CN112275298B - 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 PDF

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CN112275298B
CN112275298B CN202011320812.6A CN202011320812A CN112275298B CN 112275298 B CN112275298 B CN 112275298B CN 202011320812 A CN202011320812 A CN 202011320812A CN 112275298 B CN112275298 B CN 112275298B
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niobate
potassium tantalate
bismuth sulfide
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CN112275298A (en
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何益明
王军峰
李晓静
戴孝全
陈璐
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Zhejiang Normal University CJNU
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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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% Bi 2 S 3 /KTa 0.75 Nb 0.25 O 3 Wherein x is Bi in the catalyst 2 S 3 And KTa 0.75 Nb 0.25 O 3 X is more than or equal to 0.1 and less than or equal to 5. KTa 0.75 Nb 0.25 O 3 The material is applied to piezoelectric catalysis and photocatalysis nitrogen fixation, and N is converted under the action of ultrasonic vibration or illumination 2 Catalytically reduced to ammonia. Bi 2 S 3 The load of the converter is further increased by KTa 0.75 Nb 0.25 O 3 The performance of synthesizing ammonia by piezoelectric catalysis and photocatalysis.

Description

Bismuth sulfide composite potassium tantalate niobate catalyst, preparation method and application thereof
Technical Field
The invention relates to the field of optical 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, H 2 Is 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 and hydrogen, and has a characteristic of being easily liquefied, and thus is considered to be in proportion to H 2 Better hydrogen energy carrier. However, ammonia, like hydrogen, also suffers from high production costs. At present, the number of the current day,
Figure BDA0002792825590000011
the process is the most widely used industrial process for synthesizing ammonia, but the high temperature and high pressure are adoptedThe reaction conditions and the large amounts of greenhouse gases produced during the production are clearly out of compliance with the requirements for 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, such as g-C 3 N 4 (j.mater.chem.a 2015,3, 23435-23441), znO (j.phys.chem.c 2010,114 3 (ACS sustatin. Chem. Eng.2019,7 12408-12418) and has been extensively studied in the field of photocatalytic nitrogen fixation. Recently, the inventor group synthesizes a high-efficiency catalyst KTa 0.75 Nb 0.25 O 3 (KTN) solid solution for photocatalytic hydrogen evolution (Fuel 2019, 241. With KNbO 3 Compared 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 preparation 2 And (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. Bi 2 S 3 Is a layered metal sulfide having a narrow band gap and good visible light response. Its decoration as a cocatalyst can improve the electron-hole separation efficiency and/or increase the photoresponse range, which has been demonstrated in many composite photocatalysts. Bi 2 S 3 The 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 Bi 2 S 3 Photocatalytic N of/KTN 2 Report of fixation studies.
In addition to being an effective photocatalyst, KTN is also known for its excellent piezoelectric properties, which suggests that KTN can convert mechanical energy into electrochemical energy (Ferroelectrics, 1981, 38. In 1998, domen first applied vibrational energy to catalyze the decomposition of water to H 2 And O 2 . Since then, by mechanical energyThe catalyzed process attracts scientific attention because it can be performed in the dark and is an important complement to the photocatalytic process. BaTiO as reported by Wu et al 3 (Nano Energy 2018, 45, 44-51), xun et al reported ZnO nanofibers (Chemosphere 2018, 193, 1143-1148) and Youji et al reported BiFeO 3 The nanosheets (Angew. Chem. Int. Ed.2019, 58. 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
The invention aims to solve the problems and provides a bismuth sulfide composite potassium tantalate-niobate catalyst, a preparation method and application thereof, wherein the simple hydrothermal method is used for preparing KTa 0.75 Nb 0.25 O 3 And Bi is hydrothermally treated twice 2 S 3 Loaded to KTa 0.75 Nb 0.25 O 3 So 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 performances 2 S 3 a/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 mainly prepared from bismuth sulfide and potassium tantalate niobate, and has a general formula of x% Bi 2 S 3 /KTa 0.75 Nb 0.25 O 3 Wherein x is Bi in the catalyst 2 S 3 And KTa 0.75 Nb 0.25 O 3 X is more than or equal to 0.1 and less than or equal to 5.
