CN112354545B - Copper sulfide composite potassium tantalate niobate with p-n heterojunction structure and preparation method thereof - Google Patents
Copper sulfide composite potassium tantalate niobate with p-n heterojunction structure and preparation method thereof Download PDFInfo
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- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 41
- 239000011591 potassium Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000006104 solid solution Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 13
- 229910021642 ultra pure water Inorganic materials 0.000 description 13
- 239000012498 ultrapure water Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 5
- 238000007036 catalytic synthesis reaction Methods 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007970 homogeneous dispersion Substances 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J35/33—Electric or magnetic properties
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
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- 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
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- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention relates to the field of photoelectric materials, and particularly discloses copper sulfide composite potassium tantalate-niobate with a p-n heterojunction structure and a preparation method thereof. According to the invention, firstly, potassium tantalate-niobate is prepared through a hydrothermal reaction, and then, petal-shaped copper sulfide is loaded on a potassium tantalate-niobate solid solution through a hydrothermal treatment, so that the copper sulfide composite potassium tantalate-niobate with the p-n heterojunction structure is prepared. The copper sulfide composite potassium tantalate niobate provided by the invention can be used as a catalyst, so that the problem of how to improve the piezoelectric catalysis and photocatalytic performance of KTN is solved, and the stable catalysis of nitrogen fixation for ammonia synthesis can be achieved.
Description
Technical Field
The invention relates to the field of photoelectric materials, in particular to copper sulfide composite potassium tantalate-niobate with a p-n heterojunction structure and a preparation method thereof.
Background
Ammonia is an important chemical raw material and plays an important role in the fields of industrial and agricultural production, national defense and the like. In recent years, it has become recognized that ammonia is also an excellent hydrogen storage fuel, is easy to liquefy, store and transport, and has the advantage of high energy density. These advantages make ammonia a more desirable energy carrier than hydrogen. However, the production of ammonia is mainly realized by means of Haber-Bosch reaction, and the technology not only consumes huge energy, but also emits a large amount of greenhouse gas CO 2 。
The photocatalytic technology utilizes clean and pollution-free solar energy, shows huge application prospects in the aspects of ammonia synthesis, hydrogen production by water decomposition and pollutant removal, and is widely concerned by scientists, but the conversion mode of light energy-chemical energy means that the photocatalytic mode cannot be implemented under the condition of no light, so that the application range of the photocatalytic technology is limited. In contrast, the piezoelectric catalysis is a way to convert mechanical energy into chemical energy, i.e. under the action of external mechanical force, the surface of the piezoelectric material induces electric charge due to the piezoelectric effect, so that the dye can be degraded and nitrogen can be synthesized into ammonia. Mechanical energy such as sound, water flow and the like is ubiquitous and can be obtained at any time and any place, and the whole piezoelectric catalysis process is green and pollution-free, so that the research on piezoelectric catalysis can be used as effective supplement of a photocatalysis mode.
Potassium tantalate niobate (KTa) 0.75 Nb 0.25 O 3 Abbreviated as KTN) is a perovskite structure (ABO) 3 ) A photocatalyst. By virtue of the characteristics of no toxicity, no pollution and high stability, the method can be used for photocatalytic degradation of water pollution, photocatalytic hydrogen production and photocatalytic CO production 2 Excellent performances in reduction, photocatalysis nitrogen fixation and the like. Preparation of C/KTa by a simple two-step hydrothermal method, e.g., chen et al 0.75 Nb 0.25 O 3 The (KTN) composite photocatalyst (Fuel, 2018, 233, 486-496) remarkably improves the photocatalytic hydrogen production efficiency, and a microwave method is used for preparing KTN/g-C by taking KTN and melamine as raw materials 3 N 4 The composite photocatalyst has catalytic hydrogen production performance reaching pure phase KTN and g-C 3 N 4 2.5-fold of activity (Fuel, 2019, 241. In addition, potassium tantalate niobate is an excellent piezoelectric material (Ferroelectrics, 2020,555 (1): 109-117), indicating that the material has potential for piezoelectric catalysis.
However, no relevant report is found at present, so a method for applying KTN to photocatalytic nitrogen fixation reaction and ensuring the piezoelectric catalysis and photocatalytic performance of KTN is urgently needed, the piezoelectric catalysis and photocatalytic performance of KTN is further improved, and N can be used for fixing nitrogen 2 Catalytically reduced to ammonia.
The invention applies KTN to the photocatalysis nitrogen fixation reaction for the first time, and realizes the ultrasonic vibration. And modifying copper sulfide. The work of the present invention is highly innovative, both from the point of view of the catalyst and in the field of application.
