znCr 2 O 4 The (111) and (220) crystal face characteristic peaks of (C) are obviously present.
ZnO/ZnCr is added into a light-permeable reaction device 2 O 4 Heterojunction photocatalyst 10mg and 30mL ultrapure water, i.e. water with resistivity up to 18mΩ cm at room temperature 25 °cAnd (3) introducing high-purity nitrogen with the volume fraction of 99.999vol% under the light-shielding condition, and opening a condensed water device to perform full spectrum illumination for 1 hour. And centrifuging the reaction solution after the completion of the photoreaction, taking out 2mL, and detecting the ammonia content by using ion chromatography.
This example shows the ammonia yield at 1 hour of full spectrum irradiation as shown in FIG. 2, and the catalytic synthesis of ammonia performance reaches 31.5. Mu. Mol. G -1 ·h -1 。
Example 3
ZnO/ZnCr 2 O 4 The preparation method of the heterojunction photocatalyst comprises the following steps:
1) Preparing a mixed metal precursor solution: dissolving 0.05mol of zinc chloride hexahydrate and 0.025mol of chromium chloride nonahydrate in 40mL of water, and fully and uniformly dispersing to obtain a uniform solution;
2) Preparing a mixed alkali solution: dissolving 0.12mol of sodium hydroxide and 0.1mol of sodium carbonate in 80mL of water, and fully and uniformly dispersing to obtain a uniform solution;
3) Slowly dripping the uniform solution obtained in the step 1) and the step 2) into 20mL of pure water at the same time, and uniformly mixing to obtain a solution C;
4) Heating the solution C in an oil bath, crystallizing at 60deg.C for 18 hr to obtain a product, and naming the product as Zn 3 Cr 1 -LDH；
5) Obtaining the Zn product from the step 4) 3 Cr 1 Washing LDH with deionized water for 4 times, drying at 60deg.C for 24 hr, and grinding to obtain precursor Zn 3 Cr 1 -LDH；
6) Precursor Zn 3 Cr 1 Placing the-LDH into a muffle furnace, and calcining at 500 ℃ for 2 hours to obtain a product ZnO/ZnCr 2 O 4 Heterojunction photocatalyst and named Zn 3 Cr 1 -5。
ZnO/ZnCr obtained in this example 2 O 4 As can be seen from the graph in FIG. 1, the XRD spectrum of the heterojunction photocatalyst is shown in FIG. 1, and under this condition, the synthesized Zn 3 Cr 1 -5 the photocatalyst forms distinct ZnO with distinct peaks of (101), (100), (002) and (311) crystal planes. At the same time, znCr 2 O 4 The (111) and (220) crystal face characteristic peaks of (C) are obviously present.
ZnO/ZnCr is added into a light-permeable reaction device 2 O 4 10mg of heterojunction photocatalyst and 30mL of ultrapure water, namely water with the resistivity reaching 18MΩ cm at the room temperature of 25 ℃, and under the condition of avoiding light, high-purity nitrogen with the volume fraction of 99.999vol% is introduced, and a condensed water device is opened to carry out full spectrum illumination for 1 hour. And centrifuging the reaction solution after the completion of the photoreaction, taking out 2mL, and detecting the ammonia content by using ion chromatography.
This example shows the ammonia yield at 1 hour of full spectrum irradiation as shown in FIG. 2, and the catalytic synthesis of ammonia performance reaches 11.5. Mu. Mol. G -1 ·h -1 。
Example 4
1) Preparing a mixed metal precursor solution: dissolving 0.1mol of zinc chloride hexahydrate and 0.025mol of chromium chloride nonahydrate in 40mL of water, and fully and uniformly dispersing to obtain a uniform solution;
2) Preparing a mixed alkali solution: dissolving 0.12mol of sodium hydroxide and 0.1mol of sodium carbonate in 80mL of water, and fully and uniformly dispersing to obtain a uniform solution;
3) Slowly dripping the uniform solution obtained in the step 1) and the step 2) into 20mL of pure water at the same time, and uniformly mixing to obtain a solution C;
4) Heating the solution C in an oil bath, crystallizing at 60deg.C for 18 hr to obtain a product, and naming the product as Zn 4 Cr 1 -LDH；
5) Obtaining the Zn product from the step 4) 4 Cr 1 Washing LDH with deionized water for 4 times, drying at 60deg.C for 24 hr, and grinding to obtain precursor Zn 4 Cr 1 -LDH；
6) Precursor Zn 4 Cr 1 Placing the-LDH into a muffle furnace, and calcining at 500 ℃ for 2 hours to obtain a product ZnO/ZnCr 2 O 4 Heterojunction photocatalyst and named Zn 4 Cr 1 -5。
ZnO/ZnCr obtained in this example 2 O 4 As can be seen from the graph in FIG. 1, the XRD spectrum of the heterojunction photocatalyst is shown in FIG. 1, and under this condition, the synthesized Zn 4 Cr 1 -5 photocatalyst shapeThe (101), (100), (002) and (311) crystal face characteristic peaks are obvious. At the same time, znCr 2 O 4 The (111) and (220) crystal face characteristic peaks of (C) are obviously present.
