CN112456514A - Application of bismuth sulfide catalyst with sulfur vacancy - Google Patents
Application of bismuth sulfide catalyst with sulfur vacancy Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 38
- 239000011593 sulfur Substances 0.000 title claims abstract description 38
- 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 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 44
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 12
- 238000007146 photocatalysis Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- RBWFXUOHBJGAMO-UHFFFAOYSA-N sulfanylidenebismuth Chemical class [Bi]=S RBWFXUOHBJGAMO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- 239000011941 photocatalyst Substances 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002073 nanorod Substances 0.000 description 5
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 5
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 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 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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Classifications
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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
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- 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
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides an application of a bismuth sulfide catalyst with a sulfur vacancy, which is used for visible-near infrared light catalysis, wherein the visible-near infrared light catalysis is applied to nitrogen fixation. The sulfur-containing vacancy bismuth sulfide catalyst prepared by the invention is stable, efficient, low in price, environment-friendly and wide in application prospect in energy, environmental pollution, treatment and the like; water is used as a reducing agent, and the yield of ammonia gas under sunlight is 122.9 mu mol g‑1h‑14.3 times of other bismuth sulfide with a small amount of sulfur vacancy; the yield of ammonia gas under near infrared light is 58.6 mu mol g‑1h‑1And is 2.6 times of that of other bismuth sulfides containing a small amount of sulfur vacancies.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a preparation method of a bismuth sulfide nanorod photocatalyst containing a sulfur vacancy and application of the bismuth sulfide nanorod photocatalyst in visible-near infrared light catalysis and nitrogen fixation.
Background
Nitrogen is an indispensable element on earth, but nitrogen in the atmosphere cannot be directly utilized, so that the problem of nitrogen fixation attracts much attention. The traditional industrial nitrogen fixation reduces nitrogen into ammonia by Haber method, which needs to be carried out at high temperature (300-. In order to save energy and protect the environment, it is urgent to find a new method to circumvent the problems caused by the Haber method.
Since 1977 first reported that nitrogen can undergo a photoreduction reaction on the surface of iron-doped titanium dioxide, the photocatalytic nitrogen fixation technology brings new prospects for the nitrogen fixation field. However, the photocatalytic nitrogen fixation reaction needs to satisfy the following conditions: 1, under the irradiation of sunlight, photoproduction electrons generated by the semiconductor photocatalyst can break N [ identical to ] N in nitrogen molecules; 2, the semiconductor photocatalyst has a proper band gap structure, the position of a conduction band is generally lower than-0.09 eV (vs NHE), so that nitrogen is reduced into ammonia, and the position of a valence band is generally higher than 1.23eV (vs NHE), so that water is oxidized into oxygen; 3, in the solar nitrogen fixation reaction, most of the photocatalyst can only absorb and utilize ultraviolet-visible light and only accounts for 50% of the solar energy, so that the utilization of the solar energy is improved by modifying the semiconductor photocatalyst; 4, in order to realize the purposes of protecting the environment and saving energy, the semiconductor photocatalyst has the characteristics of reutilization, contribution to recovery, no toxicity, no harm and the like.
Recent studies have shown that sulfides are of great interest in the field of photocatalytic nitrogen fixation, for example: indium sulfide, molybdenum disulfide, cadmium sulfide, and the like. Bismuth sulfide (Bi)2S3) The solar spectrum with the wavelength of more than 700nm can be absorbed by the solar cell; the appropriate band gap structure is beneficial to the generation of photo-generated electron hole pairs; and the raw materials are cheap and easy to obtain, and the production process is simple to operate. However, the traditional bismuth sulfide has no good nitrogen fixation capability, so that in order to improve the nitrogen fixation efficiency, the bismuth sulfide containing sulfur vacancies is a novel material in the field of photocatalytic nitrogen fixation, and also has the performance of near-infrared nitrogen fixation, which has important significance in the field of photocatalytic nitrogen fixation.
Disclosure of Invention
The invention provides an application of a bismuth sulfide nanorod photocatalyst in visible-near infrared nitrogen fixation, and aims to solve the problems that the conventional bismuth sulfide has no good nitrogen fixation capability and near infrared nitrogen fixation performance, and industrial nitrogen fixation wastes energy and damages the environment.