Disclosure of Invention
The invention provides copper sulfide composite potassium tantalate-niobate with a p-n heterojunction structure and a preparation method thereof in order to solve the problems, and KTa is prepared by a simple hydrothermal method 0.75 Nb 0.25 O 3 And loading CuS to KTa by secondary hydrothermal 0.75 Nb 0.25 O 3 A p-n heterojunction structure is formed on the catalyst to improve the photocatalytic and piezoelectric catalytic performances, and finally the CuS/KTN composite catalyst with excellent piezoelectric catalytic and photocatalytic nitrogen fixation performances is obtained.
One of the purposes of the invention is to provide a composition, and the specific technical scheme is as follows:
a composition consists of copper sulfide and potassium tantalate niobate, wherein the molar ratio of the copper sulfide to the potassium tantalate niobate is 1-15%.
Further, the molar ratio of the copper sulfide to the potassium tantalate niobate is 10%.
Further, the mol ratio of the copper sulfide to the potassium tantalate niobate is 2.5 percent
Further, the potassium tantalate niobate is KTa 0.75 Nb 0.25 O 3 Solid solution.
The second purpose of the invention is to provide copper sulfide composite potassium tantalate niobate with a p-n heterojunction structure, which has the following specific technical scheme:
the copper sulfide composite potassium tantalate-niobate with the p-n heterojunction structure is KTa 0.75 Nb 0.25 O 3 Solid solution.
Further, the molar ratio of the copper sulfide to the potassium tantalate niobate is 10%.
Further, the mol ratio of the copper sulfide to the potassium tantalate niobate is 2.5 percent
The invention also aims to provide application of the copper sulfide composite potassium tantalate niobate with the p-n heterojunction structure, and the specific technical scheme is as follows:
the copper sulfide composite potassium tantalate niobate is applied to preparation of the composite catalyst in the technical scheme, and the composite catalyst can be used for photocatalysis and piezoelectric catalysis.
The fourth purpose of the invention is to provide a method for preparing copper sulfide composite potassium tantalate-niobate with a p-n heterojunction structure, which has the following specific technical scheme:
a method for preparing copper sulfide composite potassium tantalate niobate with a p-n heterojunction structure comprises the following steps,
(1)weighing a proper amount of Ta 2 O 5 And Nb 2 O 5 Adding KOH aqueous solution and stirring to obtain mixed solution;
(2) Carrying out hydrothermal reaction, cooling, washing and drying on the mixed solution to obtain a potassium tantalate niobate solid solution;
(3) Dispersing the potassium tantalate-niobate solid solution to obtain a suspension;
(4) And adding copper chloride and sodium sulfide into the suspension, stirring, performing hydrothermal treatment, precipitating, washing and drying to obtain the copper sulfide composite potassium tantalate-niobate with the p-n heterojunction structure.
Further, said Ta in step (1) 2 O 5 And Nb 2 O 5 In a molar ratio of 3:1.
further, the temperature of the hydrothermal reaction is 160-260 ℃, and the reaction time is 12-48h; the drying temperature is 60 ℃.
Further, the molar ratio of the copper chloride to the sodium sulfide is 1:2.
further, the temperature of the hydrothermal treatment is 140 ℃, and the temperature of the drying is 60 ℃.
The fifth purpose of the invention is to provide the application of the copper sulfide composite potassium tantalate niobate prepared by the technical scheme, and the specific technical scheme is as follows:
the copper sulfide composite potassium tantalate-niobate prepared by the method in the fourth technical scheme is applied to the catalysis of nitrogen fixation and ammonia synthesis.
The invention has the advantages that:
1. the preparation process of the CuS/KTN (copper sulfide and potassium tantalate niobate composite) composite catalyst prepared by the invention utilizes a simple hydrothermal method and is simple to operate.
2. The CuS/KTN prepared by the method has photocatalytic and piezoelectric catalytic performances, and has a good practical application prospect.
3. The optimized CuS/KTN catalyst photocatalytic and piezoelectric catalytic ammonia production rates are 166.4 mu mol.L respectively -1 ·g cat -1 And 36.2. Mu. Mol. L -1 ·g cat -1 Are respectively pure phase KTa 0.75 Nb 0.25 O 3 The ammonia generating rate of the photocatalysis and the piezoelectricity catalysis is 3.2 times and 11 times, and the ammonia generating performance of the photocatalysis and the piezoelectricity catalysis is excellent. By combining the two points, the CuS/KTN composite catalyst with the p-n heterojunction structure prepared by the hydrothermal method
Drawings
FIG. 1 is an XRD pattern of examples 2 and 4 of the present invention and comparative examples 1 and 2.
