CN112275298A - Bismuth sulfide composite potassium tantalate niobate catalyst, preparation method and application thereof - Google Patents
Bismuth sulfide composite potassium tantalate niobate catalyst, preparation method and application thereof Download PDFInfo
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- CN112275298A CN112275298A CN202011320812.6A CN202011320812A CN112275298A CN 112275298 A CN112275298 A CN 112275298A CN 202011320812 A CN202011320812 A CN 202011320812A CN 112275298 A CN112275298 A CN 112275298A
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- potassium tantalate
- bismuth sulfide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 34
- 239000011591 potassium Substances 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 239000006104 solid solution Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- CTKARXHBRUYYMT-UHFFFAOYSA-N [K].[Bi].[S] Chemical compound [K].[Bi].[S] CTKARXHBRUYYMT-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 238000005286 illumination Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 17
- 239000012498 ultrapure water Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- -1 hydrogen Chemical compound 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000007036 catalytic synthesis reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007970 homogeneous dispersion Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910003334 KNbO3 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000011941 photocatalyst Substances 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
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000004044 response Effects 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
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000005303 weighing 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
-
- 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
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- 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)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a bismuth sulfide composite potassium tantalate niobate catalyst, a preparation method and application thereof, wherein the general formula of the catalyst is x% Bi2S3/KTa0.75Nb0.25O3Wherein x is Bi in the catalyst2S3And KTa0.75Nb0.25O3X is more than or equal to 0.1 and less than or equal to 5. KTa of the invention0.75Nb0.25O3The material is applied to piezoelectric catalysis and photocatalysis nitrogen fixation, and N is converted under the action of ultrasonic vibration or illumination2Catalytically reduced to ammonia. Bi2S3The load of the generator is further increased by KTa0.75Nb0.25O3The performance of synthesizing ammonia by piezoelectric catalysis and photocatalysis.
Description
Technical Field
The invention relates to the field of light and mechanical vibration combined catalyst materials, in particular to a bismuth sulfide composite potassium tantalate-niobate catalyst and a preparation method and application thereof.
Background
As an ideal green fuel, H2Is considered as a future alternative to fossil energy. However, the high production cost and the difficulty in storage and transportation greatly limit the application prospect. Ammonia consists of one nitrogen atom and three hydrogen atoms, is easily decomposed into nitrogen gas and hydrogen gas, and has an easy-to-liquefy characteristic, and is therefore considered to be specific to H2Better hydrogen energy carrier. However, ammonia, like hydrogen, also suffers from high production costs. At present, the number of the current day,
the process is the most widely used industrial ammonia synthesis process, but the high temperature and high pressure reaction conditions and the large amount of greenhouse gases generated in the production process obviously do not meet the requirements of sustainable development. Therefore, it is worth researching to find a green, energy-saving and efficient ammonia synthesis method.
The use of light energy and a semiconductor catalyst for nitrogen fixation is reported for the first time in 1977, and the method has the advantages of mild reaction conditions, low energy consumption and zero carbon emission, similar to biological nitrogen fixation. Thanks to these advantages, a range of semiconductor materials have been produced, for example g-C3N4(J.Mater.chem.A 2015, 3: 23435-23441), ZnO (J.Phys.chem.C 2010,114: 2622-2632), and KNbO3(ACS sustatin. chem. Eng.2019, 7: 12408-12418) and has been extensively studied in the field of photocatalytic nitrogen fixation. Recently, the inventor group synthesized a high-efficiency catalyst KTa0.75Nb0.25O3(KTN) solid solution for photocatalytic hydrogen evolution (Fuel 2019, 241: 1-11). With KNbO3Compared with the synthesized KTN solid solution, the conduction band of the synthesized KTN solid solution is wider, and the position of the synthesized KTN solid solution is more negative, which shows that the photo-generated electrons in the KTN have stronger reducibility and better mobility. The two advantages enable the KTN solid solution to have higher photocatalysis H preparation2And (4) performance. Meanwhile, the KTN is a potential effective catalyst for photocatalytic nitrogen fixation, and the design and preparation of the KTN-based composite material are feasible methods for realizing efficient photocatalytic nitrogen fixation. Bi2S3Is a layered metal sulfide having a narrow band gap and good visible light response. It can be used as cocatalyst for decoration to improve electronHole separation efficiency and/or increase of the photoresponse range, which have been demonstrated in many composite photocatalysts. Bi2S3The appropriate band potential was exhibited for KTN, indicating that it is also a suitable promoter for KTN. To the best of our knowledge, there is no disclosure of Bi2S3Photocatalytic N of/KTN2Report of fixation studies.