Further, the potassium tantalate niobate is KTa 0.75 Nb 0.25 O 3 Solid 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 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 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) 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 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 application of the bismuth sulfide composite potassium tantalate-niobate prepared by the method in the third technical scheme in the synthesis of ammonia by catalyzing and fixing nitrogen.
The invention has the advantages that:
1. bi prepared by the invention 2 S 3 Composite catalyst of/KTN (bismuth sulfide composite potassium tantalate niobate)The preparation process utilizes a simple hydrothermal method, and is simple to operate.
2. Bi prepared by the invention 2 S 3 The KTN has both photocatalytic and piezoelectric catalytic performances and has good practical application prospect.
3. Optimized Bi 2 S 3 The ammonia production rates of the/KTN catalyst photocatalysis and the piezoelectric catalysis are 561.6 mu mol.L respectively -1 ·g cat -1 And 14.9. 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 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 points 2 S 3 the/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 vibration 2 Conversion to NH 3 . 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 chart 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 synthesis ammonia activity in examples 1 to 5 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 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 (0.0075 mol) of Ta was further weighed 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 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 24h. 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 an oven at 60 deg.C for 12 hr to obtain white KTa 0.75 Nb 0.25 O 3 Solid solution.
(2) Weighing 9.6027gNa 2 S·9H 2 O, prepared as 100mL Na 2 The S solution (0.40 mol/L) was used. 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, and removing 0.1mL of the Na by pipette 2 The S solution is dripped into the suspension, evenly stirred by magnetic force, and then added with 0.0049gBi (NO) 3 ) 3 ·5H 2 O crystal, magnetically stirring for 40min, transferring to a hydrothermal reaction kettle with 100mL polytetrafluoroethylene lining, and heating at 120 ℃ 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 4 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 16 hours in a vacuum atmosphere to obtain the desired product, 0.1% Bi 2 S 3 /KTN。
Example 2
(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 Placing 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 pipette 2 The S solution is dripped into the suspension, the suspension is stirred evenly by magnetic force, and then 0.0121gBi (NO) is added 3 ) 3 ·5H 2 O crystal, magnetically stirring for 40min, transferring to a hydrothermal reaction kettle with 100mL polytetrafluoroethylene lining, and heating at 120 ℃ 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 4 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 16 hours in a vacuum atmosphere to obtain the desired product, 0.25% Bi 2 S 3 /KTN。
Example 3
(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 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 pipette 2 The S solution is dripped into the suspension, is stirred evenly by magnetic force, and then is added with 0.0243gBi (NO) 3 ) 3 ·5H 2 O crystal is magnetically stirred for 40min and transferred to a hydrothermal reaction kettle containing 100mL of polytetrafluoroethylene lining, and then is heated for 12h at 120 ℃. After the reaction was completed and cooled to room temperature, the supernatant was poured off, and the reaction mixture was centrifuged and washed 4 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 16 hours in a vacuum atmosphere to obtain the desired product, 0.5% Bi 2 S 3 /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 Placing 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 pipette 2 S solution is dripped into the suspension and stirred by magnetic forceMixing, adding 0.0485gBi (NO) 3 ) 3 ·5H 2 O crystal, magnetically stirring for 40min, transferring to a hydrothermal reaction kettle with 100mL polytetrafluoroethylene lining, and heating at 120 ℃ 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 4 times with a mixed solution of ultrapure water and alcohol, and the washed solution was put into a vacuum oven and dried at 60 ℃ for 16 hours in a vacuum atmosphere to obtain the objective product 1% Bi 2 S 3 /KTN。
Example 5
(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 put into a 100mL beaker containing 55mL of ultrapure water, sonicated at 120W for 30min to form a homogeneous dispersion, and 5mL of the Na powder was pipetted 2 Adding S solution dropwise into the suspension, stirring with magnetic force, and adding 0.2425gBi (NO) 3 ) 3 ·5H 2 O crystal, magnetically stirring for 40min, transferring to a hydrothermal reaction kettle with 100mL polytetrafluoroethylene lining, and heating at 120 ℃ 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 4 times with a mixed solution of ultrapure water and alcohol, and the washed solution was put into a vacuum oven and dried at 60 ℃ for 16 hours in a vacuum atmosphere to obtain the objective product 5% Bi 2 S 3 /KTN。
Comparative example 1
The procedure of (1) in example 1 was repeated.