In order to achieve the above object, the present invention provides a use of a bismuth sulfide catalyst having a sulfur vacancy.
The bismuth sulfide catalyst with the sulfur vacancy is applied as a catalyst for visible-near infrared light catalysis nitrogen fixation.
Preferably, the visible-near infrared photocatalysis is applied to nitrogen fixation.
The bismuth sulfide catalyst with sulfur vacancy is used in the visible-near infrared photocatalysis process.
Preferably, the bismuth sulfide catalyst with sulfur vacancy is used in the visible-near infrared light catalytic nitrogen fixation process. The invention has the advantages that:
1. the bismuth sulfide material containing the sulfur vacancy is used as a photocatalyst to be applied to the field of photocatalysis, and the catalyst is stable, efficient, low in price, environment-friendly and simple in operation method, so that the application prospect in energy, environmental pollution, treatment and the like is wide;
2. the sulfur-containing vacancy bismuth sulfide prepared by the invention can fully utilize near infrared light in photocatalysis nitrogen fixation, greatly broadens the light absorption range, increases the utilization rate of sunlight and has good photocatalysis nitrogen fixation performance;
3. the sulfur-containing vacancy bismuth sulfide prepared by the invention is used for nitrogen fixation in visible-near infrared light catalysis, water is used as a reducing agent, and the yield of ammonia gas under sunlight is 122.9 mu mol g-1h-1The yield of ammonia gas under near infrared light is 2.1 times that of the ammonia gas under near infrared light, and the yield of the ammonia gas is 4.3 times that of the bismuth sulfide in other sulfur vacancy; the yield of ammonia gas under near infrared light is 58.6 mu mol g-1h-12.6 times of bismuth sulfide of other sulfur vacancy.
Drawings
FIG. 1 is an XRD diffractogram of the catalysts of examples 1-3;
FIG. 2 is a scanning electron micrograph of the catalyst of example 1;
FIG. 3 is a transmission electron microscope photograph of the catalyst of example 1;
FIG. 4 is a graph of the UV-vis absorption spectra of the catalysts of examples 1-3;
FIG. 5 is a spectrum of the forbidden band width estimation of the catalysts of examples 1-3;
FIG. 6 is a graph of current versus time for the catalysts of examples 1-3;
FIG. 7 is a graph of the AC impedance of the catalysts of examples 1-3;
FIG. 8 is a graph showing the effect of visible light photocatalytic nitrogen fixation of the catalysts of examples 1-3;
FIG. 9 is a graph showing the visible-near infrared photocatalytic nitrogen fixation effect of the catalyst of example 1.
Detailed Description
In order to facilitate understanding of the invention, the invention will be explained in detail with reference to the following examples and accompanying drawings in the examples, but the invention is not limited to the examples. If those skilled in the art should make insubstantial modifications and adaptations to the present invention based on the teachings herein, they are still within the scope of the present invention.
The invention mainly comprises the following steps:
s1, respectively dissolving bismuth nitrate pentahydrate and sodium sulfide nonahydrate in an ethylene glycol solvent, stirring after ultrasonic treatment until the solution is clear, then dropwise adding the dissolved sodium sulfide nonahydrate solution into the bismuth nitrate solution, and continuously stirring until a black mixed solution is obtained;
s2, carrying out hydrothermal reaction on the black mixed solution at the constant temperature of 180 ℃ for 1-5h, cooling to room temperature, centrifugally separating out precipitates, and washing with water and absolute ethyl alcohol respectively;
and S3, drying to obtain a powdery sample.