In addition to being an effective photocatalyst, KTN is known for its excellent piezoelectric properties, indicating that KTN can convert mechanical energy into electrochemical energy (Ferrooelectrics, 1981, 38: 825-828). In 1998, Domen first applied vibrational energy to catalyze the decomposition of water to H2And O2. Since then, the catalytic process initiated by mechanical energy has attracted the attention of scientists, as it can be carried out in the dark and is an important complement to photocatalytic processes. BaTiO as reported by Wu et al3(Nano Energy 2018, 45: 44-51), Xun et al reported ZnO nanofiber (Chemosphere 2018, 193: 1143-3The nanosheets (Angew. chem. int. Ed.2019, 58: 11779-. Like the above piezoelectric catalyst, KTN solid solution is also considered to be an excellent piezoelectric material, indicating that it has a great potential in piezoelectric catalysis.
Disclosure of Invention
In order to solve the problems, the invention provides a bismuth sulfide composite potassium tantalate-niobate catalyst, a preparation method and application thereof, wherein KTa is prepared by utilizing a simple hydrothermal method0.75Nb0.25O3And Bi is hydrothermally treated twice2S3Load to KTa0.75Nb0.25O3So as to improve the photocatalytic and piezoelectric catalytic performances of the Bi, and finally obtain the Bi with excellent piezoelectric catalytic and photocatalytic nitrogen fixation performances2S3a/KTN composite catalyst.
One of the purposes of the invention is to provide a bismuth sulfide composite potassium tantalate niobate catalyst, and the specific technical scheme is as follows:
a bismuth sulfide composite potassium tantalate niobate catalyst is prepared from bismuth sulfide and tantalumPotassium niobate of general formula x% Bi2S3/KTa0.75Nb0.25O3Wherein x is Bi in the catalyst2S3And KTa0.75Nb0.25O3X is more than or equal to 0.1 and less than or equal to 5.
Further, the potassium tantalate niobate is KTa0.75Nb0.25O3Solid solution.
Further, the molar ratio of the bismuth sulfide to the potassium tantalate niobate is 0.25%.
The second purpose of the invention is to provide an application of the bismuth sulfide composite potassium tantalate niobate catalyst, and the specific technical scheme is as follows:
the bismuth 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 invention also aims to provide a preparation method of the bismuth sulfide composite potassium tantalate niobate, which has the following specific technical scheme:
a method for preparing a bismuth sulfide composite potassium tantalate niobate catalyst comprises the following steps,
1) mixing Ta2O5And Nb2O5Adding KOH aqueous solution and stirring to obtain mixed solution;
2) carrying out hydrothermal reaction, cooling, washing and drying on the mixed solution obtained in the step 1) to obtain a potassium tantalate-niobate solid solution;
3) dispersing the potassium tantalate-niobate solid solution in the step 2) to obtain a suspension;
4) adding bismuth nitrate and sodium sulfide into the suspension obtained in the step 3), stirring, performing hydrothermal treatment, precipitating, washing and drying to obtain bismuth sulfide composite potassium tantalate niobate.
Further, said Ta in step (1)2O5And Nb2O5In a molar ratio of 3: 1.
further, the temperature of the hydrothermal reaction is 160-260 ℃, and the reaction time is 12-48 h; the drying temperature is 60 ℃.
Further, the molar ratio of the bismuth nitrate to the sodium sulfide is 1: 4.
further, the temperature of the hydrothermal treatment is 140 ℃, and the temperature of the drying is 60 ℃.
The fourth purpose of the invention is to provide the application of the bismuth sulfide composite potassium tantalate-niobate prepared by the technical scheme, and the specific technical scheme is as follows:
the bismuth sulfide composite potassium tantalate-niobate prepared by the method in the third technical scheme is applied to the synthesis of ammonia by catalyzing nitrogen fixation.
The invention has the advantages that:
1. bi prepared by the invention2S3The preparation process of the/KTN (bismuth sulfide and potassium tantalate niobate) composite catalyst utilizes a simple hydrothermal method and is simple to operate.
2. Bi prepared by the invention2S3The KTN has both photocatalytic and piezoelectric catalytic performances and has good practical application prospect.
3. Optimized Bi2S3The ammonia generating rates of the/KTN catalyst photocatalysis and the piezoelectric catalysis are 561.6 mu mol.L respectively-1·gcat -1And 14.9. mu. mol. L-1·gcat -1Are respectively pure phase KTa0.75Nb0.25O3The ammonia generating rate of the photocatalysis and the piezoelectricity catalysis is 4.7 times and 4 times, and the ammonia generating performance of the photocatalysis and the piezoelectricity catalysis is particularly excellent. Bi prepared by hydrothermal method by combining the above two points2S3the/KTN composite catalyst has better practical application prospect.