ZnO/ZnCr is added into a light-permeable reaction device 2 O 4 10mg of heterojunction photocatalyst and 30mL of ultrapure water, namely water with the resistivity reaching 18MΩ cm at the room temperature of 25 ℃, and under the condition of avoiding light, high-purity nitrogen with the volume fraction of 99.999vol% is introduced, and a condensed water device is opened to carry out full spectrum illumination for 1 hour. And centrifuging the reaction solution after the completion of the photoreaction, taking out 2mL, and detecting the ammonia content by using ion chromatography.
This example shows the ammonia yield at 1 hour of full spectrum irradiation as shown in FIG. 2, and the catalytic synthesis of ammonia performance reaches 7.5. Mu. Mol. G -1 ·h -1 。
Examples 5 to 7
ZnO/ZnCr 2 O 4 The preparation method of heterojunction photocatalyst is the same as in example 2, except that the precursor Zn is changed 2 Cr 1 Calcination temperature of LDH, in particular as shown in table 1. The ZnO/ZnCr is prepared 2 O 4 The heterojunction photocatalyst was used for photocatalytic synthesis of ammonia, and the procedure was as in example 2, and the results are shown in table 1.
TABLE 1 different ZnO/ZnCr 2 O 4 Production of ammonia from heterojunction photocatalyst catalyzed synthesis of ammonia
| Examples numbering | Calcination temperature (. Degree. C.) | Ammonia yield (. Mu. Mol. G) -1 ·h -1 ) |
| Example 5 | 300 | 13.6 |
| Example 6 | 400 | 14.3 |
| Example 2 | 500 | 31.5 |
| Example 7 | 600 | 14.5 |
As is clear from Table 1, the ammonia yield is greatly related to the calcination temperature of the precursor when the full spectrum is irradiated for 1 hour, and the higher the calcination temperature is, the higher the ammonia yield is, the best catalytic synthesis ammonia performance is achieved when the calcination temperature reaches 500 ℃, and the highest ammonia yield reaches 31.5 mu mol.g -1 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the When the calcining temperature is too high, the ZnO/ZnCr is obtained 2 O 4 Heterojunction photocatalyst performance is degraded mainly due to the too high calcination temperature, znO/ZnCr 2 O 4 The particle size of the heterojunction photocatalyst is obviously increased, so that the interface content is reduced, the transmission of photo-generated electron holes is not facilitated, and the catalytic performance is reduced.
Comparative example 1
A preparation method of a ZnO photocatalyst comprises the following steps:
1) Preparing a mixed metal precursor solution: dissolving 0.05mol of zinc chloride hexahydrate and 0.1mol of sodium hydroxide in 20mL of water, and fully dispersing to obtain a uniform solution;
2) Centrifuging the uniform solution obtained in the step 1), washing with deionized water for 4 times, drying at 60 ℃ for 24 hours, and grinding to obtain a product Zn (OH) 2 ；
3) The product Zn (OH) obtained in the step 2) is treated 2 Placing the mixture in a muffle furnace, calcining the mixture in air at 500 ℃ for 2 hours to obtain the ZnO photocatalyst, and naming the ZnO photocatalyst as ZnO.
As is clear from the graph in FIG. 3, the XRD patterns of the ZnO photocatalyst obtained in this comparative example show that under this condition, the characteristic peaks of the (101), (100), (002) and (311) crystal planes of the synthesized ZnO are apparent.
The ZnO photocatalyst prepared by the method is used for synthesizing ammonia by photocatalysis, and comprises the following steps:
10mg of ZnO photocatalyst and 30mL of ultrapure water, namely water with the resistivity reaching 18MΩ cm at the room temperature of 25 ℃, are added into a light-permeable reaction device, high-purity nitrogen with the volume fraction of 99.999vol% is introduced under the condition of avoiding light, and a condensed water device is opened to carry out full spectrum illumination for 1 hour. And centrifuging the reaction solution after the completion of the photoreaction, taking out 2mL, and detecting the ammonia content by using ion chromatography.