Dissolving the catalyst in deionized water; after ultrasonic stirring is carried out uniformly, nitrogen is continuously introduced for 30min in the dark; after light sources with different wavelengths are formed by different optical filters, nitrogen is continuously introduced for 120min in illumination; extracting samples at intervals of 30min, filtering off catalyst, and measuring with Nashin's reagent methodNH determination4 +。
Example 1
Dissolving 1.94g of bismuth nitrate pentahydrate in 30mL of glycol solution at room temperature, fully performing ultrasonic treatment, and stirring for 20min to obtain a clear solution, wherein the solution is marked as solution A; dissolving 1.44g of sodium sulfide nonahydrate in 10mL of glycol solution at room temperature, fully performing ultrasonic treatment, and stirring for 20min to obtain a clear solution, wherein the solution is marked as solution B; and dropwise adding the solution B into the solution A, and continuously stirring for 30min to obtain a black mixed solution. Putting the mixed solution into a 50mL high-pressure reaction kettle, carrying out constant-temperature reaction at 180 ℃ for 3h, cooling to room temperature, carrying out centrifugal separation on precipitates, washing with water and ethanol for 3 times respectively, and drying at 60 ℃ to obtain a final product Bi2S3-3。
Example 2
Dissolving 1.94g of bismuth nitrate pentahydrate in 30mL of glycol solution at room temperature, fully performing ultrasonic treatment, and stirring for 20min to obtain a clear solution, wherein the solution is marked as solution A; dissolving 1.44g of sodium sulfide nonahydrate in 10mL of glycol solution at room temperature, fully performing ultrasonic treatment, and stirring for 20min to obtain a clear solution, wherein the solution is marked as solution B; and dropwise adding the solution B into the solution A, and continuously stirring for 30min to obtain a black mixed solution. Putting the mixed solution into a 50mL high-pressure reaction kettle, carrying out constant-temperature reaction at 180 ℃ for 1h, cooling to room temperature, carrying out centrifugal separation on precipitates, washing with water and ethanol for 3 times respectively, and drying at 60 ℃ to obtain a final product Bi2S3-1。
Example 3
Dissolving 1.94g of bismuth nitrate pentahydrate in 30mL of glycol solution at room temperature, fully performing ultrasonic treatment, and stirring for 20min to obtain a clear solution, wherein the solution is marked as solution A; dissolving 1.44g of sodium sulfide nonahydrate in 10mL of glycol solution at room temperature, fully performing ultrasonic treatment, and stirring for 20min to obtain a clear solution, wherein the solution is marked as solution B; and dropwise adding the solution B into the solution A, and continuously stirring for 30min to obtain a black mixed solution. Putting the mixed solution into a 50mL high-pressure reaction kettle, carrying out constant-temperature reaction at 180 ℃ for 5h, cooling to room temperature, carrying out centrifugal separation on precipitates, washing with water and ethanol for 3 times respectively, and drying at 60 ℃ to obtain a final product Bi2S3-5。
FIG. 1 shows X-ray diffraction patterns of bismuth sulfide photocatalysts containing sulfur vacancies obtained in examples 1-3, which are compared with PDF standard cards to show that Bi has been successfully synthesized2S3。
FIG. 2 shows a scanning electron microscope image of the bismuth sulfide photocatalyst containing sulfur vacancies obtained in example 1, wherein the obtained morphology is formed by stacking nanorods.
FIG. 3 shows a transmission electron microscope image of the bismuth sulfide photocatalyst containing sulfur vacancies obtained in example 1, and clearly shows that the morphology thereof is a nanorod structure.
FIG. 4 shows the UV-vis absorption spectra of the bismuth sulfide photocatalyst containing sulfur vacancies obtained in examples 1-3, wherein the absorption edge is red-shifted with the increase of sulfur vacancies in the sample, and the photoresponse range is obviously widened.
FIG. 5 shows Tauc profiles of bismuth sulfide photocatalysts containing sulfur vacancies obtained in examples 1-3, which are used for estimating the forbidden band width.
FIG. 6 shows the photocurrent-time curves of the bismuth sulfide photocatalysts containing sulfur vacancies obtained in examples 1-3, and the photocurrent intensity is increased along with the increase of sulfur vacancies in the sample, which shows that the sulfur vacancies are beneficial to the generation of photo-generated carriers.
FIG. 7 shows the AC-impedance diagram of the bismuth sulfide photocatalyst containing sulfur vacancies obtained in examples 1-3, and the resistance decreases with the increase of sulfur vacancies in the sample, which illustrates that the sulfur vacancies can effectively trap electrons and inhibit the recombination of photo-generated electron holes.
Application example 1
Examples 1-3 samples were subjected to visible light photocatalytic nitrogen fixation to synthesize ammonia.