The invention applies KTN to the photocatalysis nitrogen fixation reaction for the first time and simultaneously realizes the purpose of adding N under the ultrasonic vibration2Conversion to NH3. The modification of bismuth sulfide greatly improves the catalytic efficiency, even reaches one of the most efficient levels in the field at present.
Drawings
FIG. 1 is an XRD pattern of examples 1 to 5 of the present invention and comparative examples 1 and 2.
FIG. 2 is a Raman diagram of examples 1 to 5 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 5 and comparative examples 1 and 2 of the present invention.
FIG. 6 is a graph showing the activity of the piezoelectric catalytic synthesis of ammonia in examples 1 to 5 and comparative examples 1 and 2 of the present invention.
Fig. 7 is a cycle test chart of example 2 of the present invention.
FIG. 8 is a graph showing the piezoelectric-photocatalytic synthesis ammonia activity in example 2 of the present invention and comparative examples 1 and 2.
Detailed Description
The present invention is further described in detail by the following examples, comparative examples and drawings, it is to be understood that the specific examples described herein are for purposes of illustration only and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Example 1
The embodiment provides a preparation method of bismuth sulfide composite potassium tantalate niobate, which comprises the following steps:
(1) 44.80g of KOH solid were dissolved in 40mL of ultrapure water by an analytical balance, and 3.315g (0.0075mol) of Ta was further weighed2O5And 0.665g (0.0025mol) Nb2O5Slowly adding into the KOH solution, magnetically stirring for 1h, transferring into a liner made of 100mL LPPL material, adding ultrapure water to make the total volume of the suspension to be 80mL, uniformly stirring with a glass rod, and then placing into a hydrothermal reaction kettle for hydrothermal reaction at 200 ℃ for 24 h. 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; drying in oven at 60 deg.C for 12 hr to obtain white KTa0.75Nb0.25O3Solid solution.
(2) Weighing 9.6027gNa2S·9H2O, prepared as 100mL Na2The S solution (0.40mol/L) was ready for use. 1.23g (0.005mol) KTa were weighed out0.75Nb0.25O3Placing the powder in a 100mL beaker containing 55mL of ultrapure water, sonicating at 120W for 30min to form a homogeneous dispersion, and removing 0.1mL of the Na by pipette2The S solution was added dropwise to the suspension, and then the suspension was magnetically stirred and added with 0.0049gBi (NO)3)3·5H2O crystal, magnetically stirring for 40min, transferring to a hydrothermal reaction kettle with 100mL polytetrafluoroethylene lining, and heating at 120 ℃ for 12 h. After the reaction is finished and the temperature is cooled to room temperature, the supernatant is poured off, the mixed solution of ultrapure water and alcohol is used for centrifugal washing for 4 times, the mixture is put into a vacuum oven and dried for 16 hours at the temperature of 60 ℃ in a vacuum environment, and the target product of 0.1 percent Bi is obtained2S3/KTN。
Example 2
(1) The procedure of (1) in example 1 was repeated.
(2) 1.23g (0.005mol) KTa were weighed out0.75Nb0.25O3Placing the powder in a 100mL beaker containing 55mL of ultrapure water, sonicating at 120W for 30min to form a homogeneous dispersion, and removing 0.25mL of the Na by pipette2The S solution is added into the suspension dropwise, the mixture is stirred evenly by magnetic force, and then 0.0121gBi (NO) is added3)3·5H2O crystal, magnetically stirring for 40min, transferring to a hydrothermal reaction kettle with 100mL polytetrafluoroethylene lining, and heating at 120 ℃ for 12 h. After the reaction is finished and the temperature is cooled to room temperature, the supernatant is poured off, the mixed solution of ultrapure water and alcohol is used for centrifugal washing for 4 times, the mixture is put into a vacuum oven and dried for 16 hours at the temperature of 60 ℃ in a vacuum environment, and the target product of 0.25 percent Bi is obtained2S3/KTN。
Example 3
(1) The procedure of (1) in example 1 was repeated.