FIG. 2 is a Raman diagram of examples 1 to 4 of the present invention and comparative examples 1 and 2.
FIG. 3 is an SEM photograph of example 2 of the present invention.
FIG. 4 is a graph showing transient photocurrent curves of example 2 of the present invention and comparative examples 1 and 2.
FIG. 5 is a graph showing the photocatalytic ammonia synthesis activity in examples 1 to 4 of the present invention and comparative examples 1 and 2.
FIG. 6 is a graph showing the activity of the piezoelectric catalytic synthesis of ammonia in examples 1 to 4 and comparative examples 1 and 2 of the present invention.
Fig. 7 is a cycle test chart of example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, it being understood that the present invention is not limited to the particular examples described herein, but is capable of modification or alteration in detail and without departing from the spirit and scope of the invention.
Example 1
(1) 44.80g of KOH solid were weighed out on an analytical balance, dissolved in 40ml of ultrapure water, and 3.315g (0.0075 mol) of Ta were weighed out 2 O 5 And 0.665g (0.0025 mol) Nb 2 O 5 Slowly adding into the KOH solution, magnetically stirring for 1h, transferring into 100ml of PPL material lining, adding ultrapure water to make the total volume of the suspension to be 80ml, stirring uniformly with a glass rod, and then placing into a hydrothermal reaction kettle, and performing hydrothermal reaction for 24h at 200 ℃. After the reaction is finished and the temperature is cooled to room temperature, pouring out the supernatant, and centrifugally washing the supernatant for 3 times by using a mixed solution of ultrapure water and alcohol; placing theDrying in a drying oven at 60 deg.C for 12 hr to obtain white KTa 0.75 Nb 0.25 O 3 Solid solution.
(2) Weighing 0.8524gCuCl 2 ·2H 2 O and 2.4018gNa 2 S·9H 2 O, respectively preparing into 100ml of CuCl 2 Solution (0.05 mol/L) and Na 2 The S solution (0.1 mol/L) was ready for use. Weighing 1.23g (0.005 mol) KTa 0.75 Nb 0.25 O 3 Placing the powder in a 100ml beaker containing 55ml of ultrapure water, sonicating at 120W for 30min to form a homogeneous dispersion, removing 7.5ml of the above CuCl stock by pipette 2 Dropwise adding the solution into the suspension, magnetically stirring for 0.5 hr, and removing 7.5ml of the Na 2 And dropwise adding the S solution into the suspension, magnetically stirring for 0.5h, transferring into a hydrothermal reaction kettle containing 100ml of polytetrafluoroethylene lining, and performing hydrothermal reaction at 140 ℃ for 12h. After the reaction was completed and cooled to room temperature, the supernatant was decanted, washed 3 times with a mixed solution of ultrapure water and alcohol, placed in a vacuum oven, and dried at 60 ℃ for 12 hours under a vacuum atmosphere to obtain the target product of 7.5% CuS/KTN.
Example 2
(1) The procedure of (1) in example 1 was repeated.
(2) 1.23g (0.005 mol) KTa are weighed 0.75 Nb 0.25 O 3 Placing the powder into a 100ml beaker containing 50ml of ultrapure water, performing 120W ultrasonic treatment for 30min to form a uniform dispersion, and removing 10ml of 0.05mol/L CuCl by using a liquid-moving machine 2 The solution was added dropwise to the suspension, magnetically stirred for 0.5h, and then 10ml of 0.1mol/L Na was removed by a pipette 2 And dropwise adding the S solution into the suspension, magnetically stirring for 0.5h, transferring into a hydrothermal reaction kettle containing 100ml of polytetrafluoroethylene lining, and performing hydrothermal reaction at 140 ℃ for 12h. After the reaction was completed and cooled to room temperature, the supernatant was poured off, and the reaction mixture was centrifuged and washed 3 times with a mixed solution of ultrapure water and alcohol, and the resulting mixture was put into a vacuum oven and dried at 60 ℃ for 12 hours in a vacuum atmosphere to obtain the objective product, i.e., 10% CuS/KTN.
Example 3
(1) The procedure of (1) in example 1 was repeated.