This comparative example, whose ammonia yield is shown in FIG. 4 and whose catalytic synthesis performance reaches 2.5. Mu. Mol.g, was irradiated for 1 hour on the full spectrum -1 ·h -1 。
Comparative example 2
ZnCr 2 O 4 The preparation method of the photocatalyst comprises the following steps:
1) Preparing a mixed metal precursor solution: dissolving 0.002mol of zinc chloride hexahydrate, 0.004mol of chromium chloride nonahydrate and 1.111g of polyvinylpyrrolidone (PVP for short) in 40mL of water, and fully dispersing to obtain a uniform solution A;
2) Adding 0.02mol of sodium hydroxide into the uniform solution A, and stirring at 60 ℃ for 0.5 hour to obtain a uniform solution B;
3) Placing the uniform solution B into a polytetrafluoroethylene lining, and heating in an autoclave at 200 ℃ for 10 hours; centrifuging and washing with deionized water for 4 times, drying at 60 ℃ for 24 hours, and grinding to obtain a product precursor product;
4) Placing the precursor product obtained in the step 3) in a muffle furnace, and calcining at 300 ℃ for 4 hours to obtain a ZnCr product 2 O 4 Photocatalyst, and named ZnCr 2 O 4 。
Pair of principal and subordinateZnCr obtained in proportion 2 O 4 As can be seen from the graph in FIG. 3, the XRD spectrum of the photocatalyst is shown in FIG. 3, and under this condition, the synthesized ZnCr 2 O 4 The (111) and (220) crystal face characteristic peaks exist obviously.
ZnCr prepared by the method 2 O 4 The photocatalyst is used for photocatalytic synthesis of ammonia and comprises the following steps:
ZnO/ZnCr is added into a light-permeable reaction device 2 O 4 10mg of heterojunction photocatalyst and 30mL of ultrapure water, namely water with the resistivity reaching 18MΩ cm at the room temperature of 25 ℃, and under the condition of avoiding light, high-purity nitrogen with the volume fraction of 99.999vol% is introduced, and a condensed water device is opened to carry out full spectrum illumination for 1 hour. And centrifuging the reaction solution after the completion of the photoreaction, taking out 2mL, and detecting the ammonia content by using ion chromatography.
This comparative example, whose ammonia yield is shown in FIG. 4 and whose catalytic synthesis performance reaches 0.4. Mu. Mol. G, when irradiated for 1 hour with full spectrum -1 ·h -1 。
Comparative example 3
ZnO/ZnCr 2 O 4 The preparation method of the heterojunction photocatalyst is the same as that of comparative example 2, and the difference is that 0.004mol of ZnO is added into the mixed metal precursor solution in the step 1).
ZnO/ZnCr prepared by the method 2 O 4 Heterojunction photocatalyst for photocatalytic Ammonia Synthesis Using the procedure of example 2 and the resulting product was designated ZnO/ZnCr 2 O 4 。
This comparative example, whose ammonia yield is shown in FIG. 4 and whose catalytic synthesis performance reaches 16.6. Mu. Mol.g, was irradiated for 1 hour on the full spectrum -1 ·h -1
Comparative example 4
Physical mixing ZnO/ZnCr 2 O 4 The preparation method of the heterojunction photocatalyst comprises the following steps:
10mg ZnO and 11mg ZnCr are mixed 2 O 4 Physical mixing, grinding uniformly, and obtaining the product, which is named as physical mixing.
Preparing the abovePhysical mixing of ZnO/ZnCr 2 O 4 The heterojunction photocatalyst was used for photocatalytic synthesis of ammonia, and the procedure was as in example 2. The ammonia yield at 1 hour of full spectrum irradiation is shown in FIG. 4, which shows that the catalytic synthesis of ammonia can reach 9. Mu. Mol.g -1 ·h -1 。
Examples 8 to 10, comparative example 5
ZnO/ZnCr 2 O 4 The procedure for the preparation of heterojunction photocatalyst was as in example 2. The ZnO/ZnCr is prepared 2 O 4 Heterojunction photocatalyst was used for photocatalytic synthesis of ammonia, the procedure was the same as in example 2, except that the time of full spectrum irradiation was changed, and the results are shown in table 2.