(2) 1.23g (0.005mol) KTa were weighed out0.75Nb0.25O3Placing the powder in a 100mL beaker containing 55mL of ultrapure water, sonicating at 120W for 30min to form a homogeneous dispersion, and removing 0.5mL of the Na by pipette2Adding S solution dropwise into the suspension, magnetically stirring, and adding 0.0243gBi (NO)3)3·5H2O crystal, magnetically stirring for 40min, transferring to hydrothermal reaction kettle containing 100mL polytetrafluoroethylene liningAnd heating at 120 ℃ for 12 h. After the reaction is finished and the temperature is cooled to room temperature, the supernatant is poured off, the mixed solution of ultrapure water and alcohol is used for centrifugal washing for 4 times, the mixture is put into a vacuum oven and dried for 16 hours at the temperature of 60 ℃ in a vacuum environment, and the target product of 0.5 percent Bi is obtained2S3/KTN。
Example 4
(1) The procedure of (1) in example 1 was repeated.
(2) 1.23g (0.005mol) KTa were weighed out0.75Nb0.25O3Placing the powder in a 100mL beaker containing 55mL of ultrapure water, sonicating at 120W for 30min to form a homogeneous dispersion, and removing 1mL of the Na by pipette2Adding S solution dropwise into the suspension, magnetically stirring, and adding 0.0485gBi (NO)3)3·5H2O crystal, magnetically stirring for 40min, transferring to a hydrothermal reaction kettle with 100mL polytetrafluoroethylene lining, and heating at 120 ℃ for 12 h. After the reaction is finished and the temperature is cooled to room temperature, the supernatant is poured off, the mixed solution of ultrapure water and alcohol is used for centrifugal washing for 4 times, the mixture is put into a vacuum oven and dried for 16 hours at the temperature of 60 ℃ in a vacuum environment, and the target product of 1 percent Bi is obtained2S3/KTN。
Example 5
(1) The procedure of (1) in example 1 was repeated.
(2) 1.23g (0.005mol) KTa were weighed out0.75Nb0.25O3Placing the powder in a 100mL beaker containing 55mL of ultrapure water, sonicating at 120W for 30min to form a homogeneous dispersion, and removing 5mL of the Na by pipette2Adding S solution dropwise into the suspension, magnetically stirring, and adding 0.2425gBi (NO)3)3·5H2O crystal, magnetically stirring for 40min, transferring to a hydrothermal reaction kettle with 100mL polytetrafluoroethylene lining, and heating at 120 ℃ for 12 h. After the reaction is finished and the temperature is cooled to room temperature, the supernatant is poured off, the mixed solution of ultrapure water and alcohol is used for centrifugal washing for 4 times, the obtained product is put into a vacuum oven and dried for 16 hours at the temperature of 60 ℃ in a vacuum environment, and the target product of 5 percent Bi is obtained2S3/KTN。
Comparative example 1
The procedure of (1) in example 1 was repeated.
Comparative example 2
A100 mL beaker was weighed to 1.9214gNa2S·9H2O, dissolved sufficiently in 70mL of ultrapure water, and 0.9701gBi (NO) was weighed out3)·5H2O is slowly added to the above Na2S·9H2Stirring O solution for 40min, transferring to 100mL inner lining made of polytetrafluoroethylene, placing into a reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 12h, naturally cooling to room temperature, pouring out supernatant, centrifuging and washing with ultrapure water and absolute ethyl alcohol for 6 times, placing into a vacuum drying oven, and carrying out vacuum drying for 16h under a vacuum environment to obtain a target product Bi2S3And (4) nanorods.
Experiment for synthesizing ammonia by photocatalysis
(1) 0.1g of catalyst, 190mL of ultrapure water, and 10mL of anhydrous methanol (chemical formula: CH)3OH, 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 mode to ensure adsorption-desorption balance, taking a No. 0 sample (taking 6.5mL of 10mL of a centrifuge tube), turning on a lamp (taking 6.5mL of PLS-SXE300 xenon lamp of Beijing Pofely science and technology Limited), 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 reacting with NH4 +The standard curve determines the ammonia content.
Piezoelectric catalytic synthesis of ammonia experiment
(1) 0.1g of catalyst, 190mL of ultrapure water, and 10mL of anhydrous methanol (chemical formula CH)3OH as a sacrificial agent, 5% by volume, i.e. 5 vol%) was added to a 250mL beaker;
(2) sealing the mouth 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 10mL of a centrifugal tube), then putting the beaker into an ultrasonic machine (taking a JP-020S type ultrasonic machine of Jie union cleaning equipment Limited in 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 reacting with NH4 +The standard curve determines the ammonia content.