Comparative example 2
A100 mL beaker was weighed to 1.9214gNa 2 S·9H 2 O, adding 70mL of ultrapure water to fully dissolve, and weighing 0.9701gBi (NO) 3 )·5H 2 O was slowly added to the above Na 2 S·9H 2 Stirring 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 Bi 2 S 3 And (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) 3 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 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 NH 4 + 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) 3 OH as 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 NH 4 + The standard curve determines the ammonia content.
The photocatalytic ammonia synthesis activities of examples 1 to 5 and comparative examples 1 and 2 are shown in FIG. 5, in which comparative example 1 is KTN and comparative example 2 is Bi 2 S 3 (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 the comparative examples 1 to 5 and comparative examples 1 and 2, the example 2 had the best photocatalytic and piezoelectric catalytic synthesis ammonia activity, and the rates reached 561.6. Mu. Mol. G cat -1 ·h -1 And 14.9. Mu. Mol. G cat -1 ·h -1 Which 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 g cat -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 added 2 S 3 Lower, only diffraction peaks of KTN are observed, but with Bi 2 S 3 Increase in the content of Bi, bi was observed in example 5 2 S 3 Characteristic peak of diffraction of (1). This is characterized by Raman (FIG. 2, using λ) ex Ar of =514nm + Laser-excited catalyst) was further confirmed. With Bi 2 S 3 The increase in the content gradually weakens the raman peak of KTN, 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 observed 2 S 3 Nanorods are attached to KTN cubes. The above results confirmed that examples 1 to 5 are Bi 2 S 3 Composite 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 Bi 2 S 3 The 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 be 2 S 3 the/KTN catalyst shows excellent photocatalysis and piezoelectricityAnd (4) catalytic performance.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any modifications, equivalents, improvements and the like that are made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The application of the bismuth sulfide composite potassium tantalate niobate catalyst in the catalysis of nitrogen fixation to synthesize ammonia is characterized in that the catalyst is mainly prepared from bismuth sulfide and potassium tantalate niobate, and the general formula is x% Bi 2 S 3 /KTa 0.75 Nb 0.25 O 3 Wherein x is Bi in the catalyst 2 S 3 And KTa 0.75 Nb 0.25 O 3 X is more than or equal to 0.1 and less than or equal to 5.
2. The application of the bismuth sulfide composite potassium tantalate-niobate catalyst in ammonia synthesis by catalysis and nitrogen fixation according to claim 1, wherein the potassium tantalate-niobate is KTa 0.75 Nb 0.25 O 3 Solid solution.
3. The use of the bismuth sulfide composite potassium tantalate-niobate catalyst in the catalysis of nitrogen fixation synthesis of ammonia according to claim 1, wherein the molar ratio of bismuth sulfide to potassium tantalate-niobate is 0.25%.
4. The application of the bismuth sulfide composite potassium tantalate-niobate catalyst in catalysis of nitrogen fixation for ammonia synthesis according to claim 1, wherein the catalyst is used for photocatalysis and/or piezoelectric catalysis.
5. The application of the bismuth sulfide composite potassium tantalate-niobate catalyst in the catalysis of nitrogen fixation for ammonia synthesis according to claim 1, wherein the preparation method of the catalyst comprises the following steps:
1) Mixing 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 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 use of the bismuth sulfide composite potassium tantalate-niobate catalyst in the catalysis of nitrogen fixation for ammonia synthesis according to claim 5, wherein the Ta in step (1) is 2 O 5 And Nb 2 O 5 In a molar ratio of 3:1.
7. the application of the bismuth sulfide composite potassium tantalate-niobate catalyst in the catalysis of nitrogen fixation for ammonia synthesis according to claim 5, wherein the hydrothermal reaction is carried out at 160-260 ℃ for 12-48h.
8. The application of the bismuth sulfide composite potassium tantalate-niobate catalyst in the catalysis of nitrogen fixation synthesis of ammonia according to claim 5, wherein the molar ratio of bismuth nitrate to sodium sulfide is 1:4.
9. the application of the bismuth sulfide composite potassium tantalate-niobate catalyst in catalysis of nitrogen fixation synthesis of ammonia according to claim 5, wherein the temperature of hydrothermal treatment is 120 ℃ and the temperature of drying is 60 ℃.
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