TABLE 2 different ZnO/ZnCr 2 O 4 Production of ammonia from heterojunction photocatalyst catalyzed synthesis of ammonia
| Examples numbering | Illumination (minutes) | Ammonia yield (. Mu. Mol. G) -1 ) |
| Comparative example 5 | 0 | 0 |
| Example 8 | 15 | 6.8 |
| Example 9 | 30 | 16.3 |
| Example 10 | 45 | 25.4 |
| Example 2 | 60 | 31.5 |
As can be seen from Table 2, the ammonia production is highly dependent on the illumination time under full spectrum illumination. Within a certain range, the higher the ammonia yield is as the illumination time increases; when the illumination time is shorter, the catalytic reaction just starts to react, and the ammonia synthesis efficiency is more gentle; when the illumination time is prolonged, the catalytic ammonia synthesis efficiency is correspondingly improved.
Comparative example 6
ZnO/ZnCr 2 O 4 The preparation method of the heterojunction photocatalyst comprises the following steps:
1) Preparing a uniform solution: 0.0375mol of zinc chloride hexahydrate, 0.025mol of chromium chloride nonahydrate, 0.12mol of sodium hydroxide and 0.1mol of sodium carbonate are dissolved in 120mL of water, and the solution is fully and uniformly dispersed to obtain a uniform solution;
2) Slowly dripping the uniform solution obtained in the step 1) into 20mL of pure water, and uniformly mixing to obtain a solution C;
3) Heating the solution C in an oil bath, and crystallizing at 60 ℃ for 18 hours to obtain a substance X;
4) Washing the substance X obtained in the step 4) with deionized water for 4 times, drying at 60 ℃ for 24 hours, and grinding to obtain a precursor; designated as Zn 1.5 Cr 1 -LDH-mix。
5) Placing the precursor in a muffle furnace, calcining at 500 ℃ for 2 hours to obtain a product catalyst named Zn 1.5 Cr 1 -5-mix。
As can be seen from the graphs of XRD patterns of the precursor obtained in this comparative example and the precursor of example 1 shown in FIG. 5, under these conditions, zn was synthesized 1.5 Cr 1 Obvious crystallinity of the LDH-mix hydrotalcite precursorThe increase shows that the particle size of the precursor synthesized under the condition is relatively larger, and the specific surface area of the two-dimensional nano material is reduced to a certain extent, which is not beneficial to the improvement of the catalytic activity.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (6)
1. ZnO/ZnCr 2 O 4 The application of the heterojunction photocatalyst in the photocatalytic synthesis of ammonia is characterized in that the photocatalytic synthesis of ammonia is the reaction of photocatalytic nitrogen and water, and the application comprises the following steps:
ZnO/ZnCr in a light-permeable reaction device 2 O 4 Mixing heterojunction photocatalyst and ultrapure water to obtain a mixed solution, introducing high-purity nitrogen under the light-shielding condition, opening a condensed water device, and carrying out full spectrum illumination for 10 minutes to 1 hour;
the ZnO/ZnCr 2 O 4 The heterojunction photocatalyst is prepared by the following steps:
uniformly mixing zinc salt, chromium salt and water to obtain a solution A;
providing an alkaline aqueous solution, denoted as solution B;
adding the solution A and the solution B into pure water at the same time, and uniformly mixing to obtain a solution C;
crystallizing, washing and drying the solution C to obtain hydrotalcite nano-sheets;
calcining the hydrotalcite nano-sheet to obtain the ZnO/ZnCr 2 O 4 Heterojunction photocatalysts;
the crystallization temperature is 60-80 ℃ and the crystallization time is 12-18 hours;
the calcining atmosphere is air; the calcination temperature was 500℃and the time was 2 hours.
2. The use according to claim 1, wherein the alkaline substance in the alkaline aqueous solution comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
3. The use according to claim 1, wherein the concentration of zinc salt in the solution a is 0.9375-2.5 mol-L -1 The concentration of the chromium salt is 0.625-1.25mol.L -1 。
4. The use according to claim 1, characterized in that the pH of the alkaline solution B is maintained between 10 and 14.
5. The use according to claim 1, characterized in that in the mixed solution ZnO/ZnCr 2 O 4 The concentration of the heterojunction photocatalyst is 0.33-0. g.L -1 。
6. The use according to claim 1, wherein the period of time for passing high purity nitrogen in the absence of light is 0.5-1 hour.
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