(2) Weighing 1.23g (0.005 mol) KTa 0.75 Nb 0.25 O 3 Powder ofPlacing into a 100ml beaker containing 45ml of ultrapure water, performing 120W ultrasonic treatment for 30min to form a uniform dispersion, and removing 12.5ml of 0.05mol/L CuCl by using a pipette 2 The solution was added dropwise to the suspension, magnetically stirred for 0.5h, and 12.5ml of 0.1mol/L Na was removed by pipette 2 And dropwise adding the S solution into the suspension, magnetically stirring for 0.5h, transferring into a hydrothermal reaction kettle containing 100ml of polytetrafluoroethylene lining, and performing hydrothermal reaction at 140 ℃ for 12h. After the reaction was completed and cooled to room temperature, the supernatant was poured off, and the reaction mixture was centrifuged and washed 3 times with a mixed solution of ultrapure water and alcohol, and then placed in a vacuum oven and dried at 60 ℃ for 12 hours in a vacuum atmosphere to obtain the objective product (12.5% CuS/KTN).
Example 4
(1) The procedure of (1) in example 1 was repeated.
(2) Weighing 1.23g (0.005 mol) KTa 0.75 Nb 0.25 O 3 The powder was placed in a 100ml beaker containing 40ml of ultrapure water and sonicated at 120W for 30min to form a homogeneous dispersion. Remove 15ml0.05mol/L of CuCl with a pipette 2 Dropwise adding the solution into the suspension, magnetically stirring for 0.5h, and removing 15ml0.1mol/L Na by using a pipette 2 And dropwise adding the S solution into the suspension, magnetically stirring for 0.5h, transferring into a hydrothermal reaction kettle containing 100ml of polytetrafluoroethylene lining, and performing hydrothermal reaction at 140 ℃ for 12h. After the reaction was completed and cooled to room temperature, the supernatant was poured off, and the reaction mixture was centrifuged and washed 3 times with a mixed solution of ultrapure water and alcohol, and the resulting solution was put into a vacuum oven and dried at 60 ℃ for 12 hours in a vacuum atmosphere to obtain the objective product 15% CuS/KTN.
Photocatalytic synthesis of ammonia experiment
(1) 0.1g of catalyst, 190ml of ultrapure water and 10ml of absolute ethanol (chemical formula: C) were weighed 2 H 5 OH, as sacrificial agent, 5% by volume, i.e. 5 vol%) was added to a 250ml beaker.
(2) Wrapping the beaker with tinfoil, stirring for 1h in a shading manner to ensure adsorption-desorption balance, taking a No. 0 sample (taking 6.5ml of 10ml of a centrifugal tube), turning on a lamp (taking 6.5ml of PLS-SXE300 xenon lamp of Beijing Pofely science and technology Limited) and taking 5 samples in sequence every 1h, wherein the whole experiment takes 6h;
(3) Centrifuging to separate catalyst, collecting supernatant, adding 20 μ L potassium sodium tartrate as national standard masking agent by pipette, reacting for 10min, and adding 30 μ L Nashin's reagent;
(4) Standing for 12min, measuring absorbance from sample No. 0 to sample No. 5 with ultraviolet-visible spectrophotometer, recording absorbance value at 420nm, and reacting with NH 4 + standard curve to determine ammonia content.
Piezoelectric catalytic synthesis of ammonia experiment
(1) 0.1g of catalyst, 190ml of ultrapure water and 10ml of methanol (chemical formula: CH) were weighed 3 OH as sacrificial agent, 5% by volume, i.e. 5 vol%) was added to a 250ml beaker;
(2) Sealing the opening of the beaker by using a preservative film, stirring for 1h in a sealing manner to ensure adsorption-desorption balance, taking a sample No. 0 (taking 6.5ml of a 10ml centrifugal tube), then putting the beaker into an ultrasonic machine (taking a JP-020S type ultrasonic machine of Jie union cleaning equipment Limited, shenzhen as an ultrasonic source), adding water to the beaker to enable the water to overflow the liquid level in the beaker, keeping the uniform height, carrying out ultrasonic treatment at the power of 60W, taking one sample (taking 6.5ml of one sample) every 1h, sequentially taking 5 samples, and taking 6h for the whole experiment;
(3) Centrifuging to separate catalyst, collecting supernatant, adding 20 μ L potassium sodium tartrate as national standard masking agent by pipette, reacting for 10min, and adding 30 μ L Nashin's reagent;
(4) Standing for 12min, measuring absorbance from sample No. 0 to sample No. 5 with ultraviolet-visible spectrophotometer, recording absorbance value at 420nm, and collecting absorbance value with NH 4 + standard curve to determine ammonia content.