The photocatalytic ammonia synthesis activities of examples 1-5 and comparative examples 1 and 2 are shown in FIG. 5, in which comparative example 1 is KTN and comparative example 2 is Bi2S3(the same applies below). 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 examples 1 to 5 and comparative examples 1 and 2, example 2 had the best photocatalytic and piezoelectric catalytic synthesis ammonia activity, and the rates reached 561.6. mu. mol. gcat -1·h-1And 14.9. mu. mol. gcat -1·h-1Which are 4.7 times and 4 times, respectively, of comparative example 1. If the example 2 is placed in the environment of illumination and ultrasonic vibration at the same time, higher catalytic nitrogen fixation efficiency is obtained, and the generation rate of ammonia reaches 581.0 mu mol gcat -1·h-1(FIG. 8), the catalytic activity of example 2 did not decrease and increase after six cycles, indicating that the material had higher stability (FIG. 7).
FIG. 1 is an XRD pattern of examples 1 to 5 and comparative examples 1 and 2. It can be seen that in example 2, Bi is added2S3Is low, only diffraction peaks of KTN are observed, but with Bi2S3Increase in the content of Bi, Bi was observed in example 52S3Characteristic peak of diffraction of (1). This is characterized in Raman (FIG. 2, by λ)ex514nm Ar+Laser-excited catalyst) was further confirmed. With Bi2S3Increased content, Raman of KTNThe peak gradually decreased, which can be attributed to the shielding effect of the supported bismuth sulfide. FIG. 3 is an SEM photograph of example 2. Bi can be observed2S3Nanorods are attached to KTN cubes. The above results confirmed that Bi is contained in examples 1 to 52S3Composite catalyst for modifying KTN. FIG. 4 shows the photo-current spectra of example 2 and comparative examples 1 and 2. Example 2 was observed to have a higher response photocurrent, indicating that Bi2S3The compound of the compound and KTN enables the compound to have higher carrier separation capacity, thereby prolonging the service life of photo-generated electrons, promoting more electrons to participate in photocatalysis and piezoelectric catalysis nitrogen fixation reaction, and finally enabling Bi to be2S3the/KTN catalyst shows 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 (10)
1. The bismuth sulfide composite potassium tantalate niobate catalyst is characterized in that the catalyst is mainly prepared from bismuth sulfide and potassium tantalate niobate, and the general formula of the catalyst is x% Bi2S3/KTa0.75Nb0.25O3Wherein x is Bi in the catalyst2S3And KTa0.75Nb0.25O3X is more than or equal to 0.1 and less than or equal to 5.
2. The bismuth sulfide composite potassium tantalate-niobate catalyst of claim 1, wherein the potassium tantalate-niobate is KTa0.75Nb0.25O3Solid solution.
3. The bismuth sulfide composite potassium tantalate-niobate catalyst of claim 1, wherein the molar ratio of bismuth sulfide to potassium tantalate-niobate is 0.25%.
4. The use of the bismuth sulfide potassium tantalate niobate complex catalyst of claim 1, wherein the catalyst is used for photocatalysis and/or piezo-catalysis.
5. The preparation method of the bismuth sulfide composite potassium tantalate niobate catalyst is characterized by comprising the following steps of:
1) mixing Ta2O5And Nb2O5Adding KOH aqueous solution and stirring to obtain mixed solution;
2) carrying out hydrothermal reaction, cooling, washing and drying on the mixed solution obtained in the step 1) to obtain a potassium tantalate-niobate solid solution;
3) dispersing the potassium tantalate-niobate solid solution in the step 2) to obtain a suspension;
4) adding bismuth nitrate and sodium sulfide into the suspension obtained in the step 3), stirring, performing hydrothermal treatment, precipitating, washing and drying to obtain bismuth sulfide composite potassium tantalate niobate.
6. The method for preparing the bismuth sulfide composite potassium tantalate-niobate catalyst according to claim 5, wherein the Ta in step (1) is2O5And Nb2O5In a molar ratio of 3: 1.
7. the method as claimed in claim 5, wherein the hydrothermal reaction temperature is 160-260 ℃ and the reaction time is 12-48 h.
8. The method for preparing the bismuth sulfide composite potassium tantalate-niobate catalyst according to claim 5, wherein the molar ratio of the bismuth nitrate to the sodium sulfide is 1: 4.
9. the method for preparing the bismuth sulfide composite potassium tantalate-niobate catalyst according to claim 5, wherein the temperature of the hydrothermal treatment is 120 ℃ and the temperature of the drying is 60 ℃.
10. Use of the bismuth sulfide composite potassium tantalate-niobate catalyst prepared by the method of any one of claims 5 to 9 in the catalysis of nitrogen fixation for ammonia synthesis.
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