20mg of catalyst and 100mL of deionized water were weighed into a quartz photocatalytic reactor and sonicated until the catalyst was uniformly dispersed in the water. Introducing pure nitrogen with a flow rate of 80mL/min for 30min in a dark state under the condition of introducing condensed water and keeping the water temperature at 15 ℃, extracting 5mL of solution, filtering the catalyst by using a filter with a pore diameter of 0.22 mu m, and then measuring NH by a Nashin's reagent method4+Concentration; starting a 300W xenon lamp source, carrying out photocatalytic reaction for 120min, extracting 5mL of solution every 30min, filtering out the catalyst by using a filter with the pore diameter of 0.22 mu m, and then feeding into the reactorNH determination by Rona's reagent method4+And (4) concentration.
Application example 2
Examples 1-3 samples were subjected to visible light photocatalytic nitrogen fixation to synthesize ammonia.
20mg of catalyst and 100mL of deionized water were weighed into a quartz photocatalytic reactor and sonicated until the catalyst was uniformly dispersed in the water. Introducing pure nitrogen with a flow rate of 80mL/min for 30min in a dark state under the condition of introducing condensed water and keeping the water temperature at 15 ℃, extracting 5mL of solution, filtering the catalyst by using a filter with a pore diameter of 0.22 mu m, and then measuring NH by a Nashin's reagent method4+Concentration; starting a 300W xenon lamp source, adding a 700nm optical filter to make only near infrared light, carrying out photocatalytic reaction for 120min, extracting 5mL solution every 30min, filtering the catalyst by using a filter with the aperture of 0.22 μm, and then measuring NH by a Nashin reagent method4+And (4) concentration.
FIG. 8 shows the photocatalytic nitrogen fixation effect of visible light in two hours of the bismuth sulfide photocatalyst containing sulfur vacancies obtained in examples 1-3, wherein the photocatalyst in example 1 has the best photocatalytic nitrogen fixation effect, water is used as a reducing agent, and the yield of ammonia gas is 122.9 mu mol g-1h-1Example 2 photocatalyst Ammonia gas production 28.4. mu. mol g-1h-1Example 3 photocatalyst Ammonia gas production 64.3. mu. mol g-1h-1. FIG. 9 shows the nitrogen fixation effect of the sulfur vacancy-containing bismuth sulfide photocatalyst obtained in example 1 under visible light and near infrared light, wherein the yield of ammonia gas under near infrared light is 58.6 mu mol g-1h-1. Therefore, the higher the concentration of the sulfur vacancy is, the better the photocatalysis nitrogen fixation effect is.
Due to limited space, the whole test data cannot be listed, and only part of the test data is provided to support the beneficial effects of the invention.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (4)
1. The application of bismuth sulfide catalyst with sulfur vacancy is characterized in that the bismuth sulfide catalyst is used as a catalyst for visible-near infrared light catalysis.
2. Use of a bismuth sulfide catalyst with sulfur vacancies according to claim 1, wherein the visible-near infrared photocatalysis is used for nitrogen fixation.
3. The use of a bismuth sulfide catalyst with sulfur vacancies is characterized in that the bismuth sulfide catalyst with sulfur vacancies is used in a visible-near infrared photocatalysis process.
4. Use of a bismuth sulfide catalyst with sulfur vacancies according to claim 3, characterized in that the bismuth sulfide catalyst with sulfur vacancies is used in a visible-near infrared photocatalytic nitrogen fixation process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115500256A (en) * | 2022-11-05 | 2022-12-23 | 北京化工大学 | Photocatalysis nitrogen fixation plant water planting growth device |
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2020
- 2020-12-04 CN CN202011402953.2A patent/CN112456514A/en active Pending
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| HONGLI SUN等: "Defect-Type-Dependent Near-Infrared-Driven Photocatalytic Bacterial Inactivation by Defective Bi2S3 nanorods", 《CHEMSUSCHEM》 * |
| 孙明禄等: "Bi系光催化材料结构调控方法及其在环境能源领域的应用研究进展", 《华中农业大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115500256A (en) * | 2022-11-05 | 2022-12-23 | 北京化工大学 | Photocatalysis nitrogen fixation plant water planting growth device |
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Application publication date: 20210309 |