The photocatalytic ammonia synthesis activities of examples 1 to 4 and comparative examples 1 and 2 are shown in FIG. 5, in which comparative example 1 is KTN and comparative example 2 is CuS (the same applies hereinafter). The activity of the piezoelectric catalytic synthesis of ammonia is shown in FIG. 6. By comparing the photocatalytic synthesis ammonia activity and the piezoelectric catalytic synthesis ammonia activity of comparative examples 1 to 4 and comparative examples 1 and 2, example 2 had the best photocatalytic and piezoelectric catalytic synthesis ammonia activity, and the rates reached 167.4. Mu. Mol. G cat -1 ·h -1 And 36.2. Mu. Mol. G cat -1 ·h -1 3.5 times and 11 times, respectively, as compared with comparative example 1. If example 2 is placed in the ring of light and ultrasonic vibration at the same timeUnder the condition, higher catalytic nitrogen fixation efficiency is obtained, and the generation rate of ammonia reaches 198 mu mol g cat -1 ·h -1 (FIG. 7), after six cycles, the catalytic activity of example 2 remained unchanged, indicating that the material has higher stability.
FIG. 1 is an XRD pattern of examples 2 and 4 and comparative examples 1 and 2. It can be seen that only the diffraction peak of KTN is observed in the examples due to the lower content of CuS. However, raman characterization (FIG. 2) confirmed the presence of CuS in examples 1-4. As the content of CuS increases, it can be observed that the raman peak of CuS gradually increases, while the raman peak of KTN gradually decreases. FIG. 3 is an SEM photograph of example 2. It was observed that CuS nanoparticles adhered to KTN cubes. The above results confirm that examples 1-4 are composite catalysts of CuS modified KTN. FIG. 4 shows the photo-current spectra of example 2 and comparative examples 1 and 2. It can be observed that the embodiment 2 has higher response photocurrent, which indicates that the combination of CuS and KTN makes it have higher carrier separation capability, thereby prolonging the lifetime of photo-generated electrons, prompting more electrons to participate in the photocatalytic and piezoelectric catalytic nitrogen fixation reactions, and finally making the CuS/KTN catalyst show excellent photocatalytic and piezoelectric catalytic performances.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The application of the copper sulfide composite potassium tantalate-niobate with the p-n heterojunction structure in the synthesis of ammonia by catalyzing nitrogen fixation is characterized in that the copper sulfide composite potassium tantalate-niobate is composed of copper sulfide and potassium tantalate-niobate, and the molar ratio of the copper sulfide to the potassium tantalate-niobate is 1% -15%; the potassium tantalate niobate is KTa 0.75 Nb 0.25 O 3 Solid solution.
2. Use according to claim 1, wherein the molar ratio of copper sulphide to potassium tantalate niobate is 10%.
3. The use according to claim 1, wherein the preparation method of the copper sulfide composite potassium tantalate niobate comprises the following steps:
weighing a proper amount of Ta 2 O 5 And Nb 2 O 5 Adding KOH aqueous solution and stirring to obtain mixed solution;
carrying out hydrothermal reaction, cooling, washing and drying on the mixed solution to obtain a potassium tantalate niobate solid solution;
dispersing the potassium tantalate niobate solid solution to obtain a suspension;
and adding copper chloride and sodium sulfide into the suspension, stirring, performing hydrothermal treatment, precipitating, washing and drying to obtain the copper sulfide composite potassium tantalate-niobate with the p-n heterojunction structure.
4. Use according to claim 3, characterized in that in step (1) the Ta 2 O 5 And Nb 2 O 5 In a molar ratio of 3:1.
5. the use according to claim 3, wherein the hydrothermal reaction is carried out at a temperature of 160-260 ℃ and for a reaction time of 12-48h.
6. Use according to claim 3, wherein the molar ratio of copper chloride to sodium sulphide is 1:2.
7. use according to claim 3, wherein the temperature of the hydrothermal treatment is 140 ℃ and the temperature of the drying is 60 ℃.
8. The use of claim 1, wherein the copper sulfide composite potassium tantalate niobate has piezoelectric catalysis and photocatalytic nitrogen fixation properties.
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| US5476720A (en) * | 1992-12-18 | 1995-12-19 | Guenter; Peter | Films of KTN and KTAO3 |
| CN106831331A (en) * | 2016-12-29 | 2017-06-13 | 厦门大学 | A kind of method that photocatalytic conversion methyl alcohol prepares ethylene glycol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476720A (en) * | 1992-12-18 | 1995-12-19 | Guenter; Peter | Films of KTN and KTAO3 |
| CN106831331A (en) * | 2016-12-29 | 2017-06-13 | 厦门大学 | A kind of method that photocatalytic conversion methyl alcohol prepares ethylene glycol |
Non-Patent Citations (1)
| Title |
|---|
| Effectively H2 generation over CdS/KTa0.75Nb0.25O3 composite via water splitting;Pingxing Xing et al.，;《Journal of Colloid and Interface Science》;20190529;第552卷;第622–632页 * |
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